Coated active material, electrode mixture, battery, and coating liquid

Abstract

To provide a coated active material capable of suppressing a resistance increase even when an electrode active material having a high nickel ratio and a coating layer containing phosphorus are combined with each other.SOLUTION: In the present disclosure, there is provided a coated active material including an electrode active material and a coating layer that covers the electrode active material. The electrode active material includes an Li element, an M element (M is a metal other than Li and at least contains Ni), and an O element, a molar ratio (Ni / M) of the Ni to the M is 80% or more, the coating layer includes a B element, a P element, an La element, and an O element, and a molar ratio (La / P) of the La element to the P element is 0.005 or more and 0.15 or less.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to a coated active material, an electrode mixture, a battery, and a coating liquid. [Background technology]

[0002] In recent years, the development of batteries has been actively pursued. For example, in the automotive industry, development of batteries for use in electric vehicles (BEVs), plug-in hybrid vehicles (PHEVs), and hybrid electric vehicles (HEVs) is underway. It is also known that the surface of the electrode active material used in batteries is coated with a phosphorus-based coating solution.

[0003] For example, Patent Document 1 discloses composite particles including positive electrode active material particles and a coating film containing a phosphorus compound, which coats at least a portion of the surface of the positive electrode active material particles. Patent Document 1 also discloses that the positive electrode active material particles are mixed with an aqueous coating liquid containing phosphorus (aqueous coating liquid), and the mixture is dried to produce the composite particles. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2023-136753 Summary of the Invention [Problem to be solved by the invention]

[0005] Electrode active materials with a high nickel content are promising in terms of increasing capacity. On the other hand, when an aqueous coating solution containing phosphorus comes into contact with an electrode active material with a high nickel content, H + and Li + It is believed that an exchange reaction occurs with Ni, generating highly resistive NiO, resulting in an increase in resistance. This is a particular issue when an electrode active material with a high nickel ratio is combined with an aqueous coating solution containing phosphorus (a coating layer containing phosphorus).

[0006] The present disclosure has been made in consideration of the above-described circumstances, and has as its main object to provide a coated active material that can suppress an increase in resistance even when an electrode active material with a high nickel ratio is combined with a coating layer containing phosphorus. [Means for solving the problem]

[0007] [1] A coated active material having an electrode active material and a coating layer that coats the electrode active material, the electrode active material contains a Li element, an M element (M is a metal other than Li and contains at least Ni), and an O element; a molar ratio of Ni to M (Ni / M) of 80% or more; the coating layer contains a B element, a P element, a La element, and an O element, The coated active material has a molar ratio of the La element to the P element (La / P) of 0.005 or more and 0.15 or less.

[0008] [2] The coated active material according to [1], wherein the La / P is 0.01 or more and 0.11 or less.

[0009] [3] The coated active material according to [1] or [2], wherein the molar ratio of the B element to the P element (B / P) is 0.5 or more and 2.0 or less.

[0010] [4] The coated active material according to any one of [1] to [3], wherein the coating layer has a coverage of 75% or more of the electrode active material.

[0011] [5] The coated active material according to any one of [1] to [4], wherein the M further contains at least one of Co, Mn, and Al.

[0012] [6] An electrode mixture comprising the coated active material according to any one of [1] to [5] and at least one of a conductive material and a binder.

[0013] [7] The electrode mixture according to [6], wherein the electrode mixture contains a solid electrolyte.

[0014] [8] The electrode mixture according to [7], wherein the solid electrolyte is a sulfide solid electrolyte.

[0015] [9] A battery having a positive electrode layer, a negative electrode layer, and an electrolyte layer disposed between the positive electrode layer and the negative electrode layer, A battery in which the positive electrode layer or the negative electrode layer contains the electrode mixture according to any one of [6] to [8].

[0016]

[10] The battery according to [9], wherein the positive electrode layer contains the electrode mixture.

[0017]

[11] The battery according to [9] or

[10] , wherein the electrolyte layer contains a solid electrolyte.

[0018]

[12] A coating solution for forming the coating layer in the coated active material according to any one of claims [1] to [8], The coating liquid contains a solute containing B, P, and La elements, and water as a solvent, a molar ratio of the La element to the P element (La / P) of 0.001 or more and 0.100 or less; The coating liquid has an absorbance of 0.1 or less. [Effects of the Invention]

[0019] The coated active material according to the present disclosure exhibits the effect of being able to suppress an increase in resistance even when an electrode active material with a high nickel ratio is combined with a coating layer containing phosphorus. [Brief explanation of the drawings]

[0020] [Figure 1] 1 is a schematic cross-sectional view illustrating a coated active material according to the present disclosure. [Figure 2] FIG. 1 is a schematic cross-sectional view illustrating a battery according to the present disclosure. [Figure 3] 1 is a graph showing the resistance of batteries fabricated in Examples 1 to 5 and Comparative Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0021] The coated active material, electrode mixture, battery, and coating liquid according to the present disclosure will be described in detail below.

[0022] A. Coated active material FIG. 1 is a schematic cross-sectional view illustrating an example of a coated active material according to the present disclosure. The coated active material 10 shown in FIG. 1 includes an electrode active material 1 and a coating layer 2 that coats the electrode active material 1. The electrode active material 1 includes a Li element, an M element (M is a metal other than Li and contains at least Ni), and an O element. The molar ratio of Ni to M (Ni / M) is 80% or more. Meanwhile, the coating layer 2 includes a B element, a P element, a La element, and an O element, and the molar ratio of La to P (La / P) is 0.005 or more and 0.15 or less.

[0023] According to the present disclosure, by adding La element to the coating layer, an electrode active material with a high nickel ratio can be obtained that can suppress an increase in resistance even when combined with a coating layer containing phosphorus. As mentioned above, Patent Document 1 discloses that composite particles are produced by mixing positive electrode active material particles with an aqueous coating liquid containing phosphorus and drying the mixture. On the other hand, an electrode active material with a high nickel ratio is promising from the viewpoint of increasing capacity. When an aqueous coating liquid containing phosphorus comes into contact with an electrode active material with a high nickel ratio, H + and Li + It is estimated that an exchange reaction occurs with LiNiO2, producing highly resistive NiO. As a result, resistance increases. For example, if the electrode active material is LiNiO2, the following reaction is estimated to occur: LiNiO2+ H + → NiOOH + Li+ NiOOH → NiO + 0.5H2O + 0.25O2

[0024] In particular, when an aqueous coating liquid containing phosphorus is used, the presence of P element is thought to facilitate retention of moisture in the coating layer, accelerating the exchange reaction. In contrast, in the present disclosure, the addition of La element, which has a high affinity with P element, is thought to prevent moisture from accumulating in the coating layer, thereby suppressing the exchange reaction. Therefore, an increase in resistance can be suppressed. Furthermore, since the coating layer contains P element, the chemical stability of the coating layer is improved. Furthermore, since the coating layer contains B element in addition to P element, the ionic conductivity of the coating layer can be improved while improving its chemical stability.

[0025] 1.Coating layer The coating layer in the present disclosure is a layer that coats the electrode active material. The coating layer also contains B, P, and O elements. The coating layer may further contain Li. The coating layer also preferably contains a PO4 structure.

[0026] In the coating layer, the molar ratio of La to P (La / P) is usually 0.005 or more and 0.15 or less, and may be 0.01 or more and 0.11 or less. If La / P is too small, the resistance suppression effect of La may not be sufficiently obtained. On the other hand, if La / P is too large, manufacturing may become difficult.

[0027] In the coating layer, the molar ratio of B element to P element (B / P) is not particularly limited, but may be, for example, 0.5 to 2.0, 0.8 to 1.25, or 0.9 to 1.11. When the coating layer further contains Li element, the molar ratio of Li element to the total of P element and B element (Li / (P+B)) is not particularly limited, but may be, for example, 0.3 to 1.2, or 0.5 to 1.0.

[0028] The coverage of the coating layer with respect to the electrode active material is not particularly limited, but may be, for example, 75% or more, or 80% or more. If the coverage is too low, it may be impossible to sufficiently suppress the increase in resistance caused by a high-resistance layer resulting from the reaction between the electrode active material and the electrolyte. On the other hand, the coverage may be 100% or less. The coverage in the present disclosure is determined by calculating the element ratio from the intensity ratio of each major element based on X-ray photoelectron spectroscopy (XPS) measurement, and expressing the ratio of the elements contained in the coating layer to the total of the elements contained in the electrode active material and the elements contained in the coating layer.

[0029] The thickness of the coating layer is not particularly limited, but may be, for example, 1 nm to 100 nm, or may be 5 nm to 50 nm, or may be 10 nm to 30 nm. The thickness of the coating layer is determined as the average thickness of multiple samples (e.g., 100 or more samples) observed by, for example, a scanning electron microscope (SEM) or a transmission electron microscope (TEM).

[0030] 2. Electrode active material The electrode active material in the present disclosure typically contains Li, M, and O elements. M is a metal (including metalloids) other than Li, and contains at least Ni. M other than Ni may be a transition metal or a metal (including metalloids) belonging to Groups 13 to 16 of the periodic table. Furthermore, M other than Ni may be one type of metal or two or more types of metals. Among these, M other than Ni is preferably at least one of Co, Mn, Al, V, and Fe.

[0031] The molar ratio of Ni to M (Ni / M) is usually 80% or more, may be 85% or more, or may be 90% or more, while Ni / M may be 100% or less.

[0032] The electrode active material may contain a nonmetallic element such as P in addition to Li, M, and O. The crystalline structure of the electrode active material is not particularly limited, and examples thereof include a rock salt layer structure, a spinel structure, and an olivine structure.

[0033] An example of the composition of the electrode active material is LiNi x Co y Al z O2 (0.80≦x, 0≦y, 0≦z, x+y+z=1). x is usually 0.80 or more, and may be 0.85 or more, or 0.90 or more. y may be 0 or more than 0. Furthermore, y is, for example, 0.20 or less. z may be 0 or more than 0. Furthermore, z is, for example, 0.10 or less.

[0034] Another example of the composition of the electrode active material is LiNi a Co b Mn c O2 (0.80≦a, 0≦b, 0≦c, a+b+c=1). a is usually 0.80 or more, and may be 0.85 or more, or 0.90 or more. b may be 0 or more than 0. Also, b is, for example, 0.20 or less. c may be 0 or more than 0. Also, c is, for example, 0.20 or less.

[0035] The electrode active material is usually in the form of particles. 50 is, for example, 100 nm or more, may be 1 μm or more, or may be 5 μm or more. 50 is, for example, 50 μm or less, and may be 20 μm or less. 50 corresponds to the particle size equivalent to a cumulative 50% by volume measured using a laser diffraction particle size distribution analyzer.

[0036] 3.Coated active material The coated active material of the present disclosure is typically used in batteries. The electrode active material in the coated active material may be either a positive electrode active material or a negative electrode active material, with the former being preferred. The method for producing the coated active material is not particularly limited, but may include, for example, a method including a preparation step of preparing an electrode active material and a coating liquid, and a coating layer formation step of coating the electrode active material with the coating liquid and drying the coating liquid to form a coating layer.

[0037] In the preparation step, an electrode active material and a coating liquid are prepared. The electrode active material is the same as described above in "A. Coated active material." Meanwhile, the coating liquid will be described later in "D. Coating liquid." In the coating layer formation step, the electrode active material is coated with the coating liquid and dried to form a coating layer. Examples of methods for coating the electrode active material with the coating liquid and drying it include spray drying. The present disclosure can also provide a method for producing a coated active material that includes the above-mentioned preparation step and coating layer formation step.

[0038] B. Electrode composite material The electrode mixture in the present disclosure contains the coated active material described above, and at least one of a conductive material and a binder.

[0039] According to the present disclosure, by using the above-described coated active material, an electrode mixture can be obtained that can suppress an increase in resistance even when an electrode active material with a high nickel ratio is combined with a coating layer containing phosphorus.

[0040] The electrode mixture contains a coated active material and at least one of a conductive material and a binder. The coated active material is the same as that described above in "A. Coated Active Material." The electrode active material in the coated active material may be a positive electrode active material or a negative electrode active material, with the former being preferred. That is, the electrode mixture may be a positive electrode mixture or a negative electrode mixture, with the former being preferred.

[0041] The proportion of the coated active material in the electrode mixture is, for example, 20% by weight or more, or may be 30% by weight or more, or 40% by weight or more. If the proportion of the coated active material is too low, sufficient energy density may not be obtained. On the other hand, the proportion of the coated active material is, for example, 80% by weight or less, or may be 70% by weight or less, or may be 60% by weight or less. If the proportion of the coated active material is too high, the ionic conductivity and electronic conductivity of the electrode mixture may relatively decrease.

[0042] The electrode mixture contains at least one of a conductive material and a binder. Examples of conductive materials include carbon materials, metal particles, and conductive polymers. Examples of carbon materials include particulate carbon materials such as acetylene black (AB) and ketjen black (KB), and fibrous carbon materials such as carbon fiber, carbon nanotubes (CNT), and carbon nanofibers (CNF). Examples of binders include rubber-based binders and fluoride-based binders.

[0043] The electrode mixture may further contain a solid electrolyte. The solid electrolyte may be an organic solid electrolyte such as a gel electrolyte, or an inorganic solid electrolyte such as a sulfide solid electrolyte or an oxide solid electrolyte. Among these, the solid electrolyte is preferably a sulfide solid electrolyte, because it has high ionic conductivity.

[0044] The sulfide solid electrolyte typically contains at least Li and S. Preferably, the sulfide solid electrolyte further contains Me (Me is at least one of P, As, Sb, Si, Ge, Sn, B, Al, Ga, and In). The sulfide solid electrolyte may also contain a halogen element such as F, Cl, Br, or I.

[0045] The sulfide solid electrolyte may be a glass-based (amorphous) sulfide solid electrolyte, a glass-ceramic sulfide solid electrolyte, or a crystalline sulfide solid electrolyte. The sulfide solid electrolyte may have a crystalline phase. Examples of the crystalline phase include, for example, Thio-LISICON type crystalline phase, argyrodite type crystalline phase, and LGPS type crystalline phase.

[0046] The composition of the sulfide solid electrolyte is not particularly limited. For example, xLi2S·(1-x)P2S5 (0.5≦x<1), yLiI·zLiBr·(100-y-z)(xLi2S·(1-x)P2S5) (0.5≦x<1, 0≦y≦30, 0≦z≦30) can be mentioned. In these compositions, it is preferable that x satisfies 0.7≦x≦0.8. Also, as another example of the composition of the sulfide solid electrolyte, Li 7-x-2y PS 6-x-y X y can be mentioned. X is at least one of F, Cl, Br, and I, and x and y satisfy 0≦x, 0≦y. Also, as another example of the composition of the sulfide solid electrolyte, Li 4-x Me 1-x P x S4 (0<x<1) can be mentioned. Me is at least one of Al, Zn, In, Ge, Si, Sn, Sb, Ga, and Bi.

[0047] C. Battery FIG. 2 is a schematic cross-sectional view illustrating the battery in the present disclosure. The battery 20 shown in FIG. 2 includes a positive electrode layer 11, a negative electrode layer 12, an electrolyte layer 13 disposed between the positive electrode layer 11 and the negative electrode layer 12, a positive electrode current collector 14 for collecting current from the positive electrode layer 11, and a negative electrode current collector 15 for collecting current from the negative electrode layer 12. In the present disclosure, the positive electrode layer 11 or the negative electrode layer 12 contains the electrode binder described in the above "B. Electrode Binder".

[0048] According to the present disclosure, by using the above-described electrode composite, a battery can be obtained in which an increase in resistance is suppressed even when an electrode active material with a high nickel ratio is combined with a coating layer containing phosphorus. As described above, the electrode composite may be a positive electrode composite or a negative electrode composite, but the former is preferred. Below, details of the battery when the electrode composite is a positive electrode composite will be described.

[0049] 1. Positive electrode layer The positive electrode layer in the present disclosure contains the above-described electrode mixture (positive electrode mixture). The electrode mixture is the same as that described above in "B. Electrode mixture," and therefore will not be described here. The positive electrode layer may also contain an electrolyte, if necessary. The electrolyte is the same as that described in "3. Electrolyte Layer." The thickness of the positive electrode layer is, for example, 0.1 μm or more and 1000 μm or less, or may be 0.1 μm or more and 500 μm or less, or may be 0.1 μm or more and 100 μm or less. The positive electrode layer can be formed, for example, by coating the electrode mixture (positive electrode mixture) on a positive electrode current collector.

[0050] 2. Negative electrode layer The negative electrode layer is a layer containing at least a negative electrode active material, and may also contain at least one of an electrolyte, a conductive material, and a binder, as necessary.

[0051] Examples of the negative electrode active material include metal active materials such as Li, Si-based active materials, carbon active materials such as graphite, and Li4Ti5O 12 Examples of oxide active materials include:

[0052] The negative electrode active material is preferably a Si-based active material, as this allows for a higher battery capacity. The Si-based active material is an active material whose main component is Si. The Si-based active material may be simple Si, a Si alloy, or a Si oxide. The Si-based active material may have a diamond-type crystalline phase, a clathrate I crystalline phase, or a clathrate II crystalline phase. In the clathrate I or II crystalline phase, multiple Si elements form a polyhedron (cage) containing pentagons or hexagons. This polyhedron has a space inside that can encapsulate Li ions, thereby suppressing volumetric changes during charging and discharging.

[0053] The shape of the negative electrode active material may be, for example, particulate. 50 is not particularly limited, but may be, for example, 10 nm or more, or may be 100 nm or more. 50 is, for example, 50 μm or less, and may be 20 μm or less.

[0054] The electrolyte used in the negative electrode layer is the same as that described in "3. Electrolyte Layer." The conductive material and binder used in the negative electrode layer are the same as those described in "B. Electrode Mixture" above, and therefore will not be described here. The thickness of the negative electrode layer is, for example, 0.1 μm or more and 1000 μm or less, or may be 0.1 μm or more and 500 μm or less, or may be 0.1 μm or more and 100 μm or less.

[0055] 3. Electrolyte layer The electrolyte layer is a layer formed between the positive electrode layer and the negative electrode layer, and contains at least an electrolyte. The electrolyte may be a solid electrolyte or a liquid electrolyte (electrolytic solution).

[0056] The solid electrolyte is similar to that described above in "B. Electrode Composite," and therefore will not be described here. The electrolyte preferably contains a supporting salt and a solvent. Examples of supporting salts (lithium salts) for the lithium-ion conductive electrolyte include inorganic lithium salts such as LiPF6, LiBF4, LiClO4, and LiAsF6, and organic lithium salts such as LiCF3SO3, LiN(CF3SO2)2, LiN(C2F5SO2)2, LiN(FSO2)2, and LiC(CF3SO2)3. Examples of solvents used in the electrolyte include cyclic esters (cyclic carbonates) such as ethylene carbonate (EC), propylene carbonate (PC), and butylene carbonate (BC), and chain esters (chain carbonates) such as dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethyl methyl carbonate (EMC). The electrolyte preferably contains two or more solvents.

[0057] The thickness of the electrolyte layer is, for example, 0.1 μm or more and 1000 μm or less, or may be 0.1 μm or more and 500 μm or less, or may be 0.1 μm or more and 100 μm or less.

[0058] 4. Other configurations The battery according to the present disclosure preferably includes a positive electrode current collector that collects current from the positive electrode layer and a negative electrode current collector that collects current from the negative electrode layer. Examples of materials for the positive electrode current collector include stainless steel, aluminum, nickel, iron, titanium, and carbon. On the other hand, examples of materials for the negative electrode current collector include stainless steel, copper, nickel, and carbon.

[0059] The battery of the present disclosure may further include a restraining jig that applies a restraining pressure to the positive electrode layer, the electrolyte layer, and the negative electrode layer in the thickness direction. In particular, when the electrolyte layer is a solid electrolyte layer, it is preferable to apply a restraining pressure to form good ion conduction paths and electron conduction paths. The restraining pressure is, for example, 0.1 MPa or more, or may be 1 MPa or more, or may be 5 MPa or more. Meanwhile, the restraining pressure is, for example, 100 MPa or less, or may be 50 MPa or less, or may be 20 MPa or less.

[0060] 5.Battery The type of battery in the present disclosure is not particularly limited, but is typically a lithium-ion battery. The battery in the present disclosure may be a liquid battery containing an electrolytic solution as an electrolyte layer, or a solid battery having a solid electrolyte layer as an electrolyte layer. The solid battery may be a semi-solid battery or an all-solid battery. The battery in the present disclosure may be a primary battery or a secondary battery, but a secondary battery is preferred because it can be repeatedly charged and discharged and is useful, for example, as an in-vehicle battery.

[0061] Examples of uses of the battery include power sources for vehicles such as hybrid electric vehicles (HEVs), plug-in hybrid electric vehicles (PHEVs), electric vehicles (BEVs), gasoline-powered vehicles, and diesel-powered vehicles. In particular, it is preferable to use the battery as a driving power source for hybrid electric vehicles (HEVs), plug-in hybrid electric vehicles (PHEVs), or electric vehicles (BEVs). The battery may also be used as a power source for mobile objects other than vehicles (for example, trains, ships, and aircraft), and may also be used as a power source for electrical appliances such as information processing devices.

[0062] D. Coating liquid The coating liquid in the present disclosure is a coating liquid for forming the coating layer in the coated active material described above in "A. Coated Active Material." The coating liquid contains a solute containing B, P, and La, and water as a solvent. The molar ratio of La to P (La / P) is 0.001 or more and 0.100 or less. The absorbance of the coating liquid is 0.1 or less.

[0063] According to the present disclosure, by adding La element so as to obtain a predetermined absorbance, a coating liquid can be obtained that can suppress an increase in resistance even when combined with an electrode active material having a high nickel ratio.

[0064] The coating solution contains a solute containing B, P, and La, and water as a solvent. The solute may further contain O. In particular, the solute preferably contains a PO4 structure. The coating solution may further contain Li.

[0065] In the coating solution, the molar ratio of La to P (La / P) is usually 0.001 or more and 0.100 or less, and may be 0.003 or more and 0.080 or less. If La / P is too small, the resistance suppression effect of La may not be sufficiently obtained. On the other hand, if La / P is too large, production may become difficult.

[0066] In the coating solution, the molar ratio of B element to P element (B / P) is not particularly limited, but may be, for example, 0.5 to 2.0, 0.8 to 1.25, or 0.9 to 1.11. Furthermore, when the coating solution further contains Li element, the molar ratio of Li element to the total of P element and B element (Li / (P+B)) is not particularly limited, but may be, for example, 0.3 to 1.2, or 0.5 to 1.0.

[0067] The absorbance of the coating liquid is usually 0.1 or less, and may be 0.05 or less, or may be 0.001 or less. The method for measuring the absorbance is as described in the Examples below.

[0068] The method for preparing the coating solution is not particularly limited, and examples thereof include a method in which a solute containing a B source, a P source, and a La source is dissolved in water as a solvent. The B source is not particularly limited as long as it is a simple substance or compound containing the B element, and examples thereof include boric acid (H3BO3). The P source is not particularly limited as long as it is a simple substance or compound containing the P element, and examples thereof include orthophosphoric acid (H3PO4) and metaphosphoric acid (HPO3). The coating solution preferably also contains an O source. Examples of the O source include the O element contained in the B source or P source described above. The solute may also contain a Li source. The Li source is not particularly limited as long as it is a simple substance or compound containing the Li element, and examples thereof include lithium hydroxide monohydrate (LiOH·H2O).

[0069] The present disclosure is not limited to the above-described embodiments. The above-described embodiments are merely examples, and any configuration that is substantially identical to the technical idea described in the claims of the present disclosure and that provides similar effects is included within the technical scope of the present disclosure. [Example]

[0070] [Comparative Example 1] (Preparation of coating liquid) Metaphosphoric acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and ion-exchanged water were mixed in a weight ratio of metaphosphoric acid:ion-exchanged water = 4.52:191.8 to obtain an aqueous solution. Boric acid (manufactured by Nacalai Tesque, Inc.) was added to the obtained aqueous solution and dissolved therein so that the molar ratio of B element to P element (B / P) was 1.0. This resulted in a coating liquid.

[0071] (Preparation of coated active material) The coating solution thus obtained was coated with active material particles (LiNi 0.81 Co 0.15 Al 0.04 O2, particle size D 50= 4.5 μm) was dispersed in the slurry to prepare a slurry. The solid content of the slurry was 69 wt %. Next, the slurry was dried using a spray dryer manufactured by BUCHI (product name: Mini Spray Dryer B-290) to form a coating layer on the surface of the active material particles. The supply air temperature of the spray dryer was 200°C, and the supply air volume was 0.45 m 3 The active material particles with the coating layer formed thereon were then heat-treated in the air to obtain a coated active material. The heat treatment temperature was 200° C. and the heat treatment time was 5 hours.

[0072] [Example 1] Metaphosphoric acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and ion-exchanged water were mixed in a weight ratio of metaphosphoric acid:ion-exchanged water = 4.52:191.8 to obtain an aqueous solution. Boric acid (manufactured by Nacalai Tesque, Ltd.) was added to the obtained aqueous solution and dissolved so that the molar ratio of B element to P element (B / P) was 1.0. Furthermore, lanthanum oxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added and dissolved so that the molar ratio of La element to P element (La / P) was 0.003. This resulted in a coating liquid. A coated active material was obtained in the same manner as in Comparative Example 1, except that the obtained coating liquid was used.

[0073] [Examples 2 to 5] Except for changing the molar ratio of La element to P element (La / P) to 0.006, 0.01, 0.05, and 0.075, respectively, coating solutions were obtained in the same manner as in Example 1. Except for using the obtained coating solutions, coated active materials were obtained in the same manner as in Comparative Example 1.

[0074] Comparative Example 2 A coating liquid was obtained in the same manner as in Example 1, except that the molar ratio of La element to P element (La / P) was changed to 0.100. A coated active material was obtained in the same manner as in Comparative Example 1, except that the obtained coating liquid was used.

[0075] [evaluation] (Absorbance measurement) The absorbance of the coating solutions obtained in Examples 1 to 5 and Comparative Examples 1 and 2 was measured. Specifically, 3.5 mL of the coating solution was added to a quartz cell (10 mm × 10 mm × 45 mm), and the absorbance was measured using an ultraviolet-visible spectrophotometer (product name UV-1280, manufactured by Shimadzu Corporation). When the absorbance was measured at a wavelength of 660 nm, it was confirmed that the concentration of insoluble particles present in the coating solution was extremely low in Examples 1 to 5 and Comparative Example 1 (see, for example, JIS-K0101). On the other hand, in Comparative Example 2, the coating solution was found to be cloudy when visually observed, so absorbance measurement was not performed. The results are shown in Table 1.

[0076] (Measurement of coverage and La / P) The coverage of the coated active materials obtained in Examples 1 to 5 and Comparative Examples 1 and 2 was measured by X-ray photoelectron spectroscopy (XPS). Specifically, surface elemental analysis of the coated active materials was performed using an X-ray photoelectron spectrometer (ULVAC-PHI, PHI X-tool). Narrow scan analysis was performed with a pass energy of 224 eV. Subsequently, the element ratios were calculated from the intensity values ​​of the detected C1s, O1s, P2p, Ni2p3, Co2p3, Al2p, B1s, and La3d3 using analysis software (MultiPak, ULVAC-PHI), and the value [%] of (La + P + B) / (La + P + B + Ni + Co + Al) was determined as the coverage. The molar ratio of La to P (La / P) was also calculated from the element ratios. The results are shown in Table 1.

[0077] (resistance measurement) The coated active materials obtained in Examples 1 to 5 and Comparative Examples 1 and 2 were used as the positive electrode active material to fabricate batteries, and the resistance was measured.

[0078] First, a positive electrode slurry was prepared by mixing the positive electrode active material (coated active material), sulfide solid electrolyte (10LiI-15LiBr-75Li3PS4), conductive material (VGCF), binder (SBR), and dispersion medium (heptane). The mixing ratio of the positive electrode active material to the sulfide solid electrolyte was positive electrode active material:sulfide solid electrolyte = 6:4 (volume ratio). The amounts of the conductive material and binder were each 3 parts by weight per 100 parts by weight of the positive electrode active material. The positive electrode slurry was thoroughly stirred using an ultrasonic homogenizer, and then coated onto the surface of a positive electrode current collector (Al foil) to form a coating film. The coating film was dried at 100°C for 30 minutes on a hot plate. This resulted in a positive electrode blank. A disk-shaped positive electrode was cut out from the positive electrode blank. The area of ​​the positive electrode was 1 cm. 2 It was.

[0079] Next, a negative electrode and a solid electrolyte layer were prepared. The negative electrode active material was graphite. The same sulfide solid electrolyte was used between the positive electrode, the solid electrolyte layer, and the negative electrode. A stack was formed by stacking the positive electrode, the solid electrolyte layer, and the negative electrode in this order in a cylindrical jig. A power generating element was formed by pressing the stack. A battery (all-solid-state battery) was obtained by connecting terminals to the power generating element. The open circuit voltage (OCV) of the obtained all-solid-state battery was adjusted to 2.03 V, and then constant current discharge was performed. The voltage drop over 5 seconds was divided by the current amount to measure the battery resistance. The discharge current rate was 2.5 C. The resistance of the battery of Comparative Example 1 was set as the reference (1.00), and the resistance of the batteries of each Example and each Example was evaluated by relativizing it. The results are shown in Table 1 and FIG. 3.

[0080] [Table 1]

[0081] As shown in Table 1, in Examples 1 to 5 and Comparative Example 1, the La / P value in the coating layer was larger than the La / P value in the coating liquid. This is presumably due to the segregation of La. Furthermore, as shown in Table 1 and FIG. 3, it was confirmed that Examples 1 to 5 had lower resistance than Comparative Example 1. In this way, it was confirmed that adding La to the coating layer can suppress an increase in resistance even when an electrode active material with a high nickel ratio is combined with a coating layer containing phosphorus. On the other hand, in Comparative Example 2, the coating liquid became cloudy and was confirmed to be a dispersion rather than a solution. Therefore, a deviation in composition occurred, and the desired coated active material could not be obtained. [Explanation of symbols]

[0082] 1...electrode active material 2...Covering layer 10...Coated active material 11...Positive electrode layer 12...Anode layer 13...electrolyte layer 14...Positive electrode current collector 15...Negative electrode current collector 20...battery

Claims

1. A coated active material having an electrode active material and a coating layer that coats the electrode active material, the electrode active material has a Li element, an M element (M is a metal other than Li and contains at least Ni), and an O element; a molar ratio of Ni to M (Ni / M) of 80% or more; the coating layer contains a B element, a P element, a La element, and an O element, A coated active material, wherein a molar ratio of the La element to the P element (La / P) is 0.005 or more and 0.15 or less.

2. 2. The coated active material according to claim 1, wherein the La / P is 0.01 or more and 0.11 or less.

3. 2. The coated active material according to claim 1, wherein a molar ratio of the B element to the P element (B / P) is 0.5 or more and 2.0 or less.

4. The coated active material according to claim 1 , wherein a coverage rate of the coating layer with respect to the electrode active material is 75% or more.

5. The coated active material according to claim 1 , wherein the M further contains at least one of Co, Mn, and Al.

6. An electrode mixture comprising the coated active material according to any one of claims 1 to 5 and at least one of a conductive material and a binder.

7. The electrode mixture according to claim 6 , wherein the electrode mixture contains a solid electrolyte.

8. The electrode mixture according to claim 7 , wherein the solid electrolyte is a sulfide solid electrolyte.

9. A battery having a positive electrode layer, a negative electrode layer, and an electrolyte layer disposed between the positive electrode layer and the negative electrode layer, A battery, wherein the positive electrode layer or the negative electrode layer contains the electrode mixture according to claim 6.

10. The battery according to claim 9 , wherein the positive electrode layer contains the electrode mixture.

11. 10. The battery of claim 9, wherein the electrolyte layer comprises a solid electrolyte.

12. A coating liquid for forming the coating layer in the coated active material according to any one of claims 1 to 5, the coating liquid contains a solute containing a B element, a P element, and a La element, and water as a solvent; a molar ratio of the La element to the P element (La / P) of 0.001 or more and 0.100 or less; The coating liquid has an absorbance of 0.1 or less.

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