Battery

Abstract

To solve a problem in which negative electrode active material particles expand and contract due to charging and discharging when silicon is used as the negative electrode active material particles.SOLUTION: In order to suppress the expansion or contraction of negative electrode active material particles that occur during charging and discharging, a graphene compound is used to bind or fix a negative electrode active material particle or multiple negative electrode active material particles. In an all-solid-state secondary battery, the interface between the solid electrolyte and the negative electrode, or the interface between the solid electrolyte and the positive electrode, has the highest resistance. In order to reduce this interfacial resistance, at least the negative electrode active material particles are wrapped in a graphene compound to increase conductivity. Alternatively, the positive electrode active material particles are wrapped in a graphene compound to increase conductivity. Because a graphene compound allows carrier ions, such as lithium ions, to pass through, the graphene compound does not inhibit the movement of lithium ions between the positive and negative electrodes during charging or discharging.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] One aspect of the present invention relates to a product, a method, or a method of manufacture. Alternatively, the present invention relates to a process. This relates to machines, manufacturers, or compositions of matter. One aspect of the present invention relates to a semiconductor device, display device, light-emitting device, energy storage device, lighting device, or electronic The present invention relates to equipment or methods for manufacturing such equipment, particularly electronic equipment and its operating systems. Regarding the stem.

[0002] In this specification, "electronic equipment" refers to all devices that have an energy storage device. Electro-optical devices and information terminal devices with energy storage devices are all electronic devices. [Background technology]

[0003] There is a great deal of development going on in electronic devices that users carry with them and electronic devices that users wear on their devices.

[0004] Electronic devices carried by users or worn by users are examples of primary energy storage devices. It operates using batteries or rechargeable batteries as a power source. Electronic devices carried by the user are intended for long-term use. It is desirable to do so, and for that purpose, a large-capacity secondary battery should be used. When a battery is built in, high-capacity rechargeable batteries become large and heavy, which is a problem. Development is underway to create small, thin, and high-capacity rechargeable batteries that can be built into electronic devices.

[0005] A liquid such as an organic solvent is used as a medium to move lithium ions, which are carrier ions. Lithium-ion secondary batteries, which use liquid, are widely used. However, secondary batteries that use liquid In this case, since a liquid is used, there are issues with the decomposition reaction of the electrolyte depending on the operating temperature range and operating potential. There are issues with leakage of electrolyte from the secondary battery to the outside. Furthermore, secondary batteries that use liquid electrolytes are prone to leakage. There is a risk of fire due to this.

[0006] Fuel cells are a type of secondary battery that does not use liquid, but they use precious metals for the electrodes and solid electrolyte material It is also an expensive device.

[0007] Furthermore, there is a type of energy storage device called a solid-state battery that uses a solid electrolyte as a secondary battery that does not use liquid. It is known. For example, Patent Document 1, Patent Document 2, etc. are disclosed. Also, Patent Document 3. The electrolyte of the lithium-ion secondary battery is one of the following: solvent, gel, or solid electrolyte. It is stated that it should be used.

[0008] Patent Document 4 discloses an example in which graphene oxide is used as the positive electrode active material layer of a solid-state battery.

[0009] Furthermore, solid-state batteries using graphene have also been disclosed, such as in Patent Document 5. [Prior art documents] [Patent Documents]

[0010] [Patent Document 1] Japanese Patent Publication No. 2012-230889 [Patent Document 2] Japanese Patent Publication No. 2012-023032 [Patent Document 3] Japanese Patent Publication No. 2013-229308 [Patent Document 4] Japanese Patent Publication No. 2013-229315 [Patent Document 5] Japanese Patent Publication No. 2018-98200 [Overview of the Initiative] [Problems that the invention aims to solve]

[0011] To provide an all-solid-state secondary battery with higher safety than conventional lithium-ion secondary batteries.

[0012] By using an all-solid-state secondary battery, problems such as leakage of the electrolyte solution and deterioration due to deterioration of the electrolyte solution, which were problems of secondary batteries using an electrolyte solution, have been solved, but other problems remain. Moreover, when silicon is used as the negative electrode active material particles of an all-solid-state secondary battery, there is a problem that the negative electrode active material particles expand and contract during charge and discharge.

[0013] In addition, it has been found that there is a problem of micro short circuit (hereinafter referred to as micro short) occurring even in an all-solid-state secondary battery. Therefore, in an all-solid-state secondary battery, suppressing the occurrence of short circuit or micro short between the positive electrode and the negative electrode is also one of the problems.

[0014]

[0015]

Means for Solving the Problems

[0015] In order to solve the above problems and suppress the expansion or contraction of the negative electrode active material particles caused by charge and discharge, a graphene compound is used to bind or fix the negative electrode active material particles or a plurality of negative electrode active material particles.

[0016] In an all-solid-state secondary battery, the interface between the solid electrolyte and the negative electrode or the interface between the solid electrolyte and the positive electrode has the highest resistance. In order to reduce this interface resistance, at least the negative electrode active material particles are wrapped with a graphene compound to increase conductivity. Or, the positive electrode active material particles are wrapped with a graphene compound to increase conductivity. Since the graphene compound allows carrier ions, such as lithium ions, to pass through, it does not inhibit the movement of lithium ions between the positive electrode and the negative electrode during charging or discharging.

[0017]

[0018] Furthermore, graphene compounds can be used to bind negative electrode active material particles or multiple negative electrode active material particles. By fixing it, the generation of by-reactants (such as precipitates) is inhibited, and the occurrence of microshorts is prevented. It can be suppressed.

[0018] A microshort refers to a tiny short circuit inside a secondary battery. It's not a case of the positive and negative electrodes of the battery being short-circuited to the point where charging and discharging are impossible, but rather a very small short circuit. This refers to the phenomenon where a small short-circuit current flows for a period of 10 nanoseconds to less than 1 microsecond. Yes. The cause of microshorts is that multiple charge-discharge cycles occur, affecting the positive electrode active material particles. Due to the uneven distribution of current, localized current concentration occurs in parts of the positive and negative electrodes, causing separation. Some parts of the data may cease to function, or side reaction products (such as precipitates) may be generated. It is about doing it.

[0019] Furthermore, repeated micro-short circuits can cause abnormal overheating of the secondary battery and even lead to fire. This could lead to a serious accident.

[0020] Therefore, to prevent local current concentration from occurring in a part of the negative electrode and a part of the positive electrode, the surface of the negative electrode and The structure is designed to enhance conductivity by encasing and fixing the inside with a graphene compound.

[0021] One configuration disclosed herein comprises positive electrode active material particles containing carrier ions and a plurality of negative electrodes. The material comprises at least active material particles, a plurality of solid electrolyte particles, and a graphene compound. The graphene compound fixes the negative electrode active material particles, and during charging, carrier ions pass through the graphene. This is an all-solid-state battery in which the negative electrode active material particles are incorporated.

[0022] Furthermore, the configuration of another invention comprises a plurality of positive electrode active material particles containing carrier ions, and a plurality of negative electrode active It comprises material particles, a plurality of solid electrolyte particles, and a plurality of graphene compounds, and one or This is an all-solid-state battery in which multiple negative electrode active material particles are fixed with one or more graphene compounds. .

[0023] In this specification, graphene has a carbon hexagonal lattice structure and is a single layer of graphene. or including multilayer graphene with 2 to 100 layers. Single-layer graphene (one graphene) Fen) is sp 2 This refers to a sheet of carbon molecules consisting of one atomic layer with bonds. The term "graphene" refers to either multilayer graphene or multiple single layers of graphene. Furthermore, graphene is not limited to being composed solely of carbon, but also contains oxygen, hydrogen, and functional groups. It can also bind with and can be called a graphene compound. Graphene compounds are graphene quantum cells. It contains graphene compounds, which have excellent electrical properties such as high conductivity and high flexibility. It may also possess excellent physical properties such as flexibility and high mechanical strength. Graphene compounds have a planar shape. Graphene compounds have low contact resistance. It enables contact. Furthermore, even thin materials can have very high conductivity, allowing for efficient utilization with small amounts. Conductive paths can be formed within the material layer. By using a spray drying device, active materials The graphene compound may be formed as a coating to cover the entire surface of the material. Examples of compounds include graphene, multigraphene, graphene quantum dots, or RG It is particularly preferable to use O. Here, RGO is, for example, graphene oxide (graph This refers to compounds obtained by reducing ene oxides (GO).

[0024] Furthermore, the configuration of another invention comprises a plurality of positive electrode active material particles containing carrier ions, and a plurality of negative electrode active It comprises material particles, a plurality of solid electrolyte particles, and a plurality of graphene compounds, and one or This is an all-solid-state battery in which multiple positive electrode active material particles are fixed with one or more graphene compounds. .

[0025] In the above configuration, an oxide containing lithium and cobalt is used as the positive electrode active material particles. It is preferable that the positive electrode active material particles have a crystalline structure represented by the space group R-3m, for example. It is even more preferable to do so. These positive electrode active material particles, especially when the charging depth is deep, It is preferable that the structure has a pseudo-spinel structure, as described later.

[0026] Furthermore, the concentration of halogens such as fluorine in the surface layer of the positive electrode active material particles is greater than the average concentration of the entire particle. It is preferable that the halogen is present in the surface layer, which is the region in contact with the electrolyte. This effectively improves corrosion resistance to hydrofluoric acid.

[0027] Thus, the surface layer of the positive electrode active material particles has a higher fluorine concentration than the interior, and is different from the interior. It is preferable that the composition is such that it has a crystalline structure that is stable at room temperature. Therefore, the surface layer may have a different crystal structure from the interior. For example, positive electrode active material At least a portion of the surface layer of the fine particles may have a rock salt-type crystalline structure. When the surface and interior have different crystal structures, the orientation of the crystals in the surface and interior is roughly the same. This is preferable.

[0028] The surface layer of the positive electrode active material particles contains at least element M, and in the discharge state, it also contains element A. It is necessary to have a pathway for the insertion and removal of element A. Note that element A is a carrier ion and These are metals. Examples of element A include alkali metals such as lithium, sodium, and potassium. , and Group 2 elements such as calcium, beryllium, and magnesium can be used. If sodium is selected, the carrier ion is the sodium ion.

[0029] Element M is, for example, a transition metal. Examples of transition metals include cobalt, manganese, and nickel. At least one of the KELs can be used. A positive electrode material according to one aspect of the present invention is, for example, element M and It contains one or more of cobalt, nickel, and manganese, and is particularly preferred to contain cobalt. It seems so. Also, at the position of element M, there is no change in valence, such as aluminum, and it is the same as element M. It may also contain elements that can take on a valency, more specifically, trivalent typical elements.

[0030] Furthermore, the configuration involves encasing both the positive electrode active material particles and the negative electrode active material particles in their respective graphene compounds. It may also be said that its composition consists of multiple positive electrode active material particles containing carrier ions and multiple first Both the solid electrolyte particles and the first graphene compound are encapsulated, at least partially or completely, and multiple Both a number of negative electrode active material particles and a number of second solid electrolyte particles are connected to a second graphene compound. A second graphene compound that overlaps with the first graphene compound, at least partially or completely enclosing it. This is an all-solid-state battery that has a third solid electrolyte particle between the components.

[0031] Furthermore, the configuration of another invention includes a plurality of positive electrode active material particles containing carrier ions and a plurality of first solids Multiple groups of body electrolyte particles, each encased in a first graphene compound, are adjacent to each other, forming multiple negative electrode activity The material particles and multiple second solid electrolyte particles are encased in a second graphene compound, and the first graph The whole has a third solid electrolyte particle between the group of graphene compounds and the second graphene compound which overlaps. It is a solid-state battery.

[0032] In each of the above configurations, the first, second, and third solid electrolyte particles have the same component. When using materials with specific components, the manufacturing cost can be reduced because common materials are used. Furthermore, the first, second, and third solid electrolyte particles may each be made of different materials. When this is done, use a material that is compatible with the positive electrode active material particles used for the first solid electrolyte particles. First, a material that is compatible with the negative electrode active material particles is used for the second solid electrolyte particles. "Compatible" means... This refers to the absence of unwanted by-products during charging and discharging by contact.

[0033] By using the above configuration, it is possible to prevent the generation of by-reactants (such as precipitates) at the negative electrode, and the microphone This can suppress the occurrence of short circuits.

[0034] All-solid-state batteries do not use flammable organic solvents inside the battery, which allows for the simplification of safety devices and manufacturing. It offers excellent cost-effectiveness and productivity.

[0035] Furthermore, by performing a reduction treatment on graphene oxide, graphene or graphene A compound is formed.

[0036] Graphene oxide contains epoxy groups, carbonyl groups, carboxyl groups, hydroxyl groups, etc. In polar solutions, the oxygen in the functional group of graphene oxide becomes negatively charged. Because it is electrically charged, different types of graphene oxide do not easily aggregate. For this reason, in polar liquids... In this configuration, graphene oxide is easily dispersed uniformly.

[0037] Furthermore, in each of the above configurations, the solid electrolyte particles are sulfide-based solid electrolytes or oxide-based solid electrolytes. Quality can be used.

[0038] Examples of sulfide-based solid electrolytes include Li2S-SiS2-Li3PO4 and Li2S -P2S5, Li2S-SiS2-Ga2S3, LiI-Li2S-P2S5, LiI- Li2S-B2S3, LiI-Li2S-SiS2, Li3PO4-Li2S-SiS2 Examples include lithium composite sulfide materials such as Li4SiO4-Li2S-SiS2.

[0039] Furthermore, oxide-based solid electrolytes include LiPON, Li2O, Li2CO3, and Li2M oO4, Li3PO4, Li3VO4, Li4SiO4, LLT(La 2 / 3-x Li3 x TiO3), LLZ(Li7La3Zr2O 12 ) and lithium composite oxides and oxidation Lithium materials are one example.

[0040] LLZ is a garnet-type oxide containing Li, La, and Zr, and Al, Ga, or It may also be a compound containing Ta.

[0041] Furthermore, polymer-based solid electrolytic materials such as PEO (polyethylene oxide) formed by coating methods, etc., are also used. A composite material may be used. Furthermore, a composite material containing the inorganic solid electrolyte and polymer solid electrolyte described above. A typical solid electrolyte may also be used.

[0042] In this specification, the surface layer of particles such as active materials refers to the region from the surface up to approximately 10 nm. This refers to the surface. Surfaces created by cracks or fissures can also be called the surface. Furthermore, the area deeper than the surface layer is also called the surface. , internally.

[0043] In this specification, etc., layered rock salt-type crystals of composite oxides containing lithium and transition metals The structure has a rock salt-type ionic arrangement in which cations and anions are arranged alternately, and transition metals Because lithium is arranged in a regular pattern to form a two-dimensional plane, two-dimensional diffusion of lithium is possible. This refers to a crystal structure. It may also have defects such as vacancies in cations or anions. Strictly speaking, a layered rock salt crystal structure is a structure in which the lattice of rock salt crystals is distorted. There is.

[0044] Furthermore, in this specification and elsewhere, a rock salt-type crystal structure is defined as a structure in which cations and anions are arranged alternately. This refers to a structure that is characterized by the presence of a cation or anion. A deficiency in either a cation or anion is also acceptable.

[0045] Furthermore, in this specification, etc., the pseudo-spinel type of composite oxide containing lithium and a transition metal The crystal structure of cobalt is space group R-3m, and although it is not a spinel-type crystal structure, it is cobalt Magnesium and other ions occupy the 6-coordinate position of oxygen, and the arrangement of cations is similar to that of a spinel. This refers to a crystal structure that possesses symmetry. Note that pseudo-spinel crystal structures are found in light elements such as lithium. The element may occupy the oxygen 4-coordinate position, and in this case as well, the ion arrangement is similar to that of the spinel type. It has symmetry.

[0046] Furthermore, the pseudo-spinel type crystal structure, although having Li randomly between layers, is a CdCl2 type. It can also be said that it is a crystal structure similar to the crystal structure. The crystal structure is when lithium nickelate is charged to a depth of charge of 0.94 (Li 0.06 Ni It has a crystal structure similar to that of O2, but is pure lithium cobaltate or a layered structure containing a large amount of cobalt. It is known that rock salt-type cathode active material particles do not usually adopt this crystal structure.

[0047] Layered rock salt crystals, and the anions of rock salt crystals, have a cubic close-packed structure (face-centered cubic lattice structure). ) takes this form. It is also presumed that pseudo-spinel crystals adopt a cubic close-packed structure for anions. When they come into contact, there exists a crystal plane in which the orientation of the cubic close-packed structure composed of anions is aligned. However, the space group of layered rock salt crystals and pseudo-spinel crystals is R-3m, and rock salt The space groups of type crystals are Fm-3m (the space group of a typical rock salt type crystal) and Fd-3m (the simplest). Because it is different from the space group of rock salt crystals that have symmetry, the crystal planes that satisfy the above conditions The Lars index differs between layered rock salt crystals, pseudo-spinel crystals, and rock salt crystals. In layered rock salt crystals, pseudo-spinel crystals, and rock salt crystals, anions When the orientations of the cubic close-packed structures that are formed are aligned, we say that the crystal orientations are roughly the same. There is.

[0048] The approximate agreement of the crystal orientation in the two regions can be seen in TEM (transmission electron microscope) images and STE (spherical spectroscopy) images. M (Scanning Transmission Electron Microscope) image, HAADF-STEM (High-angle scattering annular dark-field scanning transmission electron microscope) image. The determination should be made based on images from a microscope, ABF-STEM (annular bright-field scanning transmission electron microscope), etc. This can be done. X-ray diffraction (XRD), electron diffraction, neutron diffraction, etc. can also be used as criteria for judgment. Yes, it is possible. In TEM images, the arrangement of cations and anions can be observed as a repetition of bright and dark lines. It can be inferred. When the orientation of the cubic close-packed structure is aligned in layered rock salt crystals and rock salt crystals, the crystal In between, the angle between the repetition of bright and dark lines is 5 degrees or less, more preferably 2.5 degrees or less. The condition can be observed. Furthermore, light elements such as oxygen and fluorine are clearly visible in TEM images, etc. In some cases, it may not be possible to discern this, but in such cases, the alignment of the metal elements can be determined by their arrangement. ru.

[0049] Furthermore, in this specification, the theoretical capacity of the positive electrode active material refers to the insertion and removal capacity of the positive electrode active material. This refers to the amount of electricity that would be generated if all the lithium were to be desorbed. For example, the theoretical capacity of LiCoO2 is 27 The theoretical capacity of LiNiO2 is 274mAh / g, and the theoretical capacity of LiMn2O4 is 4mAh / g. The capacity is 148mAh / g.

[0050] Furthermore, in this specification, etc., the charging depth when all insertable and removable lithium is inserted. The degree is 0, and the charge depth when all the insertable and detachable lithium in the positive electrode active material has been detached is 1. Let's assume that's the case.

[0051] Furthermore, in this specification, charging means moving lithium ions from the positive electrode to the negative electrode within the battery. This refers to the movement of electrons, specifically from the negative electrode to the positive electrode in an external circuit. Therefore, the process of releasing lithium ions is called charging. Also, the charging depth is 0.7 or higher. Positive electrode active materials with a voltage of 0.9 or less are sometimes referred to as positive electrode active materials charged with high voltage.

[0052] Similarly, discharge is the movement of lithium ions from the negative electrode to the positive electrode within a battery, and externally... This refers to the movement of electrons from the positive electrode to the negative electrode in a circuit. The positive electrode active material is lithium. The insertion of ions is called discharge. Also, the positive electrode active material has a charge depth of 0.06 or less, The positive electrode active material, which has been discharged to more than 90% of its charge capacity from a state of being charged at high voltage, This refers to the positive electrode active material that has been discharged for a certain amount of time. [Effects of the Invention]

[0053] By using a graphene compound to encase and fix negative electrode active material particles or positive electrode active material particles. This relieves stress caused by expansion or contraction of the negative electrode active material particles or positive electrode active material particles. Therefore, the negative electrode active material particles or positive electrode active material particles expand or during charging or discharging. This can prevent deterioration of properties due to shrinkage. [Brief explanation of the drawing]

[0054] [Figure 1] Figure 1 is an example of a schematic cross-sectional view of a secondary battery showing one aspect of the present invention. [Figure 2] Figure 2 shows an example of a negative electrode illustrating one aspect of the present invention. [Figure 3] Figure 3 shows an example of a negative electrode illustrating one aspect of the present invention. [Figure 4] Figure 4 shows an example of a negative electrode illustrating one aspect of the present invention. [Figure 5] Figure 5A is a perspective view of an all-solid-state battery, and Figure 5B is a cross-sectional view thereof. [Figure 6] Figures 6A, 6B, 6C, and 6D are perspective views of an all-solid-state battery. [Figure 7] Figures 7A and 7B show perspective views of an all-solid-state battery. [Figure 8] Figures 8A, 8B, and 8C show examples of vehicles. [Figure 9] Figures 9A, 9B, 9C, 9D, and 9E are perspective views showing examples of electronic devices. [Figure 10] Figure 10 is a perspective view showing an example of an energy storage device. [Figure 11] Figure 11 illustrates an example of a method for preparing a positive electrode active material. [Modes for carrying out the invention]

[0055] The embodiments of the present invention will be described in detail below with reference to the drawings. However, the present invention is... Not limited to the following description, the form and details can be modified in various ways, as any person skilled in the art would know. This is easily understood. Furthermore, the present invention shall be interpreted as being limited to the contents of the embodiments described below. It's not something that can be done.

[0056] (Embodiment 1) In this embodiment, the positive electrode, the oxide solid electrolyte, the negative electrode, and the surface of the negative electrode are subjected to reduction The processed graphene oxide is attached and fixed to suppress expansion and contraction due to charging and discharging, and also to facilitate ion transfer. This document presents an example of fabricating an all-solid-state secondary battery with improved conductivity.

[0057] Figure 1 shows a conceptual diagram of the cross-sectional structure of a solid-state battery.

[0058] Multiple solid electrolyte particles 105 are present between the positive electrode current collector 111 and the negative electrode current collector 110. The positive electrode current collector and negative electrode current collector can be made from known metal materials that can be used in all-solid-state batteries. Possible, Cu, Ni, Al, V, Au, Pt, Mg, Fe, Ti, Cr, Zn, Ge, In The current collector shall include one or more types selected from the following.

[0059] Solid-state batteries include thin-film all-solid-state batteries and bulk all-solid-state batteries. Thin-film all-solid-state batteries are thin-film batteries. This is an all-solid-state battery obtained by stacking particles, and bulk-type all-solid-state batteries are obtained by stacking fine particles. This is an all-solid-state battery obtained by [the following process]. Figure 1 shows an example of a bulk-type all-solid-state battery. .

[0060] As shown in Figure 1, positive electrode active material particles 104 are located near the positive electrode current collector 111, and the negative electrode current collector The negative electrode active material particles 103 are located near 110, and solid electrolyte particles fill the gaps between them. Child 105 is positioned.

[0061] The negative electrode active material particles undergo charge-discharge reactions through alloying and dealloying reactions with lithium. Elements that can be used include silicon, tin, gallium, and aluminum. Germanium, lead, antimony, bismuth, silver, zinc, cadmium, indium, etc. Materials containing at least one of these elements can be used. Such elements have a capacity compared to carbon. The capacity is large, and silicon in particular has a high theoretical capacity of 4200 mAh / g. Therefore, negative electrode active material It is preferable to use silicon for the particles. Alternatively, compounds containing these elements can also be used. Good. For example, SiO, Mg2Si, Mg2Ge, SnO, SnO2, Mg2Sn, Sn S2, V2Sn3, FeSn2, CoSn2, Ni3Sn2, Cu6Sn5, Ag3Sn ,Ag3Sb,Ni2MnSb,CeSb3,LaSn3,La3Co2Sn7,CoS Examples include b3, InSb, and SbSn. Here, alloying and dealloying reactions with lithium occur. Elements capable of undergoing charge-discharge reactions, and compounds containing such elements, are called alloy materials. There are cases where this is the case.

[0062] In this specification, SiO refers to silicon monoxide, for example. Alternatively, SiO refers to Si O x It can also be expressed as follows. Here, it is preferable that x has one neighboring value. For example, x is A value of 0.2 to 1.5 is preferred, and a value of 0.3 to 1.2 is more preferred.

[0063] Furthermore, titanium dioxide (TiO2) and lithium titanium oxide (L) are used as negative electrode active material particles. i4Ti5O 12 ), lithium-graphite intercalation compound (Li x C6), niobium pentoxide (Nb2 Oxides such as O5, tungsten oxide (WO2), and molybdenum oxide (MoO2) are used. It is possible.

[0064] Furthermore, the first graphite is placed so as to surround the negative electrode current collector 110 and the multiple negative electrode active material particles 103. A first graphene compound 101 is provided. The negative electrode active material particles are provided using the first graphene compound 101. The first graphite is fixed to the negative electrode current collector 110. The negative electrode active material particles or a plurality of negative electrode active material particles are bound or fixed using compound 101. This inhibits the generation of by-reactants (such as precipitates) and suppresses the occurrence of micro-shorts. It is possible.

[0065] Furthermore, the first graphene compound 101 together with multiple negative electrode active material particles 103 forms multiple solids It also encases body electrolyte particles.

[0066] In Figure 1, multiple solid electrolyte particles 105 are placed between the positive electrode current collector 111 and the negative electrode current collector 110. A layer is provided consisting of solid electrolyte particles 105 and a first graphene compound 101. This example shows a case where the same components as the enclosed solid electrolyte particles are used.

[0067] Furthermore, a configuration including at least a positive electrode current collector 111 and positive electrode active material particles 104 is considered a positive electrode. It functions and has a configuration in which this positive electrode is surrounded by a second graphene compound 102.

[0068] Furthermore, in Figure 1, the solid electrolyte particle 105 is encased in a second graphene compound 102. This shows an example using a material having the same components as solid electrolyte particles. First graphene. The spacing between compound 101 and the second graphene compound 102 is the material for the solid electrolyte particles 105. Depending on the circumstances, the thickness should be between 0.1 μm and 1 mm, preferably between 1 μm and 100 μm.

[0069] The first graphene compound 101 contains solid electrolyte particles, negative electrode active material particles 103, and a negative electrode current collector. Figure 2 shows a schematic cross-sectional view of the wrapped 110. After obtaining the state shown in Figure 2, firing and pressing processes are carried out. You may apply this.

[0070] After arranging the negative electrode active material particles 103 and solid electrolyte particles on the negative electrode current collector 110, Reduced acid surrounds the current collector 110, solid electrolyte particles, and negative electrode active material particles 103. Attach graphene oxide (RGO).

[0071] The compound obtained by reducing graphene oxide is called "RGO (Reduced Graphene) It is sometimes called "graphene oxide." Note that RGO contains graphene oxide. Not all of the oxygen was eliminated; some oxygen or oxygen-containing atoms remained bonded to the carbon. In some cases, RGO may exist. For example, RGO may contain epoxy groups, carboxyl groups, or other carbonyl groups. Alternatively, it may have functional groups such as hydroxyl groups. In this specification, graphene compounds are defined as follows: It may contain a graphene precursor. A graphene precursor is a substance used to produce graphene. This refers to the substance used, and graphene precursors include, for example, the aforementioned graphene oxide, It may also contain graphite oxide, etc. Furthermore, it may contain alkali metals such as graphene and oxygen. Graphene containing elements other than carbon, such as those mentioned above, is sometimes referred to as a graphene analog. In books and other publications, graphene compounds also include graphene analogs. It includes graphene quantum dots.

[0072] Then, the second graphene compound 102 forms the solid electrolyte particles, the positive electrode active material particles 104, and the positive electrode. After wrapping the current collector 111, the first graphene compound 101 and the second graphene compound 1 Solid-state batteries are fabricated by layering multiple solid electrolyte particles 105 between layers 02. Therefore, the timing of adding the solid electrolyte particles during manufacturing differs for each type. Depending on the manufacturing process, the same material may be used for the negative electrode active material, positive electrode active material, and solid electrolyte particles. Even if they are present, some may undergo alteration. In Figure 1, each solid electrolyte particle is shown as identical. ru.

[0073] In reality, a gap is created between the positive electrode current collector 111 and the negative electrode current collector 110 by pressurization. Multiple types of particles may be used to fill the container so that it is completely consumed.

[0074] At this stage, the laminate shown in Figure 1 is obtained. To bond them together, the laminate is subjected to heat treatment and plywood. A reduction process is performed to improve density. Heating may also be performed simultaneously during the pressing process.

[0075] Furthermore, the resulting laminate is housed in an outer casing such as a laminate film or a metal can. This allows for the fabrication of all-solid-state batteries.

[0076] (Embodiment 2) In this embodiment, an example that differs in some respects from Embodiment 1 will be described below with reference to Figure 3.

[0077] Figure 3 shows an example in which the current collector is constructed without being encased in a graphene compound. The first graphene compound 101 surrounds the decomposed particles and the negative electrode active material particles 103. This is an example of that.

[0078] By stacking it with the positive electrode shown in Embodiment 1, an all-solid-state battery can be manufactured. Cut.

[0079] Furthermore, after constructing the positive electrode without enclosing the positive electrode current collector with the second graphene compound 102, Figure 2 A solid-state battery may be fabricated by stacking it with the negative electrode.

[0080] This embodiment can be freely combined with Embodiment 1.

[0081] (Embodiment 3) In this embodiment, an example that differs in some respects from Embodiment 1 will be described below with reference to Figure 4.

[0082] Figure 4 shows multiple groups encased in the first graphene, specifically solid electrolyte particles and This shows a configuration in which negative electrode active material particles 103 are encapsulated in the first graphene compound 101. (Figure 4) This shows seven groups. Furthermore, solid electrolyte particles are placed in the gaps between them. ru.

[0083] By stacking the negative electrode shown in Figure 4 with the positive electrode shown in Embodiment 1, an all-solid-state battery can be formed. It is possible to produce this.

[0084] Furthermore, similar to the negative electrode shown in Figure 4, the second graphene compound 102 constitutes multiple groups. After forming the positive electrode, it may be stacked with the negative electrode shown in Figure 4 to create an all-solid-state battery.

[0085] Furthermore, after constructing the positive electrode without enclosing the positive electrode current collector with the second graphene compound 102, Figure 4 A solid-state battery may be fabricated by stacking it with the negative electrode.

[0086] This embodiment can be freely combined with Embodiment 1 or Embodiment 2.

[0087] For example, the positive electrode using a graphene compound as shown in Figure 3, and the embodiment shown A solid-state battery may be fabricated by combining it with the negative electrode shown in Figure 4.

[0088] (Embodiment 4) This embodiment shows an example of a method for manufacturing a positive electrode.

[0089] An example of a method for preparing a positive electrode active material will be explained using Figure 11.

[0090] As shown in step S11 of Figure 11, first the fluorine source is used as the material for mixture 902. Prepare lithium fluoride and magnesium fluoride, which is a source of magnesium. Lithium fluoride has a relatively low melting point of 848°C and melts easily in the annealing process described later. Therefore, it is preferable. Lithium fluoride can be used as both a lithium source and a fluorine source. Furthermore, magnesium fluoride can be used as both a fluorine source and a magnesium source. Cut.

[0091] In this embodiment, lithium fluoride (LiF) is prepared as the fluorine source and lithium source. Magnesium fluoride (MgF2) will be prepared as the fluorine source and magnesium source. (Step S11 in Figure 11). Lithium fluoride (LiF) and magnesium fluoride (MgF2) The ratio is preferably LiF:MgF2=x:1 (0≦x≦1.9), and LiF: MgF2=x:1 (0.1≦x≦0.5) is more preferable, and LiF:MgF2=x:1( A more preferable scenario is when x = 0.33 (neighborhood).

[0092] Furthermore, if the following mixing and grinding steps are to be performed wet, a solvent will be prepared. The solvent will be A Ketones such as cetone, alcohols such as ethanol and isopropanol, ethers, and dio Xane, acetonitrile, N-methyl-2-pyrrolidone (NMP), etc. can be used. It is more preferable to use an aprotic solvent that does not react easily with lithium. In this embodiment, acetone is used (see step S11 in Figure 11).

[0093] Next, the materials of the above mixture 902 are mixed and ground (step S12 in Figure 11). Mixing can be done dry or wet, but wet mixing allows for finer grinding. It is preferable. For mixing, for example, a ball mill, bead mill, etc. can be used. When using a medium, it is preferable to use, for example, zirconia balls. It is preferable to thoroughly perform the mixing and grinding steps to finely pulverize the mixture 902.

[0094] The mixed and ground materials described above are collected (step S13 in Figure 11) to obtain mixture 902. (Step S14 in Figure 11).

[0095] The mixture 902 preferably has a D50 of 600 nm or more and 20 μm or less, It is more preferable that the particle size is between 1 μm and 10 μm. The mixture 90 is thus finely powdered. If 2, then when mixed with a composite oxide containing lithium, a transition metal, and oxygen in a later step... This makes it easier to uniformly adhere mixture 902 to the surface of the composite oxide particles. If the mixture 902 is uniformly attached to the surface, after heating, leakage will occur to the surface layer of the composite oxide particles. It is preferable because it is easy to distribute halogens and magnesium in the surface layer. If there is a region that does not contain magnesium, the aforementioned pseudo-spinel type crystal will form in the charged state. It may be difficult to form a structure.

[0096] Next, prepare the lithium source as shown in step S25. A composite oxide containing pre-synthesized lithium, transition metal, and oxygen is used.

[0097] For example, as pre-synthesized lithium cobalt oxide, manufactured by Nippon Chemical Industrial Co., Ltd. Lithium cobalt oxide particles (product name: Cellseed C-10N) can be used. The average particle size (D50) is approximately 12 μm, and by glow discharge mass spectrometry (GD-MS)... In the impurity analysis, the magnesium concentration and fluorine concentration were 50 ppm wt or less. Calcium, aluminum, and silicon concentrations are 100 ppm wt or less, nickel Sulfur concentration is 150 ppm wt or less, sulfur concentration is 500 ppm wt or less, arsenic concentration is 11 00 ppm wt or less, and the concentration of other elements other than lithium, cobalt, and oxygen is 150 This is lithium cobalt oxide with a concentration of less than ppm wt.

[0098] The composite oxide having lithium, transition metal, and oxygen in step S25 has defects and strain. It is preferable to have a layered rock salt type crystal structure with few impurities. It is preferable that it be a composite oxide. A composite oxide having lithium, a transition metal and oxygen is preferable. A high concentration of pure substances increases the likelihood of a crystal structure with many defects or distortions.

[0099] Next, the mixture 902 is mixed with a composite oxide having lithium, a transition metal, and oxygen. (Step S31 in Figure 11) in a composite oxide having lithium, a transition metal, and oxygen. The number of atoms TM of the transition metal and the number of atoms MgMix1 of magnesium in mixture 902 The ratio of TM:MgMix1 is preferably 1:y (0.005 ≤ y ≤ 0.05). It is preferable that TM:MgMix1=1:y(0.007≦y≦0.04). Furthermore, a ratio of approximately TM:MgMix1 = 1:0.02 is even more preferable.

[0100] The mixing in step S31 is performed in order to avoid destroying the composite oxide particles, as is the case with the mixing in step S12. It is preferable to use milder conditions. For example, a higher rotational speed than the mixing in step S12. It is preferable to have conditions with less or shorter duration. Also, dry processing is gentler than wet processing. It can be said that these are favorable conditions. For mixing, for example, a ball mill or bead mill can be used. To do so. When using a ball mill, for example, zirconia balls can be used as the media. It is preferable.

[0101] The materials mixed above are collected (step S32 in Figure 11) to obtain mixture 903 (Figure 1 Step 1 (S33).

[0102] Next, the mixture 903 is heated. This step is annealed to distinguish it from the previous heating step. Alternatively, it may involve a second heating process.

[0103] Annealing is preferably carried out at an appropriate temperature and time. The particle size of the composite oxide having lithium, transition metal and oxygen in step S25 It varies depending on conditions such as composition. If the particles are small, a lower temperature or Shorter durations may be preferable in some cases.

[0104] For example, if the average particle size (D50) of the particles in step S25 is about 12 μm, annealing The temperature is preferably between 600°C and 950°C. The annealing time is, for example, 3 hours or more. Preferably, 10 hours or more is preferred, more preferably 60 hours or more.

[0105] On the other hand, if the average particle size (D50) of the particles in step S25 is about 5 μm, the annealing temperature The temperature is preferably between 600°C and 950°C. The annealing time is, for example, between 1 hour and 10 hours. Less than 1 hour is preferable, and around 2 hours is more preferable.

[0106] The cooling time after annealing is preferably, for example, 10 hours or more and 50 hours or less.

[0107] When mixture 903 is annealed, the material with the lowest melting point in the mixture (e.g., lithium fluoride) is annealed first. It is thought that um (melting point 848°C) melts and is distributed on the surface layer of the composite oxide particles. The presence of this molten material causes a decrease in the melting point of other materials, and when other materials melt, It is measured. For example, when magnesium fluoride (melting point 1263°C) melts, the composite oxide particles It is thought to be distributed in the surface layer.

[0108] The elemental diffusion of this mixture 903 is more pronounced in the surface and within the composite oxide particles than within them. The reaction is faster near grain boundaries. Therefore, magnesium and halogens are concentrated in the surface layer and near grain boundaries. As described later, the magnesium concentration in the surface layer and near the grain boundaries is higher than in the interior. When the value is high, changes in the crystal structure can be suppressed more effectively.

[0109] The annealed material is recovered (step S35 in Figure 11) to obtain mixture 904. Step S36 in Figure 11).

[0110] Next, as shown in step S50, the mixture 904 and the pulverized nickel hydroxide are mixed. Then, the mixed material is recovered (step S51). The pulverized nickel hydroxide is Step S15 involves mixing nickel hydroxide and acetone beforehand, and Step S16 involves recovering the mixture. Let's do it. Step S16 yields finely powdered nickel hydroxide (step S17).

[0111] The materials mixed in step S50 are collected in step S51 to obtain mixture 905 (Figure 11). Step S52).

[0112] Next, in steps S53 to S55, metal Z is added to the positive electrode active material. The addition of metal Z can be done using, for example, liquid-phase methods such as the sol-gel method, solid-phase methods, and sputtering. Methods such as vapor deposition, CVD (chemical vapor deposition), and PLD (pulsed laser deposition) The method can be applied.

[0113] As shown in Figure 11, first in step S52, the metal source is prepared. When applying the sol-gel method, prepare the solvent used in the sol-gel method. As a metal source, use a metal a Lucooxides, metal hydroxides, metal oxides, etc. can be used. Metal Z is aluminum. In the case of M, for example, the number of cobalt atoms in lithium cobalt oxide is set to 1, and the metal source is The concentration of aluminum present should be between 0.001 and 0.02 times. In the case of the metal, for example, the number of cobalt atoms in lithium cobalt oxide is set to 1. The nickel concentration in the source should be between 0.001 and 0.02 times. In the case of luminium and nickel, for example, the raw cobalt contained in lithium cobalt oxide Assuming the number of particles is 1, the concentration of aluminum in the metal source is between 0.001 times and 0.02 times. Furthermore, the nickel concentration in the metal source should be between 0.001 times and 0.02 times.

[0114] Here, as an example, the sol-gel method is applied, and aluminum isopropoxy is used as the metal source. The following example shows the use of isopropanol as the solvent.

[0115] Next, the aluminum alkoxide is dissolved in alcohol, and then lithium cobaltate is added. The particles are mixed (step S53 in Figure 11).

[0116] The required amount of metal alkoxide varies depending on the particle size of lithium cobalt oxide. For example, When using luminium isopropoxide, the particle size (D50) of lithium cobaltate is 20 For particles of approximately μm size, the number of cobalt atoms in lithium cobalt oxide is considered to be 1, and aluminum The aluminum concentration in the isopropoxide is between 0.001 times and 0.02 times. It is preferable to add it.

[0117] Next, a mixture of an alcoholic solution of metal alkoxide and lithium cobalt oxide particles is added to water. Stir in a steam-containing atmosphere. Stirring can be done, for example, with a magnetic stirrer. The stirring time is necessary to allow the water in the atmosphere and the metal alkoxide to undergo hydrolysis and polycondensation reactions. Any sufficient amount of time is fine, for example, 4 hours at 25°C and 90% RH humidity (Relative It can be performed under conditions of humidity (relative humidity). Also, humidity control, In an atmosphere where temperature control is not available, for example, in the atmospheric environment inside a fume hood You may then stir the mixture. In such cases, it is preferable to increase the stirring time. For example, you could leave it at room temperature for 12 hours or more.

[0118] By reacting water vapor in the atmosphere with metal alkoxides, it is possible to achieve a higher rate than when adding liquid water. This also allows the sol-gel reaction to proceed slowly. Furthermore, metal alkoxides and water can be reacted at room temperature. By doing so, for example, when heating at a temperature exceeding the boiling point of the solvent alcohol, The sol-gel reaction can be carried out slowly. This allows for the formation of a high-quality coating layer with uniform thickness.

[0119] After the above processing is complete, the precipitate is recovered from the mixture (step S54 in Figure 11). Recovery Methods such as filtration, centrifugation, and evaporation to dryness can be applied. The precipitate is metallic aluminum. The cooxide can be washed with the same alcohol used to dissolve it. When applicable, separation of the solvent and precipitate is not required in this step, for example. For example, the precipitate can be recovered in the next step (step S54), the drying process.

[0120] Next, the recovered residue is dried to obtain a mixture (step S54 in Figure 11). For example, it can be vacuum-dried or air-dried at 80°C for more than 1 hour but less than 4 hours.

[0121] Next, the resulting mixture is heated (step S55 in Figure 11).

[0122] The heating time should preferably be set so that the holding time within the heating temperature range is between 1 hour and 80 hours. It seems so.

[0123] The heating temperature should be less than 1000°C, preferably between 700°C and 950°C. A temperature of around 850°C is even more preferable.

[0124] Furthermore, heating is preferably carried out in an oxygen-containing atmosphere.

[0125] In this embodiment, the heating temperature is set to 850°C and maintained for 2 hours, and the temperature rise is 200 The temperature is set to °C / h, and the oxygen flow rate is 10 L / min.

[0126] The heating temperature in step S55 is lower than the heating temperature in step S34. preferable.

[0127] <Step S56, Step S57> Next, the cooled particles are collected (step S56 in Figure 11). Furthermore, the particles are sieved. It is preferable to apply it to the above process. In the above process, the mixture 906 that can be used as a positive electrode active material is It can be manufactured (step S57 in Figure 11).

[0128] Mixtures 902, 903, 904, 905, and 906 obtained in the above manufacturing process are all It can be used as a positive electrode active material.

[0129] Mixture 902 is a positive electrode active material having lithium, magnesium, and fluorine components. The materials, mixtures 903 and 904, consist of lithium, cobalt, and magnesium components. It is a positive electrode active material having a fluorine component.

[0130] Furthermore, mixture 905 contains lithium, cobalt, magnesium, and nickel components. The positive electrode active material material has a lithium component and a fluorine component, and the mixture 906 has a lithium component and a fluorine component. It contains nitrite, magnesium, nickel, aluminum, and fluorine components. It is a positive electrode active material.

[0131] A slurry was prepared by dispersing graphene oxide in a solvent, and mixtures 902, 903, and 904 were prepared. Multiple positive electrode active material particles, prepared using either 905 or 906, are placed on the positive electrode current collector. The particles are placed in a designated area, and a slurry is applied to cover multiple positive electrode active material particles, then allowed to dry. By performing a reduction treatment, graphene can be attached to the surface of the positive electrode active material.

[0132] This embodiment can be freely combined with other embodiments.

[0133] For example, a solid-state battery can be manufactured by combining it with Embodiment 1.

[0134] (Embodiment 5) Figure 1 shown in Embodiment 1 is a diagram illustrating the conceptual cross-sectional structure of a solid-state battery, and shows the positive electrode current collector 1 Solid electrolyte particles 105 are present between 11 and the negative electrode current collector 110. For wrapping item 101, one of the methods shown in Figures 2, 3, or 4 can be selected.

[0135] Furthermore, it is preferable to use a package with excellent airtightness as the sealing container for all-solid-state batteries. Furthermore, ceramic or resin packages are used. Also, when sealing, outside air is removed. It is preferable to perform the procedure in a sealed, isolated atmosphere, for example, inside a glove compartment.

[0136] Figure 5A shows an all-solid-state secondary battery having external electrodes 71 and 72 and sealed with a package material. A perspective view is shown. Such all-solid-state rechargeable batteries can be directly mounted on circuit boards, etc. Cut.

[0137] Furthermore, an example of a cross-section cut along the dotted line in Figure 5A is shown in Figure 5B. The lamination consists of a flat plate with an electrode layer 73 A package member 70a provided with a, a frame-shaped package member 70b, and an electrode layer on a flat plate. The package component 70c, which has 73b provided, is enclosed and sealed by the structure. The package components 70a, 70b, and 70c use insulating materials, such as resin materials or ceramics. It is possible to be there.

[0138] The external electrode 71 is electrically connected to the positive electrode layer 50a via the electrode layer 73a, and acts as a positive electrode. It is possible. Furthermore, the external electrode 72 is electrically connected to the negative electrode layer 50c via the electrode layer 73b. It functions as a negative electrode.

[0139] Figure 5B shows an example where a stack of positive electrode layer 50a, solid electrolyte layer 50b, and negative electrode layer 50c is considered as one set. As shown, multiple sets can be stacked on top of each other.

[0140] Furthermore, Figure 6A shows an example of a laminate-type secondary battery, which differs from the packaging method shown in Figure 5A. This is shown in Figures 6B, 6C, and 6D.

[0141] Figure 6A shows the external view of the positive electrode 503 and the negative electrode 506. The positive electrode 503 has a positive electrode current collector 501. Furthermore, the positive electrode active material layer 502 is formed on the surface of the positive electrode current collector 501. Also, the positive electrode 503 The positive electrode current collector 501 has a region in which part is exposed (hereinafter referred to as the tab region). The negative electrode current collector 504 is formed on the surface of the negative electrode current collector 504. Furthermore, the negative electrode 506 has a region where the negative electrode current collector 504 is partially exposed, i.e., a tab region. The area and shape of the tab regions of the positive and negative electrodes are not limited to the example shown in Figure 6A.

[0142] First, the negative electrode 506, the solid electrolyte layer 507, and the positive electrode 503 are stacked. Figure 6B shows the stacked layers. The negative electrode 506, solid electrolyte layer 507, and positive electrode 503 are shown. Here, there are 5 sets of negative electrodes and 4 sets of positive electrodes. An example of how to use them together is shown. Next, the joining of the tab regions of the positive electrode 503 and the tab region of the outermost positive electrode. The positive lead electrode 510 is joined to the region. For joining, ultrasonic welding or the like can be used. Similarly, the bonding of the tab regions of the negative electrode 506 and the negative electrode lead to the tab region of the outermost negative electrode. The electrode 511 is joined.

[0143] Next, the negative electrode 506, the solid electrolyte layer 507, and the positive electrode 503 are placed on the outer casing 509. The electrolyte layer 507 is a material layer containing solid components that can conduct lithium ions (ceramic Any material (such as buck) will suffice. For example, the solid electrolyte layer 507 may be ceramic powder or glass powder. The end is slurryed and formed into a sheet. The definition of ceramic is that of an oxide, regardless of whether it is metallic or nonmetallic. It is a material made of inorganic compounds such as ions, carbides, nitrides, and borides. Glass is amorphous. It is defined as a material that exhibits a glass transition phenomenon, but when it is microcrystalline, it becomes ceramic glass. It is sometimes called [a specific term]. Because ceramic glass is crystalline, it is confirmed by X-ray diffraction. This is possible. As the solid electrolyte, oxide solid electrolytes, sulfide solid electrolytes, etc., can be used. This can be done. In addition, the positive electrode active material layer 502 and the negative electrode active material layer 505 also contain a solid electrolyte. Furthermore, a conductive additive may be included. Any conductive additive can be a material that has electronic conductivity. For example, carbon materials, metallic materials, etc., can be used.

[0144] Furthermore, the oxide solid electrolytes used as positive electrode active material particles include Li3PO4 and Li 3BO3, Li4SiO4, Li4GeO4, LiNbO3, LiVO2, LiTiO3 LiZrO3 and the like can be used. Furthermore, a composite compound of these may also be used. For example, Li3BO3-Li4SiO4 can be cited. Also, the table of solid electrolytes The surface may be at least partially covered with a coating layer of 1 nm or more and 20 nm or less, and the coating layer uses a Li-ion conductive oxide as the material.

[0145] Examples of the oxide solid electrolyte used as the negative electrode active material particles include Nb2O5, Li4Ti5 O 12 , SiO, etc. In this specification, etc., SiO refers to, for example, monosilicon. Alternatively, SiO refers to a material with a higher silicon composition compared to SiO2 and can also be represented as SiO x . Here, x preferably has a value near 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.

[0146] Examples of the sulfide solid electrolyte used as the positive electrode active material particles include materials containing Li and S, specifically, Li7P3S , Li2S - SiS2, Li2S - P2S5, etc. 11 can be listed.

[0147] Next, as shown in FIG. 6C, the exterior body 509 is bent at the portion indicated by the dashed line. Then, the outer peripheral portion of the exterior body 509 is joined. The exterior body 509 is a laminated film obtained by laminating a metal foil and an organic resin film. For example, an aluminum foil or a stainless steel foil is used, and for joining, for example, thermocompression bonding or the like may be used. In this way, the laminated secondary battery 500 shown in FIG. 6D can be manufactured. Also, here, an example of joining using a single laminated film has been shown, but a configuration in which two laminated films are overlapped and the peripheral portions are adhered and sealed may also be used.

[0148] A plurality of laminated secondary batteries 500 are used as one battery module for an electric vehicle, etc. It can be mounted anywhere.

[0149] Figure 7A shows three laminated rechargeable batteries 500 arranged on a first plate 521 and a second plate. This is a perspective view showing how it is sandwiched and fixed between the parts of T524. As shown in Figure 7B, the fixing device 5 Using 25a and fixing device 525b, the first plate 521 and the second plate 524 By fixing the distance between them, three 500 rechargeable batteries can be pressurized.

[0150] Figures 7A and 7B show an example using three laminate-type secondary batteries 500, but It is not limited to this; you can also use four or more 500 rechargeable batteries, and if you use ten or more, It can be used as a power source for small vehicles, and if more than 100 are used, it can be used as a large-scale power source for vehicles. It can also be used in this way. Furthermore, it includes protection circuits to prevent overcharging and monitors temperature rise. A temperature sensor may be provided on the laminated secondary battery 500. The shape of the secondary battery is They are not limited to laminated types; there are also coin-shaped, cylindrical, and rectangular types.

[0151] In all-solid-state batteries, by applying a predetermined pressure in the stacking direction of the stacked positive and negative electrodes, internal pressure is applied. The contact state of the interface in the part can be kept good. A predetermined pressure is applied in the stacking direction of the positive and negative electrodes. By applying force, it is possible to suppress the expansion in the stacking direction caused by charging and discharging of all-solid-state batteries. This can improve the reliability of all-solid-state batteries.

[0152] (Embodiment 6) This embodiment shows an example in which a vehicle is equipped with an all-solid-state secondary battery, which is one aspect of the present invention. Examples of both include automobiles, motorcycles, and bicycles.

[0153] When all-solid-state batteries are installed in vehicles, hybrid electric vehicles (HEVs) and electric vehicles (EVs) will be used. or next-generation clean energy vehicles such as plug-in hybrid vehicles (PHEVs) It can be expressed.

[0154] Figure 8 illustrates a vehicle using an all-solid-state secondary battery, which is one embodiment of the present invention. Figure 8A The automobile 8400 shown is an electric vehicle that uses an electric motor as a power source for driving. Yes. Alternatively, an electric motor and an engine can be appropriately selected and used as the power source for propulsion. It is a hybrid vehicle capable of doing so. Vehicle 8400 has an all-solid-state secondary battery 8404. It has an energy storage system. The all-solid-state secondary battery 8404 drives the electric motor 8406. In addition, it also powers light-emitting devices such as headlights 8401 and interior lights (not shown). It can supply power. Also, if the all-solid-state secondary battery 8404 malfunctions, the power supply will stop. To prevent the hazard lights from turning off, the vehicle has a separate, independent system for the drive system. It is preferable to provide a secondary battery.

[0155] Furthermore, the all-solid-state secondary battery 8404 is used in the speedometer and tachometer of the automobile 8400. It can supply power to display devices such as monitors. Furthermore, the all-solid-state secondary battery 8404 is It can supply power to the navigation system and other components of the 8400 automobile.

[0156] The automobile 8500 shown in Figure 8B plugs into the all-solid-state secondary battery that the automobile 8500 has. It can be charged by receiving power from an external charging facility using methods such as contactless power supply. Figure 8B shows the all-solid-state charging system installed on the vehicle 8500, powered by a ground-mounted charging device 8021. It shows the state where the secondary battery 8024 is being charged via the cable 8022. When charging is carried out, the charging method, connector specifications, etc. may be appropriately performed according to a predetermined method such as CHAdeMO (registered trademark) or Combo. The charging device 8021 may be a charging station provided in a commercial facility or may also be a household power source. For example, by plug-in technology, the all-solid-state secondary battery 8024 mounted in the vehicle 8500 can be charged by external power supply. Charging can be performed by converting AC power into DC power via a conversion device such as an AC-DC converter . As the all-solid-state secondary battery 8024, the all-solid-state secondary battery shown in Embodiment 2 is used .

[0157] Also, although not shown in the figure, a power receiving device can be mounted on the vehicle, and power can be supplied and charged to the vehicle non-contact from a power transmission device on the ground . In the case of this non-contact power supply method, by incorporating the power transmission device into a road or an outer wall, charging can be performed not only while the vehicle is parked but also while it is running . Also, using this non-contact power supply method, power can be transmitted and received between vehicles . Furthermore, a solar cell can be provided on the exterior of the vehicle, and the all-solid-state secondary battery can be charged when the vehicle is parked or running . For such non-contact power supply, an electromagnetic induction method or a magnetic field resonance method can be used .

[0158] Also, FIG. 8C is an example of a two-wheeled vehicle using an all-solid-state secondary battery according to an aspect of the present invention. The scooter 8600 shown in FIG. 8 C includes an all-solid-state secondary battery 8602, a side mirror 8601, and a direction indicator lamp 8603 . The all-solid-state secondary battery 8602 can supply electricity to the direction indicator lamp 8603 .[[ID=B]]

[0159] ​Furthermore, the scooter 8600 shown in Figure 8C has a solid-state secondary battery 86 in the under-seat storage compartment 8604. It can store 02. The all-solid-state secondary battery 8602 is small and the under-seat storage 8604 is Even if there are some, they can be stored in the under-seat storage compartment 8604.

[0160] This embodiment can be appropriately combined with descriptions of other embodiments.

[0161] (Embodiment 7) In this embodiment, using Figures 9 and 10, the solid battery described in the previous embodiment is used to power This section explains an example of implementation in a child device.

[0162] First, using Figures 9A to 9C, we will demonstrate how a solid-state battery, which is one embodiment of the present invention, is mounted in a small electronic device. Let me explain an example.

[0163] Figure 9A shows an example of a mobile phone. The mobile phone 2100 is assembled into the housing 2101. In addition to the integrated display unit 2102, there are operation buttons 2103, an external connection port 2104, and a speaker. It is equipped with 2105, microphone 2106, etc. The mobile phone 2100 uses a solid battery 2 It has 107. The solid battery 2107 incorporates any of the embodiments 1 to 5 described above. These are solid-state batteries manufactured using a combination of methods, resulting in a highly reliable battery that suppresses the occurrence of micro-shorts. That is the case.

[0164] The 2100 mobile phone offers mobile phone calls, email, document viewing and creation, music playback, and internet connectivity. It can run various applications such as internet communication and computer games. .

[0165] The operation button 2103 is used for setting the time, as well as turning the power on and off, and turning wireless communication on and off. It has various functions such as operation, silent mode activation and deactivation, and power saving mode activation and deactivation. This can be done. For example, the operating system built into the mobile phone 2100 The system also allows you to freely configure the function of the operation button 2103.

[0166] Furthermore, the mobile phone 2100 is capable of performing standardized short-range wireless communication. For example, by communicating with a wireless headset, hands-free communication is possible. They can also talk.

[0167] Furthermore, the mobile phone 2100 is equipped with an external connection port 2104, and can connect to other information terminals. Data can be exchanged directly via this. Also, via external connection port 2104... It can also be charged wirelessly. Note that the charging operation is performed wirelessly without going through the external connection port 2104. It may also be done by electricity.

[0168] The mobile phone 2100 preferably has a sensor. For example, a fingerprint sensor. Human body sensors such as pulse sensors and body temperature sensors, as well as touch sensors, pressure sensors, and acceleration sensors. It is preferable that the following are installed:

[0169] Figure 9B is a perspective view of a device also known as a tobacco-containing smoking device (electronic cigarette). In this electronic cigarette 2200, a heating element 2201 and a power supply to the heating element 2201 are included. It has a solid battery 2204. When stick 2202 is inserted into it, stick 220 2 is heated by the heating element 2201. To enhance safety, overcharging and over-discharging of the solid battery A protective circuit to prevent electric shock may be electrically connected to the solid battery 2204. The solid battery shown in Figure 9B The battery 2204 has external terminals so that it can be connected to a charging device. The solid battery 2204 is Since this is the tip when held, it is desirable that the overall length be short and the weight be light. Because a solid-state battery according to one aspect of the present invention is highly safe, it can be used safely for long periods of time. We can offer the 2200, a small and lightweight e-cigarette that is suitable for various uses.

[0170] Figure 9C shows an unmanned aerial vehicle 2300 having multiple rotors 2302. 0 is a solid battery 2301, a camera 2303, and an antenna (not shown), which are all aspects of the present invention. It has (not). The unmanned aerial vehicle 2300 can be remotely controlled via an antenna. Because a solid-state battery according to one aspect of the invention is highly safe, it can be used safely for long periods of time. It is suitable as a solid-state battery to be mounted on the Unmanned Aerial Vehicle 2300.

[0171] Next, using Figures 9D and 9E, we will illustrate an example of mounting a solid-state battery, which is one aspect of the present invention, in a vehicle. I will explain.

[0172] Figure 9D shows an electric motorcycle 2400 using a solid-state battery according to one embodiment of the present invention. 00 represents a solid battery 2401, a display unit 2402, and a handle 2403, which are one aspect of the present invention. To provide: The solid-state battery 2401 can supply electricity to the motor that provides the power. Unit 2402 displays the remaining charge of the solid battery 2401, the speed of the electric motorcycle 2400, the level status, etc. It is possible.

[0173] Figure 9E shows an example of an electric bicycle using a solid-state battery according to one embodiment of the present invention. Electric bicycle 250 0 comprises a battery pack 2502. The battery pack 2502 is a solid battery according to one embodiment of the present invention. It holds.

[0174] The battery pack 2502 can supply power to the motor that assists the driver. Furthermore, the 2502 battery pack can be removed from the 2500 electric bicycle and carried separately. The battery pack 2502 and electric bicycle 2500 have a display unit that can show the remaining battery level, etc. It is acceptable to have it.

[0175] The house shown in Figure 10 is an energy storage system 2612 having a solid battery, which is one aspect of the present invention. It has a solar panel 2610. The energy storage system 2612 has a solar panel 2610 and It is electrically connected via wiring 2611, etc. It is also connected to the energy storage system 2612 and is ground-mounted. A type 2604 charging device may be electrically connected. The electricity can be used to charge the energy storage system 2612. The power obtained is used to charge the solid battery 2602 of the vehicle 2603 via the charging device 2604. It can be electrically charged.

[0176] The electricity stored in the energy storage system 2612 can also supply power to other electronic devices in the house. This is possible. Therefore, even when power cannot be supplied from the commercial power source due to a power outage, etc., this By using the energy storage system 2612 according to one aspect of the invention as an uninterruptible power supply, electronic devices It will become available for use.

[0177] This embodiment can be used in appropriate combination with other embodiments. [Explanation of Symbols]

[0178] 50a: Positive electrode layer, 50b: Solid electrolyte layer, 50c: Negative electrode layer, 70a: Package material, 7 0b: Package component, 70c: Package component, 71: External electrode, 72: External electrode, 7 3a: electrode layer, 73b: electrode layer, 101: first graphene compound, 102: second graphene compound Fen compound, 103: negative electrode active material particles, 104: positive electrode active material particles, 105: solid electrolyte Particles, 110: Negative electrode current collector, 111: Positive electrode current collector, 500: Secondary battery, 501: Positive electrode Current collector, 502: Positive electrode active material layer, 503: Positive electrode, 504: Negative electrode current collector, 505: Negative electrode active material 506: Solid electrode, 507: Solid electrolyte layer, 509: Outer casing, 510: Positive electrode lead electrode 511: Negative lead electrode, 521: Plate, 524: Plate, 525a: Fixing device , 525b: Fixture, 902: Mixture, 903: Mixture, 904: Mixture, 905: Mixture compound, 906: mixture, 2100: mobile phone, 2101: housing, 2102: display, 2 103: Operation buttons, 2104: External connection port, 2105: Speaker, 2106: My K, 2107: Solid battery, 2200: Electronic cigarette, 2201: Heating element, 2202: Ste IC, 2204: Solid state battery, 2300: Unmanned aircraft, 2301: Solid state battery, 2302: Rotor, 2303: Camera, 2400: Electric motorcycle, 2401: Solid battery, 2402: Display unit, 2403: Handle, 2500: Electric bicycle, 2502: Battery pack, 2602 :Solid-state battery, 2603:Vehicle, 2604:Charging device, 2610:Solar panel, 261 1: Wiring, 2612: Energy storage system, 8021: Charging device, 8022: Cable, 802 4: All-solid-state secondary battery, 8400: Automobile, 8401: Headlight, 8404: All-solid-state Next battery, 8406: electric motor, 8500: automobile, 8600: scooter, 8601: Side mirrors, 8602: All-solid-state rechargeable battery, 8603: Turn signal lights, 8604: Under-seat storage Na

Claims

1. Multiple negative electrode active material particles, Multiple solid electrolyte particles, The system comprises a plurality of negative electrode active material particles and a graphene compound enclosing the plurality of solid electrolyte particles, A battery in which lithium ions that have passed through the graphene compound during charging are incorporated into the plurality of negative electrode active material particles.

2. Multiple negative electrode active material particles, Multiple solid electrolyte particles, The system comprises a plurality of negative electrode active material particles and graphene quantum dots enclosing the plurality of solid electrolyte particles, A battery in which lithium ions that pass through the graphene quantum dots during charging are incorporated into the plurality of negative electrode active material particles.

3. In claim 1 or claim 2, A battery in which the plurality of negative electrode active material particles have elements capable of performing charge and discharge reactions through alloying and dealloying reactions with lithium.

4. In claim 3, A battery having one of the elements selected from silicon, tin, gallium, aluminum, germanium, lead, antimony, bismuth, silver, zinc, cadmium, and indium.

5. In claim 1 or claim 2, A battery in which the plurality of negative electrode active material particles have compounds of elements capable of performing charge and discharge reactions through alloying and dealloying reactions with lithium.

6. In claim 5, The compound is 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 , a battery having one selected from InSb and SbSn.

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