Lithium ion secondary battery

Abstract

Provided is a novel lithium ion secondary battery. This lithium ion secondary battery has a positive electrode and a negative electrode. The positive electrode has positive electrode active material particles. The positive electrode active material particles include lithium, cobalt, oxygen, magnesium, fluorine, nickel, and aluminum. The positive electrode active material particles have a surface layer section having an edge region, and an interior section. The interior section has an R-3m space group layered rock salt-type crystal structure. When a side-by-side arrangement of bright spots on the surface of the positive electrode active material particles as observed in a cross-sectional STEM image of a surface where lithium is inserted / extracted is treated as a first row, at least a portion of a fourth row through a ninth row that are located in the interior direction of the positive electrode active material particles have characteristics of a spinel-type crystal structure. In a STEM-EELS analysis of the fourth row through the ninth row, magnesium and nickel are detected at positions where only the Wyckoff position 16c of an Fd-3m space group overlaps, and nickel is detected at a position where only the Wyckoff position 16d overlaps.

Description

Lithium-ion secondary battery

[0001] One embodiment of the present invention relates to an object, a method, or a manufacturing method. Alternatively, the present invention relates to a process, a machine, manufacture, or a composition of matter. One embodiment of the present invention relates to a power storage device including a secondary battery, a semiconductor device, a display device, a light-emitting device, a lighting device, an electronic device, or a manufacturing method thereof.

[0002] In this specification, the term "electronic device" refers to any device having a power storage device, and includes electro-optical devices having a power storage device, information terminal devices having a power storage device, and the like.

[0003] In recent years, there has been active development of various types of energy storage devices, such as lithium-ion secondary batteries, lithium-ion capacitors, air batteries, and all-solid-state batteries. Demand for high-power, high-capacity lithium-ion secondary batteries has expanded rapidly in line with the development of the semiconductor industry, and they have become indispensable in today's information society as a rechargeable energy source.

[0004] In particular, there is a high demand for secondary batteries with a large discharge capacity per weight and excellent cycle characteristics for mobile electronic devices, etc. To meet this demand, improvements to the positive electrode active material of the positive electrode of secondary batteries have been actively pursued (e.g., Patent Documents 1 and 2). Research is also being conducted on the crystalline structure of positive electrode active material particles (Non-Patent Documents 1 to 3).

[0005] X-ray diffraction (XRD) is one of the techniques used to analyze the crystal structure of positive electrode active material particles. XRD data can be analyzed using the Inorganic Crystal Structure Database (ICSD) introduced in Non-Patent Document 4. For example, the lattice constant of lithium cobalt oxide described in Non-Patent Document 5 can be referenced from the ICSD. For Rietveld analysis, the analysis program RIETAN-FP (Non-Patent Document 6) can be used. VESTA (Non-Patent Document 7) can be used as software for drawing crystal structures.

[0006] Also, image processing software such as ImageJ (Non-Patent Documents 8 to 10) is known. By using this software, for example, the shape of positive electrode active material particles can be analyzed.

[0007] Microelectron diffraction is also effective for identifying the crystalline structure of positive electrode active material particles, particularly the crystalline structure of the surface layer. The analysis program ReciPro (Non-Patent Document 11), for example, can be used to analyze the electron diffraction pattern. Furthermore, STEM (Scanning Transmission Electron Microscope)-EDX (Energy Dispersive X-ray Spectroscopy) can be used for elemental analysis of the positive electrode active material. Non-Patent Document 12 is known as the detection limit (also referred to as the lower detection limit) when using STEM-EDX.

[0008] Lithium cobalt oxide is LiCoO with a layered rock salt crystal structure of space group R-3m, which is often used as a positive electrode active material for secondary batteries. ２ In addition, LiTiO of the space group Fd-3m ２ LiCoO of the type crystal structure ２ is known (Non-Patent Documents 13 and 14). LiTiO in the space group Fd-3m ２ LiCoO of the type crystal structure ２ Li ２ Ti ２ O ４ Structure: LT-LiCoO ２ This structure is also called a spinel-type LiCoO structure, which has lithium at the 16c position, cobalt at the 16d position, and oxygen at the 32e position in the Wyckoff positions (Non-Patent Document 15). The basic skeleton of this crystal structure is similar to that of a spinel-type crystal structure having atoms at the 8a, 16d, and 32e positions. ２ It is also called a modified spinel structure, a spinel-related structure, a structure having a spinel framework, or simply a spinel-type crystal structure without distinguishing between these.

[0009] JP 2018-206747 A JP 2022-070247 A

[0010] Toyoki Okumura et al.,“Correlation of lithium ion distribution and X−ray absorption near−edge structure in O3−and O2−lithium cobalt oxides from first−principle calculation”,Journal of Materials Chemistry,2012,22,p.17340−17348T.Motohashi,et al.,“Electronic phase diagram of the layered cobalt oxide system Li▲x▼CoO▲2▼(0.0≦x≦1.0)”,Physical Review B,80(16);165114Zhaohui Chen et al.,“Staging Phase Transitions in Li▲x▼CoO▲2▼”,Journal of The Electrochemical Society,2002,149(12)A1604−A1609A.Belsky,et al.,“New developments in the Inorganic Crystal Structure Database(ICSD):accessibility in support of materials research and design”,Acta Cryst.,(2002)B58 364−369.J.Akimoto,Y.Gotoh,Y.Oosawa,“Synthesis and structure refinement of LiCoO▲2▼ single crystals”Journal of Solid State Chemistry(1998)141,p.298−302.F.Izumi and K.Momma,“Three−Dimensional Visualization in Powder Diffraction”Solid State Phenom.130,15−20(2007)K.Momma and F.Izumi,”VESTA 3 for three−dimensional visualization of crystal,"Volumetric and morphology data" J. Appl. Cryst. (2011). 44, 1272−1276 Rasband, W. S., ImageJ, U.S. National Institutes of Health, Bethesda, Maryland, USA, http: / / rsb.info.nih.gov / ij / , 1997−2012. Schneider, C. A., Rasband, W. S., Eliceiri, K. W. "NIH Image to ImageJ: 25 years of image analysis". Nature Methods 9, 671−675, 2012. Abramoff, M. D., Magelhães, P. J., Ram, S. J. "Image Processing with ImageJ". Biophotonics International, volume 11, issue 7, pp. 36−42, 2004. Seto, Y. & Ohtsuka, M. "Recipro: free and open-source multipurpose crystallographic software integrating a crystal model database and viewer, diffraction and microscopy simulators, and diffraction data analysis tools" (2022). J. Appl. Cryst. 55. Keiichi Fukunaga, Yukito Kondo, "Detection Limit by TEM / STEM-EDS", Microscopy, 53.3, pp. 134−139. (2018) Antaya, M., Cearns, K., Preston, J. S., Reimers, J. N., & Dahn, J. R. In situ growth of layered, spinel, and rock-salt LiCoO▲2▼ by laser ablation deposition. Journal of applied physics, 76(5), 2799−2806, (1994). Maiyalagan, T., Jarvis, K. A., Therese, S., Ferreira, P. J., & Manthiram,A. Spinel-type lithium cobalt oxide as a bifunctional electrocatalyst for the oxygen evolution and oxygen reduction reactions. Nature communications, 5(1), 3949, (2014). W. Fischer, E. Koch, “14.2 Symbols and properties of lattice complexes”, International tables for crystallography Volume A, Fifth edition (ISBN: 0-7923-6590-9), Springer, (2005), pp. 848-872. ,

[0011] Lithium-ion secondary batteries have room for improvement in various aspects, such as output characteristics, discharge capacity, cycle characteristics, reliability, safety, and cost. For example, the surface of positive electrode active material particles may be coated with an inert oxide to suppress changes in the crystalline structure of the surface of the positive electrode active material particles. However, this coating may inhibit the intercalation and deintercalation of lithium ions. If the intercalation and deintercalation of lithium ions is inhibited, there is concern about deterioration in secondary battery characteristics, such as a decrease in discharge capacity during high-rate discharge (also known as a decrease in output characteristics or a decrease in rate characteristics) and a decrease in charge / discharge capacity in low-temperature environments.

[0012] In view of the above, an object of one embodiment of the present invention is to provide positive electrode active material particles that can be used in a lithium ion secondary battery and that promote the insertion and desorption of lithium ions. Another object is to provide positive electrode active material particles or a composite oxide in which a decrease in discharge capacity during high-rate discharge is suppressed. Another object is to provide positive electrode active material particles or a composite oxide in which a decrease in discharge capacity in a low-temperature environment is suppressed. Another object is to provide positive electrode active material particles or a composite oxide in which a decrease in discharge capacity during charge and discharge cycles is suppressed. Another object is to provide positive electrode active material particles or a composite oxide whose crystal structure is not easily destroyed even after repeated charge and discharge. Another object is to provide positive electrode active material particles or a composite oxide with a large discharge capacity. Another object is to provide a secondary battery that is safe or highly reliable, an electronic device including the secondary battery, or a vehicle including the secondary battery.

[0013] Another object of one embodiment of the present invention is to provide positive electrode active material particles, a composite oxide, a power storage device, or a manufacturing method thereof.

[0014] Note that the description of these problems does not preclude the existence of other problems. Note that one embodiment of the present invention does not necessarily solve all of these problems. Note that problems other than these can be extracted from the description in the specification, drawings, and claims.

[0015] One embodiment of the present invention is a lithium-ion secondary battery that includes a positive electrode and a negative electrode. The positive electrode includes positive electrode active material particles that include lithium, cobalt, oxygen, magnesium, fluorine, nickel, and aluminum. The positive electrode active material particles have a surface portion having an edge region and an interior portion. The interior portion has a layered rock-salt crystal structure of space group R-3m. Magnesium, fluorine, and nickel are detected in a cross-sectional STEM-EDX image of the edge region. When a row of bright spots of the positive electrode active material particles observed in the cross-sectional STEM image of the edge region is designated as a first row from the surface side, at least a portion of fourth to ninth rows of the positive electrode active material particles has a characteristic of a spinel crystal structure.

[0016] In the above, it is preferable that bright spots with high brightness and bright spots with low brightness are alternately arranged in the depth direction in at least a part of the cobalt layer in the fourth to ninth rows observed in a cross-sectional STEM image.

[0017] In the above, it is preferable that in at least a portion of the lithium layers in the fourth to ninth columns observed in a cross-sectional STEM image, bright spots with high brightness and regions in which no clear bright spots are observed are arranged alternately in the depth direction.

[0018] Another aspect of the present invention is a positive electrode active material particle having lithium cobalt oxide, the lithium cobalt oxide having magnesium, aluminum, and nickel, and a volume resistivity of the lithium cobalt oxide powder of 1.0 × 10 at a pressure of 64 MPa. ８ Ω・cm or more 5.0×10 ８ The positive electrode active material particles have a resistivity of Ω cm or less, and in an XPS analysis of lithium cobalt oxide, when the concentration of cobalt is taken as 1, the magnesium concentration ratio (Mg / Co) is 0.50 or more and 0.90 or less, and in the XPS analysis, the full width at half maximum of the Mg1s peak is 1.0 eV or more and 2.6 eV or less.

[0019] In the positive electrode active material particles, when the magnesium concentration is set to 1, the fluorine concentration ratio (F / Mg) is preferably 0.10 or more and 0.20 or less in XPS analysis. When the cobalt concentration is set to 1, the aluminum concentration ratio (Al / Co) is preferably 0.01 or more and 0.04 or less, and the nickel concentration ratio (Ni / Co) is preferably 0.01 or more and 0.07 or less in XPS analysis.

[0020] Alternatively, one embodiment of the present invention is a lithium-ion secondary battery that includes a positive electrode and a negative electrode. The positive electrode includes positive electrode active material particles including lithium, cobalt, oxygen, magnesium, fluorine, nickel, and aluminum. The positive electrode active material particles include a surface portion having an edge region and an interior. The interior has a layered rock-salt crystal structure of space group R-3m. When a row of bright spots of the positive electrode active material particles observed in a cross-sectional HAADF-STEM image of the edge region is designated as a first row from the surface side, at least a part of fourth to ninth rows located toward the interior of the positive electrode active material particles has characteristics of a spinel crystal structure. In STEM-EELS analysis of the fourth to ninth rows of the positive electrode active material particles, magnesium and nickel are detected at a position where only Wyckoff position 16c of space group Fd-3m overlaps in the <110> direction, and nickel is detected at a position where only Wyckoff position 16d overlaps in the <110> direction.

[0021] Alternatively, one embodiment of the present invention is a lithium-ion secondary battery that includes a positive electrode and a negative electrode. The positive electrode includes positive electrode active material particles including lithium, cobalt, oxygen, magnesium, fluorine, nickel, and aluminum. The positive electrode active material particles include a surface portion having an edge region and an interior. The interior has a layered rock-salt crystal structure of the space group R-3m. When a row of bright spots of the positive electrode active material particles observed in a cross-sectional HAADF-STEM image of the edge region is defined as a first row from the surface side, at least a part of fourth to ninth columns located toward the interior of the positive electrode active material particles has characteristics of a spinel crystal structure. STEM-EELS analysis of the fourth to ninth columns of the positive electrode active material particles includes lithium sites where magnesium and nickel are detected, cobalt sites where magnesium and nickel are detected, and cobalt sites where nickel is detected.

[0022] Alternatively, one embodiment of the present invention includes a positive electrode and a negative electrode. The positive electrode includes positive electrode active material particles including lithium, cobalt, oxygen, magnesium, fluorine, nickel, and aluminum. The positive electrode active material particles have a surface portion having an edge region and an interior portion. The interior portion has a layered rock-salt crystal structure of the space group R-3m. When a row of bright spots of the positive electrode active material particles observed in a cross-sectional HAADF-STEM image of the edge region is defined as a first row from the surface side, at least some of lithium layers in fourth to ninth columns located toward the interior of the positive electrode active material particles are and in at least a portion of the cobalt layer of the fourth to ninth columns of the positive electrode active material particles, second bright spots having high brightness and third bright spots having low brightness are alternately arranged in the depth direction. In a STEM-EELS analysis of the fourth to ninth columns of the positive electrode active material particles, magnesium and nickel are detected in the first bright spots, the third bright spots, and the first regions, and nickel is detected in the second bright spots.

[0023] In the above STEM-EELS analysis, it is preferable that divalent cobalt and trivalent cobalt are detected at the position of the third bright spot.

[0024] In the above, the positive electrode active material particles preferably have a magnesium concentration ratio (Mg / Co) of 0.005 or more and 0.03 or less, and a nickel concentration ratio (Ni / Co) of 0.003 or more and 0.01 or less, when the cobalt concentration is taken as 1, as determined by EPMA analysis.

[0025] A positive electrode having any one of the above positive electrode active material particles is used, lithium metal is used for the negative electrode, and a mixture of lithium hexafluorophosphate, ethylene carbonate, diethyl carbonate, and 2 wt % vinylene carbonate is used for the electrolyte, and the battery is charged at a constant current of 0.5 C (where 1.0 C = 200 mA / g is satisfied) up to a voltage of 4.58 V in a 45°C environment, and then charged at a constant voltage until the current value reaches 0.05 C. When the positive electrode is analyzed by powder X-ray diffraction using CuKα1 radiation in an argon atmosphere, the XRD pattern preferably has diffraction peaks at least at 2θ = 18.85 ± 0.20° and 2θ = 45.15 ± 0.10°.

[0026] A positive electrode having any one of the above positive electrode active material particles is used, lithium metal is used for the negative electrode, and a mixture of lithium hexafluorophosphate, ethylene carbonate, diethyl carbonate, and 2 wt % vinylene carbonate is used for the electrolyte, and the battery is charged at a constant current of 0.5 C (where 1.0 C = 200 mA / g) up to a voltage of 4.60 V in a 25°C environment, and then charged at a constant voltage until the current value reaches 0.05 C. When the positive electrode is analyzed by powder X-ray diffraction using CuKα1 radiation in an argon atmosphere, the XRD pattern preferably has diffraction peaks at least at 2θ = 19.25 ± 0.12° and 2θ = 45.47 ± 0.10°.

[0027] One embodiment of the present invention is a method for producing positive electrode active material particles, the method including: a first step of mixing lithium cobalt oxide and lithium fluoride to prepare a first mixture; a second step of heating the first mixture at a temperature of 900° C. to 950° C. for a time period of 2 hours to 10 hours; a third step of mixing a magnesium source with the first mixture to prepare a second mixture; a fourth step of heating the second mixture at a temperature of 850° C. to 950° C. for a time period of 2 hours to 60 hours; a fifth step of mixing a nickel source and an aluminum source with the second mixture to prepare a third mixture; and a sixth step of heating the third mixture at a temperature of 800° C. to 900° C. for a time period of 2 hours to 20 hours.

[0028] In the above-described method for producing positive electrode active material particles, when EELS analysis is performed on a portion of the first mixture that has been subjected to the second step within 2 nm from the surface, the valence of cobalt is preferably 2.35 or more and 2.90 or less.

[0029] Alternatively, in the above-described method for producing positive electrode active material particles, it is preferable that lithium fluoride is mixed in addition to the magnesium source in the third step.

[0030] In any one of the above-described methods for producing positive electrode active material particles, it is preferable that in the third step, magnesium fluoride is used as the magnesium source, and the number of moles of magnesium fluoride is mixed in an amount of 0.5 to 3.0 relative to 100 moles of lithium cobalt oxide.

[0031] In the fifth step of the method for producing positive electrode active material particles, nickel hydroxide is preferably used as the nickel source and aluminum hydroxide is preferably used as the aluminum source. The nickel hydroxide and aluminum hydroxide are preferably mixed so that the number of moles of nickel hydroxide is 0.05 to 4.0 and the number of moles of aluminum hydroxide is 0.05 to 4.0, respectively, when the number of moles of lithium cobalt oxide is 100.

[0032] According to one embodiment of the present invention, it is possible to provide positive electrode active material particles that can be used in lithium ion secondary batteries and that promote the insertion and desorption of lithium ions. Alternatively, it is possible to provide positive electrode active material particles or composite oxides that suppress a decrease in discharge capacity during high-rate discharge. Alternatively, it is possible to provide positive electrode active material particles or composite oxides that suppress a decrease in discharge capacity in a low-temperature environment. Alternatively, it is possible to provide positive electrode active material particles or composite oxides that suppress a decrease in discharge capacity during charge-discharge cycles. Alternatively, it is possible to provide positive electrode active material particles or composite oxides that do not easily lose their crystal structure even after repeated charge-discharge cycles. Alternatively, it is possible to provide positive electrode active material particles or composite oxides that have a large discharge capacity. Alternatively, it is possible to provide a secondary battery that is highly safe or highly reliable, an electronic device having the secondary battery, or a vehicle having the secondary battery.

[0033] According to one embodiment of the present invention, positive electrode active material particles, a composite oxide, a power storage device, or a manufacturing method thereof can be provided.

[0034] Note that the description of these effects does not preclude the existence of other effects. Note that one embodiment of the present invention does not necessarily have all of these effects. Note that effects other than these will become apparent from the description in the specification, drawings, claims, etc., and it is possible to extract other effects from the description in the specification, drawings, claims, etc.

[0035] 1A, 1B, 1C, and 1D are diagrams illustrating a method for producing positive electrode active material particles. FIG. 2 is a diagram illustrating a method for producing positive electrode active material particles. FIGS. 3A, 3B, and 3C are diagrams illustrating a method for producing positive electrode active material particles. FIG. 4A is a cross-sectional view illustrating the internal structure of a secondary battery, and FIG. 4B is a cross-sectional view illustrating the positive electrode and electrolyte of the secondary battery. FIGS. 5A and 5B are cross-sectional views illustrating positive electrode active material particles. FIGS. 6A, 6B, 6C, 6D, 6E, and 6F are cross-sectional views illustrating positive electrode active material particles. FIG. 7A is an HAADF-STEM image, and FIG. 7B is an ABF-STEM image. FIGS. 8A and 8B are cross-sectional views illustrating LiTiO ２ 9A, 9B, 9C, 9D, 9E, and 9F are schematic diagrams of the crystal structure of LiTiO ２FIG. 10 is a schematic diagram of a crystal structure. FIG. 11 is a diagram illustrating the crystal structure of a cathode active material particle. FIG. 12 is a diagram illustrating the crystal structure of a conventional cathode active material particle. FIG. 13 is a diagram illustrating an XRD pattern calculated from the crystal structure. FIG. 14 is a diagram illustrating an XRD pattern calculated from the crystal structure. FIGS. 15A, 15B, 15C, 15D, 15E, 15F, and 15G are diagrams illustrating the positional relationship of distributions in EDX-ray analysis. FIG. 16A is an exploded perspective view of a coin-type secondary battery, FIG. 16B is a perspective view of the coin-type secondary battery, and FIG. 16C is a cross-sectional perspective view thereof. FIG. 17A shows an example of a cylindrical secondary battery. FIG. 17B shows an example of a cylindrical secondary battery. FIG. 17C shows an example of a plurality of cylindrical secondary batteries. FIG. 17D shows an example of an energy storage system having a plurality of cylindrical secondary batteries. FIGS. 18A and 18B are diagrams illustrating an example of a secondary battery, and FIG. 18C is a diagram illustrating the internal state of the secondary battery. FIGS. 19A, 19B, and 19C are diagrams illustrating an example of a secondary battery. FIGS. 20A and 20B are diagrams illustrating the external appearance of a secondary battery. FIGS. 21A, 21B, and 21C are diagrams illustrating a method for manufacturing a secondary battery. FIGS. 22A, 22B, and 22C are diagrams illustrating an example of a battery pack. FIGS. 23A is a perspective view of a battery pack illustrating one embodiment of the present invention, FIG. 23B is a block diagram of the battery pack, and FIG. 23C is a block diagram of a vehicle including the battery pack. FIGS. 24A, 24B, 24C, and 24D are diagrams illustrating an example of a transportation vehicle. FIG. 24E is a diagram illustrating an example of an artificial satellite. FIGS. 25A and 25B are diagrams illustrating a power storage device according to one embodiment of the present invention. Fig. 26A is a diagram showing an electric bicycle, Fig. 26B is a diagram showing a secondary battery for the electric bicycle, and Fig. 26C is a diagram illustrating a scooter. Figs. 27A, 27B, 27C, and 27D are diagrams illustrating an example of an electronic device. Fig. 28A shows an example of a wearable device, Fig. 28B is a perspective view of a wristwatch-type device, and Fig. 28C is a diagram illustrating a side view of the wristwatch-type device. Figs. 29A and 29B are cross-sectional HAADF-STEM images of positive electrode active material particles.30A and 30B are cross-sectional HAADF-STEM images of positive electrode active material particles. FIGS. 31A and 31B are diagrams illustrating the results of cross-sectional STEM-EDX analysis of positive electrode active material particles. FIGS. 32A and 32B are diagrams illustrating the results of cross-sectional STEM-EDX analysis of positive electrode active material particles. FIGS. 33A, 33B, 33C, and 33D are diagrams illustrating the results of cross-sectional STEM-EDX analysis of positive electrode active material particles. FIGS. 34A, 34B, 34C, and 34D are diagrams illustrating the results of cross-sectional STEM-EDX analysis of positive electrode active material particles. FIGS. 35A and 35B are diagrams illustrating the results of cross-sectional STEM-EDX analysis of positive electrode active material particles. FIGS. 36A and 36B are diagrams illustrating the results of cross-sectional STEM-EDX analysis of positive electrode active material particles. FIGS. 37A, 37B, 37C, and 37D are diagrams illustrating the results of cross-sectional STEM-EDX analysis of positive electrode active material particles. FIGS. 38A, 38B, 38C, and 38D are diagrams illustrating the results of cross-sectional STEM-EDX analysis of positive electrode active material particles. FIGS. 39A and 39B are diagrams illustrating the results of cross-sectional STEM-EDX analysis of positive electrode active material particles. FIGS. 40A and 40B are diagrams illustrating the results of cross-sectional STEM-EDX analysis of positive electrode active material particles. FIGS. 41A, 41B, 41C, and 41D are diagrams illustrating the results of cross-sectional STEM-EDX analysis of positive electrode active material particles. FIGS. 42A, 42B, 42C, and 42D are diagrams illustrating the results of cross-sectional STEM-EDX analysis of positive electrode active material particles. FIGS. 43A and 43B are graphs illustrating the results of XPS analysis. 44A and 44B are graphs illustrating the results of a discharge rate test. FIGS. 45A and 45B are graphs illustrating the results of a charge / discharge cycle test. FIGS. 46A and 46B are graphs illustrating the results of a charge / discharge cycle test. FIGS. 47A and 47B are graphs illustrating the results of a charge / discharge cycle test. FIG. 48 is a graph illustrating the results of a DSC test. FIG. 49 is a cross-sectional HAADF-STEM image of a positive electrode active material particle. FIG. 50 is a black-and-white inverted view of a cross-sectional HAADF-STEM image of a positive electrode active material particle. FIG. 51 is a diagram illustrating the results of a cross-sectional STEM-EELS analysis of a positive electrode active material particle. FIG. 52 is a diagram illustrating the results of a cross-sectional STEM-EELS analysis of a positive electrode active material particle.Fig. 53 is a diagram illustrating the results of cross-sectional STEM-EELS analysis of positive electrode active material particles. Fig. 54 is a diagram illustrating the results of cross-sectional STEM-EELS analysis of positive electrode active material particles. Fig. 55 is a graph illustrating the results of XRD analysis of a positive electrode in a high-voltage charged state. Fig. 56 is a graph illustrating the results of XRD analysis of a positive electrode in a high-voltage charged state. Fig. 57 is a graph illustrating the results of XRD analysis of a positive electrode in a high-voltage charged state. Figs. 58A and 58B are cross-sectional HAADF-STEM images of positive electrode active material particles.

[0036] Hereinafter, examples of embodiments of the present invention will be described with reference to the drawings, etc. However, the present invention should not be construed as being limited to the following examples. The embodiments of the present invention can be modified within the scope of the spirit of the present invention.

[0037] In this specification, space groups are expressed using short notation in international notation (or Hermann-Mauguin notation). Crystal planes and crystal directions are expressed using Miller indices. In crystallography, space groups, crystal planes, and crystal directions are expressed by adding a superscript bar to the numbers. However, due to formatting constraints, in this specification, instead of adding a bar above the numbers, a minus sign (-) may be added before the numbers. Individual orientations indicating directions within a crystal are expressed using [ ], collective orientations indicating all equivalent directions are expressed using < >, individual planes indicating crystal planes are expressed using ( ), and collective planes with equivalent symmetry are expressed using {}. For ease of understanding the structure, trigonal crystals represented by the space group R-3m are generally expressed as a hexagonal composite hexagonal lattice. Unless otherwise specified, the space group R-3m will also be expressed as a composite hexagonal lattice in this specification. Miller indices may also be expressed as (hkil) rather than (hkl). Here, i is −(h+k).

[0038] In this specification and the like, the term "particle" is not limited to referring only to spherical particles (having a circular cross-sectional shape), and examples of the cross-sectional shape of individual particles include ellipsoids, rectangles, trapezoids, triangles, squares with rounded corners, and asymmetric shapes, and further, individual particles may have an irregular shape.

[0039] The theoretical capacity of a positive electrode active material refers to the amount of electricity when all of the intercalable and deintercalable lithium contained in the positive electrode active material is deintercalated. For example, LiCoO ２ The theoretical capacity of LiNiO is 274 mAh / g. ２ The theoretical capacity of LiMn is 275mAh / g. ２ O ４ The theoretical capacity of the battery is 148 mAh / g.

[0040] The amount of lithium remaining in the positive electrode active material that can be inserted or removed can be determined by x in the composition formula, for example, Li ｘ MO ２ In the above formula, M represents a transition metal, and unless otherwise specified in this specification, M is cobalt and / or nickel. In the case of a positive electrode active material in a lithium ion secondary battery, x can be expressed as (theoretical capacity - charging capacity) / theoretical capacity. For example, Li ｘ MO ２ When a lithium ion secondary battery using as a positive electrode active material is charged at 219.2 mAh / g, Li ０．２ MO ２ Or we can say x = 0.2. ｘ MO ２ The small value of x in the formula means, for example, 0.1<x≦0.24.

[0041] When properly synthesized lithium cobalt oxide is used in the positive electrode, the stoichiometric ratio is approximately satisfied. ２ and x = 1. The lithium cobalt oxide contained in the lithium ion secondary battery after discharge is also LiCoO ２ It can be said that x = 1. The state where discharge is completed (discharged state) here refers to a state where the voltage is 2.5 V or less at a current of 100 mA / g or less, for example.

[0042] When determining the current value per weight of the positive electrode active material, if the weight of the positive electrode active material contained in the positive electrode is unknown, the weight of the positive electrode active material can be determined by the following analysis. Generally, a positive electrode includes a positive electrode current collector and a positive electrode active material layer, and the positive electrode active material layer includes a positive electrode active material, a binder, and a conductive material. When the positive electrode is a coated electrode in which a positive electrode active material layer is coated on a metal foil of the positive electrode current collector, the positive electrode current collector and the positive electrode active material layer can be easily separated. Therefore, the weight ratio of the positive electrode current collector and the positive electrode active material layer in the positive electrode can be calculated by separating the positive electrode current collector and the positive electrode active material layer and measuring their weights. Furthermore, the weight of the positive electrode active material contained in the positive electrode active material layer can be calculated by analyzing the weight ratio of the positive electrode active material, the binder, and the conductive material.

[0043] The weight ratio of the positive electrode active material contained in the positive electrode active material layer can be analyzed by, for example, thermogravimetry-differential thermal analysis (TG-DTA). Specifically, using the positive electrode active material layer as a sample, TG-DTA is performed in an inert atmosphere, followed by an analysis in an oxygen-containing atmosphere. The weight ratio of the positive electrode active material, binder, and conductive material contained in the positive electrode active material layer can be calculated based on the weight change between the analyses. For example, the conditions for the analysis in an inert atmosphere include heating from 25°C to 600°C at a rate of 20°C / min in a 100% He atmosphere, and then cooling from 600°C to 300°C at a rate of 20°C / min, and measuring the weight loss during this process. The weight loss in this analysis in an inert atmosphere can be attributed to the decomposition of an organic compound, such as PVDF, used as the binder. Furthermore, as an example of an analysis in an oxygen-containing atmosphere, after the completion of the above-mentioned analysis in an inert atmosphere, 80% He and 20% O ２ The weight loss is measured as the temperature is increased from 300°C to 800°C at a rate of 20°C / min in an oxygen atmosphere. The weight loss in this analysis in an oxygen-containing atmosphere can be considered to be due to the combustion of the conductive material, which is mainly composed of carbon. In this way, the weight ratio of the positive electrode active material in the positive electrode active material layer can be determined.

[0044] Li ｘ MO ２ It is preferable that the charge capacity and / or discharge capacity used to calculate x in the above should be measured under conditions that are free of or minimally affected by short-circuiting and / or decomposition of the electrolyte, etc. For example, data from a lithium-ion secondary battery that has experienced a sudden change in capacity that is considered to be due to a short circuit should not be used to calculate x.

[0045] The space group of the positive electrode active material and the like is identified by XRD, electron diffraction, neutron diffraction, etc. Therefore, in this specification and the like, "belonging to a certain space group," "belonging to a certain space group," or "being a certain space group" can be rephrased as "identified with a certain space group."

[0046] Furthermore, if the anions have a structure in which three layers are stacked with a shift between them, such as ABCABC, it is called a cubic close-packed structure. Therefore, the anions do not need to be strictly cubic lattices. At the same time, since real crystals always have defects, the analysis results do not necessarily have to be theoretical. For example, in an FFT (fast Fourier transform) pattern such as an electron diffraction pattern or a TEM (transmission electron microscope) image, spots may appear at positions slightly different from the theoretical positions. For example, if the deviation from the theoretical position and orientation is 5° or less, or 2.5° or less, it can be said to have a cubic close-packed structure.

[0047] In this specification and the like, the positive electrode active material particles may be expressed as a positive electrode active material, a composite oxide, a positive electrode material, a positive electrode material, a positive electrode material for secondary batteries, a positive electrode material for lithium ion secondary batteries, or the like.

[0048] Furthermore, when describing the characteristics of individual particles in the following embodiments, etc., it is not necessary for all particles to have that characteristic. For example, if 50% or more, preferably 66% or more, and more preferably 90% or more of three or more randomly selected positive electrode active material particles have that characteristic, it can be said that there is a sufficient effect of improving the characteristics of the positive electrode active material and a secondary battery including the same.

[0049] Unless otherwise specified, the materials contained in the secondary battery (positive electrode active material particles, negative electrode active material, electrolyte, separator, etc.) will be described in their pre-degradation state. A decrease in discharge capacity due to aging and burn-in treatments during secondary battery manufacturing is not considered to be degradation. For example, a secondary battery consisting of a single cell or a battery pack can be said to be in its pre-degradation state if it has a discharge capacity of 97% or more of its rated capacity. For secondary batteries for portable devices, the rated capacity conforms to JIS C 8711:2019. For other secondary batteries, the rated capacity conforms not only to the above JIS standard but also to various JIS and IEC standards for electric vehicle propulsion, industrial use, etc.

[0050] In this specification and the like, the state of the materials of a secondary battery before deterioration may be referred to as an initial product or initial state, and the state after deterioration (the state when the secondary battery has a discharge capacity of less than 97% of the rated capacity) may be referred to as a product in use or a state in use, or a used product or a used state.

[0051] In this specification, the (001) plane and the (003) plane may be collectively referred to as the (00l) plane. In this specification, the (00l) plane may also be referred to as the C plane, the basal plane, or the like. In addition, in lithium cobalt oxide, lithium has a two-dimensional diffusion path. In other words, it can be said that the lithium diffusion path exists along the plane. In this specification, a plane where the lithium diffusion path is exposed, that is, a plane where lithium is inserted and extracted (specifically, a plane other than the (00l) plane), may be referred to as an edge plane.

[0052] In this specification, etc., secondary particles refer to particles formed by aggregation of primary particles. Also in this specification, etc., primary particles refer to particles that do not have grain boundaries on their appearance. Also in this specification, etc., single particles refer to particles that do not have grain boundaries on their appearance. Also in this specification, etc., single crystals refer to crystals in a state where there are no grain boundaries inside the particles, and polycrystals refer to crystals in a state where there are grain boundaries inside the particles. Polycrystals can be said to be an aggregate of multiple crystallites, and grain boundaries can be said to be the interface that exists between two or more crystallites. In polycrystals, it is preferable that the crystallites are aligned in orientation.

[0053] In this specification etc., the term "A and / or B" may be used, but this is an example of a description that includes only A, only B, or both A and B.

[0054] A short circuit in a secondary battery not only causes problems in the charging and / or discharging operations of the secondary battery, but may also lead to heat generation and fire. To achieve a safe secondary battery, it is preferable that a short circuit be suppressed even at a high charging voltage. The positive electrode of the battery according to one embodiment of the present invention suppresses a short circuit even at a high charging voltage. Therefore, a battery that achieves both high discharge capacity and safety can be obtained.

[0055] Ordinal numbers such as "first" and "second" used in this specification are used to avoid confusion between components and do not indicate any order or ranking, such as order of placement or stacking. Even if a term is not used in this specification, an ordinal number may be used in the claims to avoid confusion between components. Even if a term is used in this specification, a different ordinal number may be used in the claims. Even if a term is used in this specification, the ordinal number may be omitted in the claims.

[0056] 1A to 3C are diagrams illustrating a method for manufacturing the positive electrode active material particles 100, which are a positive electrode active material for a battery according to one embodiment of the present invention.

[0057] The method of adding the additive element A is important for producing the positive electrode active material particles 100. At the same time, it is also important that the crystallinity inside the positive electrode active material particles is good.

[0058] Therefore, in the process of producing the positive electrode active material particles 100, it is preferable to first synthesize lithium cobalt oxide by mixing a first lithium source and a cobalt source and performing a heat treatment, then mix the lithium cobalt oxide with a second lithium source and perform a heat treatment, and then mix an additive element source and perform a heat treatment.

[0059] In a method of synthesizing lithium cobalt oxide containing the additive element A by simultaneously mixing the additive element source with the first lithium source and the cobalt source, it is difficult to increase the concentration of the additive element A in the surface layer portion of the positive electrode active material particles. Furthermore, if the additive element source is simply mixed without heating after the lithium cobalt oxide is synthesized, the additive element A will simply adhere to the lithium cobalt oxide without forming a solid solution therein. Without sufficient heating, it is difficult to achieve a good distribution of the additive element A. For this reason, it is preferable to mix the additive element source with the lithium cobalt oxide after synthesizing it and then perform a heat treatment.

[0060] However, if the temperature of the heat treatment is too high, cation mixing occurs, increasing the possibility that the additive element A, for example, magnesium, enters the cobalt site. ｘ CoO ２ When x in the matrix is ​​small, the layered rock salt crystal structure of R-3m is not maintained. Furthermore, if the heat treatment temperature is too high, there are concerns about adverse effects such as the reduction of cobalt to divalent and the evaporation of lithium.

[0061] [Initial Heating] Therefore, it is preferable to mix lithium cobalt oxide with a second lithium source and heat it (also referred to as initial heating) before mixing it with the additive element source and heating it. Here, it is preferable to use a material that functions as a flux, such as lithium fluoride, as the second lithium source.

[0062] It is also preferable to thoroughly mix the lithium cobalt oxide and the second lithium source, for example, by using a ball mill.

[0063] In the step of thoroughly mixing the lithium cobalt oxide and the second lithium source, there is an effect of eliminating adhesion between particles of the lithium cobalt oxide.

[0064] Furthermore, by adding a material that functions as a flux as the second lithium source, there is an effect of suppressing re-adhesion of lithium cobalt oxide particles to each other when the lithium cobalt oxide after the initial heating is mixed with the additive element source and heated in the subsequent step.

[0065] If the additive element A is added and heated in a state in which the lithium cobalt oxide particles are stuck together, there is a risk that the additive element A will not be sufficiently distributed in the stuck parts. Therefore, when the sticking is resolved in a later process, for example, in a pressure process after coating on a positive electrode current collector, a surface to which the additive element A is not sufficiently added will be exposed, and there is a risk that deterioration will begin from that surface when the lithium cobalt oxide is used in a secondary battery. Therefore, it is preferable to suppress the sticking of the lithium cobalt oxide particles together using the method described above, and then mix the additive element source and heat the mixture.

[0066] Furthermore, by adding a flux in the initial heating step, when the lithium cobalt oxide after the initial heating is mixed with the additive element source and heated in the subsequent step, a melting point depression occurs near the surface of the lithium cobalt oxide. By lowering the melting point in this way, it becomes easy to achieve a good distribution of the additive element A at a temperature where cation mixing is unlikely to occur.

[0067] Therefore, the heating temperature in the initial heating is preferably a temperature equal to or higher than the melting point of the second lithium source. For example, when lithium fluoride is used as the second lithium source, the heating temperature is preferably higher than 848°C (e.g., 850°C or higher), which is the melting point of lithium fluoride, and more preferably 900°C or higher. Furthermore, the heating temperature in the initial heating is preferably equal to or lower than the temperature used to synthesize lithium cobalt oxide (e.g., 950°C or lower). That is, in the initial heating, lithium cobalt oxide and lithium fluoride are preferably mixed and heated at a temperature of 900°C or higher and 950°C or lower.

[0068] Furthermore, by using lithium cobalt oxide that has undergone the above initial heating, it is possible to suppress lithium deficiency that occurs due to lithium evaporation in the subsequent step of mixing additional element A and heating.

[0069] The lithium cobalt oxide that has undergone the above-mentioned initial heating preferably has a higher proportion of layered rock salt type crystal structures in the surface layer compared to the lithium cobalt oxide before the initial heating. For example, the lithium cobalt oxide that has undergone the above-mentioned initial heating preferably has layered rock salt type crystal structures in a portion within 2 nm from the surface of 35% or more, more preferably 45% or more. Furthermore, when EELS analysis is performed, the valence of cobalt is preferably 2.35 or more, more preferably 2.45 or more. The abundance of layered rock salt type crystal structures is one factor indicating that lithium deficiency is suppressed.

[0070] On the other hand, it is preferable that the entire surface layer of the lithium cobalt oxide does not have a layered rock-salt type crystal structure. For example, the solid solubility limit of magnesium in pure lithium cobalt oxide is extremely low. In order to dissolve magnesium and other additive elements A in a sufficient concentration, it is preferable that the surface layer of the lithium cobalt oxide has a rock-salt type crystal structure. Therefore, it is preferable that the lithium cobalt oxide that has undergone the above-mentioned initial heating has a layered rock-salt type crystal structure in the portion within 2 nm from the surface, less than 100%, more preferably 90% or less. Furthermore, when EELS analysis is performed, the valence of cobalt is preferably less than 3.00, more preferably 2.90 or less.

[0071] That is, in the lithium cobalt oxide that has undergone the above initial heating, the layered rock salt type crystal structure is preferably 35% or more but less than 100%, more preferably 35% or more but less than 90%, and even more preferably 45% or more but less than 90% in the portion within 2 nm from the surface. Furthermore, when EELS analysis is performed, the valence of cobalt is preferably 2.35 or more but less than 3.00, more preferably 2.35 or more but less than 2.90, and even more preferably 2.45 or more but less than 2.90.

[0072] <<Method 1 for Producing Positive Electrode Active Material Particles 100>> Method 1 for producing positive electrode active material particles 100, which undergoes heat treatment and initial heating, will be described with reference to FIGS. 1A to 1D. FIG.

[0073] <Step S11> In step S11 shown in FIG. 1B, a first lithium source (Li source 1) and a cobalt source (Co source) are prepared as the first lithium and transition metal materials, respectively, which are starting materials.

[0074] As the first lithium source, it is preferable to use a compound containing lithium, such as lithium carbonate, lithium hydroxide, lithium nitrate, lithium fluoride, etc. It is preferable that the lithium source has high purity, and it is preferable to use a material with a purity of, for example, 99.99% or higher.

[0075] As the cobalt source, it is preferable to use a compound containing cobalt, such as tricobalt tetroxide or cobalt hydroxide.

[0076] The cobalt source preferably has a high purity, for example, a material with a purity of 3N (99.9%) or higher, preferably 4N (99.99%) or higher, more preferably 4N (99.995%) or higher, and even more preferably 5N (99.999%) or higher. By using a high-purity material, impurities in the positive electrode active material particles can be controlled. As a result, the capacity of the secondary battery is increased and / or the reliability of the secondary battery is improved.

[0077] In addition, the cobalt source preferably has high crystallinity, and preferably has, for example, single crystal grains. The crystallinity of the cobalt source can be evaluated using a TEM image, a STEM image, a HAADF-STEM (High-angle Annular Dark Field Scanning TEM) image, an ABF-STEM (Annular Bright-Field Scanning Transmission Electron Microscope) image, or an X-ray diffraction, electron diffraction, neutron diffraction, or the like. The above-mentioned methods for evaluating crystallinity can be applied not only to the evaluation of cobalt sources but also to the evaluation of other crystallinity.

[0078] <Step S12> Next, in step S12 shown in FIG. 1B, the first lithium source and the cobalt source are pulverized and mixed to prepare a mixed material. The pulverization and mixing can be performed by either a dry or wet method. The wet method allows for finer particle pulverization and mixing. When using the wet method, a solvent is prepared. Examples of solvents that can be used include ketones such as acetone, alcohols such as ethanol and isopropanol, ether, dioxane, acetonitrile, and N-methyl-2-pyrrolidone (NMP). It is preferable to use an aprotic solvent that is less likely to react with lithium. In this embodiment, dehydrated acetone with a purity of 99.5% or higher is used. It is preferable to mix the first lithium source and the cobalt source with dehydrated acetone with a purity of 99.5% or higher, with a water content reduced to 10 ppm or less, and then pulverize and mix them. Using dehydrated acetone with the above purity can reduce potential impurities.

[0079] A ball mill, a bead mill, or the like can be used as a means for pulverizing and mixing. When using a ball mill, aluminum oxide balls or zirconium oxide balls are preferably used as pulverizing media. Zirconium oxide balls are preferred because they emit less impurities. Furthermore, when using a ball mill, a bead mill, or the like, it is preferable to set the peripheral speed to 100 mm / s or more and 2000 mm / s or less in order to suppress contamination from the media. In this embodiment, the peripheral speed is set to 838 mm / s (rotation speed 400 rpm, ball mill diameter 40 mm).

[0080] <Step S13> Next, in step S13 shown in FIG. 1B , the mixed material is heated. The heating is preferably performed at a temperature of 800°C or higher and 1100°C or lower, more preferably 850°C or higher and 1050°C or lower, more preferably 900°C or higher and 1050°C or lower, even more preferably 900°C or higher and 950°C or lower, and even more preferably around 900°C. If the temperature is too low, the decomposition and melting of the first lithium source and the cobalt source may be insufficient. On the other hand, if the temperature is too high, lithium may evaporate from the first lithium source and / or cobalt may be excessively reduced, resulting in defects. For example, cobalt may change from trivalent to divalent, causing oxygen defects or the like.

[0081] If the heating time is too short, lithium cobalt oxide will not be synthesized, but if it is too long, productivity will decrease. For example, the heating time is preferably 1 hour or more and 100 hours or less, and more preferably 2 hours or more and 20 hours or less.

[0082] The temperature rise rate depends on the heating temperature reached, but is preferably 80° C. / h to 250° C. / h. For example, when heating at 1000° C. for 10 hours, the temperature rise rate can be 200° C. / h.

[0083] Heating is preferably carried out in an atmosphere with little water, such as dry air, for example, an atmosphere with a dew point of -50°C or less, more preferably an atmosphere with a dew point of -80°C or less. In this embodiment, heating is carried out in an atmosphere with a dew point of -93°C. In addition, in order to suppress impurities that may be mixed into the material, the CH ４ , CO, CO ２ , and H ２ It is preferable that the impurity concentrations of the above are each 5 ppb (parts per billion) or less.

[0084] An oxygen-containing atmosphere is preferred as the heating atmosphere. For example, dry air can be continuously introduced into the reaction chamber. In this case, the flow rate of the dry air is preferably 10 L / min. The method of continuously introducing oxygen into the reaction chamber and allowing oxygen to flow through the reaction chamber is called flow.

[0085] When the heating atmosphere is an atmosphere containing oxygen, a method of preventing oxygen from flowing may be used. For example, a method of reducing the pressure of the reaction chamber and then filling it with oxygen (which may also be called purging) may be used to prevent the oxygen from entering or leaving the reaction chamber. For example, the reaction chamber may be reduced in pressure to -970 hPa on a differential pressure gauge based on atmospheric pressure, and then filled with oxygen to 50 hPa.

[0086] After heating, the material may be cooled naturally, but it is preferable that the time required for the temperature to drop from the specified temperature to room temperature is within a range of 10 to 50 hours. However, cooling to room temperature is not necessarily required, as long as the material is cooled to a temperature acceptable for the next step.

[0087] The heating in this step may be carried out using a rotary kiln or a roller hearth kiln. Heating in a rotary kiln can be carried out while stirring, whether in a continuous or batch system.

[0088] The container for containing the object to be heated during heating is preferably an aluminum oxide crucible or an aluminum oxide setter (also called a sheath). An aluminum oxide crucible is a material that is almost free of impurities. In this embodiment, a setter made of aluminum oxide with a purity of 99.9% is used. It is preferable to cover the crucible or setter before heating, as this prevents the material from volatilizing. Mullite-cordierite may also be used as the material for the crucible and setter.

[0089] Furthermore, it is preferable to use a used crucible rather than a new one. In this specification, a new crucible refers to one that has undergone two or fewer heating processes with materials containing lithium, transition metal M, and / or additive element A. A used crucible refers to one that has undergone three or more heating processes with materials containing lithium, transition metal M, and / or additive element A. This is because using a new crucible may result in some of the materials, including lithium fluoride, being absorbed, diffused, migrated, and / or adhered to the sheath during heating. If some of the materials are lost as a result of this, there is a growing concern that the distribution of elements, particularly in the surface layer of the positive electrode active material particles, may not fall within the desired range. On the other hand, this risk is less likely with a used crucible.

[0090] After heating, the material may be crushed and sieved as necessary. When recovering the heated material, it may be transferred from the crucible to a mortar and then recovered. It is preferable to use a zirconium oxide mortar. Zirconium oxide mortars are made of a material that does not easily release impurities. Specifically, a zirconium oxide mortar with a purity of 90% or more, preferably 99% or more, is used. Heating conditions equivalent to those of step S13 can also be applied to heating steps other than step S13, which will be described later.

[0091] <Step S14> By the above steps, lithium cobalt oxide (LiCoO ２ ) can be synthesized. ２ ) into the starting material LiCoO in step S10 of FIG. ２ It can be used as:

[0092] Although an example of producing lithium cobalt oxide by a solid phase method as in steps S11 to S14 has been shown, lithium cobalt oxide may also be produced by a coprecipitation method or a hydrothermal method.

[0093] 1A, a second lithium source (Li source 2) is prepared. As the second lithium source, for example, lithium fluoride is preferably used.

[0094] <Step S16> Next, in step S16 shown in FIG. 1A, lithium cobalt oxide and the second lithium source are mixed. The mixing in step S16 is preferably performed under milder conditions than in step S12 so as not to destroy the shape of the lithium cobalt oxide particles. For example, the mixing conditions are preferably lower in rotation speed or shorter in time than in step S12. It can also be said that a dry method provides milder conditions than a wet method. For example, a ball mill, a bead mill, or the like can be used for mixing. When using a ball mill, it is preferable to use zirconium oxide balls as the media, for example.

[0095] <Step S17> Next, in step S17 shown in FIG. 1A, the lithium cobalt oxide and the second lithium source are heated. The heating is preferably performed at a temperature of 800°C to 1000°C, more preferably 850°C to 950°C, and even more preferably 900°C to 950°C. The heating time is preferably 1 hour to 60 hours, more preferably 2 hours to 20 hours, more preferably 2 hours to 10 hours, and even more preferably 2 hours to 6 hours. Because this is the first heating of the lithium cobalt oxide, the heating in step S17 is sometimes referred to as initial heating. Alternatively, because it is performed before step S33 described below, it may be referred to as preheating or pretreatment. By performing steps S16 and S17, lithium cobalt oxide with a smooth surface can be obtained.

[0096] Note that pre-synthesized lithium cobalt oxide may be used in step S14. In this case, steps S11 to S13 can be omitted. Even when pre-synthesized lithium cobalt oxide is used, lithium cobalt oxide with a smooth surface can be obtained by performing steps S16 and S17.

[0097] <Step S20> Next, as shown in step S20, it is preferable to add the additional element A to the lithium cobalt oxide that has undergone the initial heating. When the additional element A is added to the lithium cobalt oxide that has undergone the initial heating, the additional element A can be added evenly. Therefore, it is preferable to add the additional element A after the initial heating. The step of adding the additional element A will be described with reference to FIGS. 1C and 1D.

[0098] <Steps S21 to S23> The steps of preparing a source of additional element A (A source) will be described with reference to Fig. 1C. A lithium source may be prepared together with the source of additional element A.

[0099] The additive element A may be, for example, one or more elements selected from magnesium, fluorine, nickel, aluminum, zirconium, vanadium, iron, manganese, chromium, niobium, arsenic, zinc, silicon, sulfur, phosphorus, and boron. Also, one or two elements selected from bromine and beryllium may be used.

[0100] <Step S21> Step S21 shown in Fig. 1C will be described. When magnesium is selected as the additional element A, the source of the additional element can be called a magnesium source (Mg source). As the magnesium source, magnesium fluoride, magnesium oxide, magnesium hydroxide, magnesium carbonate, or the like can be used. Furthermore, a plurality of the above-mentioned magnesium sources may be used.

[0101] When fluorine is selected as the additive element A, the source of the additive element can be called a fluorine source (F source). Examples of the fluorine source include lithium fluoride (LiF), magnesium fluoride (MgF ２ ), aluminum fluoride (AlF ３ ), cobalt fluoride (CoF ２ , CoF ３ ), nickel fluoride (NiF ２ ), zirconium fluoride (ZrF ４ ), vanadium fluoride (VF ５ ), manganese fluoride, iron fluoride, chromium fluoride, niobium fluoride, zinc fluoride (ZnF ２ ), calcium fluoride (CaF ２), sodium fluoride (NaF), potassium fluoride (KF), barium fluoride (BaF ２ ), cerium fluoride (CeF ３ , CeF ４ ), lanthanum fluoride (LaF ３ ), or sodium aluminum hexafluoride (Na ３ AlF ６ ) can be used. Among these, lithium fluoride is preferred because it has a relatively low melting point of 848°C and is easily melted in the heating step described below. When lithium fluoride is used as the fluorine source, the lithium fluoride can also be called a third lithium source.

[0102] Magnesium fluoride can be used as both a fluorine source and a magnesium source, and lithium fluoride can be used as a lithium source. Another lithium source that can be used in step S21 is lithium carbonate.

[0103] The fluorine source is fluorine (F ２ ), fluorocarbon, sulfur fluoride, or oxygen fluoride (OF ２ , O ２ F ２ , O ３ F ２ , O ４ F ２ , O ５ F ２ , O ６ F ２ , O ２ In the heating step described below, a gas such as fluorine may be used and mixed into the atmosphere. Also, a plurality of the above-mentioned fluorine sources may be used.

[0104] In this embodiment, lithium fluoride (LiF) is prepared as the fluorine source, and magnesium fluoride (MgF) is prepared as the fluorine source and magnesium source. ２ Lithium fluoride and magnesium fluoride are prepared as LiF:MgF ２ The effect of lowering the melting point is greatest when the molar ratio is about 65:35. On the other hand, if the amount of lithium fluoride is too high, there is a concern that the lithium will be excessive and the cycle characteristics will deteriorate. Therefore, the molar ratio of lithium fluoride to magnesium fluoride is set to LiF:MgF ２=x:1 (0≦x≦1.9), and LiF:MgF ２ =x:1 (0.1≦x≦0.5) is more preferable, and LiF:MgF ２ = x: 1 (x = 0.33 or its vicinity) is more preferable. In this specification, "or its vicinity" refers to a value that is greater than 0.9 times and smaller than 1.1 times the value.

[0105] 1C, the magnesium source and the fluorine source are pulverized and mixed. This step can be performed under pulverization and mixing conditions selected from those described in step S12.

[0106] 1C, the pulverized and mixed materials are collected to obtain a source of the additional element A (A source). Note that the source of the additional element A shown in step S23 contains a plurality of starting materials and can be called a mixture.

[0107] The particle size of the mixture is preferably D50 (median diameter) of 600 nm to 10 μm, more preferably 1 μm to 5 μm. Even when a single material is used as the additive element source, the D50 (median diameter) is preferably 600 nm to 10 μm, more preferably 1 μm to 5 μm.

[0108] Such a finely powdered mixture (including the case where only one type of additive element A is contained) can be easily adhered to the surfaces of lithium cobalt oxide particles when mixed with lithium cobalt oxide in a later step. Uniform adhesion of the mixture to the surfaces of lithium cobalt oxide particles is preferable because it can easily distribute or diffuse the additive element A evenly in the surface layer portion of the positive electrode active material particles 100 after heating.

[0109] <Step S21> A step different from that shown in FIG. 1C will be described with reference to FIG. 1D. In step S21 shown in FIG. 1D, four types of additive element sources to be added to lithium cobalt oxide are prepared. That is, the types of additive element sources shown in FIG. 1D are different from those shown in FIG. 1C. A lithium source may be prepared together with the additive element sources.

[0110] As sources of four additive elements, a magnesium source (Mg source), a fluorine source (F source), a nickel source (Ni source), and an aluminum source (Al source) are prepared. The magnesium source and the fluorine source can be selected from the compounds described with reference to FIG. 1C. Nickel oxide, nickel hydroxide, etc. can be used as the nickel source. Aluminum oxide, aluminum hydroxide, etc. can be used as the aluminum source.

[0111] <Steps S22 and S23> Steps S22 and S23 shown in FIG. 1D are the same as the steps described in FIG. 1C.

[0112] <Step S31> Next, in step S31 shown in FIG. 1A, the lithium cobalt oxide that has been initially heated is mixed with an additional element A source (A source).

[0113] In the present embodiment, the number of magnesium atoms contained in the additive element A source is preferably 0.50% or more and 3.0% or less, more preferably 0.75% or more and 2.0% or less, and still more preferably 0.75% or more and 1.0% or less, relative to the number of cobalt atoms contained in the lithium cobalt oxide.

[0114] The mixing conditions in step S31 are preferably milder than those in step S12 so as not to destroy the shape of the lithium cobalt oxide particles. For example, it is preferable to use conditions with a lower rotation speed or a shorter mixing time than those in step S12. It can also be said that dry mixing provides milder conditions than wet mixing. For example, a ball mill, a bead mill, or the like can be used for mixing. When using a ball mill, it is preferable to use zirconium oxide balls as the medium.

[0115] In this embodiment, dry mixing is performed in a ball mill using zirconium oxide balls with a diameter of 1 mm at 150 rpm for 1 hour in a dry room with a dew point of −100° C. or higher and −10° C. or lower.

[0116] 1A, the mixed materials are collected to obtain a mixture 903. When collecting the materials, sieving may be performed as necessary.

[0117] 1A to 1D illustrate a fabrication method in which the additional element A is added only after initial heating, but the present invention is not limited to the above method. The additional element A may be added at a different timing or multiple times. The timing may vary depending on the element.

[0118] <Step S33> Next, in step S33 shown in FIG. 1A, the mixture 903 is heated.

[0119] For example, as a source of the additive element A, MgF ２ When LiF and MgF ２ Since the eutectic point of is around 742°C, it is preferable that the heating temperature in step S33 be 742°C or higher.

[0120] Also, LiCoO ２ :LiF:MgF ２ A mixture obtained by mixing the components so that the molar ratio is 100:0.33:1 exhibits an endothermic peak at around 830°C in differential scanning calorimetry (DSC). This endothermic peak is thought to be due to melting of the mixture, so the heating temperature is preferably 830°C or higher. Therefore, the heating in step S33 is preferably carried out at a temperature of 800°C or higher and 1000°C or lower, more preferably 830°C or higher and 950°C or lower, and even more preferably 850°C or higher and 950°C or lower. The heating time is preferably 1 hour or higher and 60 hours or lower, and more preferably 2 hours or higher and 20 hours or lower.

[0121] 1A , LiF, which is the second lithium source added in steps S16 and S17, may function as a flux. This function allows the heating temperature in step S33 to be lower than the decomposition temperature of lithium cobalt oxide, for example, to a temperature between 742° C. and 950° C., and allows the additive element A, such as magnesium, to be present in the surface layer portion, thereby enabling the production of positive electrode active material particles with excellent characteristics.

[0122] Regarding the heating time, the heating time varies depending on conditions such as the heating temperature, the size and composition of the lithium cobalt oxide in step S14, etc. When the lithium cobalt oxide is small, a lower heating temperature or a shorter heating time may be preferable than when the lithium cobalt oxide is large.

[0123] <Step S34> Next, in step S34 shown in FIG. 1A , the heated material is recovered to obtain positive electrode active material particles 100. At this time, the recovered particles can be crushed by sieving as necessary. Through the above steps, the positive electrode active material particles 100 of one embodiment of the present invention can be produced. The positive electrode active material particles of one embodiment of the present invention have a smooth surface.

[0124] <<Method 2 for Producing Positive Electrode Active Material Particles 100>> Next, a method 2 for producing positive electrode active material particles 100, which is one embodiment of the present invention and differs from method 1 for producing positive electrode active material particles 100, will be described with reference to Figures 2 to 3C. Method 2 for producing positive electrode active material particles differs from method 1 mainly in the number of times the additive element A is added and the mixing method. For other descriptions, the description of method 1 can be referred to.

[0125] In FIG. 2, steps S11 to S17 are carried out in the same manner as in FIGS. 1A and 1B to prepare lithium cobalt oxide that has undergone initial heating.

[0126] <Step S20a> Next, as shown in step S20a, it is preferable to add an additional element A1 to the lithium cobalt oxide that has undergone the initial heating.

[0127] <Step S21> In steps S21 to S23 shown in Fig. 3A, a first additive element source (A1 source) is prepared. The first additive element source can be selected from the additive elements A described in step S21 shown in Fig. 1C and used. For example, one or more selected from magnesium and fluorine can be suitably used as the additive element A1. Fig. 3A illustrates an example in which a magnesium source (Mg source) and a fluorine source (F source) are used as the first additive element source.

[0128] Steps S21 to S23 shown in Fig. 3A can be performed under the same conditions as steps S21 to S23 shown in Fig. 1C. As a result, an additional element source (Al source) can be obtained in step S23.

[0129] Furthermore, steps S31 to S33 shown in FIG. 2 can be performed in the same manner as steps S31 to S33 shown in FIG. 1A.

[0130] <Step S34a> Next, the material heated in step S33 is recovered to produce lithium cobalt oxide containing the additional element A1. To distinguish it from the lithium cobalt oxide in step S14, this is called a composite oxide.

[0131] <Step S40> In step S40 shown in Fig. 2, a second additive element source (A2 source) is prepared. This will be described with reference to Figs. 3B and 3C.

[0132] <Step S41> In steps S41 to S43 shown in FIG. 3B, a second additive element source (A2 source) is prepared. The additive element A2 contained in the second additive element source can be selected from the additive elements A described in step S21 shown in FIG. 1D. For example, the additive element A2 can be one or more selected from nickel, boron, zirconium, and aluminum. FIG. 3B illustrates an example in which a nickel source (Ni source) and an aluminum source (Al source) are used as the second additive element source. Examples of nickel sources that can be used include nickel hydroxide and nickel fluoride. Examples of aluminum sources that can be used include aluminum hydroxide and aluminum fluoride.

[0133] The number of nickel atoms contained in the second additive element source (A2 source) is preferably 0.05% or more and 4.0% or less, more preferably 0.20% or more and 2.0% or less, and even more preferably 0.20% or more and 1.0% or less, relative to the number of cobalt atoms in the lithium cobalt oxide. For example, when nickel hydroxide is used as the nickel source, when the number of moles of lithium cobalt oxide in step S10 is taken as 100, the number of moles of nickel hydroxide contained in the second additive element source is preferably 0.05 or more and 4.0 or less (0.05 mol% or more and 4.0 mol% or less), more preferably 0.20 or more and 2.0 or less (0.20 mol% or more and 2.0 mol% or less), and even more preferably 0.20 or more and 1.0 or less (0.20 mol% or more and 1.0 mol% or less).

[0134] The number of aluminum atoms contained in the second additive element source (A2 source) is preferably 0.05% to 4.0% of the number of cobalt atoms in the lithium cobalt oxide, more preferably 0.20% to 2.0%, and even more preferably 0.20% to 1.0%. For example, when aluminum hydroxide is used as the aluminum source, when the number of moles of lithium cobalt oxide in step S10 is taken as 100, the number of moles of aluminum hydroxide contained in the second additive element source is preferably 0.05 to 4.0 (0.05 mol% to 4.0 mol%), more preferably 0.20 to 2.0 (0.20 mol% to 2.0 mol%), and even more preferably 0.20 to 1.0 (0.20 mol% to 1.0 mol%).

[0135] Steps S41 to S43 shown in Fig. 3B can be performed under the same conditions as steps S21 to S23 shown in Fig. 1D. As a result, an additional element source (A2 source) can be obtained in step S43.

[0136] 3C shows a modified example of the steps described with reference to FIG. 3B. In step S41 shown in FIG. 3C, a nickel source (Ni source) and an aluminum source (Al source) are prepared, and in step S42a, they are pulverized. That is, in step S43 shown in FIG. 3C, a plurality of second additive element sources (A2 sources) are prepared.

[0137] <Steps S51 to S53> Next, steps S51 to S53 shown in FIG. 2 can be performed under the same conditions as steps S31 to S34 shown in FIG. 1A. The heating in step S53 is preferably performed at 800°C or higher and 1000°C or lower, more preferably 800°C or higher and 950°C or lower, and even more preferably 800°C or higher and 900°C or lower. The heating time is preferably 1 hour or higher and 60 hours or lower, more preferably 2 hours or higher and 20 hours or lower, and even more preferably 2 hours or higher and 10 hours or lower. The heating in step S53 is preferably performed at a lower heating temperature and for a shorter heating time than in step S33. Through the above steps, the cathode active material particle 100 of one embodiment of the present invention can be produced in step S54. The cathode active material particle of one embodiment of the present invention has a smooth surface.

[0138] 2 to 3C , in production method 2, the addition of the additional element A to lithium cobalt oxide is carried out separately as additional element A1 and additional element A2. By separately adding the additional element A1 and the additional element A2, the distribution of each additional element A in the depth direction can be changed. For example, it is possible to distribute the additional element A1 so that its concentration is higher in the surface layer portion of the positive electrode active material particle than in the interior of the positive electrode active material particle, and to distribute the additional element A2 so that its concentration is higher in the interior than in the surface layer portion.

[0139] The content of this embodiment can be freely combined with the content of other embodiment modes.

[0140] Embodiment 2 In this embodiment, a battery and positive electrode active material particles according to one embodiment of the present invention will be described.

[0141] [Battery] A lithium ion battery according to one embodiment of the present invention includes a positive electrode, a negative electrode, and an electrolyte. When the electrolyte contains an electrolytic solution, the battery also includes a separator between the positive electrode and the negative electrode. The battery may further include an exterior body that covers at least a portion of the periphery of the positive electrode, the negative electrode, and the electrolyte.

[0142] In this embodiment, a description will be given mainly of a positive electrode and positive electrode active material particles of a battery according to one embodiment of the present invention. Note that the positive electrode active material particles are the positive electrode active material particles 100 whose manufacturing method is described in Embodiment 1. Details of the remaining components of the lithium-ion battery according to one embodiment of the present invention will be described in Embodiment 3.

[0143] 4A is a cross-sectional schematic diagram illustrating the internal structure of a lithium-ion battery 10. The lithium-ion battery 10 has a positive electrode 11, a negative electrode 12, and a separator 13. The positive electrode 11 has a positive electrode current collector 21 and a positive electrode active material layer 22 on the positive electrode current collector 21, and the negative electrode 12 has a negative electrode current collector 31 and a negative electrode active material layer 32. As shown in the figure, the positive electrode active material layer 22 and the negative electrode active material layer 32 face each other with the separator 13 interposed therebetween. Although not shown in FIG. 4A , electrolytes are present in the voids of the positive electrode active material layer 22, the voids of the separator 13, and the voids of the negative electrode active material layer 32.

[0144] 4A illustrates one positive electrode 11, one negative electrode 12, and one separator 13, the lithium ion battery of one embodiment of the present invention is not limited to this structure. The lithium ion battery may have a structure including two positive electrodes 11, two negative electrodes 12, and two separators 13, or may have more than two electrodes stacked. Furthermore, the lithium ion battery may have a wound structure instead of the stacked structure illustrated in FIG. 4A.

[0145] FIG. 4B is an enlarged view of a portion A enclosed by a dashed line in FIG. 4A.

[0146] The positive electrode active material layer 22 includes positive electrode active material particles 100 (also referred to as a first positive electrode active material), second positive electrode active material particles 200, and a conductive material 41. Although not shown, the positive electrode active material layer 22 may include a binder in addition to the positive electrode active material particles 100, the second positive electrode active material particles 200, and the conductive material 41.

[0147] Furthermore, the voids in the positive electrode active material layer 22 are preferably filled with the electrolyte 51 as shown in the figure. For example, it is preferable that 60% or more of the voids in the positive electrode active material layer 22 be filled with the electrolyte 51, more preferably 70% or more of the voids, more preferably 80% or more of the voids, more preferably 90% or more of the voids, more preferably 95% or more of the voids, and most preferably 99% or more of the voids. The voids in the positive electrode active material layer 22 refer to regions in the positive electrode active material layer 22 other than those filled with solid components (such as positive electrode active material particles and conductive material).

[0148] [Positive Electrode] The positive electrode 11 has a positive electrode current collector 21 and a positive electrode active material layer 22. The positive electrode active material layer 22 has positive electrode active material particles 100.

[0149] <Positive Electrode Active Material Particles 100> The positive electrode active material particles 100 have the function of absorbing and releasing lithium ions during charging and discharging. The positive electrode active material particles used in one embodiment of the present invention can be made of a material that exhibits minimal deterioration during charging and discharging (hereinafter also referred to as "charging and discharging"), even at high charging voltages (hereinafter also referred to as "high charging voltages"). Specifically, positive electrode active material particles (composite oxides) having a particle diameter (median diameter (D50)) of 10 μm to 50 μm, preferably 10 μm to 25 μm, obtained by the method for producing positive electrode active material particles described in embodiment 1 can be used. The positive electrode active material particles 100 contain one or more of an additive element X, an additive element Y, and an additive element Z. The additive element X, the additive element Y, and the additive element Z will be described in detail in the section <Containing Elements>. Note that the additive element X, the additive element Y, and the additive element Z may be collectively referred to as additive element A.

[0150] The positive electrode active material particles 100 are the main constituent material of the positive electrode active material layer 22, and the weight of the positive electrode active material particles 100 is preferably 50% or more, more preferably 60% or more, and even more preferably 70% or more of the weight of the solid components of the positive electrode active material layer 22. If the particle diameter of the positive electrode active material particles 100 is too small, the surface area becomes too large, which may result in excessive reaction between the positive electrode active material particle surface and the electrolyte. For this reason, the particle diameter (median diameter (D50)) of the positive electrode active material particles is preferably 10 μm or more. Furthermore, if the particle diameter of the positive electrode active material particles is larger than the thickness of the active material layer described below, the particle density of the active material layer cannot be increased, so the particle diameter of the largest particle is preferably 50 μm or less.

[0151] The particle size can be measured using a particle size distribution meter (laser diffraction particle size distribution measuring device) using a laser diffraction / scattering method. D50 is the particle size when the cumulative amount in the cumulative curve of the particle size distribution measurement results accounts for 50%. The measurement of particle size is not limited to laser diffraction particle size distribution measurement, and the major axis of the particle cross section may be measured by analysis such as SEM (Scanning Electron Microscope) or TEM. Note that, as a method for measuring D50 by analysis such as SEM or TEM, for example, 20 or more particles are measured, a cumulative curve is created, and the particle size when the cumulative amount accounts for 50% can be taken as D50.

[0152] Furthermore, it is preferable that all of the active material particles in the positive electrode active material layer 22 (i.e., the positive electrode active material particles 100 and the second positive electrode active material particles 200) have a small difference in depth of charge during charging and discharging. This is because if the difference in depth of charge is large, particles with a high depth of charge are more likely to deteriorate. To mitigate the difference in depth of charge, the conductive material 41 and / or binder in the positive electrode active material layer 22 do not necessarily have to be uniformly distributed. For example, there may be cases where particles near the current collector have a high depth of charge and particles farther from the current collector have a lower depth of charge. Therefore, it is preferable that the conductive material 41 in the region farther from the current collector is more abundant than in the region near the current collector.

[0153] Unless otherwise specified in this specification, the "charging voltage" is expressed based on the potential of lithium metal. Furthermore, in this specification, the "high charging voltage" refers to a charging voltage of, for example, 4.5 V or higher, preferably 4.55 V or higher, more preferably 4.6 V or higher, 4.65 V or higher, or 4.7 V or higher.

[0154] As mentioned above, in this specification, a "high charging voltage" is defined as 4.6 V or higher based on the potential when the negative electrode is made of lithium metal, but when the potential when the negative electrode is made of a carbon material (e.g., graphite) is used as the reference, a "high charging voltage" is defined as 4.5 V or higher. In short, in the case of a half cell using lithium metal as the negative electrode, a charging voltage of 4.6 V or higher is defined as a high charging voltage, and in the case of a full cell using a carbon material (e.g., graphite) as the negative electrode, a charging voltage of 4.5 V or higher is defined as a high charging voltage.

[0155] Positive electrode active material particles 100 that are less susceptible to deterioration due to repeated charging and discharging at a high charging voltage will be described with reference to FIGS. 5A to 6F. FIG.

[0156] 5A and 5B are cross-sectional views of a positive electrode active material particle 100 according to one embodiment of the present invention. Enlarged views of the vicinity of A-B in FIG. 5B are shown in FIGS. 6A to 6C. Enlarged views of the vicinity of C-D in FIG. 5B are shown in FIGS. 6D to 6F.

[0157] 5A, the positive electrode active material particle 100 has a surface layer portion 100a and an inner portion 100b. In these drawings, the boundary between the surface layer portion 100a and the inner portion 100b is indicated by a dashed line.

[0158] The surface layer 100a of the positive electrode active material particle 100 refers to a region extending from the surface to the interior within 50 nm, more preferably within 35 nm, even more preferably within 20 nm, and most preferably within 10 nm perpendicular or approximately perpendicular from the surface to the interior. Note that "approximately perpendicular" refers to an angle of 80° to 100°. Surfaces resulting from cracks and / or fissures may also be referred to as the surface. The surface layer 100a is synonymous with the near-surface, near-surface region, or shell.

[0159] The region deeper than the surface layer 100a of the positive electrode active material particle is referred to as the inner portion 100b, which is synonymous with the inner region or core.

[0160] Furthermore, when the positive electrode active material particle 100 has a layered rock salt crystal structure of space group R-3m, the surface layer portion 100a has an edge region 100a1 and a basal region 100a2, as shown in Fig. 5B . In Fig. 5A and Fig. 5B , the straight line marked (00l) represents the (00l) plane. Here, the edge region 100a1 has a surface exposed in a direction intersecting the (00l) plane, and the edge region 100a1 refers to a region extending from the surface toward the interior within 50 nm, more preferably within 35 nm, even more preferably within 20 nm, and most preferably within 10 nm perpendicular or substantially perpendicular to the surface. Here, "intersect" means that the angle formed by the perpendicular to the first surface (the (00l) surface) and the normal to the second surface (the surface of the positive electrode active material particle 100) is 10 degrees or more and 90 degrees or less, more preferably 30 degrees or more and 90 degrees or less.

[0161] The basal region 100a2 has a surface parallel to the (00l) plane, and the region extending from the surface to the interior within 50 nm, more preferably within 35 nm, even more preferably within 20 nm, and most preferably within 10 nm perpendicular or approximately perpendicular from the surface to the interior is referred to as the basal region 100a2. Note that "parallel" here means that the angle between the perpendicular to the first surface (the (00l) plane) and the normal to the second surface (the surface of the positive electrode active material particle 100) is 0 degrees or more and 5 degrees or less, more preferably 0 degrees or more and 2.5 degrees or less.

[0162] The surface of the positive electrode active material particle 100 refers to the surface of the composite oxide including the surface layer portion 100a and the interior portion 100b. The positive electrode active material particle 100 needs to contain a transition metal M capable of oxidation and reduction in order to maintain charge neutrality even when lithium ions are inserted and removed. In the positive electrode active material particle 100, the transition metal M is responsible for the oxidation and reduction reaction, and is oxidized and reduced as lithium ions are inserted and removed. When the positive electrode active material particle is subjected to analysis, a protective film may be attached to the surface, but the protective film is not included in the positive electrode active material particle. As the protective film, a single-layer film or a multi-layer film of carbon, metal, oxide, resin, etc. may be used.

[0163] The surface of the positive electrode active material particle 100 in a cross-sectional HAADF-STEM image or the like refers to the surface closest to the outside where a metal element having an atomic number greater than that of lithium is first observed. More specifically, the surface refers to the point where the atomic nucleus of the metal element having an atomic number greater than that of lithium is first observed, i.e., the point where the brightness peak is present in the cross-sectional HAADF-STEM image or the like.

[0164] Therefore, aluminum oxide (Al) that does not have lithium sites that can contribute to charge and discharge and is attached to the surface of the positive electrode active material particles 100 ２ O ３ ) are not included in the positive electrode active material particles 100. Examples of such metal oxides include metal oxides whose crystal orientation does not match that of the interior 100b.

[0165] The fact that the crystal orientations of the two regions roughly coincide can be determined from TEM images, STEM images, HAADF-STEM images, ABF-STEM images, electron diffraction patterns, etc. It can also be determined from FFT patterns of TEM images and FFT patterns of STEM images, etc. XRD, neutron diffraction, etc. can also be used as materials for determination.

[0166] It also does not include the electrolyte, decomposition products of the electrolyte, organic solvent, binder, conductive material, or compounds derived from these that are attached to the positive electrode active material particles 100 .

[0167] Since the positive electrode active material particles 100 are compounds containing a transition metal and oxygen capable of lithium insertion / extraction, the interface between the region where the transition metal M (e.g., Co, Ni, Mn, Fe, etc.) that is oxidized and reduced upon lithium insertion / extraction and oxygen is present and the region where it is not present is defined as the surface of the positive electrode active material particles. Surfaces formed by slips, cracks, and / or fissures may also be considered the surface of the positive electrode active material particles. When analyzing positive electrode active material particles, a protective film may be applied to the surface, but the protective film is not included in the positive electrode active material particles. The protective film may be a single-layer or multi-layer film of carbon, metal, oxide, resin, or the like.

[0168] <Containing Elements> The positive electrode active material particles 100 contain lithium, cobalt, oxygen, and an additional element A. Alternatively, the positive electrode active material particles 100 contain lithium cobalt oxide (LiCoO ２ ) to which an additional element A is added. However, the positive electrode active material particle 100 of one embodiment of the present invention preferably has a crystal structure described later. Therefore, the composition of lithium cobalt oxide is not strictly limited to Li:Co:O=1:1:2.

[0169] The positive electrode active material particles of a lithium-ion secondary battery must contain a transition metal capable of oxidation and reduction in order to maintain charge neutrality even when lithium ions are inserted and removed. The positive electrode active material particles 100 of one embodiment of the present invention preferably use cobalt as the transition metal responsible for the oxidation and reduction reaction. In addition to cobalt, at least one or more selected from nickel and manganese may also be used. It is preferable that the positive electrode active material particles 100 contain 75 atomic % or more, preferably 90 atomic % or more, and more preferably 95 atomic % or more of cobalt, among the transition metals contained therein, because of many advantages such as relatively easy synthesis, ease of handling, and excellent cycle characteristics.

[0170] Furthermore, when the cobalt content of the transition metals in the positive electrode active material particles 100 is 75 atomic % or more, preferably 90 atomic % or more, and more preferably 95 atomic % or more, lithium nickel oxide (LiNiO ２ ) and other composite oxides in which nickel accounts for the majority of the transition metal, ｘ CoO ２The stability is superior when x in the formula is small. This is thought to be because cobalt is less susceptible to distortion due to the Jahn-Teller effect than nickel. The strength of the Jahn-Teller effect in transition metal compounds varies depending on the number of electrons in the d orbital of the transition metal. Layered rock-salt composite oxides, such as lithium nickel oxide, in which octahedral low-spin nickel(III) accounts for the majority of the transition metal, are significantly affected by the Jahn-Teller effect, making the octahedral layers of nickel and oxygen prone to distortion. This increases the risk of crystal structure collapse during charge-discharge cycles. Furthermore, nickel ions are larger than cobalt ions and are closer in size to lithium ions. Therefore, layered rock-salt composite oxides, such as lithium nickel oxide, in which nickel accounts for the majority of the transition metal, are prone to cation mixing between nickel and lithium.

[0171] The additive element A contained in the positive electrode active material particles 100 is preferably one or more selected from magnesium, fluorine, nickel, aluminum, zirconium, vanadium, iron, manganese, chromium, niobium, arsenic, zinc, silicon, sulfur, phosphorus, boron, barium, bromine, and beryllium. When the total amount of the additive elements A contained in the positive electrode active material particles 100 is taken as 100 atomic %, if the sum of the transition metals among the additive elements A is too large, the charge / discharge capacity of the positive electrode active material particles 100 may decrease, so the additive element A is preferably less than 25 atomic %, more preferably less than 10 atomic %, and even more preferably less than 5 atomic %.

[0172] That is, the positive electrode active material particles 100 can be made of one or more of lithium cobalt oxide having magnesium, lithium cobalt oxide having magnesium and aluminum, lithium cobalt oxide having magnesium and nickel, lithium cobalt oxide having magnesium, aluminum, and nickel, lithium cobalt oxide having magnesium and fluorine, lithium cobalt oxide having magnesium, fluorine, and nickel, lithium cobalt oxide having magnesium, fluorine, nickel, and aluminum, and the like.

[0173] Furthermore, it can also be said that the positive electrode active material particles 100 can be any one or more of the following particles for use in a lithium ion battery: positive electrode active material particles having cobalt, oxygen, and magnesium; positive electrode active material particles having cobalt, oxygen, magnesium, and aluminum; positive electrode active material particles having cobalt, oxygen, magnesium, and nickel; positive electrode active material particles having cobalt, oxygen, magnesium, aluminum, and nickel; positive electrode active material particles having cobalt, oxygen, magnesium, and fluorine; positive electrode active material particles having cobalt, oxygen, magnesium, fluorine, and aluminum; positive electrode active material particles having cobalt, oxygen, magnesium, fluorine, and nickel; and positive electrode active material particles having cobalt, oxygen, magnesium, fluorine, nickel, and aluminum.

[0174] The additive element A is preferably present in a solid solution in the positive electrode active material particles 100. For example, when performing a line analysis using STEM-EDX, the position in the depth direction at which the additive element A begins to be detected is preferably located deeper than the position at which the transition metal M begins to be detected, i.e., closer to the interior of the positive electrode active material particles 100. In the line analysis using STEM-EDX in the depth direction, the position at which a certain element begins to be detected refers to the position at which the detected amount (count number) of characteristic X-rays attributable to that element begins to increase continuously.

[0175] These additional elements A further stabilize the crystal structure of the positive electrode active material particles 100 as will be described later.

[0176] The additional element A does not necessarily have to contain magnesium, fluorine, nickel, aluminum, zirconium, vanadium, iron, manganese, chromium, niobium, arsenic, zinc, silicon, sulfur, phosphorus, boron, barium, bromine, or beryllium.

[0177] For example, by making the cathode active material particles 100 substantially free of titanium, it is possible to enhance the effect of suppressing capacity reduction during repeated charging and discharging at high voltages. For example, the weight of titanium contained in the cathode active material particles 100 is preferably, for example, 600 ppm or less, and more preferably 100 ppm or less. Furthermore, when the cathode active material particles 100 are subjected to STEM-EDX analysis, it is preferable that characteristic X-rays attributable to titanium are not detected, that is, the concentration is below the lower detection limit (for example, less than 0.3 atomic%).

[0178] The surface layer 100a is the region from which lithium ions are first released during charging, and is a region where the lithium concentration is likely to be lower than that of the inner portion 100b. In addition, the atoms on the surface of the positive electrode active material particle 100 that are in the surface layer 100a can be said to be in a state where some of the bonds are broken. Therefore, the surface layer 100a is likely to become unstable, and can be said to be a region where deterioration of the crystal structure is likely to begin. On the other hand, if the surface layer 100a can be made sufficiently stable, Li ｘ CoO ２ Even when x is small, for example, 0.24 or less, the layered structure of the inner portion 100b made of cobalt and oxygen octahedra can be made less likely to break.Furthermore, displacement of the layers made of cobalt and oxygen octahedra in the inner portion 100b can be suppressed.

[0179] In order to give the surface layer portion 100a a stable composition and crystal structure, the surface layer portion 100a preferably contains an additive element A, and more preferably contains a plurality of additive elements A. Furthermore, the surface layer portion 100a preferably has a higher concentration of one or more selected from the additive elements A than the interior portion 100b. Furthermore, it is preferable that the one or more selected from the additive elements A contained in the positive electrode active material particles 100 have a concentration gradient. Furthermore, it is more preferable that the distribution of the additive elements in the positive electrode active material particles 100 differs depending on the additive element. For example, it is more preferable that the depth from the surface of the concentration peak differs depending on the additive element A. Here, the concentration peak refers to the maximum value of the concentration in the surface layer portion 100a or within 50 nm from the surface.

[0180] [Distribution] The distribution of the additional element A will be described. Figures 6A to 6C are enlarged views of the vicinity of A-B in Figure 5B and are views illustrating the edge region 100a1 of the positive electrode active material particle 100. Figures 6D to 6F are enlarged views of the vicinity of C-D in Figure 5B and are views illustrating the basal region 100a2 of the positive electrode active material particle 100.

[0181] For example, some of the additional elements A, such as magnesium, fluorine, silicon, phosphorus, and boron, preferably have a concentration gradient that increases from the interior 100b toward the surface, as shown by the gradation in Figures 6A and 6D. The additional element A having such a concentration gradient will be referred to as additional element X.

[0182] Another additional element A, such as aluminum or manganese, preferably has a concentration gradient and a concentration peak in a region deeper than the additional element X shown in Figures 6A and 6D, as shown by the density of the hatching in Figures 6B and 6E. The concentration peak may be present in the surface layer portion 100a, or may be deeper than the surface layer portion 100a. For example, it is preferable that the peak be present in a region of 5 nm to 30 nm from the surface toward the interior. The additional element A having such a concentration gradient will be referred to as additional element Y.

[0183] As shown by the presence or absence of hatching and the density of the hatching in Figures 6C and 6F, another additive element A, such as nickel or barium, may be clearly present in the edge region 100a1 but substantially absent in the basal region 100a2. Here, "clearly present" refers to a case in which a characteristic X-ray energy spectrum of the additive element is detected in a cross-sectional STEM-EDX analysis of the positive electrode active material particle 100. Furthermore, "substantially absent" refers to a case in which a characteristic X-ray energy spectrum of the additive element is not detected in a cross-sectional STEM-EDX analysis of the positive electrode active material particle 100. This also refers to the additive element being below the lower limit of detection in the STEM-EDX analysis. In this case, this also refers to the additive element being below the lower limit of detection in the STEM-EDX analysis. An additive element having such a distribution is referred to as additive element Z.

[0184] For example, magnesium ions, which are one of the additive elements X, are divalent, and magnesium ions are more stable at the lithium site than at the cobalt site in the layered rock-salt crystal structure, and therefore more likely to enter the lithium site. The presence of magnesium at an appropriate concentration at the lithium site in the surface layer 100a makes it easier to maintain the layered rock-salt crystal structure. This is because magnesium present at the lithium site is easily absorbed by CoO ２ It is presumed that this is because it functions as a pillar supporting the layers. ｘ CoO ２ When x in the formula (1) is, for example, 0.24 or less, the desorption of oxygen from around the magnesium can be suppressed. Furthermore, the presence of magnesium is expected to increase the density of the positive electrode active material particles 100. Furthermore, a high magnesium concentration in the surface layer portion 100a is expected to improve corrosion resistance to hydrofluoric acid produced by decomposition of the electrolyte.

[0185] At an appropriate concentration, magnesium does not adversely affect the lithium intercalation and deintercalation processes during charging and discharging, providing the above benefits. However, excessive magnesium may adversely affect lithium intercalation and deintercalation. Furthermore, its effect on stabilizing the crystal structure may be reduced. This is thought to be due to magnesium occupying cobalt sites in addition to lithium sites. Furthermore, excess magnesium compounds (e.g., oxides or fluorides) that do not substitute for either the lithium or cobalt sites may segregate on the surface of the positive electrode active material particles and become resistance components in secondary batteries. Furthermore, as the magnesium concentration in the positive electrode active material particles increases, the discharge capacity of the positive electrode active material particles may decrease. This is thought to be due to excessive magnesium occupancy at the lithium sites, reducing the amount of lithium contributing to charging and discharging.

[0186] Therefore, it is preferable that the amount of magnesium contained in the entire positive electrode active material particle 100 is appropriate. For example, the number of magnesium atoms is preferably 0.001 to 0.1 times the number of cobalt atoms, more preferably more than 0.01 and less than 0.04 times, and even more preferably about 0.02 times. The amount of magnesium contained in the entire positive electrode active material particle 100 referred to here may be a value obtained by performing elemental analysis of the entire positive electrode active material particle 100 using, for example, GD-MS, ICP-MS, or the like, or may be based on the value of the composition of raw materials in the process of producing the positive electrode active material particle 100.

[0187] Furthermore, aluminum, one of the additive elements Y, can exist at the cobalt site in the layered rock salt crystal structure. Because aluminum is a trivalent typical element and its valence does not change, lithium around the aluminum is less likely to move during charging and discharging. Therefore, the aluminum and its surrounding lithium function as pillars, suppressing changes in the crystal structure. Furthermore, aluminum has the effect of suppressing the elution of surrounding cobalt and improving continuous charging durability. Furthermore, because the Al—O bond is stronger than the Co—O bond, it can suppress the desorption of oxygen around the aluminum. These effects improve thermal stability. Therefore, the presence of aluminum as the additive element Y can improve safety when the positive electrode active material particle 100 is used in a secondary battery. Furthermore, the positive electrode active material particle 100 can be made to have a crystal structure that is less likely to collapse even with repeated charging and discharging.

[0188] On the other hand, an excess of aluminum may adversely affect the intercalation and deintercalation of lithium.

[0189] Therefore, it is preferable that the amount of aluminum contained in the entire positive electrode active material particle 100 is appropriate. For example, the number of aluminum atoms contained in the entire positive electrode active material particle 100 is preferably 0.05% to 4% of the number of cobalt atoms, preferably 0.1% to 2%, and more preferably 0.3% to 1.5%. Alternatively, 0.05% to 2% is preferable. Alternatively, 0.1% to 4% is preferable. The amount contained in the entire positive electrode active material particle 100 referred to here may be, for example, a value obtained by performing elemental analysis of the entire positive electrode active material particle 100 using GD-MS, ICP-MS, or the like, or may be based on the value of the composition of raw materials in the process of producing the positive electrode active material particle 100.

[0190] Nickel, which is one of the additional elements Z, can exist on either the cobalt site or the lithium site. When nickel exists on the cobalt site, it has a lower oxidation-reduction potential than cobalt, which leads to an increase in discharge capacity, which is preferable.

[0191] Furthermore, when nickel exists at the lithium site, the layer structure consisting of octahedra of cobalt and oxygen can be prevented from shifting. Also, the change in volume caused by charging and discharging is prevented. Also, the elastic modulus increases, that is, the material becomes hard. This is because nickel existing at the lithium site can also be prevented from shifting to CoO ２ This is presumably because they function as pillars supporting the layers together, which is preferable because it is expected that the crystal structure will be more stable especially in a charged state at high temperatures, for example, 45° C. or higher.

[0192] On the other hand, excessive nickel is undesirable because it increases the influence of strain due to the Jahn-Teller effect, and excessive nickel may also adversely affect the insertion and extraction of lithium.

[0193] Therefore, it is preferable that the positive electrode active material particle 100 as a whole contains an appropriate amount of nickel. For example, the number of nickel atoms contained in the positive electrode active material particle 100 is preferably more than 0% but not more than 7.5% of the number of cobalt atoms, preferably 0.05% to 4%, preferably 0.1% to 2%, and more preferably 0.2% to 1%. Alternatively, it is preferably more than 0% but not more than 4%. Alternatively, it is preferably more than 0% but not more than 2%. Alternatively, it is preferably 0.05% to 7.5%. Alternatively, it is preferably 0.05% to 2%. Alternatively, it is preferably 0.1% to 7.5%. Alternatively, it is preferably 0.1% to 4%. The amount of nickel shown here may be, for example, a value obtained by performing elemental analysis of the entire positive electrode active material particle using GD-MS, ICP-MS, or the like, or may be based on the value of the composition of raw materials in the process of producing the positive electrode active material particle.

[0194] Furthermore, fluorine, one of the additive elements X, is a monovalent anion. When some of the oxygen atoms in the surface layer 100a are substituted with fluorine, the lithium desorption energy decreases. This is because the valence of cobalt ions changes with lithium desorption (from trivalent to tetravalent in the absence of fluorine, and from divalent to trivalent in the presence of fluorine), resulting in different oxidation-reduction potentials. Therefore, when some of the oxygen atoms in the surface layer 100a of the positive electrode active material particle 100 are substituted with fluorine, it can be said that desorption and insertion of lithium ions near the fluorine atoms occurs more smoothly. Therefore, when the positive electrode active material particle 100 is used in a secondary battery, the charge / discharge characteristics, large current characteristics, etc. can be improved. Furthermore, the presence of fluorine in the surface layer 100a, which has a surface that contacts the electrolyte, can effectively improve corrosion resistance against hydrofluoric acid. Furthermore, as described in the first embodiment, when the melting point of a fluoride, such as lithium fluoride, is lower than the melting point of the other additive element source, it can function as a flux (also called a fluxing agent) that lowers the melting point of the other additive element source.

[0195] 6A and 6C, when the surface layer 100a contains both magnesium and nickel, there is a possibility that divalent nickel can exist more stably near divalent magnesium. ｘ CoO ２Even when the value of x in the formula is small, the elution of magnesium can be suppressed, which can contribute to the stabilization of the surface layer portion 100a.

[0196] Furthermore, it is preferable to have additive elements A with different distributions, such as additive element X, additive element Y, and additive element Z, in combination, since this stabilizes the crystal structure in a wider region. For example, when the positive electrode active material particle 100 has magnesium, which is one of the additive elements X, aluminum, which is one of the additive elements Y, and nickel, which is one of the additive elements Z, it can stabilize the crystal structure in a wider region than when it has only one or two of the additive elements X, Y, and Z. In this way, when the positive electrode active material particle 100 has additive element X, additive element Y, and additive element Z in combination, the surface can be sufficiently stabilized by additive element X such as magnesium and additive element Z such as nickel, so additive element Y such as aluminum is not essential to the surface. Rather, it is preferable for aluminum to be widely distributed slightly inward from the surface. For example, it is preferable for aluminum to be continuously detected in a region from the surface in a depth direction of 1 nm to 25 nm. In this way, a wide distribution of aluminum is preferable, since it stabilizes the crystal structure in a wider region.

[0197] 6C and 6F , it is preferable that the additive element Z is contained in a large amount in the edge region 100a1 (also referred to as being contained preferentially or selectively) because this improves the stability of the crystal structure of the edge region 100a1, where lithium ions enter and exit the positive electrode active material particle 100 during charging and discharging of the lithium ion battery. Furthermore, it is preferable that the additive element Z has the above-described distribution, for example, when the positive electrode active material particle 100 is lithium cobalt oxide, because this minimizes the effects of adding the additive element Z, such as a decrease in discharge voltage or a decrease in discharge capacity.

[0198] When multiple additive elements A are present as described above, the effects of each additive element A are synergistic, which can contribute to further stabilization of the surface layer portion 100a. In particular, the presence of magnesium, nickel, and aluminum is highly effective in achieving a stable composition and crystal structure, making it preferable. In particular, it is preferable that the surface layer portion 100a of the positive electrode active material particle 100 has a region where magnesium is distributed closer to the surface than aluminum. Furthermore, in addition to the region where magnesium and aluminum are distributed, it is most preferable that the surface layer portion 100a of the positive electrode active material particle 100 has a region where the nickel distribution and the magnesium distribution overlap in the edge region 100a1.

[0199] <Crystal structure> <Li ｘ CoO ２ When x is 1 in the positive electrode active material particle 100 according to one embodiment of the present invention, the positive electrode active material particle 100 is in a discharged state, that is, Li ｘ CoO ２ In the case where x = 1 in the formula (I), it is preferable that the composite oxide has a layered rock-salt type crystal structure belonging to the space group R-3m. The layered rock-salt type composite oxide has a high discharge capacity, has two-dimensional lithium ion diffusion paths, is suitable for lithium ion insertion / extraction reactions, and is excellent as a positive electrode active material particle for a secondary battery. Therefore, it is particularly preferable that the inner portion 100b, which occupies the majority of the volume of the positive electrode active material particle 100, has a layered rock-salt type crystal structure.

[0200] On the other hand, the surface layer portion 100a of the cathode active material particle 100 according to one embodiment of the present invention preferably has a function of reinforcing the inner portion 100b so that the layered structure of the transition metal M and oxygen octahedra in the inner portion 100b is not destroyed even when lithium is released from the cathode active material particle 100 upon charging. Alternatively, the surface layer portion 100a preferably functions as a barrier film for the cathode active material particle 100. Alternatively, the surface layer portion 100a, which is the outer periphery of the cathode active material particle 100, preferably reinforces the cathode active material particle 100. Here, "reinforcement" refers to suppressing structural changes in the surface layer portion 100a and inner portion 100b of the cathode active material particle 100, such as oxygen desorption.

[0201] Therefore, it is preferable that the surface layer portion 100a has a different crystal structure from the interior portion 100b. Furthermore, it is preferable that the surface layer portion 100a has a more stable composition and crystal structure than the interior portion 100b. Specifically, at least a portion of the surface layer portion 100a of the cathode active material particle 100 according to one embodiment of the present invention has characteristics of a rock salt crystal structure. Furthermore, it is preferable that at least a portion of the surface layer portion 100a has characteristics of a spinel crystal structure. Specifically, it is preferable that the cathode active material particle 100 has a crystal structure with a spinel skeleton closer to the interior portion 100b than the region having the rock salt crystal structure. More specifically ... of the space group Fd-3m, which is a crystal structure similar to a spinel crystal structure. ２ The surface layer 100a preferably has a LiTiO crystalline structure of the layered rock salt type, space group Fd-3m. ２ It is more preferable that the crystal structure has the characteristics of the three crystal structures of the spinel type and the rock salt type. Note that the crystal structure having a spinel type skeleton is sometimes collectively called a spinel type crystal structure, but strictly speaking, it is a Co crystal structure having metal atoms at the 8a site and the 16d site in the Wyckoff position. ３ O ４ Such a crystal structure is called a spinel-type crystal structure. Therefore, even if it is said in this specification that it has the characteristics of a spinel-type crystal structure, it does not necessarily mean that it is a Co ３ O ４ In this specification, the structure does not coincide with a spinel-type crystal structure such as LiTiO ２ The LiTiO 3 structure of the space group Fd-3m is sometimes referred to as a spinel' type crystal structure. ２ Regarding the description of the type crystal structure, the symmetry of the atomic positions of the crystal structure is LiTiO ２ This is a description used to indicate that the crystal structure is a crystalline structure, and is not a description to specify the constituent elements, such as "consisting of lithium, titanium, and oxygen."

[0202] Furthermore, while it is preferable that some of the additive elements A, particularly magnesium, nickel, and aluminum, have a higher concentration in the surface layer 100a than in the interior 100b, they are also preferably present randomly and in a sparse manner in the interior 100b. The presence of magnesium and aluminum at appropriate concentrations at the lithium sites in the interior 100b has the effect of making it easier to maintain the layered rock-salt crystal structure. Furthermore, the presence of nickel at an appropriate concentration in the interior 100b can suppress the shift of the layered structure consisting of the transition metal M and oxygen octahedra. Even when both magnesium and nickel are present, divalent magnesium may be more stable near divalent nickel, which can be expected to have a synergistic effect of suppressing magnesium elution. Furthermore, aluminum may be present at the cobalt site in the layered rock-salt crystal structure. Because aluminum is a trivalent typical element and its valence does not change, lithium around aluminum is less likely to move during charging and discharging. Therefore, aluminum and its surrounding lithium form CoO ２ It functions as a pillar supporting the layers and can suppress changes in the crystal structure. Aluminum also suppresses the elution of surrounding cobalt, improving the durability of continuous charging and / or storage durability in a fully charged state. Furthermore, because the Al-O bond is stronger than the Co-O bond, it can suppress the desorption of oxygen from around the aluminum.

[0203] 6A to 6E, it is preferable that the crystal structure continuously changes from the interior 100b toward the surface, or that the crystal orientations of the surface layer 100a and the interior 100b are approximately the same.

[0204] For example, it is preferable that, from the interior 100b having a layered rock salt crystal structure toward the surface, the characteristics of the layered rock salt crystal structure change sequentially from the characteristics of the layered rock salt crystal structure to the characteristics of the spinel crystal structure, and from the characteristics of the spinel crystal structure to the characteristics of the rock salt crystal structure. More specifically, in the edge region 100a1, from the interior 100b toward the outside of the positive electrode active material particle 100, a region of the layered rock salt crystal structure, LiTiO ２It is preferable that the edge region 100a1 has a structure in which a region having a layered rock-salt type crystal structure, a region having a spinel' type crystal structure, and a region having a rock-salt type crystal structure are arranged in this order from the interior 100b toward the outside of the positive electrode active material particle 100. It is also preferable that this change in crystal structure is continuous. It is also preferable that the crystal orientations of the three crystal structures, the layered rock-salt type, the spinel' type, and the rock-salt type, are approximately the same.

[0205] In this specification, the layered rock-salt crystal structure belonging to the space group R-3m possessed by a composite oxide containing lithium and a transition metal M refers to a crystal structure having a rock-salt ion arrangement in which cations and anions are alternately arranged, and in which the transition metal M and lithium are regularly arranged to form a two-dimensional plane. Therefore, this crystal structure allows for two-dimensional diffusion of lithium. Defects such as cation or anion deficiencies may also be present. Furthermore, strictly speaking, the layered rock-salt crystal structure may have a structure in which the lattice of the rock-salt crystal is distorted.

[0206] The rock salt crystal structure is a cubic crystal structure or a crystal structure that can be considered as a cubic crystal, in which cations and anions are arranged alternately. Note that cation or anion defects are also acceptable.

[0207] The characteristics of the layered rock salt type crystal structure, the characteristics of the spinel type crystal structure, and the characteristics of the rock salt type crystal structure can be determined by electron diffraction, TEM images, cross-sectional STEM images, and the like.

[0208] FIG. 7A is a cross-sectional HAADF-STEM image of the vicinity of the surface of the positive electrode active material particle 100, and FIG. 7B is a cross-sectional ABF-STEM image of the vicinity of the surface of the positive electrode active material particle 100.

[0209] In the cross-sectional HAADF-STEM image, a layered rock salt crystal structure (e.g., LiCoO ２When the HAADF-STEM image of the edge region 100a1 of the positive electrode active material particle 100 is observed from a direction perpendicular to the c-axis (for example,

[010] incidence or

[100] incidence in a layered rock-salt crystal structure), layers of bright spots with high brightness and layers of bright spots with low brightness are alternately observed in the c-axis direction, as in the region labeled "layered rock-salt" in FIG. 7A. In FIGS. 7A and 7B, bright spots or dark spots aligned in the direction indicated by the block arrows are referred to as "layers," and bright spots or dark spots aligned in the direction indicated by the dashed arrows are referred to as "rows." Similarly, in this specification, for bright spots in an HAADF-STEM image of the edge region 100a1 of the positive electrode active material particle 100 observed from a direction perpendicular to the c-axis, bright spots aligned in a direction perpendicular to the c-axis of the region having the layered rock-salt structure are referred to as "layers." Bright spots aligned in a direction intersecting the layers are referred to as "rows," and the row is selected to be the row of bright spots closest to parallel to the surface of the edge region 100a1.

[0210] In the case of a rock-salt crystal structure (e.g., CoO), such characteristics are not observed because there is no distinction between cation sites, and only a layer with an array of bright spots with high brightness is observed, as in the region marked "rock-salt" in Figure 7A.

[0211] LiTiO in FIG. ２ In the region marked "type", layers where only bright spots with high brightness are arranged and layers where bright spots with high brightness 110 and regions 111 where no clear bright spots are seen are arranged alternately in the column direction (block arrows in the figure, also called lithium layers). When such characteristics are present, the region is said to have the characteristics of a spinel-type crystal structure. Furthermore, a region having the characteristics of a spinel-type crystal structure is said to have the characteristics of a LiTiO ２ In the case of the crystalline structure, in the region 111 where no clear bright spot is observed in the HAADF-STEM image of FIG. 7A, atoms are present at Wyckoff position 16c, not at Wyckoff position 8a.

[0212] When the region 111 where no clear bright spots are observed in the HAADF-STEM image of Fig. 7A is examined in the ABF-STEM image of Fig. 7B, no atomic contrast is observed at the Wyckoff position 8a (solid circle in Fig. 7B). ２ The region labeled with type is LiTiO of space group Fd-3m. ２It can be determined that this is a type crystal structure.

[0213] 7B, the ABF-STEM image has the same characteristics as the HAADF-STEM image, although the contrast is reversed. The reason for this is that in the HAADF-STEM image, strong bright spots appear at positions where elements with large atomic numbers (e.g., cobalt) are present, whereas in the ABF-STEM image, strong bright spots appear at positions where elements with small atomic numbers (e.g., lithium) are present.

[0214] The spinel-type crystal structure can also be characterized by electron diffraction or TEM-FFT patterns.

[0215] In this specification, the surface observed in a cross-sectional HAADF-STEM image of the positive electrode active material particle 100, i.e., the row of metal elements with an atomic number higher than that of lithium closest to the outside (also referred to as a row of bright spots or a row of bright spots) is referred to as the first row. The row of metal elements with an atomic number higher than that of lithium observed next closest to the outside after the first row is referred to as the second row. The same applies to the third row and beyond. In other words, the first row, second row, third row, fourth row, and so on continue toward the inside of the particle.

[0216] For example, the first to third columns in the edge region 100a1 preferably have a rock salt crystal structure, and the fourth to ninth columns preferably have a LiTiO ２ It is preferable that the tenth and subsequent rows have a layered rock salt type crystal structure. In a cross-sectional HAADF-STEM image, when the first row on the surface side is not clearly observed, a region having a rock salt type crystal structure may be observed in the first and second rows, or only in the first row. Therefore, when a region having a rock salt type crystal structure is observed in the first and second rows, the third to eighth rows are LiTiO of the space group Fd-3m. ２ In some cases, the ordinal number of the column may be increased, such that it is preferable to have a crystal structure of the type LiTiO in the space group Fd-3m. ２ There may be cases where the width of the row in which the region having the type crystal structure is observed is small (for example, the fourth to eighth rows) or large (for example, the fourth to tenth rows).

[0217] In the cross-sectional HAADF-STEM image of the edge region 100a1, LiTiO ２ An example of observing a region having a crystalline structure of the type from the <110> direction (FIGS. 7A and 7B) will be described. ２ The <110> direction of the crystalline structure of the layered rock salt type is one of the directions perpendicular to the c-axis in the layered rock salt type structure. In this observation, in the region, the characteristics of the layered rock salt type crystalline structure change sequentially from those of the layered rock salt type crystalline structure to those of the spinel type crystalline structure, and from those of the spinel type crystalline structure to those of the rock salt type crystalline structure in the direction from the inside to the outside of the particle (depth direction). At this time, in the region characterized by the layered rock salt type crystalline structure, a first layer (lithium layer) in which no clear bright spots are observed and a second layer (cobalt layer) adjacent to the first layer in which clear bright spots are arranged are confirmed. When the viewpoint is shifted along the extension of the first layer in the direction from the inside to the outside of the particle (the direction of the block arrow in FIG. 7A ), the region characterized by the spinel type crystalline structure can be confirmed to have an alternating arrangement of high-brightness bright spots 110 and regions 111 in which no clear bright spots are observed.

[0218] In addition, in the region having the characteristics of a spinel-type crystal structure in the cross-sectional HAADF-STEM image, LiTiO ２ It may have a crystal structure of the type LiTiO in the space group Fd-3m. ２ The existence of the LiTiO type crystal structure can be confirmed by ABF-STEM images as described above. ２ LiCoO having a crystal structure of the type ２ In this case, lithium (Li) is at the 16c position, cobalt (Co) is at the 16d position, and oxygen (O) is at the 32e position. Since the lithium at the 16c position is aligned linearly in the <110> direction, this is preferable as it facilitates the movement of lithium during charge and discharge. Note that, since the 16c position and the 16d position are equivalent positions in terms of site symmetry, there are also cases where cobalt is at the 16c position, lithium is at the 16d position, and oxygen is at the 32e position.

[0219] In FIG. 8A, LiTiO ２8A shows a schematic diagram of the crystal structure of the type. In FIG. 8A, for example, region A is a position where only the Wyckoff position 16c of the space group Fd-3m overlaps in the <110> direction, and in region A, the lithium sites at position 16c are lined up. Also, for example, regions B and C are positions where the Wyckoff position 16c and the Wyckoff position 16d of the space group Fd-3m overlap in the <110> direction, and in regions B and C, the lithium site at position 16c and the cobalt site at position 16d are lined up. Also, for example, region D is a position where only the Wyckoff position 16d of the space group Fd-3m overlaps in the <110> direction, and in region D, the cobalt site at position 16d is lined up.

[0220] Region A shown in FIG. 8A is a region where lithium sites are aligned in the <110> direction, and lithium can diffuse in this direction. ２ In the crystal structure of this type, the lithium diffusion path exemplified in the above region A exists in three dimensions. ２ The three-dimensional lithium diffusion paths of the crystal structure of the mold will be described with reference to FIG. 8B.

[0221] The <110> direction, which is the diffusion path of lithium, specifically exists in six directions:

[110] , [0-11],

[101] ,

[011] , [10-1], and [1-10]. ２ Of the six three-dimensional lithium diffusion paths of the crystal structure of the type, three directions (direction 1, direction 2, and direction 3) are shown as representatives. Direction 1 indicates

[110] , direction 2 indicates

[011] , and direction 3 indicates [0-11]. In each direction, lithium sites are lined up in the thick line portion indicated by Li in the figure, and it can be seen that there are lithium diffusion paths in the three-dimensional direction.

[0222] 9A to 9F show the six directions of lithium diffusion paths in more detail. ２ LiCoO of the type crystal structure ２9A and 9B show schematic diagrams of the lithium diffusion paths indicated by dashed arrows. The arrow in Fig. 9A indicates the

[110] direction, the arrow in Fig. 9B indicates the [0-11] direction, the arrow in Fig. 9C indicates the

[101] direction, the arrow in Fig. 9D indicates the

[011] direction, the arrow in Fig. 9E indicates the [10-1] direction, and the arrow in Fig. 9F indicates the [1-10] direction.

[0223] The region having the characteristics of a spinel-type crystal structure is LiTiO ２ LiCoO having a crystal structure of the type ２ Whether or not the compound is LiTiO 3 of the space group Fd-3m can be determined by checking whether an atom exists at the 8a position in an ABF-STEM image or an HAADF-STEM image. If no atom exists at the 8a position and an atom exists at the 16c position, the compound is LiTiO 3 of the space group Fd-3m. ２ Alternatively, in a region where the characteristics of a spinel-type crystal structure are confirmed in the HAADF-STEM image, when an atomic column in which lithium is aligned in the <110> direction, an atomic column in which lithium and cobalt are aligned, and an atomic column in which cobalt is aligned are confirmed by STEM-EELS (Electron Energy-Loss Spectroscopy), the structure is LiTiO of the space group Fd-3m. ２ LiCoO having a crystal structure of the type ２ That is, in the region where the characteristics of a spinel-type crystal structure are confirmed by the HAADF-STEM image, LiTiO ２ There are two methods for determining whether a material has a crystal structure of this type: a method using ABF-STEM and a method using STEM-EELS. ２ Either of the above methods may be used to obtain the crystal structure of this type.

[0224] The above LiTiO ２In the region having the crystalline structure of the type, it is preferable to have magnesium and nickel as the additive element A at the lithium site (Wyckoff position 16c). It is also preferable to have nickel as the additive element A at the transition metal M site (cobalt site, Wyckoff position 16d). By having magnesium and nickel as the additive element A at such positions, LiTiO ２ This stabilizes the crystal structure of the mold and can prevent oxygen from being released.

[0225] Here, the layered rock salt structure of R-3m and the space group Fd-3m LiTiO ２ We will compare the crystal structure of the type with that of the type, and explain the results of simulations focusing on cobalt, nickel, and titanium to see which has a higher structural stability.

[0226] LiCoO ２ In the case of R-3m layered rock salt structure, and LiTiO ２ When compared with the crystal structure of LiNiO, the layered rock salt structure of R-3m has higher structural stability. ２ In the case of R-3m layered rock salt structure, and LiTiO ２ When compared with the case of the crystal structure of LiTiO ２ The structure stability is higher when the crystal structure is LiTiO ２ In the case of R-3m layered rock salt structure, and LiTiO ２ The layered rock salt structure of R-3m has higher structural stability than the crystal structure of R-3m. Note that all of the above calculations were performed using a calculation model assuming a charged state in which all Li has been desorbed.

[0227] As described above, LiTiO in the space group Fd-3m ２ In the case of a crystal structure of this type, it can be said that having nickel at the transition metal M site (Wyckoff position 16d) makes it possible to stabilize the structure more than when cobalt is present at the same position or when titanium is present at the same position.

[0228] Crystals having characteristics of layered rock salt crystals and spinel crystal structures (e.g., LiTiO ２ The anions of the layered rock salt type crystal, the spinel type crystal, and the rock salt type crystal have a cubic close-packed structure (face-centered cubic lattice structure). It is presumed that the anions of the O3' type crystal, which will be described later, also have a cubic close-packed structure. Therefore, the layered rock salt type crystal structure, the spinel type crystal structure, and the LiTiO ２ When the LiTiO crystalline structure and the LiTiO crystalline structure are in contact with each other, there are crystal planes where the cubic close-packed structures formed by anions are aligned. For example, as shown in the schematic diagram of the crystal structure in FIG. 10, the LiTiO crystalline structure and the LiTiO crystalline structure are in contact with each other. ２ 10 shows the crystal structure near the surface layer of a positive electrode active material particle 100 according to one embodiment of the present invention, which is considered from the examples described later.

[0229] Rock salt crystal structure, space group Fd-3m LiTiO ２ The fact that the layered rock salt type crystal structure and the layered rock salt type crystal structure are in contact with each other can also be explained as follows. ２ The layered rock salt type crystal structure is cubic, and the anions on the {111} plane of the cubic crystal structure have a triangular lattice. The layered rock salt type crystal structure has a space group of R-3m and a rhombohedral structure, but can be expressed as a composite hexagonal lattice to facilitate understanding of the structure, and the (0001) plane of the layered rock salt type has a hexagonal lattice. The triangular lattice on the cubic {111} plane has the same atomic arrangement as the hexagonal lattice on the (0001) plane of the layered rock salt type. The compatibility of the two lattices can be said to align the orientation of the cubic close-packed structure.

[0230] Thus, LiTiO in the space group Fd-3m ２ In the rock salt type crystal structure, lithium can diffuse in three dimensions. Therefore, LiTiO of the space group Fd-3m is formed between the region of the rock salt type crystal structure and the region of the layered rock salt type crystal structure. ２10 , which has a region of a crystalline structure of this type, is preferable because it results in a positive electrode active material particle with low lithium ion diffusion resistance and facilitates lithium ion insertion and desorption. Furthermore, by using such positive electrode active material particles in a secondary battery, it is possible to suppress the decrease in discharge capacity even during high-rate discharge, and to obtain a large discharge capacity, which is also preferable.

[0231] In this specification, LiTiO of a layered rock salt type crystal structure and space group Fd-3m ２ In the layered rock-salt type crystal structure and the rock-salt type crystal structure, when the orientation of the cubic close-packed structure formed by anions is aligned within 5 degrees, preferably within 2.5 degrees, it is said that the crystal orientation is approximately the same. ２ In the layered rock salt type crystal structure and the rock salt type crystal structure, when the orientation of the cubic close-packed structure formed by anions is aligned within 5 degrees, preferably within 2.5 degrees, it is said that the crystal orientation is approximately the same. ２ In the rock salt and rock salt types, the crystal structures are said to be aligned when the orientation of the cubic close-packed structures formed by anions is aligned within 5 degrees, preferably within 2.5 degrees. The orientation of the cubic close-packed structures formed by anions is, for example, the direction indicated by the block arrows in Figures 7A and 7B, which can also be called the layer direction.

[0232] <Li ｘ CoO ２ The positive electrode active material particle 100 according to one embodiment of the present invention has the above-described distribution of the additional element A and / or the crystal structure in a discharged state, and therefore, ｘ CoO ２ The crystal structure when x is small is different from that of conventional positive electrode active material particles. Here, "small x" means that 0.1<x≦0.24.

[0233] 11 to 14, Li ｘ CoO ２The change in the crystal structure accompanying the change in x in the positive electrode active material particle 100 according to one embodiment of the present invention will be described by comparing a conventional positive electrode active material particle with the positive electrode active material particle 100 according to one embodiment of the present invention.

[0234] The change in the crystal structure of conventional positive electrode active material particles is shown in FIG. 12. The conventional positive electrode active material particles shown in FIG. 12 are made of lithium cobalt oxide (LiCoO ２ )

[0235] In Figure 12, R-3m O3 is added to Li ｘ CoO ２ The crystal structure of lithium cobalt oxide with x=1 in the figure shows that lithium occupies octahedral sites and CoO ２ There are three layers. Therefore, this crystal structure is sometimes called an O3 type crystal structure. ２ The layer is defined as a structure in which an octahedron structure in which oxygen is six-coordinated to cobalt is connected in a plane with edge sharing. This is sometimes called a layer consisting of cobalt and oxygen octahedra.

[0236] It is also known that conventional lithium cobalt oxide has a crystal structure that has high lithium symmetry when x is about 0.5 and belongs to the monoclinic space group P2 / m. This structure has CoO ２ There is one layer, so it is sometimes called O1 type or monoclinic O1 type.

[0237] When x = 0, the positive electrode active material particles have a crystal structure of the trigonal space group P-3m1, and also contain CoO ２ There is one layer. Therefore, this crystal structure is sometimes called O1 type or trigonal O1 type. In addition, when the trigonal crystal is converted into a composite hexagonal lattice, it is sometimes called hexagonal O1 type.

[0238] Furthermore, when x is about 0.12, conventional lithium cobalt oxide has a crystal structure of the space group R-3m. This structure is similar to CoO, such as trigonal O1 type. ２ and LiCoO such as R-3m O ２It can also be said that this crystal structure is a structure in which the structure of and the structure of are stacked alternately. For this reason, this crystal structure is sometimes called an H1-3 crystal structure. In reality, the number of cobalt atoms per unit cell in the H1-3 crystal structure is twice that of other structures. However, in this specification, including Figure 12, the c-axis of the H1-3 crystal structure is shown as half the unit cell to make it easier to compare with other crystal structures.

[0239] As an example of an H1-3 type crystal structure, the coordinates of cobalt and oxygen in a unit cell can be expressed as Co (0, 0, 0.42150 ± 0.00016), O1 (0, 0, 0.27671 ± 0.00045), and O2 (0, 0, 0.11535 ± 0.00045). O1 and O2 are each oxygen atoms. Which unit cell should be used to represent the crystal structure of the positive electrode active material particles can be determined, for example, by Rietveld analysis of the XRD pattern. In this case, a unit cell with a small GOF (goodness of fit) value can be adopted.

[0240] Li ｘ CoO ２ When charging and discharging are repeated so that x in the formula is 0.24 or less, conventional lithium cobalt oxide undergoes repeated changes in crystal structure (i.e., non-equilibrium phase changes) between the H1-3 type crystal structure and the R-3m O3 structure in the discharged state.

[0241] However, these two crystal structures are different from CoO ２ As shown by the dotted lines and arrows in FIG. 12, in the H1-3 type crystal structure, CoO ２ The layer is significantly different from the R-3m O3 in the discharged state. Such dynamic structural changes can adversely affect the stability of the crystal structure.

[0242] Furthermore, the difference in volume between these two crystal structures is large: per the same number of cobalt atoms, the difference in volume between the H1-3 crystal structure and the discharged R-3mO3 crystal structure is greater than 3.5%, typically 3.9% or more.

[0243] In addition, the H1-3 type crystal structure has CoO like the trigonal O1 type. ２A structure with continuous layers is likely to be unstable.

[0244] Therefore, when charging and discharging are repeated so that x is 0.24 or less, the crystal structure of conventional lithium cobalt oxide collapses. This collapse of the crystal structure causes a deterioration in cycle characteristics. This is because the collapse of the crystal structure reduces the number of sites where lithium can exist stably and makes it difficult to insert and extract lithium.

[0245] In the conventional lithium cobalt oxide where x is 0.24 or less, where a large amount of Li is released, oxygen is easily released. ３＋ From Co ２＋ The layered rock salt crystal structure changes to a degraded spinel crystal structure (e.g., LiCo ２ O ４ , or Co ３ O ４ In the positive electrode active material particle 100 according to one embodiment of the present invention, LiTiO of space group Fd-3m, which has the characteristics of a spinel crystal structure and is present between the region having the layered rock salt crystal structure and the region having the rock salt crystal structure, may undergo a phase change to ２ The crystal structure of the spinel type is a crystal structure different from the crystal structure of the spinel type in the degraded state.

[0246] Furthermore, when oxygen is released, cations such as cobalt that were bound to the oxygen may dissolve into the electrolyte. If this progresses, it may lead to deterioration in which holes, also called pits or pits, are formed in the positive electrode active material particles. This may cause distortion and / or stress in the positive electrode active material particles 100.

[0247] On the other hand, in the positive electrode active material particle 100 according to one embodiment of the present invention shown in FIG. ｘ CoO ２ The change in the crystal structure between the discharge state where x is 1 and the state where x is 0.24 or less is smaller than that of conventional positive electrode active material particles. ２The layer misalignment can be reduced. Also, the volume change per cobalt atom can be reduced. Therefore, the positive electrode active material particle 100 of one embodiment of the present invention is less likely to lose its crystal structure even when repeatedly charged and discharged so that x is 0.24 or less, and excellent cycle characteristics can be achieved. Furthermore, the positive electrode active material particle 100 of one embodiment of the present invention has a Li ｘ CoO ２ When x is 0.24 or less, the positive electrode active material particles 100 can have a more stable crystal structure than conventional positive electrode active material particles. ｘ CoO ２ When the value of x in the formula (1) is kept at 0.24 or less, short circuits are unlikely to occur. In such a case, the safety of the secondary battery is further improved, which is preferable.

[0248] Li ｘ CoO ２ The crystal structure of the interior 100b of the positive electrode active material particle 100 when x is approximately 1 or 0.2 is shown in FIG. 11. The interior 100b occupies the majority of the volume of the positive electrode active material particle 100 and is the part that contributes greatly to charge and discharge. ２ The most problematic areas are layer misalignment and volume changes.

[0249] When x=1, the positive electrode active material particles 100 have the same crystal structure of R-3m O3 as conventional lithium cobalt oxide.

[0250] However, the positive electrode active material particles 100 have a different crystal structure from that of conventional lithium cobalt oxide when x is 0.24 or less, for example, about 0.2 or 0.12, which results in an H1-3 type crystal structure.

[0251] When x=0.24, the positive electrode active material particle 100 according to one embodiment of the present invention has a crystal structure belonging to the trigonal space group R-3m. ２ The layer symmetry is the same as that of O3. Therefore, this crystal structure is called an O3'-type crystal structure. This crystal structure is shown in Figure 11 with the notation R-3m O3'.

[0252] In the O3' type crystal structure, the coordinates of cobalt and oxygen in the unit cell can be expressed in the range of Co(0,0,0.5), O(0,0,x), 0.20≦x≦0.25. The lattice constant of the unit cell is 2.797≦a≦2.837 (×10 −１ nm), and 2.807≦a≦2.827 (×10 −１ The c-axis is more preferably 13.681≦c≦13.881 (×10 −１ nm), and 13.751≦c≦13.811 is more preferred.

[0253] As shown by the dotted line in FIG. 11, the difference between R-3m(O3) in the discharged state and the O3′-type crystal structure is ２ There is almost no layer misalignment.

[0254] The difference in volume per the same number of cobalt atoms between R-3m(O3) in a discharged state and the O3' type crystal structure is 2.5% or less, more specifically 2.2% or less, typically 1.8%.

[0255] In this way, in the positive electrode active material particle 100 of one embodiment of the present invention, Li ｘ CoO ２ When x is small, i.e., when a large amount of lithium is released, the change in crystal structure is suppressed compared to conventional positive electrode active material particles. Furthermore, the change in volume is also suppressed when compared per the same number of cobalt atoms. Therefore, the positive electrode active material particles 100 are resistant to collapse of their crystal structure even when repeatedly charged and discharged such that x is 0.24 or less. Therefore, the positive electrode active material particles 100 are suppressed from decreasing in charge / discharge capacity during charge / discharge cycles. Furthermore, because more lithium can be stably utilized than in conventional positive electrode active material particles, the positive electrode active material particles 100 have a large discharge capacity per weight and per volume. Therefore, by using the positive electrode active material particles 100, secondary batteries with high discharge capacity per weight and per volume can be fabricated.

[0256] The positive electrode active material particles 100 are Li ｘ CoO ２It has been confirmed that when x is 0.15 or more and 0.24 or less, it may have an O3' type crystal structure, and it is presumed that it also has an O3' type crystal structure when x is more than 0.24 and 0.27 or less. However, the crystal structure is ｘ CoO ２ The range of x is not necessarily limited to the above range, since it is affected not only by the x in the formula but also by the number of charge / discharge cycles, charge / discharge current, temperature, electrolyte, etc.

[0257] Therefore, the positive electrode active material particles 100 are Li ｘ CoO ２ When x is greater than 0.1 and equal to or less than 0.24, the entire interior 100b of the positive electrode active material particle 100 does not have to have an O3′-type crystal structure, but may contain other crystal structures, or may be partially amorphous.

[0258] Also Li ｘ CoO ２ To make the value of x small, it is generally necessary to charge at a high charging voltage. ｘ CoO ２ The state where x is small can be rephrased as a state where the battery is charged at a high charging voltage. For example, when CC / CV charging is performed at a voltage of 4.6 V or higher based on the potential of lithium metal in an environment of 25°C, an H1-3 type crystal structure appears in conventional positive electrode active material particles. Therefore, a charging voltage of 4.6 V or higher based on the potential of lithium metal can be said to be a high charging voltage.

[0259] Therefore, the positive electrode active material particle 100 of one embodiment of the present invention is preferable because it can maintain a crystal structure with R-3m O symmetry even when charged at a high charging voltage, for example, a voltage of 4.6 V or higher at 25° C. In other words, it is preferable because it can adopt an O 3′-type crystal structure when charged at a higher charging voltage, for example, a voltage of 4.65 V or higher and 4.7 V or lower at 25° C.

[0260] In some cases, the H1-3 type crystal structure is finally observed when the charge voltage is further increased, even in the positive electrode active material particle 100. Furthermore, as described above, the crystal structure is affected by the number of charge / discharge cycles, the charge / discharge current, the temperature, the electrolyte solution, and the like. Therefore, even when the charge voltage is lower, for example, even when the charge voltage is 4.5 V or more and less than 4.6 V at 25° C., the positive electrode active material particle 100 of one embodiment of the present invention may be able to adopt the O3′ type crystal structure.

[0261] In addition, when graphite is used as the negative electrode active material in a secondary battery, the voltage of the secondary battery is lower than the above by the potential of the graphite. The potential of graphite is about 0.05 V to 0.2 V with respect to the potential of lithium metal. Therefore, in the case of a secondary battery using graphite as the negative electrode active material, the potential of the positive electrode is the value obtained by subtracting the potential of the graphite from the voltage of the secondary battery.

[0262] In addition, in the O3' type crystal shown in FIG. 11, lithium is shown to exist at all lithium sites with equal probability, but this is not limited to this. It may exist unevenly at some lithium sites, or, for example, in the monoclinic O1 (Li ０．５ CoO ２ The lithium distribution can be analyzed, for example, by neutron diffraction.

[0263] The O3' type crystal structure has random lithium between layers, but CdCl ２ It can be said that this crystal structure is similar to that of the CdCl type. ２ A similar crystal structure to the Li-type is lithium nickel oxide. ０．０６ NiO ２ However, pure lithium cobaltate or layered rock salt type positive electrode active material particles containing a large amount of cobalt usually have a crystal structure similar to that of CdCl ２ It is known that it does not have a typical crystal structure.

[0264] Furthermore, it is preferable that the concentration gradient of the additive element A be similar at multiple locations in the surface layer portion 100a of the positive electrode active material particle 100. In other words, it is preferable that the reinforcement derived from the additive element A is uniformly present in the surface layer portion 100a. Even if a portion of the surface layer portion 100a is reinforced, if there is a portion without reinforcement, stress may be concentrated in the unreinforced portion. If stress is concentrated in a portion of the positive electrode active material particle 100, defects such as cracks may occur there, which may lead to breakage of the positive electrode active material particle and a decrease in discharge capacity.

[0265] However, it is not necessary for the additional element A to have the same concentration gradient throughout the entire surface layer portion 100a of the positive electrode active material particle 100. An example of the distribution of the additional element X near C-D in FIG. 5B is shown in FIG. 6D, and an example of the distribution of the additional element Y near C-D is shown in FIG. 6E.

[0266] Here, the area around C-D has an R-3m layered rock salt type crystal structure, and the surface has a (001) orientation. The (001)-oriented surface may have a different distribution of the additional element A than the other surfaces. For example, the (001)-oriented surface and its surface layer 100a may have a distribution of concentration peaks of one or more elements selected from the additional element X and the additional element Y limited to a shallower portion from the surface compared to surfaces other than the (001) orientation. Alternatively, the (001)-oriented surface and its surface layer 100a may have a lower concentration of one or more elements selected from the additional element X and the additional element Y compared to other orientations. Alternatively, the (001)-oriented surface and its surface layer 100a may have one or more elements selected from the additional element X and the additional element Y below the lower detection limit.

[0267] In the layered rock salt type crystal structure of R-3m, cations are arranged parallel to the (001) plane. ２ The structure is composed of alternately stacked layers and lithium layers parallel to the (001) plane, and the diffusion path of lithium ions is also parallel to the (001) plane.

[0268] CoO ２Since the layer is relatively stable, it is more stable for the surface of the positive electrode active material particle 100 to have a (001) orientation. The main diffusion path of lithium ions during charge and discharge is not exposed on the (001) plane.

[0269] On the other hand, the diffusion paths of lithium ions are exposed on surfaces other than those with the (001) orientation. Therefore, the surfaces other than those with the (001) orientation and the surface layer portion 100a are important regions for maintaining the diffusion paths of lithium ions, and at the same time, they are regions from which lithium ions are first desorbed and are therefore prone to instability. Therefore, reinforcing the surfaces other than those with the (001) orientation and the surface layer portion 100a is extremely important for maintaining the crystal structure of the entire positive electrode active material particle 100.

[0270] Therefore, in the positive electrode active material particle 100 according to another embodiment of the present invention, it is important that the distribution of the additional element A in the plane other than the (001) plane and in the surface layer portion 100a1 thereof is as shown in Figures 6A to 6C. On the other hand, the concentration of the additional element A in the (001) plane and in the surface layer portion 100a (basal region 100a2) thereof may be low or absent, as described above.

[0271] As described in the first embodiment, high purity LiCoO ２ In the manufacturing method of manufacturing the silicon nitride film, the additional element A is mixed in and heated after the manufacturing process, and the additional element A spreads mainly through the diffusion path of lithium ions. Therefore, it is easy to make the distribution of the additional element A in the planes other than the (001) plane and in the surface layer portion 100 a thereof fall within a preferred range.

[0272] <Grain Boundaries> In addition to the distribution described above, the additional element A contained in the positive electrode active material particles 100 of one embodiment of the present invention is more preferably at least partially distributed unevenly in and near the grain boundaries.

[0273] In this specification and the like, uneven distribution refers to the concentration of an element in a certain region being different from that in other regions, and is synonymous with segregation, precipitation, non-uniformity, bias, or the mixture of areas with high concentration and areas with low concentration.

[0274] For example, the magnesium concentration at and near the grain boundaries of the positive electrode active material particles 100 is preferably higher than that at and near the grain boundaries in the interior 100b. The fluorine concentration at and near the grain boundaries is also preferably higher than that at and near the grain boundaries in the interior 100b. The nickel concentration at and near the grain boundaries is also preferably higher than that at and near the grain boundaries in the interior 100b. The aluminum concentration at and near the grain boundaries is also preferably higher than that at and near the grain boundaries in the interior 100b.

[0275] Grain boundaries are one type of planar defect. Therefore, like surfaces, they are prone to instability and are prone to initiating changes in the crystal structure. Therefore, if the concentration of the added element A at and near the grain boundaries is high, changes in the crystal structure can be more effectively suppressed.

[0276] Furthermore, when the magnesium concentration and fluorine concentration are high at and near the grain boundaries, even if cracks occur along the grain boundaries of the positive electrode active material particles 100 of one embodiment of the present invention, the magnesium concentration and fluorine concentration become high near the cracked surface, thereby improving the corrosion resistance to hydrofluoric acid even in the positive electrode active material particles after cracks occur.

[0277] <Analysis method> A certain positive electrode active material particle is ｘ CoO ２ When x in the formula (I) is small, it can be determined whether the positive electrode active material particle 100 of one embodiment of the present invention has an O3′-type crystal structure by Li ｘ CoO ２ This can be determined by analyzing a positive electrode having positive electrode active material particles with a small x therein using XRD, electron diffraction, neutron diffraction, electron spin resonance (ESR), nuclear magnetic resonance (NMR), or the like.

[0278] XRD is particularly preferred because it can analyze the symmetry of transition metals such as cobalt contained in the positive electrode active material particles with high resolution, compare the level of crystallinity and crystal orientation, analyze lattice periodic distortion and crystallite size, and provide sufficient accuracy even when measuring a positive electrode obtained by disassembling a secondary battery. The XRD measurement method is not particularly limited, and for example, a method can be used in which the X-ray diffraction intensity is measured by changing the angle of incidence of the X-rays and setting the angle of the X-ray detector to the same as the angle of incidence (hereinafter referred to as 2θ / θ continuous scanning or θ-2θ method). XRD using 2θ / θ continuous scanning provides diffraction peaks that reflect the crystalline structure of the interior 100b of the positive electrode active material particle 100, which occupies most of the volume of the positive electrode active material particle 100.

[0279] When analyzing crystallite size by XRD, it is preferable to measure the size without the influence of the orientation of the positive electrode active material particles due to pressure, etc. For example, the positive electrode active material particles can be taken out from the positive electrode obtained by disassembling a secondary battery, and the positive electrode active material particles can be measured as a powder sample. Alternatively, the proportion of the O3' structure can be calculated by waveform separation using a reference diffraction pattern of the O3' structure, a reference diffraction pattern of the H1-3 structure, etc., in analyzing the XRD diffraction pattern.

[0280] Furthermore, when calculating the crystallite size, the XRD diffraction pattern is preferably obtained for the positive electrode active material particles alone, but may also be obtained for the positive electrode including the positive electrode active material particles as well as a current collector, a binder, a conductive material, etc. However, in the positive electrode state, the positive electrode active material particles may be oriented due to the influence of pressure, etc., during the manufacturing process. If the orientation is strong, the crystallite size of the positive electrode active material particles may not be accurately calculated. Therefore, the XRD diffraction pattern can be obtained by, for example, removing the positive electrode active material layer from the positive electrode, removing some of the binder, etc., in the positive electrode active material layer using a solvent, etc., and then filling the sample into a sample holder.

[0281] The crystallite size can be calculated using, for example, a Bruker D8 ADVANCE, a CuKα X-ray source, a 2θ of 15° to 90° increments of 0.005, and a LYNXEYE XE-T detector, and a diffraction pattern obtained using ICSD Coll. Code. 172909 as the literature value for lithium cobaltate. Analysis can be performed by the Rietveld method using DIFFRAC. TOPAS ver. 6 as crystal structure analysis software, and can be set, for example, as follows: Emission Profile: CuKa5. lam Background: Chebychev polynomia: l, 5th Instrument Primary radius: 280mm Secondary radius: 280mm Linear PSD 2Th Angular range: 2.9 FDS angle: 0.3 Full Axial Convolution Filament length: 12mm Sample length: 15mm Receiving Slit Length: 12mm Primary Sollers: 2.5 Secondary Sollers: 2.5 Corrections Specimen displacement: Refine LP Factor: 0

[0282] It is preferable to use the value of LVol-IB, which is the crystallite size corrected based on the integral width standard calculated by the above method, as the crystallite size.

[0283] Since lithium cobalt oxide tends to be (001) oriented, setting the preferred orientation to (001) may result in a better GOF (goodness of fit). The March-Dollase function or spherical harmonics can be used as the preferred orientation. Furthermore, in XRD analysis to determine crystallite size, the Rietveld method may be unsuitable for determining crystallite size if the preferred orientation is less than 0.8 or greater than 1.2 because the sample is too strongly oriented. In such cases where the Rietveld method is not suitable, it is preferable to determine the crystallite size using another refinement method that can obtain a better GOF. For example, the Whole-Powder Pattern Decomposition (WPPD) method can be used.

[0284] In addition, with the full pattern decomposition method, it is possible to calculate not only the crystallite size but also the lattice constant without being affected by the orientation of the sample.

[0285] As described above, the positive electrode active material particles 100 according to one embodiment of the present invention are ｘ CoO ２ The characteristic of this material is that there is little change in the crystal structure when x is 1 and when it is 0.24 or less. Materials in which the crystal structure that undergoes large changes when charged at high voltage accounts for 50% or more of the crystal structure are not preferable because they cannot withstand repeated high-voltage charging and discharging.

[0286] It should also be noted that simply adding an additional element A may not result in an O3'-type crystal structure. For example, even if lithium cobalt oxide containing magnesium and fluorine or lithium cobalt oxide containing magnesium and aluminum has something in common, depending on the concentration and distribution of the additional element A, Li ｘ CoO ２ In this case, x is 0.24 or less and the O3' type crystal structure accounts for 60% or more, and in other cases the H1-3 type crystal structure accounts for 50% or more.

[0287] Furthermore, even in the case of the positive electrode active material particle 100 of one embodiment of the present invention, an H1-3 type or trigonal O1 type crystal structure may be generated if x is too small, such as 0.1 or less, or under conditions where the charge voltage exceeds 4.9 V. Therefore, to determine whether or not the positive electrode active material particle 100 is one embodiment of the present invention, analysis of the crystal structure, such as XRD, and information such as the charge capacity or the charge voltage are required.

[0288] However, positive electrode active material particles with a small x may undergo a change in crystal structure when exposed to air. For example, the crystal structure may change from an O3'-type to an H1-3-type crystal structure. Therefore, it is preferable to handle all samples used for crystal structure analysis in an inert atmosphere such as an argon atmosphere.

[0289] However, even if handled in an argon atmosphere, the crystal structure of the positive electrode may change over time after the secondary battery is disassembled. Therefore, it is preferable to adopt a method that allows for rapid measurement as needed.

[0290] In the case of XRD, the detector and / or measurement start angle can be appropriately changed in order to quickly observe the main peak. For example, it is preferable to measure the main peak within 13 minutes from the start of measurement.

[0291] Furthermore, whether the distribution of the additive element A contained in the positive electrode active material particles is in the state described above can be determined by analysis using, for example, XPS, EDX, EPMA (Electron Probe Micro Analyzer), or the like.

[0292] The crystal structure of the surface layer 100 a and the grain boundaries can be analyzed by electron diffraction or the like of a cross section of the positive electrode active material particle 100 .

[0293] <Charging Method> Charging for determining whether a composite oxide is the positive electrode active material particle 100 of one embodiment of the present invention can be performed by preparing a coin cell (CR2032 type, diameter 20 mm, height 3.2 mm) using the composite oxide as a positive electrode and lithium metal as a counter electrode. The coin cell includes an electrolyte, a separator, a positive electrode can, and a negative electrode can.

[0294] More specifically, the positive electrode may be prepared by coating a positive electrode current collector made of aluminum foil with a slurry containing a mixture of positive electrode active material particles, a conductive material, and a binder.

[0295] Lithium metal can be used for the counter electrode. When a material other than lithium metal is used for the counter electrode, the voltage value of the secondary battery and the potential value of the positive electrode will be different. Unless otherwise specified, the voltage and potential in this specification refer to the potential of the positive electrode relative to the lithium metal counter electrode.

[0296] The electrolyte solution was a mixed solvent of ethylene carbonate (EC) and diethyl carbonate (DEC) in a volume ratio of 3:7, with 1 mol / L of lithium hexafluorophosphate (LiPF ６ ) to which 2 wt % of vinylene carbonate (VC) is added as an additive can be used.

[0297] The separator may be a 25 μm thick porous polypropylene film.

[0298] The positive electrode can and the negative electrode can may be made of stainless steel (SUS).

[0299] The coin cell prepared under the above conditions is charged at a desired voltage (e.g., 4.50 V, 4.55 V, 4.58 V, 4.60 V, 4.62 V, 4.65 V, 4.70 V, 4.75 V, or 4.80 V). The charging method is not particularly limited as long as charging is performed at the desired voltage for a sufficient period of time. Note that, in this specification, "approximately 4.6 V" refers to a voltage of 4.58 V or higher and 4.62 V or lower. For example, when charging by CCCV, the CC charging current can be set to 20 mA / g or higher and 100 mA / g or lower. CV charging can be completed at 2 mA / g or higher and 10 mA / g or lower. Because lithium ions diffuse slowly inside the positive electrode active material particles, charging at such a low current value is desirable to observe the phase change of the positive electrode active material particles. The temperature is set to 25°C or 45°C. After charging in this manner, the coin cell is disassembled in a glove box under an argon atmosphere and the positive electrode is removed to obtain positive electrode active material particles with a desired charge capacity. When performing various analyses, it is preferable to seal the removed positive electrode in an argon atmosphere to prevent reactions with external components. For example, XRD can be performed by sealing the removed positive electrode in a sealable sample holder under an argon atmosphere. To avoid the effects of self-discharge, it is preferable to remove the positive electrode promptly after charging is complete and subject it to analysis. Specifically, after charging is complete, disassembly of the coin cell is preferably completed within one hour, more preferably within 30 minutes.

[0300] Furthermore, when analyzing the crystal structure in the charged state after multiple charge / discharge cycles, for example, charging can be performed by constant current charging at a current value of 20 mA / g to 100 mA / g up to a desired voltage (e.g., 4.50 V, 4.55 V, 4.58 V, 4.60 V, 4.62 V, 4.65 V, 4.70 V, 4.75 V, or 4.80 V), followed by constant voltage charging until the current value reaches 2 mA / g to 10 mA / g, and then discharging at a constant current of 20 mA / g to 100 mA / g at 2.5 V. Alternatively, discharging can be performed by constant current discharging at 3.0 V at a current value of 20 mA / g to 200 mA / g.

[0301] Furthermore, when analyzing the crystal structure in the discharged state after multiple charge / discharge cycles, constant current discharge can be performed, for example, at 2.5 V and a current value of 20 mA / g or more and 200 mA / g or less, or at 3.0 V and a current value of 20 mA / g or more and 200 mA / g or less.

[0302] <XRD> The XRD measurement apparatus and conditions are not particularly limited. For example, the measurement can be performed using the following apparatus and conditions: XRD apparatus: D8 ADVANCE manufactured by Bruker; X-ray: CuKα1; output: 40 kV, 40 mA; slit width: 0.6 mm; detector: LYNXEYE XE-T; scan method: 2θ / θ continuous scan; measurement range (2θ): 15° to 90°; step width (2θ): set to 0.01°; counting time: 1 second / step; sample stage rotation: 15 rpm.

[0303] If the measurement sample is a powder, it can be placed in a glass sample holder or sprinkled on a greased silicone anti-reflective plate. If the measurement sample is a positive electrode, the positive electrode can be attached to the substrate with double-sided tape, and the positive electrode active material layer can be set to match the measurement surface required by the instrument. If the positive electrode active material layer is higher than the measurement surface required by the instrument, the diffraction pattern will be shifted overall to the higher angle side; if it is lower, the diffraction pattern will be shifted overall to the lower angle side. In this case, the diffraction pattern shift can be corrected using crystal structure analysis software, etc.

[0304] The ideal powder XRD patterns calculated from the O3' type crystal structure and the H1-3 type crystal structure model using CuKα1 radiation are shown in Figures 13 and 14. For comparison, Li ｘ CoO ２ LiCoO where x=1 ２ The ideal XRD patterns calculated from the crystal structure of LiCoO3 and the trigonal O1 with x = 0 are also shown. ２ (O3) and CoO ２The pattern of (O1) was created using Reflex Powder Diffraction, a module of Materials Studio (BIOVIA), based on the crystal structure information obtained from ICSD. The 2θ range was 15° to 75°, with a step size of 0.01 and a wavelength of λ1 of 1.540562 × 10. −１０ m and λ2 were not set, and the monochromator was single. The XRD pattern of the H1-3 type crystal structure was created in the same manner as above, based on the information on the H1-3 type crystal structure shown in Fig. 12. The XRD pattern of the O3' type crystal structure was created by estimating the crystal structure from the XRD pattern of the positive electrode active material particles of one embodiment of the present invention, fitting using TOPAS ver. 3 (crystal structure analysis software manufactured by Bruker), and creating an XRD pattern in the same manner as the others.

[0305] As shown in FIG. 13, the O3′ type crystal structure has diffraction peaks at 2θ=19.25±0.12° (19.13° or more and 19.37° or less) and 2θ=45.47±0.10° (45.37° or more and 45.57° or less).

[0306] However, as shown in FIG. 14, no peaks appear at these positions in the H1-3 type crystal structure and trigonal O1. ｘ CoO ２ It can be said that the presence of diffraction peaks at 2θ = 19.25 ± 0.12° (19.13° or more and 19.37° or less) and 2θ = 45.47 ± 0.10° (45.37° or more and 45.57° or less) when x in the particle is small is a characteristic of the positive electrode active material particle 100 of one embodiment of the present invention.

[0307] 13, for example, when charging is performed with the upper limit of the charging voltage set to a voltage slightly lower than 4.60 V (4.56 V, 4.57 V, 4.58 V, or 4.59 V), the above-mentioned diffraction peaks appear shifted to a lower angle. For example, when charging is performed with the upper limit of the charging voltage set to 4.58 V, the positive electrode active material particles 100 have diffraction peaks at 2θ = 18.85 ± 0.20° and 2θ = 45.15 ± 0.10°.

[0308] This can also be said to mean that the positions of XRD diffraction peaks are close between the crystal structures of x = 1 and x ≦ 0.24. More specifically, for the main diffraction peaks of the crystal structures of x = 1 and x ≦ 0.24 that appear at 2θ of 42° or more and 46° or less, the difference in 2θ is 0.7° or less, more preferably 0.5° or less.

[0309] The positive electrode active material particles 100 according to one embodiment of the present invention are ｘ CoO ２ When x in the formula is small, the O3'-type crystal structure is present, but not all of the O3'-type crystal structure is required. It may contain other crystal structures, or may be partially amorphous. However, when Rietveld analysis is performed on the XRD pattern, the O3'-type crystal structure is preferably 50 wt% or more, more preferably 60 wt% or more, and even more preferably 66 wt% or more. If the O3'-type crystal structure is 50 wt% or more, more preferably 60 wt% or more, and even more preferably 66 wt% or more, the positive electrode active material particles can have sufficiently excellent cycle characteristics.

[0310] Furthermore, even after 5 or more, 30 or more, 50 or more, or 100 or more charge / discharge cycles from the start of measurement, when Rietveld analysis is performed, the O3'-type crystal structure is preferably 35 wt% or more, more preferably 40 wt% or more, and even more preferably 43 wt% or more.

[0311] Furthermore, the sharpness of the diffraction peaks in the XRD pattern indicates the degree of crystallinity. Therefore, it is preferable that each diffraction peak after charging is sharp, i.e., the full width at half maximum is narrow. The full width at half maximum varies depending on the XRD measurement conditions or the value of 2θ, even for peaks arising from the same crystalline phase. Under the above-mentioned measurement conditions, for peaks observed between 2θ = 43° and 46°, the full width at half maximum is preferably, for example, 0.2° or less, more preferably 0.15° or less, and even more preferably 0.12° or less. Note that not all peaks necessarily meet this requirement. If some peaks meet this requirement, it can be said that the crystallinity of the crystalline phase is high. Such high crystallinity contributes to the stabilization of the crystal structure after sufficient charging.

[0312] The crystallite size of the O3'-type crystal structure of the positive electrode active material particles 100 is ２ Therefore, even under the same XRD measurement conditions as the positive electrode before and after charging and discharging, the ｘ CoO ２ When x in the graph is small, a clear peak of the O3' type crystal structure can be confirmed. ２ In this case, even if a part of the crystal structure resembles the O3'-type crystal structure, the crystallite size will be small and the peak will be broad and small. The crystallite size can be determined from the full width at half maximum of the XRD peak.

[0313] <XPS> XPS (X-ray Photoelectron Spectroscopy) can analyze an area from the surface to a depth of about 2 to 8 nm (usually 5 nm or less) in the case of inorganic oxides by using monochromatic aluminum Kα rays as X-rays. Furthermore, narrow scan analysis can be used to analyze the bonding state of elements. The quantitative accuracy of XPS is often about ±1 atomic %, and the lower detection limit is about 1 atomic %, although it depends on the element.

[0314] In one embodiment of the cathode active material particle 100 of the present invention, the concentration of one or more selected from the additive elements A is preferably higher in the surface layer portion 100a than in the interior portion 100b. This is equivalent to saying that the concentration of one or more selected from the additive elements A in the surface layer portion 100a is preferably higher than the average concentration throughout the cathode active material particle 100. Therefore, for example, it can be said that the concentration of one or more selected from the additive elements A in the surface layer portion 100a measured by XPS or the like is preferably higher than the average concentration of the additive elements A throughout the cathode active material particle 100 measured by ICP-MS (inductively coupled plasma mass spectrometry) or GD-MS (glow discharge mass spectrometry). For example, the magnesium concentration in at least a portion of the surface layer portion 100a measured by XPS or the like is preferably higher than the average magnesium concentration throughout the cathode active material particle 100. Furthermore, the nickel concentration in at least a portion of the surface layer portion 100a is preferably higher than the average nickel concentration throughout the cathode active material particle 100. It is also preferable that the aluminum concentration in at least a part of the surface layer portion 100a is higher than the average aluminum concentration in the entire positive electrode active material particle 100. It is also preferable that the fluorine concentration in at least a part of the surface layer portion 100a is higher than the average fluorine concentration in the entire positive electrode active material particle 100.

[0315] Note that the surface and surface layer portion 100a of the positive electrode active material particle 100 according to one embodiment of the present invention are assumed to be free of carbonates, hydroxyl groups, and the like that are chemically adsorbed after the preparation of the positive electrode active material particle 100. Furthermore, they are assumed to be free of the electrolyte, binder, conductive material, or compounds derived therefrom that are attached to the surface of the positive electrode active material particle 100. Therefore, when quantifying the elements contained in the positive electrode active material particle, corrections may be made to exclude carbon, hydrogen, excess oxygen, excess fluorine, and the like that can be detected by surface analysis such as XPS. For example, XPS can separate the types of bonds by analysis, and corrections may be made to exclude C—F bonds derived from the binder.

[0316] Furthermore, before subjecting the samples to various analyses, the positive electrode active material particles 100 and the positive electrode active material layer 22 may be washed or otherwise processed to remove the electrolyte, binder, conductive material, or compounds derived therefrom adhering to the surfaces of the positive electrode active material particles 100. While lithium may dissolve in the solvent used for washing, even in this case, the additive element A is unlikely to dissolve, and therefore the concentration and atomic ratio of the additive element A are minimally affected. For washing, it is preferable to use a method that minimizes damage to the samples, such as the positive electrode active material particles 100 and the positive electrode active material layer 22. Examples of solvents that can be used for the electrolyte solution include those that can be used in the electrolyte solution. For details about solvents that can be used for the electrolyte solution, please refer to the description of organic solvents listed in the <Electrolyte Solution> section below. Examples of suitable cleaning agents include dimethyl carbonate (DMC) and acetonitrile. Alternatively, solvents that can be used in wet mixing or grinding (e.g., N-methyl-2-pyrrolidone (NMP)) can also be used. Furthermore, the cleaning agent can be combined with ultrasonic cleaning or filtration.

[0317] The concentration of the additive element A may also be compared in terms of its ratio to cobalt. Using the ratio to cobalt is preferable because it allows comparison while reducing the influence of carbonates and the like that are chemically adsorbed after the preparation of the positive electrode active material particles. For example, the ratio Mg / Co of the number of magnesium atoms to the number of cobalt atoms measured by XPS analysis is preferably 0.400 or more and 1.20 or less, more preferably 0.500 or more and 1.00 or less, even more preferably 0.500 or more and 0.900 or less, and even more preferably 0.500 or more and 0.700 or less.

[0318] Furthermore, for example, the ratio of the number of nickel atoms to the number of cobalt atoms, Ni / Co, as determined by XPS analysis, is preferably 0.050 or more and 0.200 or less, more preferably 0.050 or more and 0.150 or less, even more preferably 0.050 or more and 0.100 or less, and even more preferably 0.050 or more and 0.070 or less.

[0319] Furthermore, the ratio of the number of aluminum atoms to the number of cobalt atoms, Al / Co, as determined by XPS analysis, is preferably 0.010 or more and 0.100 or less, more preferably 0.010 or more and 0.050 or less, and even more preferably 0.010 or more and 0.040 or less.

[0320] Furthermore, for example, the ratio F / Mg of the number of fluorine atoms to the number of magnesium atoms, as determined by XPS analysis, is preferably 0.100 or more and 1.00 or less, more preferably 0.100 or more and 0.800 or less, still more preferably 0.100 or more and 0.500 or less, still more preferably 0.100 or more and 0.300 or less, and still more preferably 0.100 or more and 0.200 or less.

[0321] The above-described range indicates that the additive element A is not attached to a narrow area on the surface of the positive electrode active material particle 100, but is widely distributed at a preferred concentration in the surface layer portion 100a of the positive electrode active material particle 100. In other words, as a result of XPS analysis of the positive electrode active material particle 100, the above-described range indicates that the crystal structure is less likely to collapse even when charging and discharging are repeated so that x is 0.24 or less, and excellent cycle characteristics can be achieved. Furthermore, good lithium insertion and desorption is possible in the positive electrode active material particle 100, and excellent rate characteristics can be achieved.

[0322] When performing XPS analysis, for example, monochromated aluminum Kα rays can be used as X-rays. Furthermore, it is preferable to use an XPS apparatus with an energy resolution such that the full width at half maximum of the Ag3d5 / 2 peak (112 eV) in the XPS spectrum of an Ag sample is 1.0 eV±0.1 eV. The take-off angle can be, for example, 45°. For example, the following XPS apparatus and measurement conditions can be used for the measurement. Measurement apparatus: Quantera II manufactured by ULVAC-PHI, Inc. X-ray: Monochromated Al Kα (1486.6 eV) Energy resolution: Full width at half maximum of the Ag3d5 / 2 peak is 1.0 eV±0.1 eV Detection area: 100 μmφ Detection depth: Approximately 4 nm to 5 nm (take-off angle 45°) Measurement spectrum: Wide scan, narrow scan for each detected element

[0323] When the positive electrode active material particle 100 according to one embodiment of the present invention is subjected to XPS analysis, the peak (Mg1s peak) representing the bond energy between magnesium and other elements is preferably equal to or greater than 1303.0 eV and less than 1305.0 eV, and more preferably about 1304.0 eV, which is a value different from the bond energy of magnesium fluoride, 1306.0 eV, and is close to the bond energy of magnesium oxide.

[0324] In the XPS analysis of the positive electrode active material particle 100 according to one embodiment of the present invention, the measured XPS spectrum may be corrected so that the C1s peak is aligned with the reference value (284.8 eV), i.e., the entire spectrum may be shifted. This can reduce the influence of differences in the XPS apparatus, differences in measurement conditions, and the like on the XPS measurement.

[0325] Furthermore, in XPS analysis of the positive electrode active material particle 100 of one embodiment of the present invention, when the Mg1s peak is analyzed to analyze the proportions of the peak component derived from the "O-Mg-O" bond, the peak component derived from the "O-Mg-F" bond, and the peak component derived from the "F-Mg-F" bond, it is preferable that the particle has a peak component derived from the O-Mg-O bond. Furthermore, the particle may contain a peak component derived from the "O-Mg-F" bond, but its proportion is preferably 30% or less of the total of the three peak components, more preferably 20% or less, and preferably 10% or less, and more preferably below the lower limit of detection. Furthermore, the particle may contain a peak component derived from the "F-Mg-F" bond, but its proportion is preferably 10% or less of the total, and more preferably below the lower limit of detection.

[0326] That is, in an XPS analysis of the positive electrode active material particle 100 of one embodiment of the present invention, when the proportions of the peak component derived from the "O-Mg-O" bond, the peak component derived from the "O-Mg-F" bond, and the peak component derived from the "F-Mg-F" bond are analyzed, the peak component derived from the "O-Mg-O" bond is preferably 70% or more, more preferably 80% or more, still more preferably 90% or more, and particularly preferably 100%. Note that when a similar analysis is performed on a positive electrode after incorporating the positive electrode active material particle 100 of one embodiment of the present invention into a secondary battery, a peak component derived from the O-Mg-O bond may be detected due to the influence of fluorine contained in the binder or the electrolyte.

[0327] A method for analyzing the Mg1s peak of an XPS spectrum in XPS analysis will be described. In analyzing the Mg1s peak, the peak component derived from the O-Mg-O bond is designated as fit peak 1, the peak component derived from the O-Mg-F bond is designated as fit peak 2, and the peak component derived from the F-Mg-F bond is designated as fit peak 3. These three fit peaks are synthesized, and the peak synthesis ratio that minimizes the difference from the Mg1s peak of the XPS spectrum obtained by XPS analysis is calculated. The area ratio of fit peak 1, fit peak 2, and fit peak 3 at this time can be assumed to be the abundance ratio of O-Mg-O bonds, O-Mg-F bonds, and F-Mg-F bonds, and the analysis results can be output.

[0328] In the above-mentioned XPS spectrum analysis method, the energy value (Ep1) at the maximum value (also called peak top) of fit peak 1 is determined by the MgO-coated LiCoO ２ The energy value at the maximum value of the Mg1s peak when measured separately as a standard sample can be referenced. The energy value at the maximum value of fit peak 3 (Ep3) can be referenced to the energy value at the maximum value of magnesium fluoride (MgF ２For example, the energy value at the maximum value of the Mg1s peak when a standard sample (for example, MGH18XB manufactured by Kojundo Chemical Research Institute, purity 99.9% (3N up)) is separately measured can be referenced. The energy value at the maximum value of fit peak 2 (Ep2) can be set to an intermediate value between Ep1 and Ep3. Ep1 is located on the lower energy side compared to Ep3. The energy value at the maximum value of a peak is also referred to as the peak position.

[0329] In the XPS analysis of the positive electrode active material particle 100 according to one embodiment of the present invention, the Mg1s peak analysis result falling within the above-described preferred range can also be determined from the peak position and full width at half maximum of the peak. For example, the full width at half maximum of the Mg1s peak is preferably 1.0 eV to 3.0 eV, more preferably 1.0 eV to 2.8 eV, and particularly preferably 1.0 eV to 2.6 eV. Note that, in the above, the peak position of the Mg1s peak is on the lower energy side than the energy value at the maximum value of the Mg1s peak when magnesium fluoride is separately measured as a standard sample.

[0330] <EDX> It is preferable that one or more selected from the additive elements A contained in the positive electrode active material particles 100 have a concentration gradient. It is more preferable that the depth from the surface of the concentration peak of the positive electrode active material particles 100 differs depending on the additive element A. The concentration gradient of the additive element A can be evaluated, for example, by exposing a cross section of the positive electrode active material particle 100 using a focused ion beam (FIB) or the like and analyzing the cross section using EDX, electron probe microanalysis (EPMA), or the like.

[0331] In EDX analysis, measuring while scanning an area and evaluating the area two-dimensionally is called EDX area analysis. Measuring while scanning linearly and evaluating the distribution of atomic concentration within positive electrode active material particles is called line analysis. Furthermore, data extracted from a linear area of ​​EDX area analysis is sometimes called line analysis. Measuring a certain area without scanning is called point analysis.

[0332] EDX area analysis (e.g., element mapping) can quantitatively analyze the concentration of the additive element A in the surface layer 100a, the interior 100b, and the vicinity of the grain boundary of the positive electrode active material particle 100. The vicinity of the grain boundary refers to the region within 10 nm from the grain boundary. EDX ray analysis can also analyze the concentration distribution and maximum value of the additive element A. Analysis using a thinned sample, such as STEM-EDX, is more suitable because it can analyze the concentration distribution in the depth direction from the surface to the center of a specific region of the positive electrode active material particle without being affected by the distribution in the depth direction.

[0333] Since the positive electrode active material particle 100 is a compound containing a transition metal and oxygen capable of lithium insertion / extraction, the interface between a region where the transition metal M (e.g., Co, Ni, Mn, Fe, etc.) that is oxidized and reduced upon lithium insertion / extraction and oxygen is present and a region where it is not present is defined as the surface of the positive electrode active material particle. When the positive electrode active material particle is subjected to analysis, a protective film may be attached to the surface, but the protective film is not included in the positive electrode active material particle. The protective film may be a single-layer or multi-layer film of carbon, metal, oxide, resin, etc.

[0334] In STEM-EDX-ray analysis or the like, in principle or due to measurement errors, the graph of the detected amount of characteristic X-rays of the element does not change sharply, and it may be difficult to precisely determine the surface. Therefore, when referring to the depth direction in STEM-EDX-ray analysis or the like, the detected amount of characteristic X-rays of the transition metal M is the average value M of the detected amount of characteristic X-rays of the internal transition metal M. ＡＶＥ and the average M of the detected amount of characteristic X-rays of the transition metal M in the background. ＢＧ The point where the detected amount of oxygen characteristic X-rays is 50% of the sum of the detected amount of oxygen characteristic X-rays and the average value O ＡＶＥ and the average value O of the detected amount of characteristic X-rays of oxygen in the background ＢＧThe reference point is the point where the detected amount of the characteristic X-rays of the transition metal M is 50% of the sum of the average value of the detected amount of the characteristic X-rays of the internal transition metal M and the average value of the detected amount of the characteristic X-rays of the background transition metal M. If the point where the detected amount of the characteristic X-rays of oxygen is 50% of the sum of the average value of the detected amount of the characteristic X-rays of the internal oxygen and the average value of the detected amount of the characteristic X-rays of the background oxygen is different from the point where the detected amount of the characteristic X-rays of oxygen is 50% of the sum of the average value of the detected amount of the characteristic X-rays of the internal oxygen and the average value of the detected amount of the characteristic X-rays of the background oxygen, this is considered to be due to the influence of metal oxides, carbonates, etc. containing oxygen attached to the surface, and therefore, the detected amount of the characteristic X-rays of the transition metal M is different from the point where ... oxygen is different from the sum of the average value of the detected amount of the characteristic X-rays of the internal transition metal M. ＡＶＥ and the average M of the detected amount of characteristic X-rays of the transition metal M in the background. ＢＧ In the case of positive electrode active material particles containing a plurality of transition metals M, the M of the transition metal element with the largest amount of characteristic X-rays detected inside can be used as the reference point. ＡＶＥ and M ＢＧ The reference point can be determined using the following formula:

[0335] The average value M of the detected amount of characteristic X-rays of the transition metal M in the background ＢＧ can be obtained by averaging the amount of characteristic X-rays of the transition metal M detected within a range of 2 nm or more, preferably 3 nm or more, from the outside of the positive electrode active material particle, while avoiding the area where the amount of characteristic X-rays of the transition metal M begins to increase. ＡＶＥ can be obtained by averaging a range of 2 nm or more, preferably 3 nm or more, at a depth of 30 nm or more, preferably more than 50 nm, from the region where the detected amount of characteristic X-rays of the transition metal M and oxygen becomes saturated and stable, for example, the region where the detected amount of characteristic X-rays of the transition metal M starts to increase. ＢＧ and the average value O of the detected amount of characteristic X-rays of oxygen inside ＡＶＥ can also be found in the same way.

[0336] Furthermore, the surface of the positive electrode active material particle 100 in a cross-sectional STEM image or the like is the boundary between an area where an image derived from the crystal structure of the positive electrode active material particle is observed and an area where an image is not observed, and is the outermost area of ​​an area where atomic columns derived from the atomic nuclei of metal elements having atomic numbers larger than that of lithium among the metal elements constituting the positive electrode active material particle are confirmed.

[0337] In STEM-EDX-ray analysis, a peak refers to a convex shape that appears on a graph of the characteristic X-ray intensity or concentration of each element. The peak intensity refers to the maximum value of the characteristic X-ray intensity or concentration of each element. The peak position refers to the position of the maximum value of the characteristic X-ray intensity or concentration of each element. The noise in STEM-EDX-ray analysis may be a measured value with a full width at half maximum that is less than the spatial resolution (R), for example, R / 2 or less.

[0338] In addition, a peak in STEM-EDX-ray analysis refers to the maximum value of a convex shape that appears in a graph of the characteristic X-ray intensity for each element, or the maximum value of the characteristic X-ray for each element. Note that noise in STEM-ED X-ray analysis may be a measured value of a full width at half maximum that is less than the spatial resolution (R), for example, R / 2 or less.

[0339] The influence of noise can be reduced by scanning the same location multiple times under the same conditions. For example, the integrated value measured after two scans can be used as the detection value for each element. The number of scans is not limited to two, and more than two scans can be performed, and the integrated value can be used as the detection value for each element.

[0340] Elemental quantification in EDX analysis can be performed using a standardless quantification method that uses the k-factor built into the analytical device and / or analytical software. Furthermore, when determining element concentrations from quantitative results, the elements of interest preferably include those used in the target material, raw materials, and pre-analysis, such as the following 14 elements: carbon, oxygen, fluorine, magnesium, aluminum, silicon, phosphorus, sulfur, calcium, titanium, iron, cobalt, nickel, and gallium. Because quantitative calculations are performed so that the total quantitative concentration of these elements equals 100%, these elements are also referred to as denominator elements.

[0341] Next, the positive electrode active material is sliced ​​to prepare a STEM cross-section sample. For example, the slice processing can be performed using an FIB-SEM device (Hitachi High-Tech XVision 200TBS). The pickup is performed using an MPS (microprobing system), and the processing conditions are preferably, for example, gradually decreasing the acceleration voltage from high to low, for example, 30 kV, 15 kV, 5 kV, and 2 kV.

[0342] STEM-EDX analysis can be performed using, for example, a STEM device (Hitachi High-Tech HF5000) and an OXFORD Ultim MAX TLE (two devices installed) as the EDX detector. During EDX analysis, the emission current of the STEM device is set to 7 μA or more and 10 μA or less, and a portion of the thinned sample with minimal depth and unevenness is measured. STEM-EDX analysis involves performing EDX area analysis to evaluate the measurement target area in two dimensions, after which any desired region can be extracted for EDX analysis using analysis software. The measurement magnification for EDX area analysis is set to a magnification that results in a linear analysis measurement pitch of approximately 0.3 nm, for example, approximately 160,000 times (320,000 times the magnification on the screen due to drift correction, which is doubled). The conditions for EDX area analysis can be 256 x 256 captured pixels, 50 μsec dwell time, and approximately 400 frames (approximately 150,000 Co counts in a qualitative spectrum). The extraction conditions for EDX ray analysis can be a line width of 256 pixels to detect as many characteristic X-rays as possible. EDX analysis can be performed using either the Netcount (Counts), which indicates the number of detected counts for an element, or the atomic %, which is obtained by multiplying the Netcount by the k factor, a coefficient specific to the element.

[0343] The STEM-EDX analysis is not limited to the above STEM device, and other STEM devices (JEM-ARM200F NEOARM manufactured by JEOL Ltd.) and EDX detectors (Dual SDD detector JED-2300T manufactured by JEOL Ltd.) can also be used.

[0344] In order to increase the spatial resolution in STEM-EDX ray analysis, it is preferable that the beam diameter of the electron beam is small. The beam diameter in STEM-EDX ray analysis is preferably 0.3 nm or less, more preferably 0.2 nm or less, and even more preferably 0.1 nm or less. Furthermore, in order to increase the analytical sensitivity in STEM-EDX ray analysis, it is preferable to increase the beam current of the electron beam. Therefore, it is preferable that the device used for STEM-EDX ray analysis is equipped with a spherical aberration corrector (Cs corrector) that can reduce the beam diameter and increase the beam current.

[0345] Furthermore, in the positive electrode active material particles 100 having magnesium and fluorine as the additive element A, the fluorine distribution preferably has a region overlapping with the magnesium distribution. For example, the difference in depth between the peak of the fluorine concentration or detection amount and the peak of the magnesium concentration or detection amount is preferably within 10 nm, more preferably within 3 nm, even more preferably within 1 nm, and even more preferably within 0.5 nm.

[0346] Furthermore, in the positive electrode active material particle 100 having nickel as the additive element A, the peak of the nickel concentration or detectable amount in the surface layer portion 100a is preferably present on the surface of the positive electrode active material particle 100 or at a depth of 3 nm from the reference point toward the center, and more preferably at a depth of 1 nm. Furthermore, in the positive electrode active material particle 100 having magnesium and nickel, the nickel distribution preferably has a region overlapping with the magnesium distribution. For example, the difference in depth between the peak of the nickel concentration or detectable amount and the peak of the magnesium concentration or detectable amount is preferably within 3 nm, and more preferably within 1 nm.

[0347] Furthermore, when the positive electrode active material particle 100 contains aluminum as the additive element A, it is preferable that, when EDX-ray analysis is performed, the peak of the magnesium, nickel, or fluorine concentration or detected amount is closer to the surface than the peak of the aluminum concentration or detected amount in the surface layer portion 100a. In other words, it is preferable that the peak of the aluminum concentration or detected amount in the surface layer portion 100a is located more inward than the peak of the magnesium, nickel, or fluorine concentration or detected amount. For example, it is preferable that the peak of the aluminum concentration or detected amount is present on the surface of the positive electrode active material particle 100 or at a depth of 0.5 nm to 50 nm from the reference point toward the center, and more preferably at a depth of 5 nm to 50 nm.

[0348] Here, how to express the positional relationship of element distribution when EDX-ray analysis is performed will be explained using Figures 15A to 15G. Figures 15A to 15F are schematic diagrams showing the concentration distribution or detection amount distribution of a first element e1 and a second element e2. Figure 15G is a schematic diagram showing the concentration distribution or detection amount distribution of a first element e1, a second element e2, and a third element e3.

[0349] For example, when the concentration distribution or detectable amount distribution of the first element e1 and the second element e2 has a shape as shown in Figure 15A, the position where the concentration or detectable amount of the second element e2 is maximum is said to be located more inward than the position where the concentration or detectable amount of the first element e1 is maximum. Also, when the concentration distribution or detectable amount distribution of the first element e1 and the second element e2 has a shape as shown in Figure 15B, the position where the concentration or detectable amount of the second element e2 is maximum is said to be located more inward than the position where the concentration or detectable amount of the first element e1 is maximum. Also, when the concentration distribution or detectable amount distribution of the first element e1 and the second element e2 has a shape as shown in Figure 15C, the position where the concentration or detectable amount of the first element e1 is maximum is said to be located more inward than the position where the concentration or detectable amount of the second element e2 is maximum. For example, when the concentration distribution or detectable amount distribution of the first element e1 and the second element e2 has a shape as shown in Figure 15D, the position where the concentration or detectable amount of the second element e2 is maximum is said to be located more inward than the position where the concentration or detectable amount of the first element e1 is maximum. For example, when the concentration distribution or detectable amount distribution of the first element e1 and the second element e2 has a shape as shown in Figure 15E, the position where the concentration or detectable amount of the first element e1 is maximum is said to be located more inward than the position where the concentration or detectable amount of the second element e2 is maximum. For example, when the concentration distribution or detectable amount distribution of the first element e1 and the second element e2 has a shape as shown in Figure 15F, the position where the concentration or detectable amount of the second element e2 is maximum is said to be located more inward than the position where the concentration or detectable amount of the first element e1 is maximum.

[0350] The expression "having an overlapping region" will be explained using an example in which the concentration distributions or detection amount distributions of a first element e1, a second element e2, and a third element e3 have the positional relationship shown in FIG. 15G. In this specification and the like, "having an overlapping region" means, for example, that the position of maximum value in the concentration distribution or detection amount distribution of at least one element is located in a range in which the concentration or detection amount in the concentration distribution or detection amount distribution of the other element is 1 / 5 or more of the maximum value. Note that when the background detection intensity in EDX-ray analysis is equal to or greater than the above-mentioned "1 / 5 of the maximum value," the "1 / 5 of the maximum value" in the above sentence shall be referred to as the "background detection intensity (also referred to as the detection limit)."

[0351] 15G, the position (p2) at which the second element e2 has a maximum value in its concentration distribution or detectable amount distribution is located in the range (hatched area in the figure) where the first element e1 has a concentration or detectable amount equal to or greater than 1 / 5 of the maximum value (or the lower detection limit) in the first element e1's concentration distribution or detectable amount distribution, and therefore the first element e1 and the second element e2 have an overlapping distribution area. Also, the position (p3) at which the third element e3 has a maximum value in its concentration distribution or detectable amount distribution is not located in the range (hatched area in the figure) where the first element e1 has a concentration or detectable amount equal to or greater than 1 / 5 of the maximum value (or the lower detection limit) in the first element e1's concentration distribution or detectable amount distribution, and therefore the first element e1 and the third element e3 do not have an overlapping distribution area.

[0352] 15G, the distribution of the second element e2 and the distribution of the third element e3 can be said to be located more inward than the distribution of the first element e1. Alternatively, the distribution of the second element e2 and the distribution of the third element e3 can be said to be biased more inward than the distribution of the first element e1.

[0353] <Powder Resistivity Measurement> The positive electrode active material particles 100 of one embodiment of the present invention have a stable crystal structure even at high voltages. The stable crystal structure of the positive electrode active material particles in a charged state can suppress a decrease in charge / discharge capacity due to repeated charge / discharge. Furthermore, in the above <EDX>, a preferred distribution of the additive element A (e.g., Mg, Al, Ni) obtained by STEM-EDX analysis of the positive electrode active material particles 100 was described. Furthermore, in the above <XPS>, a preferred ratio of the additive element A (e.g., Mg, Al, Ni) obtained by XPS analysis of the positive electrode active material particles 100 was described. Furthermore, the positive electrode active material particles 100 of one embodiment of the present invention are also characterized by their powder volume resistivity.

[0354] A feature of the positive electrode active material particles 100 according to one embodiment of the present invention is that the volume resistivity of the powder of the positive electrode active material particles 100 is 1.0×10 ８ Ω・cm or more 1.0×10 １０ The positive electrode active material particles 100 having the above volume resistivity have a stable crystal structure even at high voltages, and can be used as an indicator that the surface layer portion 100 a, which is important for the crystal structure of the positive electrode active material particles to be stable in a charged state, has been well formed.

[0355] The volume resistivity of the powder of the positive electrode active material particles 100 is 1.0×10 ８ Ω・cm or more 1.0×10 ９ It is more preferable that the resistance is Ω cm or less, and 1.0 × 10 ８ Ω・cm or more 5.0×10 ８ The positive electrode active material particles 100 having the above volume resistivity have a stable crystal structure even at high voltages, and can be used as an indicator that the surface layer portion 100 a, which is important for the crystal structure of the positive electrode active material particles to be stable in a charged state, has been well formed, and can also be used as an indicator that good lithium insertion / extraction is possible in the positive electrode active material particles.

[0356] A method for measuring the volume resistivity of the powder of the positive electrode active material particles 100 according to one embodiment of the present invention will be described.

[0357] The measurement of the volume resistivity of a powder preferably includes an instrument having a terminal for resistance measurement and a mechanism for applying pressure to the powder to be measured. The terminal for resistance measurement preferably has four terminals (also called four-probe). For example, the MCP-PD600 manufactured by Nitto Seiko Analytech Co., Ltd. can be used as a measuring device having a terminal for resistance measurement and a mechanism for applying pressure to the powder (sample) to be measured. The Loresta GXII or Hiresta UX can be used as the instrument for the four-probe method. The Loresta GXII can be used to measure low-resistivity samples, and the Hiresta UX can be used to measure high-resistivity samples. The measurement environment is preferably a stable environment such as a dry room. The dry room environment is preferably, for example, a temperature environment of 25°C and a dew point environment of -40°C or below.

[0358] Measurement of the volume resistivity of powder using the measuring device shown above will be described. First, a powder sample is set in the measuring unit. The measuring unit is structured so that the powder sample and a terminal for resistance measurement are in contact with each other and can apply pressure to the powder sample. The measuring unit also has a structure for measuring the volume of the powder sample. Specifically, the measuring unit has a cylindrical space in which the powder sample is set. The structure for measuring the volume of the powder sample described above can measure the volume occupied by the powder at that time by measuring the height of the powder set in the space.

[0359] In measuring the volume resistivity of a powder, the electrical resistance of the powder and the volume of the powder are measured while pressure is applied to the powder. The pressure applied to the powder can be measured under a variety of conditions. For example, the electrical resistance and volume of the powder can be measured under pressure conditions of 13 MPa, 25 MPa, 38 MPa, 51 MPa, and 64 MPa. The volume resistivity of the powder can be calculated from the measured electrical resistance and volume of the powder.

[0360] When the measurement described above is performed, the volume resistivity of the powder of the positive electrode active material particles 100 according to one embodiment of the present invention is 1.0×10 at a pressure of 64 MPa. ８ Ω・cm or more 1.0×10 １０ When the capacitance is 1.0×10 Ω cm or less, favorable cycle characteristics are exhibited in a charge-discharge cycle test under high voltage conditions, and ８ Ω・cm or more 1.0×10 ９ When the volume resistivity is 1.0×10 Ω cm or less, the battery exhibits favorable cycle characteristics in a charge-discharge cycle test under high voltage conditions, and also exhibits favorable discharge characteristics in a discharge rate test. ８ Ω・cm or more 5.0×10 ８ When the resistance is Ω·cm or less, more preferable discharge characteristics are exhibited in the discharge rate test.

[0361] <EPMA> The concentration of the additive element contained in the positive electrode active material particle 100 can be analyzed using EDX, but it can also be analyzed using EPMA. EPMA has a higher detection capability (also referred to as a lower detection limit) than EDX when analyzing elements present in trace amounts in a sample. Therefore, it is preferable to use EPMA when analyzing a region where a trace amount of the additive element is present.

[0362] In the EPMA analysis, a cross section of the positive electrode active material particle 100 is exposed by mechanical polishing, ion polishing, FIB, etc., and the cross section is analyzed. As the EPMA device, for example, an electron probe microanalyzer JXA-iHP200F manufactured by JEOL Ltd. can be used.

[0363] EPMA uses a wavelength-dispersive detector, so it has a higher ability to detect trace elements than EDX, which uses an energy-dispersive detector. On the other hand, the spatial resolution of EPMA analysis is inferior to that of EDX (especially STEM-EDX). Therefore, STEM-EDX is suitable for analysis focusing on the detailed distribution of added elements in the surface layer 100a of the positive electrode active material particle 100, while EPMA analysis is suitable for analysis of trace amounts of added elements in the interior 100b. Note that EPMA and EDX use different analytical methods, so the concentration values ​​obtained when analyzing the same region using each analytical method may not match.

[0364] The additive elements in the inner portion 100b of the positive electrode active material particle 100 may preferably contain trace amounts of magnesium and nickel. For example, in EPMA analysis, the ratio of the number of magnesium (Mg) atoms to the number of cobalt (Co) atoms in the inner portion 100b, Mg / Co, is preferably 0.005 or more and 0.03 or less, and more preferably about 0.01. By uniformly distributing the amount of magnesium shown here in the inner portion 100b, Li ｘ CoO ２ This is preferable because when x is small, changes in the crystal structure can be suppressed.

[0365] In addition, in the EPMA analysis, the ratio of the number of nickel (Ni) and cobalt (Co) atoms in the inner portion 100b, Ni / Co, is preferably 0.003 or more and 0.01 or less, and more preferably about 0.007. On the other hand, in the EPMA analysis, the number of titanium atoms in the inner portion 100b is preferably below the lower limit of detection. Note that the lower limit of detection for the number of titanium atoms is 0.2 at% when analyzing the interior of lithium cobalt oxide using, for example, a JXA-iHP200F.

[0366] Furthermore, the interior 100b may contain aluminum at a concentration that is not detected by EPMA analysis or is at the detection limit. The presence of aluminum in the interior 100b can stabilize the surrounding crystal structure. The detection limit for the number of aluminum atoms is 0.1 at% when analyzing the interior of lithium cobalt oxide using, for example, a JXA-iHP200F.

[0367] <Microelectron diffraction pattern> In the microelectron diffraction pattern, it is preferable to observe the characteristics of the rock salt-type crystal structure as well as the layered rock salt crystal structure. However, in the STEM image and the microelectron diffraction pattern, taking into account the above-mentioned difference in sensitivity, it is preferable that the characteristics of the rock salt-type crystal structure are not too strong in the surface layer portion 100a, particularly in the outermost surface (for example, 1 nm deep from the surface). This is because, rather than covering the outermost surface with a rock salt-type crystal structure, it is preferable to maintain the layered rock salt-type crystal structure while adding an additional element such as magnesium in the lithium layer, as this can ensure a lithium diffusion path and provide a stronger function of stabilizing the crystal structure.

[0368] Therefore, for example, when a microelectron diffraction pattern of a region at a depth of 1 nm or less from the surface and a microelectron diffraction pattern of a region at a depth of 3 nm to 10 nm are obtained, it is preferable that the difference in lattice constant calculated from these patterns be small.

[0369] <Second Positive Electrode Active Material Particles> A positive electrode according to one embodiment of the present invention can include, in addition to the positive electrode active material particles 100, second positive electrode active material particles different from the positive electrode active material particles 100. Like the positive electrode active material particles 100, the second positive electrode active material particles 200 have the function of taking in and releasing lithium ions during charge and discharge. The second positive electrode active material particles 200 used in one embodiment of the present invention can be made of a material that is similar to the positive electrode active material particles 100 except for the particle diameter, and that exhibits little deterioration during charge and discharge even at high charge voltages. Specifically, positive electrode active material particles (composite oxide) having a particle diameter (median diameter (D50)) of 0.1 μm or more and less than 9 μm, preferably 1 μm or more and 5 μm or less, can be used, which are obtained by reducing the particle diameter of the starting material and reducing the temperature or shortening the time of the heat treatment in the method for producing the positive electrode active material particles described in Embodiment 1. The second positive electrode active material particles 200 preferably contain one or more of the additional element X, the additional element Y, and the additional element Z, similarly to the positive electrode active material particles 100 described above.

[0370] The content of this embodiment can be freely combined with the content of other embodiment modes.

[0371] Embodiment Mode 3 In this embodiment mode, each element constituting a battery will be described.

[0372] [Positive Electrode] The positive electrode includes a positive electrode active material layer and a positive electrode current collector. The positive electrode active material layer includes positive electrode active material particles and may further include at least one of a conductive material and a binder. The positive electrode active material particles may be the positive electrode active material particles 100 described in Embodiments 1 and 2.

[0373] The positive electrode current collector can be, for example, a metal foil. The positive electrode can be formed by applying a slurry to a metal foil and drying it. Pressing may be performed after drying. The positive electrode is formed by forming an active material layer on the positive electrode current collector.

[0374] The term "slurry" refers to a material liquid used to form an active material layer on a positive electrode current collector, and contains an active material, a binder, and a solvent, preferably further mixed with a conductive material. Note that the slurry is also called an electrode slurry or an active material slurry, and is sometimes called a positive electrode slurry when forming a positive electrode active material layer and a negative electrode slurry when forming a negative electrode active material layer.

[0375] The positive electrode active material particles have the function of absorbing and releasing lithium ions during charge and discharge. The positive electrode active material particles 100 used as one embodiment of the present invention described above can be made of a material that is less susceptible to deterioration during charge and discharge even at high charge voltages.

[0376] <Binder> As the binder, it is preferable to use a rubber material such as styrene-butadiene rubber (SBR), styrene-isoprene-styrene rubber, acrylonitrile-butadiene rubber, butadiene rubber, ethylene-propylene-diene copolymer, etc. Furthermore, as the binder, fluororubber can be used.

[0377] Furthermore, it is preferable to use, for example, a water-soluble polymer as the binder. Examples of the water-soluble polymer that can be used include polysaccharides. Examples of the polysaccharide that can be used include cellulose derivatives such as carboxymethyl cellulose (CMC), methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, and regenerated cellulose, as well as starch. It is even more preferable to use these water-soluble polymers in combination with the above-mentioned rubber material.

[0378] Alternatively, it is preferable to use, as the binder, materials such as polystyrene, polymethyl acrylate, polymethyl methacrylate (polymethyl methacrylate, PMMA), sodium polyacrylate, polyvinyl alcohol (PVA), polyethylene oxide (PEO), polypropylene oxide, polyimide, polyvinyl chloride, polytetrafluoroethylene, polyethylene, polypropylene, polyisobutylene, polyethylene terephthalate, nylon, polyvinylidene fluoride (PVDF), polyacrylonitrile (PAN), ethylene propylene diene polymer, polyvinyl acetate, and nitrocellulose.

[0379] The binder may be used in combination with two or more of the above.

[0380] For example, a material with a particularly excellent viscosity adjusting effect may be used in combination with other materials. For example, while rubber materials have excellent adhesive strength and elasticity, it may be difficult to adjust the viscosity when mixed with a solvent. In such cases, it is preferable to mix them with a material with a particularly excellent viscosity adjusting effect. For example, a water-soluble polymer may be used as a material with a particularly excellent viscosity adjusting effect. Furthermore, as water-soluble polymers with a particularly excellent viscosity adjusting effect, the above-mentioned polysaccharides, for example, carboxymethyl cellulose (CMC), methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, and diacetyl cellulose, cellulose derivatives such as regenerated cellulose, or starch may be used.

[0381] In addition, the solubility of cellulose derivatives such as carboxymethyl cellulose can be increased by converting them into salts such as sodium or ammonium salts of carboxymethyl cellulose, making them more effective as viscosity adjusters. Higher solubility can also improve dispersibility with active materials or other components when preparing electrode slurries. In this specification, the cellulose and cellulose derivatives used as electrode binders also include their salts.

[0382] Water-soluble polymers stabilize viscosity by dissolving in water, allowing active materials and other materials combined as binders, such as styrene-butadiene rubber, to be stably dispersed in aqueous solutions. Furthermore, the presence of functional groups is expected to facilitate stable adsorption to the surface of active materials. Furthermore, many cellulose derivatives, such as carboxymethyl cellulose, contain functional groups such as hydroxyl or carboxyl groups, and the presence of these functional groups is expected to facilitate interactions between polymers, resulting in widespread coverage of the active material surface.

[0383] When the binder covering or contacting the surface of the active material forms a film, it is expected to function as a passive film and have the effect of suppressing decomposition of the electrolyte. Here, the "passive film" refers to a film with no electrical conductivity or a film with extremely low electrical conductivity. For example, when a passive film is formed on the surface of the active material, it can suppress decomposition of the electrolyte at the battery reaction potential. Furthermore, it is more desirable that the passive film suppresses electrical conductivity while still allowing lithium ions to conduct.

[0384] <Conductive Material> The conductive material is also called a conductivity imparting agent or a conductivity aid, and is made of a carbon material. By attaching the conductive material between multiple active materials, the multiple active materials are electrically connected to each other, thereby increasing the conductivity. Note that the term "attachment" does not only refer to physical adhesion between the active material and the conductive material, but also includes cases where a covalent bond is formed, bonding due to van der Waals forces, where the conductive material covers part of the surface of the active material, where the conductive material is embedded in the surface irregularities of the active material, and where the materials are electrically connected even when not in contact with each other.

[0385] The active material layers such as the positive electrode active material layer and the negative electrode active material layer preferably contain a conductive material.

[0386] As the conductive material, for example, one or more of carbon black such as acetylene black and furnace black, graphite such as artificial graphite and natural graphite, carbon fibers such as carbon nanofibers and carbon nanotubes, and graphene compounds can be used.

[0387] Examples of carbon fibers that can be used include mesophase pitch-based carbon fibers and isotropic pitch-based carbon fibers. Carbon nanofibers and carbon nanotubes can also be used as carbon fibers. Carbon nanotubes can be produced by vapor phase growth, for example.

[0388] In this specification and the like, graphene compounds include graphene, multilayer graphene, multigraphene, graphene oxide, multilayer graphene oxide, multi-graphene oxide, reduced graphene oxide, reduced multilayer graphene oxide, reduced multi-graphene oxide, graphene quantum dots, etc. Graphene compounds contain carbon, have a shape such as a plate or sheet, and have a two-dimensional structure formed by six-membered carbon rings. The two-dimensional structure formed by six-membered carbon rings may also be called a carbon sheet. Graphene compounds may have functional groups. Furthermore, graphene compounds preferably have a curved shape. Furthermore, graphene compounds may be rolled up to resemble carbon nanofibers.

[0389] The content of the conductive material relative to the total amount of the active material layer is preferably 1 wt % or more and 10 wt % or less, and more preferably 1 wt % or more and 5 wt % or less.

[0390] Unlike granular conductive materials such as carbon black, which make point contact with the active material, graphene compounds enable surface contact with low contact resistance, and therefore can improve the electrical conductivity between the granular active material and the graphene compound with a smaller amount than that of ordinary conductive materials. This allows the ratio of the active material in the active material layer to be increased, thereby increasing the discharge capacity of the battery.

[0391] Particulate carbon-containing compounds such as carbon black and graphite, or fibrous carbon-containing compounds such as carbon nanotubes, tend to fill microscopic spaces. Microscopic spaces refer to, for example, the spaces between multiple active materials. By combining a carbon-containing compound that easily fills microscopic spaces with a sheet-like carbon-containing compound such as graphene, which can impart conductivity across multiple particles, the density of the electrode can be increased, resulting in the formation of an excellent conductive path. The battery obtained by the manufacturing method of one embodiment of the present invention has high capacity density and is stable, making it effective as an in-vehicle battery.

[0392] <Positive Electrode Current Collector> The current collector can be made of a highly conductive material, such as a metal such as stainless steel, gold, platinum, aluminum, titanium, or iron, or an alloy thereof. It is preferable that the material used for the positive electrode current collector does not dissolve at the potential of the positive electrode. Aluminum alloys containing an element that improves physical properties, such as iron, silicon, titanium, neodymium, scandium, or molybdenum, can also be used. The current collector may also be made of a metal element that reacts with silicon to form a silicide. Examples of metal elements that react with silicon to form a silicide include zirconium, titanium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, cobalt, and nickel. The current collector can be in the form of a foil, plate, sheet, mesh, punched metal, expanded metal, or the like. It is preferable to use a current collector with a thickness of 5 μm to 30 μm.

[0393] [Negative Electrode] The negative electrode has a negative electrode active material layer and a negative electrode current collector. The negative electrode active material layer has a negative electrode active material, and may further have a conductive material and a binder.

[0394] <Negative Electrode Active Material> As the negative electrode active material, for example, an alloy material or a carbon material can be used.

[0395] In addition, the negative electrode active material can be an element capable of undergoing a charge-discharge reaction through alloying and dealloying reactions with lithium. For example, a material containing at least one of silicon, tin, gallium, aluminum, germanium, lead, antimony, bismuth, silver, zinc, cadmium, indium, etc. can be used. These elements have a larger capacity than carbon, and silicon in particular has a high theoretical capacity of 4200 mAh / g. For this reason, it is preferable to use silicon as the negative electrode active material. Alternatively, compounds containing these elements may be used. For example, SiO, Mg ２ Si, Mg ２ Ge, SnO, SnO ２ , Mg ２ Sn, SnS ２ , V ２ Sn ３ , FeSn ２ , CoSn ２ , Ni ３ Sn ２ , Cu ６ Sn ５ , Ag ３ Sn, Ag ３ Sb, Ni ２ MnSb, CeSb ３ , LaSn ３ , La ３ Co ２ Sn ７ , CoSb ３ , InSb, SbSn, etc. Alternatively, for example, a compound of Ti with Si, SiO or SiC may be used. Here, elements capable of undergoing charge / discharge reactions by alloying / dealloying reactions with lithium, and compounds containing such elements, may be referred to as alloy-based materials.

[0396] In this specification, "SiO" refers to, for example, silicon monoxide. ｘ Here, x preferably has a value of 1 or close to 1. For example, x is preferably 0.2 or more and 1.5 or less, and more preferably 0.3 or more and 1.2 or less.

[0397] The carbon material may be graphite, easily graphitizable carbon (soft carbon), non-graphitizable carbon (hard carbon), carbon fiber (carbon nanotube), graphene, carbon black, or the like.

[0398] Examples of graphite include artificial graphite and natural graphite. Examples of artificial graphite include mesocarbon microbeads (MCMB), coke-based artificial graphite, and pitch-based artificial graphite. Here, spherical graphite having a spherical shape can be used as the artificial graphite. For example, MCMB may have a spherical shape and is therefore preferred. Furthermore, it is relatively easy to reduce the surface area of ​​MCMB, and this may be preferred. Examples of natural graphite include flake graphite and spherical natural graphite.

[0399] When lithium ions are inserted into graphite (when a lithium-graphite intercalation compound is formed), graphite exhibits a potential as low as that of metallic lithium (0.05 V to 0.3 V vs. Li / Li ＋ This allows lithium-ion batteries using graphite to exhibit high operating voltages. Graphite is also preferred because it has advantages such as a relatively high capacity per unit volume, relatively small volume expansion, low cost, and greater safety compared to lithium metal.

[0400] Titanium dioxide (TiO ２ ), lithium titanium oxide (Li ４ Ti ５ O １２ ), lithium-graphite intercalation compound (Li ｘ C ６ ), niobium pentoxide (Nb ２ O ５ ), tungsten dioxide (WO ２ ), molybdenum dioxide (MoO ２ ) and other oxides can be used.

[0401] In addition, as the negative electrode active material, a nitride of lithium and a transition metal, Li ３ Li with N-type structure ３−ｘ M ｘ N (M=Co, Ni, Cu) can be used. For example, Li ２．６ Co０．４ N has a large discharge capacity (900 mAh / g, 1890 mAh / cm ３ ) and is preferred.

[0402] When a nitride of lithium and a transition metal is used, lithium ions are contained in the negative electrode active material, so that the positive electrode active material particles do not contain lithium ions. ２ O ５ , Cr ３ O ８ It is preferable that the negative electrode active material be a nitride of lithium and a transition metal, since it can be combined with a material such as the above. Even when a material containing lithium ions is used for the positive electrode active material particles, it is possible to use a nitride of lithium and a transition metal as the negative electrode active material by desorbing the lithium ions contained in the positive electrode active material particles in advance.

[0403] Furthermore, a material that undergoes a conversion reaction can also be used as the negative electrode active material. For example, a transition metal oxide that does not form an alloy with lithium, such as cobalt oxide (CoO), nickel oxide (NiO), or iron oxide (FeO), can be used as the negative electrode active material. Further examples of materials that undergo a conversion reaction include Fe ２ O ３ ,CuO,Cu ２ O, RuO ２ , Cr ２ O ３ oxides such as CoS ０．８９ , sulfides such as NiS and CuS, Zn ３ N ２ , Cu ３ N, Ge ３ N ４ Nitrides such as NiP ２ , FeP ２ , CoP ３ Phosphides such as FeF ３ , BiF ３ Fluorides such as:

[0404] Another example of a negative electrode is one that does not have a negative electrode active material at the end of the battery fabrication. A negative electrode that does not have a negative electrode active material can be, for example, a negative electrode that has only a negative electrode current collector at the end of the battery fabrication, in which lithium ions desorbed from positive electrode active material particles upon charging the battery deposit as lithium metal on the negative electrode current collector to form a negative electrode active material layer. A battery using such a negative electrode is sometimes called a negative electrode-free (anode-free) battery, a negative electrode-less (anode-less) battery, or the like.

[0405] When a negative electrode without a negative electrode active material is used, a film for uniforming lithium deposition may be provided on the negative electrode current collector. For example, a solid electrolyte having lithium ion conductivity can be used as the film for uniforming lithium deposition. Examples of solid electrolytes that can be used include sulfide-based solid electrolytes, oxide-based solid electrolytes, and polymer-based solid electrolytes. Among these, polymer-based solid electrolytes are suitable as films for uniforming lithium deposition because they are relatively easy to form uniformly on the negative electrode current collector. Furthermore, for example, a metal film that forms an alloy with lithium can be used as the film for uniforming lithium deposition. For example, a magnesium metal film can be used as the metal film that forms an alloy with lithium. Lithium and magnesium form a solid solution over a wide composition range, making them suitable as films for uniforming lithium deposition.

[0406] Furthermore, when a negative electrode that does not have a negative electrode active material is used, a negative electrode current collector having projections and recesses can be used. When a negative electrode current collector having projections and recesses is used, the recesses of the negative electrode current collector become cavities into which lithium contained in the negative electrode current collector can be easily deposited, and therefore, when lithium is deposited, it is possible to prevent it from forming a dendritic shape.

[0407] The conductive material and binder that can be contained in the negative electrode active material layer can be the same as the conductive material and binder that can be contained in the positive electrode active material layer.

[0408] <Negative electrode current collector> The negative electrode current collector may be made of the same material as the positive electrode current collector, or may be made of copper, etc. It is preferable that the negative electrode current collector be made of a material that does not alloy with carrier ions such as lithium.

[0409] [Electrolyte] The secondary battery has an electrolyte containing carrier ions. In this specification and the like, the electrolyte is not limited to an electrolyte containing an organic solvent that is liquid at room temperature, but also includes a solid electrolyte, and also includes an electrolyte containing both an organic solvent that is liquid at room temperature and a solid electrolyte that is solid at room temperature (semi-solid electrolyte). Note that a lithium salt dissolved in an organic solvent that is liquid at room temperature may be referred to as an electrolyte solution.

[0410] <Organic solvent that is liquid at room temperature> An example of an organic solvent that is liquid at room temperature will be described below.

[0411] The organic solvent that is liquid at room temperature is preferably an aprotic organic solvent, and for example, one or more of ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate, chloroethylene carbonate, vinylene carbonate, γ-butyrolactone, γ-valerolactone, dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), methyl formate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate (EP), propyl propionate (PP), methyl butyrate, 1,3-dioxane, 1,4-dioxane, dimethoxyethane (DME), dimethyl sulfoxide, diethyl ether, methyl diglyme, acetonitrile, benzonitrile, tetrahydrofuran, sulfolane, sultone, etc. can be used.

[0412] By using one or more flame-retardant and non-volatile ionic liquids (room-temperature molten salts) as an organic solvent that is liquid at room temperature, it is possible to prevent the battery cell from exploding or catching fire even if the internal temperature rises due to an internal short circuit or overcharging of the battery cell. The ionic liquid is composed of a cation and an anion, and includes an organic cation and an anion. Examples of organic cations used in the organic solvent include aliphatic onium cations such as quaternary ammonium cations, tertiary sulfonium cations, and quaternary phosphonium cations, and aromatic cations such as imidazolium cations and pyridinium cations. Examples of anions used in the organic solvent include monovalent amide anions, monovalent methide anions, fluorosulfonate anions, perfluoroalkylsulfonate anions, tetrafluoroborate anions, perfluoroalkylborate anions, hexafluorophosphate anions, and perfluoroalkylphosphate anions.

[0413] The lithium salt dissolved in the organic solvent is, for example, LiPF ６ , LiClO ４ , LiAsF ６ , LiBF ４ , LiAlCl ４ , LiSCN, LiBr, LiI, Li ２ SO ４ , Li ２ B １０ Cl １０ , Li ２ B １２ Cl １２ , LiCF ３ SO ３ , LiC ４ F ９ SO ３ , LiC(CF ３ SO ２ ) ３ , LiC(C ２ F ５ SO ２ ) ３ , LiN(CF ３ SO ２ ) ２ , LiN(C ４ F ９ SO ２ ) (CF３ SO ２ ), and LiN(C ２ F ５ SO ２ ) ２ One or more selected from the above can be used.

[0414] <Additives> The organic solvent may contain an additive. The additive can suppress reactive decomposition of the electrolyte solution that may occur on the positive electrode surface or the negative electrode surface when the secondary battery is operated at high voltage and / or high temperature. Examples of additives that can be used include vinylene carbonate (VC), propane sultone (PS), tert-butylbenzene (TBB), fluoroethylene carbonate (FEC), and lithium bis(oxalate)borate (LiBOB). LiBOB is particularly preferred because it easily forms a good coating. VC or FEC is preferred because it can form a good coating on the negative electrode during aging of the secondary battery or during charging in the early stages of use, thereby improving the cycle characteristics.

[0415] The compound represented by the following general formula (G1) may be contained as an additive: The compound represented by the following general formula (G1) has two cyano groups and can be called a dinitrile compound.

[0416]

[0417] In the general formula (G1), R represents a hydrocarbon having 1 to 5 carbon atoms. Preferably, in the general formula (G1), R represents a hydrocarbon having 2 to 4 carbon atoms.

[0418] Specific examples of the general formula (G1) include succinonitrile, glutaronitrile, adiponitrile (ADN), and ethylene glycol bis(propionitrile) ether (EGBE).

[0419] The structural formula (H1) of succinonitrile is shown below.

[0420]

[0421] The structural formula (H2) of glutaronitrile is shown below.

[0422]

[0423] The structural formula (H3) of adiponitrile is shown below.

[0424]

[0425] The structural formula (H4) of ethylene glycol bis(propionitrile) ether is shown below.

[0426]

[0427] As the additive, one or more dinitrile compounds can be used.

[0428] Fluorobenzene may also be added to the organic solvent. The concentration of the additive can be, for example, 0.1 wt% or more and 5 wt% or less relative to the total electrolyte solution. PS or EGBE are preferred because they form a good coating on the positive electrode during charge and discharge, improving cycle characteristics. FB is preferred because it improves the wettability of the organic solvent to the positive and negative electrodes. Dinitrile compounds are preferred because their nitrile groups orient to the positive and negative electrodes, inhibiting oxidative decomposition of the organic solvent and improving high-voltage resistance. Furthermore, dinitrile compounds are preferred because they prevent copper dissolution during overdischarge when a copper-containing current collector is used on the negative electrode. Considering the use of secondary batteries at high voltages, adding a nitrile compound is preferred.

[0429] The organic solvent does not need to be liquid at room temperature; a semi-solid material called a polymer gel electrolyte can be used instead. Using a polymer gel electrolyte increases safety against leakage and other issues. It also allows for thinner and lighter battery cells.

[0430] Examples of polymers that can be used to form gels include silicone gel, acrylic gel, acrylonitrile gel, polyethylene oxide gel, polypropylene oxide gel, and fluorine-based polymer gel.

[0431] Examples of polymers that can be used include polymers having a polyalkylene oxide structure such as polyethylene oxide (PEO), PVDF, polyacrylonitrile, and copolymers containing these. For example, PVDF-HFP, which is a copolymer of PVDF and hexafluoropropylene (HFP), can be used. The polymer formed may also have a porous shape.

[0432] [Separator] When the electrolyte contains an electrolytic solution, a separator is disposed between the positive electrode and the negative electrode. Examples of separators that can be used include those formed from cellulose-containing fibers such as paper, nonwoven fabrics, glass fibers, ceramics, or porous films made of nylon (polyamide), vinylon (polyvinyl alcohol-based fibers), polyester, acrylic, polyolefin, polyimide, or polyurethane. It is preferable that the separator be processed into a bag shape and disposed so as to enclose either the positive electrode or the negative electrode.

[0433] The separator may have a multilayer structure. For example, an organic material film such as polypropylene or polyethylene may be coated with a ceramic material, hydroxide material, fluorine material, polyamide material, or a mixture thereof. Examples of ceramic materials include aluminum oxide particles, silicon oxide particles, and magnesium oxide. Examples of hydroxide materials include magnesium hydroxide and aluminum hydroxide. Examples of fluorine materials include PVDF and polytetrafluoroethylene. Examples of polyamide materials include nylon and aramid (meta-aramid and para-aramid).

[0434] Coating with ceramic materials improves oxidation resistance, suppressing separator degradation during high-voltage charging and improving the reliability of secondary batteries. Coating with fluorine-based materials also improves adhesion between the separator and electrodes, improving output characteristics. Coating with polyamide materials, especially aramid, improves heat resistance, improving the safety of secondary batteries.

[0435] For example, both sides of a polypropylene film may be coated with a mixed material of aluminum oxide and aramid, or the surface of the polypropylene film that contacts the positive electrode may be coated with a mixed material of aluminum oxide and aramid, and the surface that contacts the negative electrode may be coated with a fluorine-based material.

[0436] When a separator with a multilayer structure is used, the safety of the secondary battery can be maintained even if the overall thickness of the separator is thin, and therefore the capacity per volume of the secondary battery can be increased.

[0437] [Exterior Body] The exterior body of the battery can be made of a metal material such as aluminum, stainless steel, or titanium, or a resin material. A film-like exterior body can also be used. Examples of films include a three-layer structure in which a highly flexible metal thin film or metal foil such as aluminum, stainless steel, titanium, copper, or nickel is provided on a film made of a material such as polyethylene, polypropylene, polycarbonate, ionomer, or polyamide, and an insulating synthetic resin film such as a polyamide resin or polyester resin is further provided on the metal thin film as the outer surface of the exterior body. Such a multilayer structure film can be called a laminate film. In this case, the laminate film may be referred to as an aluminum (aluminum) laminate film, a stainless steel laminate film, a titanium laminate film, a copper laminate film, a nickel laminate film, or the like, using the name of the material of the metal layer.

[0438] The material or thickness of the metal layer of the laminate film may affect the flexibility of the battery. For example, an aluminum laminate film having a polypropylene layer, an aluminum layer, and a nylon layer is preferably used as an exterior body for batteries that prioritize flexibility or lightweight design. Here, the thickness of the aluminum layer is preferably 50 μm or less, more preferably 40 μm or less, more preferably 30 μm or less, and even more preferably 20 μm or less. If the aluminum layer is thinner than 10 μm, there is a concern that pinholes in the aluminum layer may reduce the gas barrier properties, so the thickness of the aluminum layer is preferably 10 μm or more.

[0439] For example, a stainless steel laminate film having a polypropylene layer, a stainless steel layer, and a nylon layer is preferably used as an exterior body for batteries where physical strength or safety is important. Furthermore, a polyethylene terephthalate layer may be provided on the nylon layer. Here, the thickness of the stainless steel layer is preferably 50 μm or less, more preferably 40 μm or less, more preferably 30 μm or less, and even more preferably 20 μm or less. If the stainless steel layer is thinner than 10 μm, there is a concern that pinholes in the stainless steel layer may reduce the gas barrier property, so the thickness of the stainless steel layer is preferably 10 μm or more. In this specification, stainless steel refers to steel (an alloy of iron and carbon) containing approximately 12% or more chromium, and can be broadly classified into martensitic, ferritic, and austenitic types based on composition. It also includes stainless steels to which one or more elements selected from Ti, Nb, Mo, Cu, Ni, or Si are added.

[0440] Alternatively, for example, a titanium laminate film having a polypropylene layer, a titanium layer, and a nylon layer is preferably used. Furthermore, a polyethylene terephthalate layer may be provided on the nylon layer. Here, the thickness of the titanium layer is preferably 50 μm or less, more preferably 40 μm or less, more preferably 30 μm or less, and even more preferably 20 μm or less. If the titanium layer is thinner than 10 μm, there is a concern that pinholes in the titanium layer may reduce the gas barrier properties, so the thickness of the titanium layer is preferably 10 μm or more.

[0441] The content of this embodiment can be freely combined with the content of other embodiment modes.

[0442] Embodiment Mode 4 In this embodiment mode, examples of shapes of a secondary battery having a positive electrode manufactured by the manufacturing method described in the previous embodiment mode will be described.

[0443] [Coin-Type Secondary Battery] An example of a coin-type secondary battery will be described. Fig. 16A is an exploded perspective view of a coin-type (single-layer flat) secondary battery, Fig. 16B is an external view, and Fig. 16C is a cross-sectional view thereof. Coin-type secondary batteries are mainly used in small electronic devices.

[0444] 16A is a schematic diagram that shows the overlapping of components (upper and lower relationships and positional relationships) for ease of understanding, and therefore, FIGS. 16A and 16B are not completely identical corresponding views.

[0445] In Fig. 16A, a positive electrode 304, a separator 310, a negative electrode 307, a spacer 322, and a washer 312 are stacked. These are sealed with a negative electrode can 302 and a positive electrode can 301 by a gasket. Note that the gasket for sealing is not shown in Fig. 16A. The spacer 322 and the washer 312 are used to protect the inside or to fix the position inside the can when the positive electrode can 301 and the negative electrode can 302 are crimped together. The spacer 322 and the washer 312 are made of stainless steel or an insulating material.

[0446] A positive electrode 304 has a laminated structure in which a positive electrode active material layer 306 is formed on a positive electrode current collector 305 .

[0447] FIG. 16B is a perspective view of the completed coin-type secondary battery.

[0448] In the coin-type secondary battery 300, a positive electrode can 301, which also serves as a positive electrode terminal, and a negative electrode can 302, which also serves as a negative electrode terminal, are insulated and sealed by a gasket 303 made of polypropylene or the like. The positive electrode 304 is formed by a positive electrode current collector 305 and a positive electrode active material layer 306 provided in contact with the positive electrode current collector. The negative electrode 307 is formed by a negative electrode current collector 308 and a negative electrode active material layer 309 provided in contact with the negative electrode current collector. The negative electrode 307 is not limited to a laminated structure, and may be formed of lithium metal foil or a lithium-aluminum alloy foil.

[0449] Note that the positive electrode 304 and the negative electrode 307 used in the coin-type secondary battery 300 may each have an active material layer formed on only one surface.

[0450] The positive electrode can 301 and the negative electrode can 302 can be made of a metal such as nickel, aluminum, or titanium that is corrosion-resistant to the electrolyte, or an alloy of these metals or an alloy of these metals with other metals (e.g., stainless steel). Furthermore, to prevent corrosion by the electrolyte, etc., they are preferably coated with nickel, aluminum, or the like. The positive electrode can 301 is electrically connected to the positive electrode 304, and the negative electrode can 302 is electrically connected to the negative electrode 307.

[0451] These negative electrode 307, positive electrode 304, and separator 310 are immersed in an electrolyte solution, and as shown in FIG. 16C , the positive electrode 304, separator 310, negative electrode 307, and negative electrode can 302 are stacked in this order with the positive electrode can 301 facing downwards, and the positive electrode can 301 and the negative electrode can 302 are crimped together via a gasket 303, thereby producing a coin-type secondary battery 300.

[0452] By having the above-described configuration, the coin-type secondary battery 300 can have a high discharge capacity and excellent cycle characteristics.

[0453] [Cylindrical Secondary Battery] An example of a cylindrical secondary battery will be described with reference to Fig. 17A. As shown in Fig. 17A, a cylindrical secondary battery 616 has a positive electrode cap (battery lid) 601 on the top surface and a battery can (external can) 602 on the side and bottom surfaces. The positive electrode cap 601 and the battery can (external can) 602 are insulated by a gasket (insulating packing) 610.

[0454] 17B is a schematic diagram showing a cross section of a cylindrical secondary battery. The cylindrical secondary battery shown in FIG. 17B has a positive electrode cap (battery lid) 601 on the top surface and a battery can (external can) 602 on the side and bottom surfaces. The positive electrode cap and battery can (external can) 602 are insulated by a gasket (insulating packing) 610.

[0455] A battery element is provided inside a hollow cylindrical battery can 602, in which a strip-shaped positive electrode 604 and a negative electrode 606 are wound with a separator 605 sandwiched between them. Although not shown, the battery element is wound around a central axis. One end of the battery can 602 is closed and the other end is open. The battery can 602 can be made of a metal, such as nickel, aluminum, or titanium, or an alloy of these metals or an alloy of these metals with other metals (e.g., stainless steel), which is corrosion-resistant to the electrolyte. Furthermore, it is preferable to coat the battery can 602 with nickel, aluminum, or the like to prevent corrosion by the electrolyte. Inside the battery can 602, the wound battery element, in which the positive electrode, negative electrode, and separator are wound, is sandwiched between a pair of opposing insulating plates 608 and 609. A nonaqueous electrolyte (not shown) is poured into the battery can 602, in which the battery element is provided. The nonaqueous electrolyte may be the same as that used in coin-type secondary batteries.

[0456] Since the positive and negative electrodes used in a cylindrical storage battery are wound, it is preferable to form active materials on both sides of the current collector.

[0457] By using the positive electrode active material particles 100 described in Embodiments 1 and 2, etc., for the positive electrode 604, a cylindrical secondary battery 616 can be obtained that has a high capacity, a high discharge capacity, and excellent cycle characteristics.

[0458] A positive electrode terminal (positive electrode current collector lead) 603 is connected to the positive electrode 604, and a negative electrode terminal (negative electrode current collector lead) 607 is connected to the negative electrode 606. The positive electrode terminal 603 can be made of aluminum, and the negative electrode terminal 607 can be made of copper or other metal materials. The positive electrode terminal 603 is resistance-welded to a safety valve mechanism 613, and the negative electrode terminal 607 is resistance-welded to the bottom of the battery can 602. The safety valve mechanism 613 is electrically connected to the positive electrode cap 601 via a PTC (Positive Temperature Coefficient) element 611. The safety valve mechanism 613 cuts off the electrical connection between the positive electrode cap 601 and the positive electrode 604 when the increase in internal pressure of the battery exceeds a predetermined threshold. The PTC element 611 is a thermosensitive resistor whose resistance increases as the temperature increases, and the increased resistance limits the amount of current to prevent abnormal heat generation. The PTC element is made of barium titanate (BaTiO ３ )-based semiconductor ceramics, etc. can be used.

[0459] 17C shows an example of a power storage system 615. The power storage system 615 has a plurality of secondary batteries 616. The positive electrodes of the respective secondary batteries are in contact with and electrically connected to conductors 624 separated by insulators 625. The conductors 624 are electrically connected to a control circuit 620 via wiring 623. The negative electrodes of the respective secondary batteries are electrically connected to the control circuit 620 via wiring 626. The control circuit 620 may be a charge / discharge control circuit that performs charging and discharging, or a protection circuit that prevents overcharging and / or overdischarging.

[0460] 17D shows an example of a power storage system 615. The power storage system 615 has a plurality of secondary batteries 616, which are sandwiched between a conductive plate 628 and a conductive plate 614. The plurality of secondary batteries 616 are electrically connected to the conductive plate 628 and the conductive plate 614 by wiring 627. The plurality of secondary batteries 616 may be connected in parallel, in series, or in parallel and then further connected in series. By configuring the power storage system 615 to have a plurality of secondary batteries 616, it is possible to extract a large amount of power.

[0461] A plurality of secondary batteries 616 may be connected in parallel and then further connected in series.

[0462] Furthermore, a temperature control device may be provided between the multiple secondary batteries 616. When the secondary batteries 616 are overheated, they can be cooled by the temperature control device, and when the secondary batteries 616 are too cold, they can be heated by the temperature control device. This makes it difficult for the performance of the power storage system 615 to be affected by the outside air temperature.

[0463] 17D , the power storage system 615 is electrically connected to a control circuit 620 via wiring 621 and wiring 622. The wiring 621 is electrically connected to the positive electrodes of the plurality of secondary batteries 616 via a conductive plate 628, and the wiring 622 is electrically connected to the negative electrodes of the plurality of secondary batteries 616 via a conductive plate 614.

[0464] [Another Example of Secondary Battery Structure] An example of the structure of a secondary battery will be described with reference to FIGS. 18 and 19. FIG.

[0465] A secondary battery 913 shown in FIG. 18A has a wound body 950 provided with terminals 951 and 952 inside a housing 930. The wound body 950 is immersed in an electrolyte inside the housing 930. The terminal 952 contacts the housing 930, and the terminal 951 is not in contact with the housing 930 by using an insulating material or the like. Note that in FIG. 18A , for convenience, the housing 930 is shown separated, but in reality, the wound body 950 is covered by the housing 930, and the terminals 951 and 952 extend outside the housing 930. The housing 930 can be made of a metal material (e.g., aluminum), a composite material of metal and resin, or the like.

[0466] 18B, the housing 930 shown in Fig. 18A may be formed from a plurality of materials. For example, the secondary battery 913 shown in Fig. 18B has a housing 930a and a housing 930b bonded together, and a wound body 950 is provided in the area surrounded by the housing 930a and the housing 930b.

[0467] The housing 930a can be made of an insulating material. In particular, by using a material such as organic resin on the surface on which the antenna is formed, it is possible to prevent the secondary battery 913 from blocking the electric field. Note that if the electric field blocking effect of the housing 930a is small, the antenna may be provided inside the housing 930a. The housing 930b can be made of, for example, a metal material.

[0468] 18C shows the structure of the wound body 950. The wound body 950 has a negative electrode 931, a positive electrode 932, and a separator 933. The wound body 950 is a wound body in which the negative electrode 931 and the positive electrode 932 are stacked on top of each other with the separator 933 sandwiched therebetween, and the laminated sheet is wound. Note that multiple layers of the negative electrode 931, the positive electrode 932, and the separator 933 may be stacked.

[0469] 19A may be a secondary battery 913 having a wound body 950a as shown in Fig. 19A. The wound body 950a shown in Fig. 19A has a negative electrode 931, a positive electrode 932, and a separator 933. The negative electrode 931 has a negative electrode active material layer 931a. The positive electrode 932 has a positive electrode active material layer 932a.

[0470] By using the positive electrode active material particles 100 described in Embodiments 1 and 2 and the like for the positive electrode 932, the secondary battery 913 can have a high capacity, a high discharge capacity, and excellent cycle characteristics.

[0471] The separator 933 has a width wider than the negative electrode active material layer 931 a and the positive electrode active material layer 932 a, and is wound so as to overlap the negative electrode active material layer 931 a and the positive electrode active material layer 932 a. From the standpoint of safety, it is preferable that the negative electrode active material layer 931 a be wider than the positive electrode active material layer 932 a. A wound body 950 a having such a shape is preferable due to its high safety and productivity.

[0472] 19B , the negative electrode 931 is electrically connected to a terminal 951 by ultrasonic bonding, welding, or crimping. The terminal 951 is electrically connected to a terminal 911a. The positive electrode 932 is electrically connected to a terminal 952 by ultrasonic bonding, welding, or crimping. The terminal 952 is electrically connected to a terminal 911b.

[0473] 19C , the wound body 950 a and the electrolyte are covered by the housing 930 to form the secondary battery 913. It is preferable to provide the housing 930 with a safety valve, an overcurrent protection element, etc. The safety valve is a valve that opens when the inside of the housing 930 reaches a predetermined internal pressure to prevent the battery from exploding.

[0474] As shown in Fig. 19B, the secondary battery 913 may have multiple wound bodies 950a. Using multiple wound bodies 950a can result in a secondary battery 913 with a larger discharge capacity. For other elements of the secondary battery 913 shown in Figs. 19A and 19B, the descriptions of the secondary battery 913 shown in Figs. 18A to 18C can be referenced.

[0475] 20A and 20B show examples of external views of a laminated secondary battery, which includes a positive electrode 503, a negative electrode 506, a separator 507, an outer casing 509, a positive electrode lead electrode 510, and a negative electrode lead electrode 511.

[0476] 21A shows an external view of a positive electrode 503 and a negative electrode 506. The positive electrode 503 has a positive electrode current collector 501, and a positive electrode active material layer 502 is formed on the surface of the positive electrode current collector 501. The positive electrode 503 also has a region where the positive electrode current collector 501 is partially exposed (hereinafter referred to as a tab region). The negative electrode 506 has a negative electrode current collector 504, and a negative electrode active material layer 505 is formed on the surface of the negative electrode current collector 504. The negative electrode 506 also has a region where the negative electrode current collector 504 is partially exposed, i.e., a tab region. Note that the area or shape of the tab regions of the positive electrode and negative electrode are not limited to the example shown in FIG. 21A .

[0477] <Method for Manufacturing Laminated Secondary Battery> An example of a method for manufacturing the laminated secondary battery whose external view is shown in FIG. 20A will be described with reference to FIGS. 21B and 21C.

[0478] First, the negative electrode 506, separator 507, and positive electrode 503 are stacked. FIG. 21B shows the stacked negative electrode 506, separator 507, and positive electrode 503. Here, an example is shown in which five pairs of negative electrodes and four pairs of positive electrodes are used. This can also be called a laminate consisting of a negative electrode, a separator, and a positive electrode. Next, the tab regions of the positive electrodes 503 are joined together, and the positive electrode lead electrode 510 is joined to the tab region of the outermost positive electrode. For example, ultrasonic welding or the like may be used for joining. Similarly, the tab regions of the negative electrodes 506 are joined together, and the negative electrode lead electrode 511 is joined to the tab region of the outermost negative electrode.

[0479] Next, the negative electrode 506 , the separator 507 and the positive electrode 503 are arranged on the outer casing 509 .

[0480] Next, as shown in Fig. 21C, the exterior body 509 is folded at the portion indicated by the dashed line. Thereafter, the outer periphery of the exterior body 509 is joined. For example, thermocompression bonding or the like may be used for joining. At this time, an area (hereinafter referred to as an inlet) that is not joined is provided in a part (or one side) of the exterior body 509 so that an electrolyte can be introduced later.

[0481] Next, the electrolyte solution is introduced into the inside of the exterior body 509 through an inlet provided in the exterior body 509. The introduction of the electrolyte solution is preferably carried out under a reduced pressure atmosphere or an inert atmosphere. Finally, the inlet is joined. In this manner, the laminated secondary battery 500 can be produced.

[0482] By using the positive electrode active material particles 100 described in the first and second embodiments and the like for the positive electrode 503, a secondary battery 500 having a high capacity, a high discharge capacity, and excellent cycle characteristics can be obtained.

[0483] [Example of Battery Pack] An example of a secondary battery pack according to one embodiment of the present invention, which can be wirelessly charged using an antenna, will be described with reference to FIG.

[0484] Fig. 22A is a diagram showing the appearance of secondary battery pack 531, which has a thin rectangular parallelepiped shape (also called a thick flat plate shape). Fig. 22B is a diagram illustrating the configuration of secondary battery pack 531. Secondary battery pack 531 has circuit board 540 and secondary battery 513. Label 529 is affixed to secondary battery 513. Circuit board 540 is fixed with sticker 515. Secondary battery pack 531 also has antenna 517.

[0485] The interior of the secondary battery 513 may have a structure including a wound body or a laminated body.

[0486] 22B , the secondary battery pack 531 has a control circuit 590 on a circuit board 540. The circuit board 540 is electrically connected to the terminals 514. The circuit board 540 is also electrically connected to the antenna 517, one 551 of the positive and negative leads of the secondary battery 513, and the other 552 of the positive and negative leads.

[0487] Alternatively, as shown in FIG. 22C, the device may have a circuit system 590 a provided on the circuit board 540 and a circuit system 590 b electrically connected to the circuit board 540 via the terminals 514 .

[0488] The antenna 517 is not limited to a coil shape and may be, for example, a wire shape or a plate shape. Furthermore, antennas such as a planar antenna, an aperture antenna, a traveling wave antenna, an EH antenna, a magnetic field antenna, and a dielectric antenna may also be used. Alternatively, the antenna 517 may be a flat conductor. This flat conductor can function as one of the conductors for electric field coupling. In other words, the antenna 517 may function as one of the two conductors of a capacitor. This allows power to be exchanged not only by electromagnetic fields and magnetic fields but also by electric fields.

[0489] The secondary battery pack 531 includes a layer 519 between the antenna 517 and the secondary battery 513. The layer 519 has a function of, for example, shielding an electromagnetic field generated by the secondary battery 513. The layer 519 can be formed using, for example, a magnetic material.

[0490] The content of this embodiment can be freely combined with the content of other embodiment modes.

[0491] Embodiment 5 In this embodiment, an example of a vehicle including a secondary battery of one embodiment of the present invention will be described.

[0492] The secondary battery can be applied to a typical vehicle, such as an automobile. Examples of the automobile include next-generation clean energy automobiles, such as hybrid vehicles (HVs), electric vehicles (EVs), and plug-in hybrid vehicles (PHEVs or PHVs). The secondary battery can be used as one of the power sources mounted on the automobile. The vehicle is not limited to an automobile. Examples of the vehicle include trains, monorails, ships, submersibles (deep-sea exploration vessels, unmanned submersibles), aircraft (helicopters, unmanned aerial vehicles (drones), airplanes, rockets, and artificial satellites), electric bicycles, and electric motorcycles. The secondary battery of one embodiment of the present invention can be applied to these vehicles.

[0493] As shown in Fig. 23C, an electric vehicle is equipped with first batteries 1301a and 1301b as main driving secondary batteries, and a second battery 1311 that supplies power to an inverter 1312 that starts a motor 1304. The second battery 1311 is also called a cranking battery (also called a starter battery). The second battery 1311 only needs to have high output, and does not need to have a large capacity, and the capacity of the second battery 1311 is smaller than that of the first batteries 1301a and 1301b.

[0494] The internal structure of the first battery 1301a may be a wound type as shown in FIG. 18C or FIG. 19A, or a stacked type as shown in FIG. 20A or FIG. 20B.

[0495] In this embodiment, an example is shown in which two first batteries 1301a and 1301b are connected in parallel, but three or more batteries may be connected in parallel. Furthermore, if the first battery 1301a can store sufficient power, the first battery 1301b may be omitted. By configuring a battery pack having multiple secondary batteries, it is possible to extract large amounts of power. The multiple secondary batteries may be connected in parallel, in series, or in series after being connected in parallel. A plurality of secondary batteries is also called a battery pack.

[0496] In addition, in a secondary battery for vehicle use, a service plug or circuit breaker that can cut off high voltage without using tools is provided in the first battery 1301a in order to cut off power from multiple secondary batteries.

[0497] The power of the first batteries 1301a and 1301b is mainly used to rotate the motor 1304, but also supplies power to 42V in-vehicle components (such as an electric power steering 1307, a heater 1308, and a defogger 1309) via a DCDC circuit 1306. When a rear motor 1317 is provided for the rear wheels, the first battery 1301a is also used to rotate the rear motor 1317.

[0498] In addition, the second battery 1311 supplies power to 14V in-vehicle components (audio 1313, power windows 1314, lamps 1315, etc.) via the DCDC circuit 1310.

[0499] Next, the first battery 1301a will be described with reference to FIG. 23A.

[0500] FIG. 23A shows an example in which nine prismatic secondary batteries 1300 are combined into one battery pack 1415. Furthermore, nine prismatic secondary batteries 1300 are connected in series, with one electrode fixed by a fixing portion 1413 made of an insulator and the other electrode fixed by a fixing portion 1414 made of an insulator. While this embodiment shows an example in which the batteries are fixed by the fixing portions 1413 and 1414, they may also be housed in a battery housing box (also called a casing). Because it is expected that a vehicle will be subjected to external vibrations or shaking (such as from the road surface), it is preferable to fix multiple secondary batteries using the fixing portions 1413 and 1414 and the battery housing box. Furthermore, one electrode is electrically connected to the control circuit unit 1320 by wiring 1421. The other electrode is electrically connected to the control circuit unit 1320 by wiring 1422.

[0501] A memory circuit including a transistor using an oxide semiconductor may be used for the control circuit portion 1320. A charge control circuit or a battery control system including a memory circuit including a transistor using an oxide semiconductor may be referred to as a battery operating system (BTOS) or a battery oxide semiconductor (BTOS).

[0502] It is preferable to use a metal oxide that functions as an oxide semiconductor. For example, a metal oxide such as In-M-Zn oxide (wherein the element M is one or more selected from aluminum, gallium, yttrium, copper, vanadium, beryllium, boron, titanium, iron, nickel, germanium, zirconium, molybdenum, lanthanum, cerium, neodymium, hafnium, tantalum, tungsten, magnesium, etc.) may be used as the metal oxide. In particular, the In-M-Zn oxide that can be used as the metal oxide is preferably a C-Axis Aligned Crystal Oxide Semiconductor (CAAC-OS) or a Cloud-Aligned Composite Oxide Semiconductor (CAC-OS). Alternatively, an In—Ga oxide or an In—Zn oxide may be used as the metal oxide. The CAAC-OS is an oxide semiconductor having multiple crystalline regions, each of which has a c-axis oriented in a specific direction. The specific direction is the thickness direction of the CAAC-OS film, the normal direction to the surface on which the CAAC-OS film is formed, or the normal direction to the surface of the CAAC-OS film. The crystalline regions are regions in which the atomic arrangement is periodic. When the atomic arrangement is considered as a lattice arrangement, the crystalline regions are also regions in which the lattice arrangement is aligned.

[0503] Note that "CAC-OS" has a mosaic structure in which a material is separated into a first region and a second region, and the first region is distributed throughout the film (hereinafter, also referred to as a cloud structure). That is, CAC-OS is a composite metal oxide having a structure in which the first region and the second region are mixed. However, it may be difficult to observe a clear boundary between the first region and the second region.

[0504] For example, in the case of a CAC-OS made of an In—Ga—Zn oxide, EDX mapping obtained using EDX confirms that the CAC-OS has a structure in which a region containing In as the main component (first region) and a region containing Ga as the main component (second region) are unevenly distributed and mixed.

[0505] When a CAC-OS is used in a transistor, the conductivity due to the first region and the insulating property due to the second region act complementarily, thereby providing the CAC-OS with a switching function (a function of turning on / off). That is, a CAC-OS has a conductive function in a part of the material and an insulating function in a part of the material, and functions as a semiconductor as a whole. By separating the conductive function and the insulating function, both functions can be maximized. Therefore, by using a CAC-OS in a transistor, a high on-current (I ｏｎ ), high field-effect mobility (μ), and good switching behavior can be achieved.

[0506] Oxide semiconductors have a variety of structures, each of which has different characteristics. The oxide semiconductor of one embodiment of the present invention may include two or more of an amorphous oxide semiconductor, a polycrystalline oxide semiconductor, an a-like OS, a CAC-OS, an nc-OS, and a CAAC-OS.

[0507] Furthermore, because the control circuit unit 1320 can be used in high-temperature environments, it is preferable to use transistors using oxide semiconductors. To simplify the process, the control circuit unit 1320 may be formed using unipolar transistors. Transistors using oxide semiconductors in the semiconductor layer have a wider operating ambient temperature range than single-crystal Si transistors, from −40° C. to 150° C., and their characteristics change less even when the secondary battery overheats than single-crystal Si transistors. The off-current of transistors using oxide semiconductors is below the lower measurement limit regardless of temperature, even at 150° C., whereas the off-current characteristics of single-crystal Si transistors are highly temperature-dependent. For example, at 150° C., the off-current of single-crystal Si transistors increases, and the current on / off ratio is not sufficiently large. The control circuit unit 1320 can improve safety. Furthermore, combining the positive electrode active material particles 100 described in Embodiments 1 and 2 with a secondary battery using the positive electrode can provide a synergistic effect in terms of safety. The secondary battery and control circuit unit 1320 using the positive electrode active material particles 100 described in the first and second embodiments and the like in the positive electrode can greatly contribute to eliminating accidents such as fires caused by secondary batteries.

[0508] The control circuit unit 1320, which uses a memory circuit including transistors using oxide semiconductors, can also function as an automatic control device for a secondary battery to address 10 causes of instability, such as micro-short circuits. The functions for addressing the 10 causes of instability include overcharging prevention, overcurrent prevention, overheating control during charging, cell balancing in the battery pack, over-discharging prevention, a fuel gauge, automatic control of charging voltage and current according to temperature, control of charging current according to the degree of degradation, detection of abnormal behavior of micro-short circuits, and prediction of abnormalities related to micro-short circuits. The control circuit unit 1320 has at least one of these functions. Furthermore, the automatic control device for a secondary battery can be miniaturized.

[0509] Furthermore, a "micro-short" refers to a minute short circuit within a secondary battery, which is not so severe that the positive and negative electrodes of the secondary battery are short-circuited and render it unable to be charged or discharged, but rather refers to a phenomenon in which a small amount of short-circuit current flows at the minute short-circuited part. Even if the short-circuit occurs in a relatively short period of time and in a small location, a large voltage change occurs, and this abnormal voltage value may affect subsequent estimations.

[0510] One of the causes of micro-short circuits is said to be that multiple charge and discharge cycles cause uneven distribution of positive electrode active material particles, resulting in localized current concentration in parts of the positive electrode and negative electrode, causing parts of the separator to stop functioning, or the generation of by-products due to side reactions, resulting in micro-short circuits.

[0511] In addition to detecting micro-shorts, the control circuit 1320 can also be said to detect the terminal voltage of the secondary battery and manage the charge / discharge state of the secondary battery. For example, to prevent overcharging, it can turn off both the output transistor and the cutoff switch of the charging circuit almost simultaneously.

[0512] Next, an example of a block diagram of the battery pack 1415 shown in FIG. 23A is shown in FIG. 23B.

[0513] The control circuit 1320 includes a switch unit 1324 including at least a switch for preventing overcharging and a switch for preventing overdischarging, a control circuit 1322 for controlling the switch unit 1324, and a voltage measurement unit for the first battery 1301a. The control circuit 1320 sets upper and lower voltage limits for the secondary battery used and limits the upper limit of the current from the outside or the upper limit of the output current to the outside. The range between the lower limit and the upper limit of the secondary battery's voltage is within the recommended voltage range, and when the secondary battery falls outside this range, the switch unit 1324 activates and functions as a protection circuit. The control circuit 1320 can also be called a protection circuit because it controls the switch unit 1324 to prevent overcharging and / or overdischarging. For example, if the control circuit 1322 detects a voltage that could cause overcharging, it turns off the switch unit 1324 to cut off the current. Furthermore, a PTC element may be provided in the charge / discharge path to provide a function for cutting off the current in response to an increase in temperature. The control circuit section 1320 also has an external terminal 1325 (+IN) and an external terminal 1326 (-IN).

[0514] The switch portion 1324 can be configured by combining n-channel transistors or p-channel transistors. The switch portion 1324 is not limited to a switch having a Si transistor using single crystal silicon. For example, the switch portion 1324 may be formed using a power transistor having Ge (germanium), SiGe (silicon germanium), GaAs (gallium arsenide), GaAlAs (gallium aluminum arsenide), InP (indium phosphide), SiC (silicon carbide), ZnSe (zinc selenide), GaN (gallium nitride), or GaOx (gallium oxide; x is a real number greater than 0). Furthermore, memory elements using OS transistors can be freely arranged by stacking them on circuits using Si transistors, and therefore integration can be easily achieved. Furthermore, OS transistors can be manufactured using the same manufacturing equipment as Si transistors, and therefore can be manufactured at low cost. That is, the control circuit portion 1320 using OS transistors can be stacked on the switch portion 1324 and integrated into a single chip. The volume occupied by the control circuit section 1320 can be reduced, which allows for miniaturization.

[0515] The first batteries 1301a and 1301b primarily supply power to onboard equipment in the 42V system (high-voltage HV system), while the second battery 1311 supplies power to onboard equipment in the 14V system (low-voltage LV system). Lead-acid batteries are often used as the second battery 1311 due to their cost advantages. Lead-acid batteries have the disadvantage of being more self-discharged than lithium-ion batteries and being prone to deterioration due to a phenomenon called sulfation. Using a lithium-ion battery as the second battery 1311 offers the advantage of being maintenance-free, but after prolonged use, e.g., three years or more, there is a risk of abnormalities occurring that are difficult to identify during manufacturing. In particular, if the second battery 1311, which starts the inverter, becomes inoperable, even if the first batteries 1301a and 1301b have remaining capacity, the second battery 1311 is charged to maintain a full charge state by supplying power from the first battery to the second battery.

[0516] In this embodiment, an example is shown in which lithium ion batteries are used as both the first battery 1301a and the second battery 1311. The second battery 1311 may be a lead storage battery, an all-solid-state battery, or an electric double layer capacitor.

[0517] Furthermore, regenerative energy generated by the rotation of the tire 1316 is sent to the motor 1304 via the gear 1305, and is then charged into the second battery 1311 via the motor controller 1303 or the battery controller 1302 via the control circuit unit 1321. Alternatively, the first battery 1301a is charged from the battery controller 1302 via the control circuit unit 1320. Alternatively, the first battery 1301b is charged from the battery controller 1302 via the control circuit unit 1320. In order to efficiently charge the regenerative energy, it is desirable that the first batteries 1301a and 1301b be capable of rapid charging.

[0518] The battery controller 1302 can set the charging voltage and charging current of the first batteries 1301a and 1301b. The battery controller 1302 can set charging conditions in accordance with the charging characteristics of the secondary battery used, and can perform rapid charging.

[0519] Although not shown, when the electric vehicle is connected to an external charger, the charger plug or charger connection cable is electrically connected to the battery controller 1302. Power supplied from the external charger is charged to the first batteries 1301a and 1301b via the battery controller 1302. Some chargers are provided with a control circuit, and although the functions of the battery controller 1302 may not be used, it is preferable to charge the first batteries 1301a and 1301b via a control circuit unit 1320 to prevent overcharging. The charger plug or charger connection cable may also be provided with a control circuit. The control circuit unit 1320 is sometimes called an ECU (Electronic Control Unit). The ECU is connected to a CAN (Controller Area Network) provided in the electric vehicle. CAN is one of the serial communication standards used as an in-vehicle LAN. The ECU also includes a microcomputer. The ECU uses a CPU or a GPU.

[0520] External chargers installed at charging stations and the like include 100V-200V outlets, or three-phase 200V and 50kW. Charging can also be performed by receiving power from external charging equipment using a wireless power supply system or the like.

[0521] When rapid charging is performed, a secondary battery that can withstand high voltage charging is desired in order to charge in a short time.

[0522] Furthermore, by using graphene as a conductive material, a secondary battery with significantly improved electrical characteristics can be realized, as a synergistic effect of suppressing capacity decline and maintaining high capacity even when the electrode layer is thickened and the amount of graphene supported is increased. This is particularly effective for secondary batteries used in vehicles, and it is possible to provide a vehicle with a long driving range, specifically a driving distance of 500 km or more per charge, without increasing the ratio of the weight of the secondary battery to the total weight of the vehicle.

[0523] In particular, the secondary battery of the present embodiment described above can increase the operating voltage of the secondary battery by using the positive electrode active material particles 100 described in Embodiments 1, 2, etc., and can increase the usable capacity as the charging voltage increases. Furthermore, by using the positive electrode active material particles 100 described in Embodiments 1, 2, etc., in the positive electrode, a secondary battery for vehicles with excellent cycle characteristics can be provided.

[0524] Next, an example in which a secondary battery according to one embodiment of the present invention is mounted on a vehicle, typically a transportation vehicle, will be described.

[0525] 17D, 19C, and 23A can be installed in a vehicle to realize next-generation clean energy automobiles, such as hybrid vehicles (HVs), electric vehicles (EVs), and plug-in hybrid vehicles (PHVs). Furthermore, the secondary battery can also be installed in agricultural machinery, mopeds including electrically assisted bicycles, motorcycles, electric wheelchairs, electric carts, ships, submarines, aircraft, rockets, artificial satellites, space probes, planetary probes, or spacecraft. The secondary battery of one embodiment of the present invention can be a high-capacity secondary battery. Therefore, the secondary battery of one embodiment of the present invention is suitable for miniaturization and weight reduction and can be suitably used in transportation vehicles.

[0526] 24A to 24D illustrate examples of transportation vehicles using one embodiment of the present invention. The automobile 2001 shown in FIG. 24A is an electric automobile using an electric motor as a power source for traveling. Alternatively, it is a hybrid automobile that can appropriately select and use an electric motor or an engine as a power source for traveling. When a secondary battery is installed in a vehicle, an example of the secondary battery described in Embodiment 4 is installed in one or more locations. The automobile 2001 shown in FIG. 24A includes a battery pack 2200, which includes a secondary battery module to which multiple secondary batteries are connected. It is preferable that the automobile...

Claims

A positive electrode and a negative electrode are included. the positive electrode has positive electrode active material particles, the positive electrode active material particles contain lithium, cobalt, oxygen, magnesium, fluorine, nickel, and aluminum; The positive electrode active material particles are a surface layer portion having an edge region and an interior portion, the interior portion having a layered rock salt type crystal structure of space group R-3m; magnesium, fluorine, and nickel were detected in a cross-sectional STEM-EDX of the edge region of the positive electrode active material particle; a lithium ion secondary battery, wherein, when an arrangement of bright spots of the positive electrode active material particles observed in the cross-sectional STEM image of the edge region is defined as a first row from the surface side, at least a part of a fourth row to a ninth row of the positive electrode active material particles has a characteristic of a spinel-type crystal structure. 　 In claim 1, A lithium ion secondary battery, wherein bright spots with high brightness and bright spots with low brightness are alternately arranged in the depth direction in at least a part of the cobalt layers in the fourth to ninth columns observed in the cross-sectional STEM image. 　 In claim 1, A lithium ion secondary battery, in which bright spots with high brightness and regions where no clear bright spots are observed are alternately arranged in the depth direction in at least a portion of the lithium layers in the fourth to ninth columns observed in the cross-sectional STEM image. 　 In claim 1, the positive electrode active material particles have a fluorine concentration ratio (F / Mg) of 0.10 or more and 0.20 or less when the magnesium concentration is taken as 1, as determined by XPS analysis. 　 In claim 4, the positive electrode active material particles have a concentration ratio of the aluminum (Al / Co) of 0.01 or more and 0.04 or less, and a concentration ratio of the nickel (Ni / Co) of 0.01 or more and 0.07 or less, when the concentration of cobalt is set to 1, as determined by XPS analysis. 　 A positive electrode and a negative electrode are included. the positive electrode has positive electrode active material particles, the positive electrode active material particles contain lithium, cobalt, oxygen, magnesium, fluorine, nickel, and aluminum; The positive electrode active material particles are a surface layer portion having an edge region and an interior portion, the interior portion having a layered rock salt type crystal structure of space group R-3m; When an arrangement of bright spots of the positive electrode active material particles observed in the cross-sectional HAADF-STEM image of the edge region is designated as a first row from the surface side, at least a part of a fourth row to a ninth row located toward the inside of the positive electrode active material particles has a characteristic of a spinel-type crystal structure, In a STEM-EELS analysis of the fourth to ninth columns of the positive electrode active material particles, magnesium and nickel are detected at a position where only Wyckoff position 16c of space group Fd-3m overlaps in the <110> direction, and nickel is detected at a position where only Wyckoff position 16d of space group Fd-3m overlaps in the <110> direction. 　 A positive electrode and a negative electrode are included. the positive electrode has positive electrode active material particles, the positive electrode active material particles contain lithium, cobalt, oxygen, magnesium, fluorine, nickel, and aluminum; The positive electrode active material particles are a surface layer portion having an edge region and an interior portion, the interior portion having a layered rock salt type crystal structure of space group R-3m; When an arrangement of bright spots of the positive electrode active material particles observed in the cross-sectional HAADF-STEM image of the edge region is designated as a first row from the surface side, at least a part of a fourth row to a ninth row located toward the inside of the positive electrode active material particles has a characteristic of a spinel-type crystal structure, a lithium ion secondary battery having lithium sites where magnesium and nickel are detected, cobalt sites where magnesium and nickel are detected, and cobalt sites where nickel is detected, in a STEM-EELS analysis of the fourth to ninth columns of the positive electrode active material particles. 　 A positive electrode and a negative electrode are included. the positive electrode has positive electrode active material particles, the positive electrode active material particles contain lithium, cobalt, oxygen, magnesium, fluorine, nickel, and aluminum; a surface layer portion having an edge region and an interior portion, the interior portion having a layered rock salt type crystal structure of space group R-3m; When an arrangement of bright spots of the positive electrode active material particles observed in the cross-sectional HAADF-STEM image of the edge region is designated as a first row from the surface side, first bright spots having high brightness and first regions in which no clear bright spots are observed are alternately arranged in the depth direction in at least a part of the lithium layers of the fourth to ninth rows located toward the interior of the positive electrode active material particles, and second bright spots having high brightness and third bright spots having low brightness are alternately arranged in the depth direction in at least a part of the cobalt layers of the fourth to ninth rows of the positive electrode active material particles, a lithium ion secondary battery, wherein, in a STEM-EELS analysis of the fourth to ninth columns of the positive electrode active material particles, magnesium and nickel are detected in the first bright spot, the third bright spot, and the first region, and nickel is detected in the second bright spot. 　 In claim 8, In the STEM-EELS analysis, divalent cobalt and trivalent cobalt are detected at the third bright spot. 　 In claim 8, the positive electrode active material particles have a magnesium concentration ratio (Mg / Co) of 0.005 or more and 0.03 or less, and a nickel concentration ratio (Ni / Co) of 0.003 or more and 0.01 or less, when the cobalt concentration is taken as 1, as determined by EPMA analysis. 　 In any one of claims 1 to 10, The positive electrode is used, lithium metal is used as the negative electrode, and a mixture of lithium hexafluorophosphate, ethylene carbonate, diethyl carbonate, and 2 wt % vinylene carbonate is used as the electrolyte. In a 25°C environment, the battery was charged at a constant current of 0.5C (where 1.0C = 200mA / g) up to a voltage of 4.60V, and then charged at a constant voltage of 0.05C. a lithium ion secondary battery, wherein when the positive electrode is analyzed by XRD using CuKα1 radiation in an argon atmosphere, the XRD pattern has diffraction peaks at least at 2θ=19.25±0.12° and 2θ=45.47±0.10°.

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