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 an article, a method, or a manufacturing method. Alternatively, the present invention relates to a process, Pertaining to a machine, manufacture, or composition of matter. One embodiment of the present invention is a semiconductor device, a display device, a light-emitting device, a power storage device, a lighting device, or an electronic device. In particular, electronic equipment and its operating system Regarding the stem.

[0002] In this specification, the term "electronic device" refers to any device having a power storage device. Electro-optical devices having a power storage device, and information terminal devices having a power storage device are all electronic devices. [Background technology]

[0003] 2. Description of the Related Art Electronic devices that are carried by users or worn by users have been actively developed.

[0004] Electronic devices carried by users or worn by users are primary energy storage devices, which are examples of power storage devices. It operates on batteries or secondary batteries. Electronic devices carried by users are designed to be used for long periods of time. It is desirable to use a large-capacity secondary battery for this purpose. If a battery is built in, the problem is that a large-capacity secondary battery is large and heavy. Development is underway to develop small or thin, high-capacity secondary batteries that can be built into electronic devices.

[0005] A liquid such as an organic solvent is used as a medium for moving the lithium ions, which are carrier ions. However, secondary batteries that use liquids are widely used. In this case, since a liquid is used, there is a problem of decomposition reaction of the electrolyte depending on the temperature range and potential used. In addition, secondary batteries that use liquid electrolytes have the problem of leakage. There is a risk of fire due to

[0006] Fuel cells are secondary batteries that do not use liquids, but they use precious metals for the electrodes and solid electrolyte materials. It is also an expensive device.

[0007] In addition, there are electric storage devices called solid-state batteries that use solid electrolytes as secondary batteries that do not use liquids. For example, Patent Document 1 and Patent Document 2 are disclosed. 3. The electrolyte of the lithium ion secondary battery is either a solvent, a gel, or a solid electrolyte. It is stated that it is used.

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

[0009] Furthermore, Patent Document 5 and the like have also been disclosed as solid-state batteries using graphene. [Prior art documents] [Patent documents]

[0010] [Patent Document 1] Japanese Patent Application Laid-Open No. 2012-230889 [Patent Document 2] Japanese Patent Application Laid-Open No. 2012-023032 [Patent Document 3] Japanese Patent Application Laid-Open No. 2013-229308 [Patent Document 4] Japanese Patent Application Laid-Open No. 2013-229315 [Patent Document 5] JP 2018-98200 A Summary of the Invention [Problem to be solved by the invention]

[0011] To provide an all-solid-state secondary battery that is safer than conventional lithium-ion secondary batteries.

[0012] By using an all-solid-state secondary battery, electrolyte leakage, which was a problem with secondary batteries that use electrolyte, is eliminated. This has solved the problem of deterioration due to changes in the electrolyte, but other problems remain.

[0013] In addition, when silicon is used as the negative electrode active material particles in an all-solid-state secondary battery, the negative electrode There is a problem that the active material particles expand and contract.

[0014] In addition, there is also the problem of minute short circuits (hereinafter referred to as micro-short circuits) occurring in all-solid-state secondary batteries. Therefore, in all-solid-state secondary batteries, the problem of the Another objective is to prevent the occurrence of short circuits or micro-short circuits. [Means for solving the problem]

[0015] In order to solve the above problem, the expansion or contraction of the negative electrode active material particles caused by charging and discharging is suppressed. In order to achieve this, a graphene compound is used to bind a negative electrode active material particle or multiple negative electrode active material particles. Or fix it.

[0016] In all-solid-state secondary batteries, the interface between the solid electrolyte and the negative electrode or the interface between the solid electrolyte and the positive electrode is the most In order to reduce this interface resistance, at least the negative electrode active material particles are grapheneized. Alternatively, the positive electrode active material particles can be wrapped in a graphene compound to enhance conductivity. Graphene compounds are permeable to carrier ions, such as lithium ions, , and does not inhibit the movement of lithium ions between the positive electrode and the negative electrode during charging or discharging.

[0017] In addition, a graphene compound is used to bind or bind a negative electrode active material particle or a plurality of negative electrode active material particles. By fixing the material, the generation of by-products (precipitates, etc.) is inhibited, and the occurrence of micro-short circuits is prevented. It can be suppressed.

[0018] A micro-short circuit refers to a minute short circuit inside a secondary battery. The positive and negative electrodes of the battery are not short-circuited to the point that charging and discharging becomes impossible, but rather there is a small short circuit. This refers to the phenomenon in which a slight short-circuit current flows for a period of 10 nanoseconds or more but less than 1 microsecond. The cause of micro-short circuits is the breakdown of positive electrode active material particles due to repeated charge and discharge. The uneven distribution of the molecules causes localized current concentration in parts of the positive electrode and negative electrode, resulting in separation. This may cause parts of the data to stop functioning or may cause side reactions (such as precipitates) to occur. The purpose is to

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

[0020] Therefore, in order to prevent local current concentration on a part of the negative electrode and a part of the positive electrode, The inside is wrapped in a graphene compound and fixed in place, increasing conductivity.

[0021] One of the configurations disclosed in this specification is a positive electrode active material particle containing carrier ions and a plurality of negative electrodes. The graphene compound is a graphene-containing active material. The phene compound fixes the negative electrode active material particles, and carrier ions pass through the graphene during charging. This is an all-solid-state battery in which the negative electrode active material particles are incorporated with the cations.

[0022] In addition, another aspect of the present invention is a structure comprising a plurality of positive electrode active material particles containing carrier ions and a plurality of negative electrode active material particles. a material particle, a plurality of solid electrolyte particles, and a plurality of graphene compounds, It 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 refers to a single-layer graphene having a carbon hexagonal lattice structure. or multi-layer graphene with 2 to 100 layers. Fen) is sp 2 It refers to a sheet of carbon molecules with one atomic layer of bonds. When we refer to graphene, we are referring to multi-layer graphene or multiple single layers of graphene. In addition, graphene is not limited to being composed of only carbon, and some of it may contain oxygen, hydrogen, or functional groups. Graphene compounds can be bonded to graphene quantum dots. Graphene compounds have excellent electrical properties, such as high conductivity, and high flexibility. It may also have excellent physical properties such as flexibility and high mechanical strength. The graphene compound has a planar shape. In addition, even if they are thin, they can have very high conductivity, and can be used efficiently with a small amount. A conductive path can be formed within the material layer. The graphene compound may be formed as a coating covering the entire surface of the substrate. The compound may be, for example, graphene, multigraphene, graphene quantum dots, or RG It is particularly preferable to use RGO. Here, RGO is, for example, graphene oxide (graph It refers to a compound obtained by reducing olefin oxide (GO).

[0024] In addition, another aspect of the present invention is a structure comprising a plurality of positive electrode active material particles containing carrier ions and a plurality of negative electrode active material particles. a material particle, a plurality of solid electrolyte particles, and a plurality of graphene compounds, It 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-mentioned configuration, an oxide containing lithium and cobalt is used as the positive electrode active material particles. The positive electrode active material particles preferably have a crystal structure represented by the space group R-3m, for example. It is more preferable that the positive electrode active material particles have the following characteristics, particularly when the depth of charge is deep: It preferably has a pseudospinel structure, which will be described later.

[0026] In addition, the concentration of halogens such as fluorine in the surface layer of the positive electrode active material particles is higher than the average concentration of the entire particle. The presence of halogen in the surface layer, which is the region in contact with the electrolyte, This effectively improves corrosion resistance to hydrofluoric acid.

[0027] In this way, the surface layer of the positive electrode active material particles has a higher fluorine concentration than the inside. It is preferable that the composition has a stable crystal structure at room temperature. Therefore, the surface layer may have a different crystal structure from the inside. At least a part of the surface layer of the porous particle may have a rock salt type crystal structure. When the surface and interior have different crystal structures, the orientation of the crystals in the surface and interior must be roughly the same. It is preferable that:

[0028] The surface layer of the positive electrode active material particle contains at least element M, and also contains element A in a discharged state. It is necessary to have a path for insertion and desorption of element A. Note that element A acts as a carrier ion. The element A is, for example, an alkali metal such as lithium, sodium, or potassium. and Group 2 elements such as calcium, beryllium, and magnesium can be used. If sodium is selected, the carrier ion is a sodium ion.

[0029] The element M is, for example, a transition metal. Examples of the transition metal include cobalt, manganese, and nickel. The positive electrode material of one embodiment of the present invention can be, for example, a material containing an element M and at least one of the elements The alloy preferably contains one or more of cobalt, nickel, and manganese, and more preferably contains cobalt. In addition, it is preferable that the position of element M is replaced with a material such as aluminum that does not change the valence and is the same as element M. It may contain an element that can take a valence, more specifically, for example, a trivalent typical element.

[0030] In addition, both the positive electrode active material particles and the negative electrode active material particles are wrapped in their respective graphene compounds. The configuration may be a plurality of positive electrode active material particles containing carrier ions and a plurality of first The solid electrolyte particles and the first graphene compound are at least partially or completely wrapped together, forming a composite. Both the plurality of negative electrode active material particles and the plurality of second solid electrolyte particles are covered with a second graphene compound. a second graphene compound that at least partially or completely envelops and overlaps the first graphene compound; It is an all-solid-state battery with a third solid electrolyte particle between the two.

[0031] In addition, another aspect of the present invention is a structure comprising a plurality of positive electrode active material particles containing carrier ions and a plurality of first solid particles. A plurality of groups of electrolyte particles wrapped in a first graphene compound are adjacent to each other, and a plurality of negative electrode active The material particles and the plurality of second solid electrolyte particles are wrapped in a second graphene compound, and the first graphene compound is The whole structure has a third solid electrolyte particle between the group of graphene compounds and the second graphene compound overlapping the group of graphene compounds. 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 a material having the component is used, the manufacturing cost can be reduced because a common material is used. The first, second, and third solid electrolyte particles may be made of different materials. In this case, a material that is compatible with the positive electrode active material particles to be used is used for the first solid electrolyte particles. Therefore, a material that is compatible with the negative electrode active material particles is used for the second solid electrolyte particles. This means that no unwanted by-products are generated when the material is brought into contact with the battery for charging or discharging.

[0033] By adopting the above-mentioned configurations, the generation of by-products (precipitates, etc.) on the negative electrode is prevented, and The occurrence of short circuits can be suppressed.

[0034] All-solid-state batteries do not use flammable organic solvents inside the battery, which simplifies safety devices and makes manufacturing easier. It has excellent cost and productivity.

[0035] In addition, graphene or graphene can be obtained by subjecting graphene oxide to reduction treatment or the like. A compound is formed.

[0036] Graphene oxide contains epoxy groups, carbonyl groups, carboxyl groups, hydroxyl groups, etc. In a polar solution, the oxygen in the functional group of graphene oxide is negatively charged. Therefore, different graphene oxides are unlikely to aggregate with each other. In this case, graphene oxide tends to be dispersed uniformly.

[0037] In each of the above configurations, the solid electrolyte particles are a sulfide-based solid electrolyte or an oxide-based solid electrolyte. Quality can be used.

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

[0039] In addition, 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 other lithium composite oxides and oxides Lithium materials are included.

[0040] LLZ is a garnet-type oxide containing Li, La, and Zr, and is not affected by Al, Ga, or A compound containing Ta may also be used.

[0041] In addition, polymer solid electrolytes such as PEO (polyethylene oxide) formed by coating methods, etc. Furthermore, a composite containing the above-mentioned inorganic solid electrolyte and polymer solid electrolyte may be used. A suitable solid electrolyte may also be used.

[0042] In this specification, the surface layer of particles of active material or the like refers to the region from the surface to about 10 nm. The surface caused by cracks or fractures can also be called the surface. , called the inside.

[0043] In the present specification and the like, the layered rock salt type crystals of the composite oxide containing lithium and a transition metal The structure is a rock salt type ion arrangement in which cations and anions are arranged alternately, and The lithium atoms are regularly arranged to form a two-dimensional plane, allowing two-dimensional diffusion of lithium. It is possible for defects such as cation or anion deficiencies to exist. Strictly speaking, the layered rock salt crystal structure is a case where the lattice of the rock salt crystal is distorted. There is.

[0044] In this specification and the like, the rock salt type crystal structure refers to a structure in which cations and anions are arranged alternately. It is possible for there to be a deficiency of cations or anions.

[0045] In the present specification and the like, the pseudospinel type of the composite oxide containing lithium and a transition metal The crystal structure of this is in the space group R-3m, and is not a spinel-type crystal structure, but it is a cobalt-based Ions such as magnesium ions occupy the oxygen hexacoordinated positions, and the arrangement of cations is similar to that of spinel. It refers to a crystalline structure with symmetry. The pseudospinel type crystalline structure is characterized by the absence of light elements such as lithium. The atoms may occupy the oxygen tetracoordinate positions, and in this case the ionic arrangement is similar to that of the spinel type. It has symmetry.

[0046] The pseudospinel crystal structure has random Li between layers, but the CdCl2 type It can be said that this CdCl2-type similar crystal structure is The crystal structure is shown in Fig. 1 when lithium nickel oxide is charged to a charge depth of 0.94 (Li 0.06 Ni O2), but pure lithium cobaltate or cobalt-rich layered It is known that rock salt type positive electrode active material particles do not usually have this crystal structure.

[0047] Layered rock salt crystals and the anions of rock salt crystals are in a cubic close-packed structure (face-centered cubic lattice structure) ) It is assumed that the anions in pseudospinel crystals also have a cubic close-packed structure. When they contact, there exists a crystal plane where the orientation of the cubic close-packed structure formed by the anions is aligned. However, the space group of layered rock salt crystals and pseudospinel crystals is R-3m, and The space groups of the rock salt crystals are Fm-3m (the common rock salt crystal space group) and Fd-3m (the simplest Since the space group is different from that of rock salt crystals, which have a perfect symmetry, the crystal plane must be The Lahr index is different between layered rock salt crystals and pseudospinel crystals and between rock salt crystals. In the layered rock salt crystal, pseudospinel crystal, and rock salt crystal, When the orientation of the cubic close-packed structure is aligned, the crystal orientation is roughly the same. There is.

[0048] The crystal orientation of the two regions roughly coincides with each other, as can be seen from TEM (transmission electron microscope) images and STE M (scanning transmission electron microscope) image, HAADF-STEM (high angle annular dark field scanning transmission electron microscope) image This should be judged from images such as annular bright-field scanning transmission electron microscope (ABF-STEM) images. X-ray diffraction (XRD), electron diffraction, neutron diffraction, etc. can also be used as a basis for judgment. In TEM images, the arrangement of cations and anions is observed as repeated bright and dark lines. When the orientation of the cubic close-packed structure in the layered rock salt crystal and the rock salt crystal is aligned, the crystal The angle between the repeated bright and dark lines is 5 degrees or less, preferably 2.5 degrees or less. In addition, light elements such as oxygen and fluorine can be clearly observed in TEM images. In some cases, it may not be possible to determine the alignment of the metal elements. do.

[0049] In this specification, the theoretical capacity of the positive electrode active material is the capacity of the positive electrode active material that can be inserted and removed. The theoretical capacity of LiCoO2 is 27 4mAh / g, the theoretical capacity of LiNiO2 is 274mAh / g, the theoretical capacity of LiMn2O4 is 148mAh / g.

[0050] In this specification, the depth of charge when all intercalable and detachable lithium is intercalated is The depth of charge when all the intercalable lithium in the positive electrode active material is deintercalated is 0, and the depth of charge when all the intercalable lithium in the positive electrode active material is deintercalated is 1. Let's assume that this is the case.

[0051] In this specification, charging refers to transferring lithium ions from the positive electrode to the negative electrode in the battery. The positive electrode active material moves electrons from the negative electrode to the positive electrode in an external circuit. In this case, the process of releasing lithium ions is called charging. Also, when the charge depth is 0.7 or more, Positive electrode active materials with a voltage of 0.9 or less are sometimes referred to as positive electrode active materials charged at a high voltage.

[0052] Similarly, discharging involves transferring lithium ions from the negative electrode to the positive electrode within the battery and discharging them into the external circuit. The positive electrode active material is lithium. The insertion of ions is called discharging. The positive electrode active material is fully discharged from a high voltage charged state to 90% or more of its charge capacity. This refers to the positive electrode active material that has been discharged in minutes. [Effects of the Invention]

[0053] The graphene compound is used to fix the negative electrode active material particles or the positive electrode active material particles in a manner that wraps around them. This relieves stress caused by expansion or contraction of the negative electrode active material particles or the positive electrode active material particles. Therefore, the negative electrode active material particles or the positive electrode active material particles may expand or shrink during charging or discharging. This can prevent deterioration of characteristics due to shrinkage. [Brief explanation of the drawings]

[0054] [Figure 1] FIG. 1 is an example of a schematic cross-sectional view of a secondary battery showing one embodiment of the present invention. [Figure 2] FIG. 2 illustrates an example of a negative electrode according to one embodiment of the present invention. [Figure 3] FIG. 3 illustrates an example of a negative electrode according to one embodiment of the present invention. [Figure 4] FIG. 4 illustrates an example of a negative electrode according to one embodiment of the present invention. [Figure 5] FIG. 5A is a perspective view of an all-solid-state battery, and FIG. 5B is a cross-sectional view thereof. [Figure 6] 6A, 6B, 6C, and 6D are perspective views of all-solid-state batteries. [Figure 7] 7A and 7B are perspective views of an all-solid-state battery. [Figure 8] 8A, 8B, and 8C show examples of a vehicle. [Figure 9] 9A, 9B, 9C, 9D, and 9E are perspective views showing examples of electronic devices. [Figure 10] FIG. 10 is a perspective view illustrating an example of a power storage device. [Figure 11] FIG. 11 is a diagram illustrating an example of a method for producing a positive electrode active material. DETAILED DESCRIPTION OF THE INVENTION

[0055] Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. The present invention is not limited to the following description, and various modifications in form and details are possible by those skilled in the art. Furthermore, the present invention should not be construed as being limited to the description of the following embodiments. It is not something that can be done.

[0056] (Embodiment 1) In this embodiment, a positive electrode, an oxide solid electrolyte, a negative electrode, and a reducing agent for the surface of the negative electrode are used. The graphene oxide is attached and fixed to prevent expansion and contraction due to charging and discharging, and also improves ion conduction. An example of fabricating an all-solid-state secondary battery with improved conductivity is shown below.

[0057] FIG. 1 is a conceptual diagram showing the cross-sectional structure of a solid-state battery.

[0058] A plurality of solid electrolyte particles 105 are disposed between a positive electrode current collector 111 and a negative electrode current collector 110 . The positive electrode current collector and the negative electrode current collector can be made of a known metal material that can be used in an all-solid-state battery. Possible, Cu, Ni, Al, V, Au, Pt, Mg, Fe, Ti, Cr, Zn, Ge, In The current collector contains one or more selected from the following:

[0059] There are two types of solid-state batteries: thin-film all-solid-state batteries and bulk all-solid-state batteries. The bulk type all-solid-state battery is a battery obtained by stacking fine particles. Figure 1 shows an example of a bulk-type all-solid-state battery. .

[0060] As shown in FIG. 1, the positive electrode active material particles 104 are disposed near the positive electrode current collector 111, and the negative electrode current collector The negative electrode active material particles 103 are disposed in the vicinity of the negative electrode active material particles 110, and the solid electrolyte particles are disposed so as to fill the gaps between them. The child 105 is placed.

[0061] As negative electrode active material particles, charge / discharge reactions occur through alloying and dealloying reactions with lithium. For example, silicon, tin, gallium, and aluminum can be used. , germanium, lead, antimony, bismuth, silver, zinc, cadmium, indium, etc. Materials containing at least one of these elements can be used. These elements have a higher capacity than carbon. Silicon has a particularly high theoretical capacity of 4200mAh / g. It is preferable to use silicon for the particles. Compounds containing these elements may also be used. For example, SiO, Mg2Si, Mg2Ge, SnO, SnO2, Mg2Sn, Sn S2, V2Sn3, FeSn2, CoSn2, Ni3Sn2, Cu6Sn5, Ag3Sn ,Ag3Sb,Ni2MnSb,CeSb3,LaSn3,La3Co2Sn7,CoS b3, InSb, SbSn, etc. Here, by alloying and dealloying reaction with lithium, Elements that can undergo charge-discharge reactions and compounds containing these elements are called alloy materials. There are cases where this happens.

[0062] In this specification, SiO refers to, for example, silicon monoxide. Alternatively, SiO refers to Si O x Here, it is preferable that x has a value close to 1. For example, x can be expressed as The ratio is preferably 0.2 or more and 1.5 or less, and more preferably 0.3 or more and 1.2 or less.

[0063] In addition, the negative electrode active material particles are titanium dioxide (TiO2), lithium titanium oxide (L i4Ti5O 12 ), lithium-graphite intercalation compound (Li x C6), niobium pentoxide (Nb2 O5), tungsten oxide (WO2), molybdenum oxide (MoO2), etc. It is possible.

[0064] In addition, a first graphite layer is formed so as to surround the negative electrode current collector 110 and the plurality of negative electrode active material particles 103. The first graphene compound 101 is used to form negative electrode active material particles. A single particle or a plurality of particles of the negative electrode active material are fixed to the negative electrode current collector 110. The negative electrode active material particle or a plurality of negative electrode active material particles are bound or fixed using the compound 101. This inhibits the generation of by-products (precipitates, etc.) and suppresses the occurrence of micro-short circuits. It is possible.

[0065] The first graphene compound 101 is also formed into a plurality of solid particles together with the plurality of negative electrode active material particles 103. It also contains electrolyte particles.

[0066] In FIG. 1, a plurality of solid electrolyte particles 105 are disposed between a positive electrode current collector 111 and a negative electrode current collector 110. The solid electrolyte particles 105 and the first graphene compound 101 are This shows an example in which the same material as the solid electrolyte particles that are wrapped around it is used.

[0067] In addition, a configuration including at least the positive electrode current collector 111 and the positive electrode active material particles 104 is used as a positive electrode. The positive electrode functions as a cathode, and the cathode is wrapped with the second graphene compound 102.

[0068] In addition, in FIG. 1, the solid electrolyte particles 105 and the second graphene compound 102 are wrapped around each other. This shows an example in which a material with the same components as the solid electrolyte particles is used. The distance between the compound 101 and the second graphene compound 102 is determined by the material of the solid electrolyte particles 105. Although it depends on the size, it is set to 0.1 μm or more and 1 mm or less, preferably 1 μm or more and 100 μm or less.

[0069] The first graphene compound 101 is a solid electrolyte particle, a negative electrode active material particle 103, and a negative electrode current collector. The cross-sectional view after wrapping 110 is shown in Figure 2. After obtaining the state shown in Figure 2, firing and pressing processes are performed. may be applied.

[0070] After disposing the negative electrode active material particles 103 and the solid electrolyte particles on the negative electrode current collector 110, The reduced acid is surrounded by the current collector 110, the solid electrolyte particles, and the negative electrode active material particles 103. Deposit rGO (roughly 10 ...

[0071] The compound obtained by reducing graphene oxide is called "RGO (Reduced Graphene Oxide)." RGO is sometimes called "graphene oxide." Not all of the oxygen is eliminated, and some oxygen or atomic groups containing oxygen remain bonded to carbon. For example, RGO may contain carbonyl groups such as epoxy groups and carboxyl groups, In this specification and the like, the graphene compound may have a functional group such as a hydroxyl group. The graphene precursor may be a compound that is used to produce graphene. The graphene precursor refers to the material used, and examples of the graphene precursor include the above-mentioned graphene oxide and Graphite oxide and the like may be included. Graphene containing elements other than carbon, such as In the literature, graphene compounds also include graphene analogues. includes graphene quantum dots.

[0072] Then, the second graphene compound 102 is used to bond 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 A solid-state battery is fabricated by sandwiching and stacking multiple solid electrolyte particles 105 between the electrodes 02. Therefore, the timing of adding the solid electrolyte particles during manufacturing varies. The same material is used for the negative electrode active material, the positive electrode active material, and, depending on the manufacturing process, the solid electrolyte particles. In FIG. 1, each solid electrolyte particle is shown as being identical. do.

[0073] In practice, a gap is formed between the positive electrode current collector 111 and the negative electrode current collector 110 by pressing. It is also possible to fill a plurality of types of particles so that the number of particles is reduced as much as possible.

[0074] At this stage, the laminate shown in Figure 1 is obtained. To bond the laminate, heat treatment and protrusion are performed. The pressing step is carried out to improve the density. Heating may be carried out simultaneously with the pressing step.

[0075] The resulting laminate is then housed in an outer packaging such as a laminate film or a metal can. This makes it possible to fabricate an all-solid-state battery.

[0076] (Embodiment 2) In this embodiment, an example that is partially different from the first embodiment will be described below with reference to FIG.

[0077] Figure 3 shows an example in which the current collector is not wrapped in graphene compound. The first graphene compound 101 is wrapped around the electrolyte particles and the negative electrode active material particles 103. This is an example of this.

[0078] By combining and stacking the positive electrode shown in the first embodiment, an all-solid-state battery can be fabricated. Cut.

[0079] In addition, after forming a positive electrode without wrapping the positive electrode current collector with the second graphene compound 102, Alternatively, the cathode may be laminated with the cathode to prepare an all-solid-state battery.

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

[0081] (Embodiment 3) In this embodiment, an example that is partially different from the first embodiment will be described below with reference to FIG.

[0082] In FIG. 4, a first graphene-wrapped group, specifically, a solid electrolyte particle and The negative electrode active material particles 103 are wrapped in the first graphene compound 101. The figure shows seven groups. Solid electrolyte particles are placed in the gaps between them. do.

[0083] The negative electrode shown in FIG. 4 and the positive electrode shown in embodiment 1 are stacked together to form an all-solid-state battery. can be produced.

[0084] In addition, similar to the negative electrode shown in FIG. 4, a plurality of groups are formed with the second graphene compound 102. After forming a positive electrode, the positive electrode may be laminated with the negative electrode shown in FIG. 4 to produce an all-solid-state battery.

[0085] In addition, after forming a positive electrode without wrapping the positive electrode current collector with the second graphene compound 102, Alternatively, the cathode may be laminated with the cathode to prepare an all-solid-state battery.

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

[0087] For example, the positive electrode wrapped with a graphene compound shown in FIG. 3 and the positive electrode wrapped with a graphene compound shown in this embodiment An all-solid-state battery may be fabricated by combining it with the negative electrode shown in FIG.

[0088] (Fourth embodiment) In this embodiment, an example of a method for manufacturing a positive electrode will be described.

[0089] An example of a method for manufacturing a positive electrode active material will be described with reference to FIG.

[0090] As shown in step S11 of FIG. 11, first, a fluorine source, Prepare lithium fluoride and magnesium fluoride as a magnesium source. However, lithium fluoride has a relatively low melting point of 848°C, making it easy to melt during the annealing process described below. Lithium fluoride can be used as both a lithium source and a fluorine source. 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 a fluorine source and a lithium source, Magnesium fluoride (MgF2) will be prepared as a fluorine source and magnesium source. (Step S11 in FIG. 11). The ratio of LiF to MgF is preferably LiF:MgF2=x:1 (0≦x≦1.9), and LiF: MgF2=x:1 (0.1≦x≦0.5) is more preferable, LiF:MgF2=x:1 ( x=near 0.33) is more preferable.

[0092] If the subsequent mixing and grinding steps are to be carried out wet, a solvent is prepared. ketones such as acetone, alcohols such as ethanol and isopropanol, ethers, di- Xanthan Gum, acetonitrile, N-methyl-2-pyrrolidone (NMP), etc. can be used. It is more preferable to use an aprotic solvent that is less likely to react with lithium. In this embodiment, acetone is used (see step S11 in FIG. 11).

[0093] Next, the materials of the mixture 902 are mixed and crushed (step S12 in FIG. 11). Mixing can be done in a dry or wet manner, but the wet method allows for smaller particles to be crushed. For example, a ball mill, a bead mill, etc. can be used for mixing. When using balls, it is preferable to use zirconia balls as the media. It is preferable to carry out the above mixing and grinding steps sufficiently to pulverize the mixture 902 into fine powder.

[0094] The mixed and crushed materials are collected (step S13 in FIG. 11) to obtain a mixture 902. (Step S14 in Figure 11).

[0095] The mixture 902 preferably has a D50 of, for example, 600 nm or more and 20 μm or less. It is more preferable that the particle size is 1 μm or more and 10 μm or less. 2, when mixed with a composite oxide containing lithium, a transition metal, and oxygen in a later process, In addition, it is easy to uniformly attach the mixture 902 to the surface of the composite oxide particles. If the mixture 902 is uniformly attached to the surface of the composite oxide particles, the mixture 902 will leak onto the surface layer of the composite oxide particles after heating. This is preferable because it is easy to distribute halogen and magnesium in the surface layer. If there is a region that does not contain magnesium, the pseudospinel crystals described above will form in the charged state. It may be difficult to achieve the structure.

[0096] Next, a lithium source is prepared as shown in step S25. A composite oxide containing lithium, a transition metal, and oxygen that has been synthesized in advance is used.

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

[0098] The composite oxide containing lithium, a transition metal, and oxygen in step S25 is formed by removing defects and strain. It is preferable that the crystal structure of the layered rock salt type has few impurities. It is preferable that the composite oxide contains lithium, a transition metal, and oxygen. If a large amount of impurities is included, there is a high possibility that the crystal structure will have many defects or strains.

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

[0100] The mixing in step S31 is carried out after the mixing in step S12 in order not to destroy the particles of the composite oxide. For example, it is preferable to set the rotation speed to be milder than that of the mixing in step S12. It is preferable to use conditions with less heat or shorter time. For mixing, a ball mill, a bead mill, etc. can be used. When using a ball mill, for example, zirconia balls should be used as the media. is preferred.

[0101] The mixed materials are collected (step S32 in FIG. 11) to obtain a mixture 903 (FIG. 1 1, step S33).

[0102] Next, the mixture 903 is heated. This step is called annealing to distinguish it from the previous heating step. Or it may be called second heating.

[0103] The annealing is preferably carried out at a suitable temperature and time. The particle size and the size of the composite oxide having lithium, transition metal and oxygen in step S25 The temperature and composition of the particles vary depending on the conditions. Small particles require lower temperatures or Shorter times may be more preferable.

[0104] For example, if the average particle diameter (D50) of the particles in step S25 is about 12 μm, annealing The temperature is preferably, for example, 600° C. or higher and 950° C. or lower. The annealing time is, for example, 3 hours or longer. It is preferable that the heating time is 10 hours or more, more preferable that the heating time is 60 hours or more.

[0105] On the other hand, when the average particle diameter (D50) of the particles in step S25 is about 5 μm, the annealing temperature The annealing temperature is preferably, for example, 600° C. or higher and 950° C. or lower. The annealing time is, for example, 1 hour or higher and 10 Preferably, it is less than 1 hour, and more preferably about 2 hours.

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

[0107] When the mixture 903 is annealed, the material with a low melting point (e.g., lithium fluoride) in the mixture is first melted. It is thought that the oxide (aluminum, melting point 848°C) melts and is distributed in the surface layer of the composite oxide particles. The presence of this molten material will lower the melting point of other materials, causing them to melt. For example, magnesium fluoride (melting point 1263°C) melts and the composite oxide particles It is thought to be distributed in the surface layer.

[0108] The diffusion of elements contained in the mixture 903 is more pronounced in the surface and inner layers of the composite oxide particles than in the inner layers. Therefore, magnesium and halogens are more likely to dissolve in the surface layer and near the grain boundaries. As will be described later, the magnesium concentration in the surface layer and near the grain boundaries is higher than that in the interior. When the temperature is high, the change in the crystal structure can be more effectively suppressed.

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

[0110] Next, as shown in step S50, the mixture 904 is mixed with finely powdered nickel hydroxide. Then, the mixed material is collected (step S51). Step S15 of mixing nickel hydroxide and acetone and step S16 of recovering the mixture are performed in advance. In step S16, finely powdered nickel hydroxide is obtained (step S17).

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

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

[0113] As shown in FIG. 11, first, in step S52, a metal source is prepared. When the sol-gel method is applied, a solvent to be used in the sol-gel method is prepared. Metal Z may be aluminum, metal hydroxide, metal oxide, etc. In the case of lithium cobalt oxide, for example, the number of cobalt atoms in lithium cobalt oxide is 1, and the metal source is The concentration of aluminum in the metal Z is 0.001 times or more and 0.02 times or less. In the case of nickel, for example, the number of cobalt atoms in lithium cobalt oxide is 1, and the metal The concentration of nickel in the source should be 0.001 times or more and 0.02 times or less. In the case of aluminum and nickel, for example, the cobalt element in lithium cobalt oxide is the aluminum concentration in the metal source is 0.001 times or more and 0.02 times or less, with the number of atoms being 1; In addition, the concentration of nickel in the metal source may be 0.001 times or more and 0.02 times or less.

[0114] As an example, a sol-gel method is used, and aluminum isopropoxide is used as a metal source. An example using isopropanol as a solvent is shown below.

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

[0116] The amount of metal alkoxide required varies depending on the particle size of the lithium cobalt oxide. When aluminum isopropoxide is used, the particle size (D50) of lithium cobalt oxide is 20 If the number of cobalt atoms in lithium cobalt oxide is 1, then the number of cobalt atoms in aluminum is 1. The aluminum concentration in the isopropoxide is 0.001 to 0.02 times. It is preferable to add

[0117] Next, the mixture of the alcohol solution of metal alkoxide and the lithium cobalt oxide particles was added to water. Stirring is performed in a steam-containing atmosphere. Stirring can be performed, for example, with a magnetic stirrer. The stirring time is determined based on the time it takes for the water in the atmosphere and the metal alkoxide to undergo hydrolysis and polycondensation reactions. For example, 4 hours, 25°C, 90% RH (relative humidity). It can be done under conditions of humidity (relative humidity). and in an atmosphere that is not temperature controlled, such as the atmospheric atmosphere in a draft chamber. In such a case, it is preferable to carry out the stirring for a longer period of time. For example, it may be left at room temperature for 12 hours or more.

[0118] By reacting water vapor in the atmosphere with metal alkoxide, the reaction is more efficient than when liquid water is added. The sol-gel reaction can be carried out slowly even at room temperature. This reaction allows for a higher yield than, for example, heating at a temperature above the boiling point of the alcohol solvent. The sol-gel reaction can be carried out slowly. By carrying out the sol-gel reaction slowly, This allows the formation of a high-quality coating layer with a uniform thickness.

[0119] After the above treatment, the precipitate is collected from the mixed solution (step S54 in FIG. 11). The method of filtration, centrifugation, evaporation to dryness, etc. can be applied. It can be washed with the same alcohol as the solvent used to dissolve the cocaine. If applicable, this step may not require separation of the solvent and precipitate, e.g. For example, the precipitate may be collected in the drying step of the next step (step S54).

[0120] Next, the collected residue is dried to obtain a mixture (step S54 in FIG. 11). For example, the mixture can be dried under vacuum or by ventilation at 80° C. for 1 hour to 4 hours.

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

[0122] The heating time is preferably 1 hour or more and 80 hours or less within the heating temperature range. I wish.

[0123] The heating temperature is preferably less than 1000°C, more preferably 700°C or higher and 950°C or lower. , and more preferably about 850°C.

[0124] The heating is preferably carried out in an atmosphere containing oxygen.

[0125] In this embodiment, the heating temperature is set to 850° C. and maintained for 2 hours. °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] <Steps S56 and S57> Next, the cooled particles are collected (step S56 in FIG. 11). In the above process, the mixture 906 that can be used as the positive electrode active material is (Step S57 in FIG. 11).

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

[0129] The mixture 902 is a positive electrode active material having a lithium component, a magnesium component, and a fluorine component. The mixtures 903 and 904 are a lithium component, a cobalt component, a magnesium component, and a positive electrode active material containing a fluorine component.

[0130] The mixture 905 contains a lithium component, a cobalt component, a magnesium component, and a nickel component. and a fluorine component, and the mixture 906 is a positive electrode active material containing a lithium component, a fluorine component, and a A fluorine-containing alloy having a nickel component, a magnesium component, a nickel component, an aluminum component, and a fluorine component. It is a positive electrode active material.

[0131] Slurries were prepared by dispersing graphene oxide in a solvent, and mixtures 902, 903, 904, 905 or 906, a plurality of positive electrode active material particles are placed on a positive electrode current collector. The positive electrode active material particles are then coated with a slurry so as to cover the positive electrode active material particles, and the slurry is then dried. By performing the reduction treatment, graphene can be attached to the surface of the positive electrode active material.

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

[0133] For example, by combining this with the first embodiment, a solid-state battery can be produced.

[0134] (Embodiment 5) FIG. 1 shown in the first embodiment is a conceptual diagram showing the cross-sectional structure of a solid-state battery. The solid electrolyte particles 105 are disposed between the first graphene compound 11 and the negative electrode current collector 110. The wrapping method for the object 101 can be selected from any one of FIG. 2, FIG. 3, and FIG.

[0135] In addition, it is preferable to use a package with excellent airtightness as a sealing container for the all-solid-state battery. For this purpose, ceramic or resin packages are used. It is preferable to carry out the reaction in a shielded and sealed atmosphere, for example in a glove box.

[0136] FIG. 5A shows an all-solid-state secondary battery having external electrodes 71 and 72 and sealed with a packaging member. Such an all-solid-state secondary battery can be directly mounted on a circuit board or the like. Cut.

[0137] 5B shows an example of a cross section cut along the dotted line in FIG. 5A. a, a frame-shaped package member 70b, and a flat electrode layer The structure is such that the semiconductor device is surrounded and sealed by the package member 70c on which the semiconductor device 73b is provided. The package members 70a, 70b, and 70c are made of an insulating material, such as a resin material or ceramic. You can be there.

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

[0139] FIG. 5B shows an example in which a positive electrode layer 50a, a solid electrolyte layer 50b, and a negative electrode layer 50c are stacked together. However, a plurality of sets may be stacked.

[0140] 6A shows an example of fabricating a laminated secondary battery using a packaging method different from that shown in FIG. 5A. , as shown in Figures 6B, 6C, and 6D.

[0141] 6A shows an external view of a positive electrode 503 and a negative electrode 506. The positive electrode 503 has a positive electrode current collector 501. The positive electrode active material layer 502 is formed on the surface of the positive electrode current collector 501. The negative electrode 506 has a region where the positive electrode current collector 501 is partially exposed (hereinafter referred to as a tab region). The negative electrode active material layer 505 is formed on the surface of the negative electrode current collector 504. 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 electrode and negative electrode are not limited to the example shown in FIG. 6A.

[0142] First, the negative electrode 506, the solid electrolyte layer 507, and the positive electrode 503 are stacked. The negative electrode 506, the solid electrolyte layer 507, and the positive electrode 503 are shown. Here, five pairs of negative electrodes and four pairs of positive electrodes are shown. Next, the bonding of the tab regions of the positive electrode 503 and the bonding of the tab region of the positive electrode on the outermost surface are shown. The positive electrode lead electrode 510 is joined to the electrode region 510. For example, ultrasonic welding or the like may be used for joining. Similarly, the tab regions of the negative electrodes 506 are joined together, and the negative electrode leads to the tab regions of the negative electrodes on the outermost surface are Then, the electrode 511 is bonded.

[0143] Next, the negative electrode 506, the solid electrolyte layer 507, and the positive electrode 503 are arranged on the exterior body 509. The electrolyte layer 507 is a material layer (ceramic) containing a solid component capable of conducting lithium ions. For example, the solid electrolyte layer 507 may be made of ceramic powder or glass powder. The powder is made into a slurry and then molded into a sheet. The definition of ceramic is any material, whether metallic or non-metallic, that is made of oxide. Glass is a material made of inorganic compounds such as carbides, nitrides, and borides. It is defined as a material that exhibits glass transition phenomenon, but when it is made into a microcrystalline material, it is called ceramic glass. Because ceramic glass has crystallinity, it can be confirmed by X-ray diffraction. As the solid electrolyte, an oxide solid electrolyte, a sulfide solid electrolyte, etc. can be used. In addition, the positive electrode active material layer 502 and the negative electrode active material layer 505 may also contain a solid electrolyte. The conductive additive may be any material having electronic conductivity. For example, carbon materials, metal materials, etc. can be used.

[0144] The oxide solid electrolyte used as the positive electrode active material particles includes Li3PO4, Li 3BO3, Li4SiO4, Li4GeO4, LiNbO3, LiVO2, LiTiO3 , LiZrO3, etc. can be used. Also, composite compounds of these may be used, For example, Li3BO3-Li4SiO4 can be mentioned. The surface may be at least partially covered with a coating layer having a thickness of 1 nm to 20 nm, The material used is a Li-ion conductive oxide.

[0145] The oxide solid electrolytes used as negative electrode active material particles include Nb2O5, Li4Ti5 O 12 In this specification, SiO is, for example, monoxide It refers to silicon. Alternatively, SiO refers to a material that has a higher silicon content than SiO2. SiO x Here, it is preferable that x has a value close to 1. For example, x is preferably 0.2 or more and 1.5 or less, and more preferably 0.3 or more and 1.2 or less.

[0146] In addition, the sulfide solid electrolyte used as the positive electrode active material particles is a material containing Li and S. material, specifically Li7P3S 11 , Li2S-SiS2, Li2S-P2S5, etc. It is possible.

[0147] Next, as shown in FIG. 6C, exterior body 509 is folded at the portion indicated by the broken line. The outer periphery of the outer casing 509 is bonded. The outer casing 509 is made by laminating metal foil and organic resin film. Laminated films, such as aluminum foil or stainless steel foil, are used, and bonding is performed using, for example, In this way, a laminated secondary battery 500 shown in FIG. In this example, a single laminate film is used for bonding. The figure shows a structure in which two laminate films are stacked and the edges are bonded together to seal the film. Good too.

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

[0149] FIG. 7A shows three laminated secondary batteries 500 attached to a first plate 521 and a second plate 522. 7B is a perspective view showing how the fixing device 524 is sandwiched and fixed. 25a and fixing device 525b are used to fix the first plate 521 and the second plate 524 together. By fixing the distance between the three secondary batteries 500, pressure can be applied to the three secondary batteries 500.

[0150] 7A and 7B show an example in which three laminated secondary batteries 500 are used. The present invention is not limited to this, and four or more secondary batteries 500 can be used. If ten or more secondary batteries are used, It can be used as a power source for small vehicles, and if more than 100 units are used, it can be used as a large power source for vehicles. It can also be used as a protection circuit to prevent overcharging and to monitor temperature rise. A temperature sensor for detecting the temperature may be provided in the laminated secondary battery 500. There are other types besides laminated types, such as coin type, cylindrical type, and square type.

[0151] In all-solid-state batteries, a certain amount of pressure is applied in the stacking direction of the stacked positive and negative electrodes. The contact state of the interface at the stacking portion can be maintained in a good condition. Applying force can suppress expansion in the stacking direction due to charging and discharging of the all-solid-state battery. This makes it possible to improve the reliability of the all-solid-state battery.

[0152] (Embodiment 6) In this embodiment, an example in which an all-solid-state secondary battery according to one embodiment of the present invention is mounted on a vehicle will be described. Examples of vehicles include automobiles, motorcycles, bicycles, and the like.

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

[0154] 8A shows an example of a vehicle using an all-solid-state secondary battery according to one embodiment of the present invention. The automobile 8400 shown in FIG. 1 is an electric automobile that uses an electric motor as a power source for driving. Alternatively, an electric motor and an engine can be selected as the power source for driving. The car 8400 is a hybrid car that can be driven by a solid-state secondary battery 8404. The all-solid-state secondary battery 8404 drives the electric motor 8406. In addition, it also supplies power to light-emitting devices such as headlights 8401 and room lights (not shown). In addition, if the power supply stops due to an abnormality in the all-solid-state secondary battery 8404, In order to avoid the hazard lights not turning on due to the vehicle being turned on, It is preferable to provide a secondary battery.

[0155] In addition, the all-solid-state secondary battery 8404 is used for the speedometer, tachometer, etc. of the automobile 8400. The all-solid-state secondary battery 8404 can supply power to a display device such as a , it is possible to supply power to the navigation system and the like of the automobile 8400.

[0156] The automobile 8500 shown in FIG. 8B is a plug-in type all-solid-state secondary battery included in the automobile 8500. It can be charged by receiving power from an external charging facility using a method such as contactless power supply. FIG. 8B shows a solid-state charging system mounted on a vehicle 8500 from a ground-mounted charging device 8021. The secondary battery 8024 is shown being charged via a cable 8022. For charging methods and connector specifications, please refer to the specifications of CHAdeMO (registered trademark) and Combo. The charging device 8021 may be a charging station installed in a commercial facility. For example, plug-in technology can be used to The power supply can charge the all-solid-state secondary battery 8024 mounted on the automobile 8500. Charging is done by converting AC power to DC power via a converter such as an AC-DC converter. As the all-solid-state secondary battery 8024, the all-solid-state secondary battery shown in Embodiment 2 may be used. Use the following batteries.

[0157] Although not shown, a power receiving device is mounted on the vehicle, and power is supplied contactlessly from a power transmitting device on the ground. In this case, the power transmission device is installed on the road or on the exterior wall. By incorporating this, charging can be done not only when the vehicle is stopped but also while the vehicle is moving. The vehicle may transmit and receive power between them using the same method. A solar cell may be provided in the vehicle to charge the all-solid-state secondary battery while the vehicle is stopped or running. For contactless power supply, an electromagnetic induction method or a magnetic field resonance method can be used.

[0158] 8C shows an example of a two-wheel vehicle using the all-solid-state secondary battery of one embodiment of the present invention. The scooter 8600 shown in C has an all-solid-state secondary battery 8602, a side mirror 8601, a directional indicator The all-solid-state secondary battery 8602 supplies electricity to the direction indicator light 8603. It is possible.

[0159] In addition, the scooter 8600 shown in FIG. 8C has an all-solid-state secondary battery 86 in the under-seat storage 8604. 02 can be stored. The all-solid-state secondary battery 8602 is small and can be stored under the seat 8604. Even if there is, it can be stored in the under-seat storage space 8604.

[0160] This embodiment mode can be combined with the descriptions of other embodiment modes as appropriate.

[0161] (Embodiment 7) In this embodiment, the solid-state battery described in the previous embodiment will be explained with reference to FIGS. 9 and 10. An example of implementation in a child device will be described.

[0162] First, referring to FIGS. 9A to 9C, a solid-state battery according to one embodiment of the present invention will be mounted on a small electronic device. An example will be explained.

[0163] FIG. 9A shows an example of a mobile phone. A mobile phone 2100 is assembled in a housing 2101. In addition to the built-in display unit 2102, operation buttons 2103, an external connection port 2104, a speaker, 2105, a microphone 2106, etc. The mobile phone 2100 is equipped with a solid-state battery 2 The solid state battery 2107 is a combination of any one of the first to fifth embodiments. This is a highly reliable solid-state battery that suppresses the occurrence of micro-short circuits. is.

[0164] The mobile phone 2100 is a device that can be used for mobile phone calls, e-mails, viewing and creating documents, playing music, and internet. It can run various applications such as internet communication and computer games. .

[0165] The operation button 2103 is used to set the time, turn the power on and off, and turn wireless communication on and off. It has various functions such as operation, silent mode activation and deactivation, power saving mode activation and deactivation, etc. For example, the operating system installed in the mobile phone 2100 can The system also allows the functions of the operation buttons 2103 to be freely set.

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

[0167] The mobile phone 2100 also has an external connection port 2104, and can be connected to other information terminals via a connector. Data can be exchanged directly via the external connection port 2104. Charging can also be 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, such as a fingerprint sensor. , pulse sensors, body temperature sensors, and other human body sensors, as well as touch sensors, pressure sensors, and acceleration sensors , etc. are preferably installed.

[0169] FIG. 9B is a perspective view of a device also called a tobacco-containing smoking device (electronic cigarette). The electronic cigarette 2200 includes a heating element 2201 and a power supply for the heating element 2201. The stick 2202 has a solid-state battery 2204. When the stick 2202 is inserted into the battery, the stick 220 2 is heated by a heating element 2201. To enhance safety, the solid-state battery is protected from overcharging and overdischarging. A protection circuit to prevent discharge may be electrically connected to the solid-state battery 2204. The battery 2204 has an external terminal so that it can be connected to a charging device. Since this is the tip when held, it is desirable that the total length is short and the weight is light. The solid-state battery according to one embodiment of the present invention is highly safe and can be used safely for a long period of time. It is possible to provide a small and lightweight electronic cigarette 2200 that can be used.

[0170] FIG. 9C shows unmanned aerial vehicle 2300 having multiple rotors 2302. 2300 includes a solid-state battery 2301 according to an embodiment of the present invention, a camera 2303, and an antenna (not shown). The unmanned aerial vehicle 2300 can be remotely controlled via an antenna. The solid-state battery according to one embodiment of the present invention is highly safe and can be used safely for a long period of time. , and is suitable as a solid-state battery to be mounted on the unmanned aerial vehicle 2300.

[0171] Next, an example of mounting a solid-state battery according to one embodiment of the present invention on a vehicle will be described with reference to FIGS. 9D and 9E. I will explain.

[0172] FIG. 9D shows an electric motorcycle 2400 using a solid-state battery according to one embodiment of the present invention. 2400 includes a solid-state battery 2401, a display unit 2402, and a handle 2403, which are an embodiment of the present invention. The solid-state battery 2401 can supply electricity to the motor that powers it. The display unit 2402 displays the remaining charge of the solid-state battery 2401, the speed of the electric motorcycle 2400, the horizontal state, etc. It is possible.

[0173] FIG. 9E shows an example of an electric bicycle using a solid-state battery according to one embodiment of the present invention. The battery pack 2502 includes a solid-state battery according to one embodiment of the present invention. It has.

[0174] The battery pack 2502 can provide electricity to a motor that assists the driver. The battery pack 2502 can be removed from the electric bicycle 2500 and carried around. The battery pack 2502 and the electric bicycle 2500 are provided with a display that can display the remaining battery power, etc. It may have.

[0175] The house in FIG. 10 includes a power storage system 2612 including a solid-state battery which is one embodiment of the present invention. The solar panel 2610 is connected to the power storage system 2612. Electrically connected via wiring 2611, etc. Also, the storage system 2612 and the ground-mounted A charging device 2604 of the same type may be electrically connected. The power can be stored in the power storage system 2612. The obtained power is charged to a solid-state battery 2602 of the vehicle 2603 via a charging device 2604. It can be charged.

[0176] The electricity stored in the electricity storage system 2612 can also be used to power other electronic devices in the home. Therefore, even when power cannot be supplied from the commercial power source due to a power outage, this The power storage system 2612 according to one embodiment of the present invention can be used as an uninterruptible power supply, It will be available for use.

[0177] This embodiment mode can be implemented in appropriate combination with other embodiment modes. [Explanation of symbols]

[0178] 50a: positive electrode layer, 50b: solid electrolyte layer, 50c: negative electrode layer, 70a: packaging member, 7 0b: packaging member, 70c: packaging member, 71: external electrode, 72: external electrode, 7 3a: electrode layer, 73b: electrode layer, 101: first graphene compound, 102: second graphene compound Phen 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: negative electrode; 507: solid electrolyte layer; 509: outer casing; 510: positive electrode lead electrode 511: negative lead electrode, 521: plate, 524: plate, 525a: fixing fixture , 525b: Fixture, 902: Mixture, 903: Mixture, 904: Mixture, 905: Mixture compound, 906: mixture, 2100: mobile phone, 2101: housing, 2102: display, 2 103: Operation button, 2104: External connection port, 2105: Speaker, 2106: Microphone 2107: Solid-state 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-state battery, 2402: Display unit, 2403: Handlebar, 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 secondary battery secondary batteries, 8406: electric motors, 8500: automobiles, 8600: scooters, 8601: Side mirror, 8602: All-solid-state secondary battery, 8603: Turn signal light, 8604: Under-seat storage Na

Claims

1. A plurality of negative electrode active material particles; a plurality of solid electrolyte particles; a graphene compound that wraps the plurality of negative electrode active material particles and the plurality of solid electrolyte particles, The battery, wherein lithium ions that have passed through the graphene compound during charging are taken up by the plurality of negative electrode active material particles.

2. A plurality of negative electrode active material particles; a plurality of solid electrolyte particles; graphene quantum dots surrounding the plurality of negative electrode active material particles and the plurality of solid electrolyte particles, The battery, wherein lithium ions that have passed through the graphene quantum dots during charging are taken up by the plurality of negative electrode active material particles.

3. In claim 1 or claim 2, The plurality of negative electrode active material particles contain an element capable of undergoing a charge / discharge reaction by alloying / de-alloying reaction with lithium.

4. In claim 3, The battery, wherein the element comprises one selected from silicon, tin, gallium, aluminum, germanium, lead, antimony, bismuth, silver, zinc, cadmium, and indium.

5. In claim 1 or claim 2, The plurality of negative electrode active material particles have a compound of an element capable of undergoing a charge / discharge reaction by alloying / dealloying reaction 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 , InSb, and SbSn.

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