Electrode active material layer, electrode, all-solid-state battery

Abstract

To provide an electrode active material layer which can achieve superior cycle and rate characteristics when used for batteries.SOLUTION: The electrode active material layer hereof comprises an active substance and a solid electrolyte, in which at least part of the solid electrolyte is in a net-like form.SELECTED DRAWING: Figure 2

Description

[Technical Field]

[0001] The present invention relates to an electrode active material layer, an electrode, and an all-solid-state battery. [Background technology]

[0002] In recent years, electronics technology has made remarkable progress, with efforts being made to make portable electronic devices smaller, lighter, thinner, and more multifunctional. Accordingly, there is a strong demand for batteries that serve as the power source for electronic devices to be smaller, lighter, thinner, and more reliable, and all-solid-state batteries that use solid electrolytes have attracted attention.

[0003] In all-solid-state batteries, when an inorganic solid electrolyte is used as the solid electrolyte and an organic material is used as the electrode, there is no need to worry about leakage of the organic electrolyte or gas generation, making them highly safe. For this reason, all-solid-state batteries are attracting more attention. Furthermore, compared to liquid-based batteries, all-solid-state batteries are less likely to experience reactions other than battery reactions. For this reason, all-solid-state batteries are also expected to have a longer lifespan.

[0004] Examples of methods for manufacturing all-solid-state batteries include sintering and powder molding. In the sintering method, an anode, a solid electrolyte layer, and a cathode are stacked and then sintered to form an all-solid-state battery. The sintering method is known to be able to bond well the interfaces between the solid electrolyte layer and the cathode layer, and between the solid electrolyte layer and the anode layer. In the powder molding method, an anode, a solid electrolyte layer, and a cathode are stacked and then pressure is applied to form an all-solid-state battery.

[0005] Patent Document 1 discloses an all-solid-state battery manufactured using a sintering method. The all-solid-state battery disclosed in Patent Document 1 is disclosed to have a porosity of 5% to 50% in either the positive electrode layer or the negative electrode layer. The all-solid-state battery disclosed in Patent Document 1 is configured as described above in order to mitigate expansion and contraction of electrode active materials, such as the positive electrode active material and the negative electrode active material, during charging and discharging. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2012-99225 Summary of the Invention [Problem to be solved by the invention]

[0007] However, the battery provided with the electrode active material layer disclosed in Patent Document 1 did not provide sufficient cycle characteristics.

[0008] The present invention has been made in view of the above problems, and has an object to provide an electrode active material layer that can realize excellent cycle characteristics and rate characteristics when used in a battery. [Means for solving the problem]

[0009] The present inventors have conducted extensive research to solve the above-mentioned problems. As a result, they have succeeded in producing an electrode active material layer containing a solid electrolyte having a network structure, and have found that when such an electrode active material layer is used in an all-solid-state battery, excellent cycle characteristics and rate characteristics can be obtained. That is, in this embodiment, the following means are provided.

[0010] (1) The electrode active material layer according to the first aspect of the present invention is An electrode active material layer including an active material and a solid electrolyte, At least a portion of the solid electrolyte is reticulated.

[0011] (2) In the electrode active material layer according to the above embodiment, the network-like solid electrolyte may be a solid electrolyte represented by the following formula (1): Li 2+a E 1-b G b D c X d ···(1) (In formula (1), E is at least one element selected from the group consisting of Al, Sc, Y, Zr, Hf, and lanthanides; G is at least one element selected from the group consisting of Na, K, Rb, Cs, Mg, Ca, Sr, Ba, B, Si, Al, Ti, Cu, Sc, Y, Zr, Nb, Ag, In, Sn, Sb, Hf, Ta, W, Au, and Bi; D is at least one group selected from the group consisting of CO3, SO4, BO3, PO4, NO3, SiO3, OH, and O2; X is at least one selected from the group consisting of F, Cl, Br, and I; 0≦a<1.5, 0≦b<0.5, 0≦c≦5.0, 0 <d≦6.1である)。

[0012] (3) In the electrode active material layer according to the above embodiment, The mesh-like portion of the solid electrolyte is made of a plurality of overlapping fibers, In an image obtained by observing a cross section perpendicular to the in-plane direction of the electrode active material layer with a scanning electron microscope, When the maximum length of each of the plurality of fibers in the direction in which the aspect ratio is small is defined as the diameter of the fiber, Ten fibers selected from the plurality of fibers in order of diameter in the field of view may have an average diameter of 5 nm or more and 30 nm or less.

[0013] (4) In the electrode active material layer according to the above aspect, The mesh-like portion of the solid electrolyte is made of a plurality of overlapping fibers, In an image obtained by observing a cross section perpendicular to the in-plane direction of the electrode active material layer with a scanning electron microscope, the area of a mesh portion surrounded by the plurality of fibers or the plurality of fibers and the active material and / or the solid electrolyte is defined as a mesh portion area; The average area of the 10 mesh part areas selected in descending order of mesh part area is 70 nm 2 More than 8000nm 2 It may be the following:

[0014] (5) An electrode according to a second aspect of the present invention comprises the electrode active material layer according to the above aspect.

[0015] (6) An all-solid-state battery according to a third aspect of the present invention includes the electrode according to the above aspect. [Effects of the Invention]

[0016] When the electrode active material layer according to this embodiment is used in a battery, excellent cycle characteristics and rate characteristics can be obtained. [Brief explanation of the drawings]

[0017] [Figure 1] FIG. 1 is a cross-sectional view of an all-solid-state battery according to one embodiment of the present invention. [Figure 2] FIG. 2 is a cross-sectional view schematically illustrating a main part of an electrode active material layer according to one embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0018] The present invention will be described in detail below with reference to the drawings as appropriate. The drawings used in the following description may show characteristic parts enlarged for the sake of clarity, and the dimensional ratios, number, and arrangement of each component may differ from the actual ones. The materials, dimensions, numbers, numerical values, arrangement, etc. exemplified in the following description are merely examples, and the present invention is not limited thereto. Appropriate changes can be made within the scope of the present invention.

[0019] First, the direction will be defined. The direction in which positive electrode active material layers 1B and negative electrode active material layers 2B (described later) are stacked is the stacking direction. The stacking direction is also the in-plane direction in which positive electrode active material layers 1B and negative electrode active material layers 2B (described later) extend.

[0020] [All-solid battery] 1 is an enlarged schematic cross-sectional view of a main portion of an all-solid-state battery 100 according to this embodiment. The all-solid-state battery 100 includes an energy storage element 10 and an exterior body 20. The energy storage element 10 is accommodated in an accommodation space K within the exterior body 20. The energy storage element 10 includes a laminate 4 and external terminals 12 and 14. The external terminals 12 and 14 electrically connect the laminate 4 to the outside.

[0021] The exterior body 20 has, for example, a metal foil 22 and resin layers 24 laminated on both sides of the metal foil 22. The exterior body 20 is, for example, a metal laminate film in which a metal foil is coated on both sides with a polymer film (resin layer). The metal foil 22 is, for example, aluminum foil. The resin layer 24 is, for example, a polymer film such as polypropylene. The resin layers 24 on the inside and outside may be different. For example, the outer resin layer may be made of a polymer with a high melting point, such as polyethylene terephthalate (PET) or polyamide (PA), and the inner resin layer may be made of a material with high heat resistance, oxidation resistance, and reduction resistance, such as polyethylene (PE) or polypropylene (PP).

[0022] The laminate 4 includes, for example, at least one positive electrode layer 1, at least one negative electrode layer 2, and a solid electrolyte layer 3 between the positive electrode layer 1 and the negative electrode layer 2. The positive electrode layer 1 is an example of a first electrode layer, and the negative electrode layer 2 is an example of a second electrode layer. One of the first electrode layer and the second electrode layer functions as a positive electrode, and the other functions as a negative electrode. One end of each of the positive electrode layer 1 and the negative electrode layer 2 is connected to external terminals 12 and 14 of the corresponding polarity.

[0023] The all-solid-state battery 100 is charged and discharged by the exchange of ions between the positive electrode layer 1 and the negative electrode layer 2 via the solid electrolyte layer 3. Although a laminated type battery is shown in FIG. 1, a wound type battery may also be used. The all-solid-state battery 100 is used, for example, in laminated batteries, prismatic batteries, cylindrical batteries, coin batteries, button batteries, etc.

[0024] "Positive electrode layer" As shown in FIG. 1, the positive electrode layer 1 includes, for example, a positive electrode current collector 1A and a positive electrode active material layer 1B.

[0025] (Positive electrode current collector) The positive electrode current collector 1A is, for example, a current collector made of powder, foil, punching, or expansion. The positive electrode current collector 1A preferably has a high conductivity. For example, metals such as silver, palladium, gold, platinum, aluminum, copper, nickel, titanium, stainless steel, and their alloys, or conductive resins can be used.

[0026] (Positive electrode active material layer) The positive electrode active material layer 1B is formed on one or both sides of the positive electrode current collector 1A. The positive electrode active material layer 1B is an example of the electrode active material layer according to the present embodiment. The positive electrode active material layer 1B includes a positive electrode active material and a solid electrolyte, and may further include a conductive auxiliary agent and a binder as necessary. At least a part of the solid electrolyte provided in the positive electrode active material layer 1B is a network solid electrolyte. In the present embodiment, the materials used to form the positive electrode active material layer 1B may be collectively referred to as a positive electrode mixture.

[0027] The positive electrode active material is not particularly limited as long as it can reversibly progress the release and occlusion of lithium ions, and the desorption and insertion of lithium ions, and known positive electrode active materials used in lithium ion secondary batteries can be used. The positive electrode active material is, for example, lithium cobalt oxide (LiCoO2), lithium nickel oxide (LiNiO2), lithium manganese spinel (LiMn2O4), and the general formula: LiNi x Co y Mn z M a O2 (x + y + z + a = 1, 0 ≦ x ≦ 1, 0 ≦ y ≦ 1, 0 ≦ z ≦ 1, 0 ≦ a ≦ 1, M is one or more elements selected from Al, Mg, Nb, Ti, Cu, Zn, Cr), lithium vanadium compounds (LiV2O5, Li3V2(PO4)3, LiVOPO4), olivine-type LiMPO4 (where M represents one or more elements selected from Co, Ni, Mn, Fe, Mg, V, Nb, Ti, Al, Zr), lithium titanate (Li4Ti5O 12 ), LiNi x Co y Al z O2 (0.9 < x + y + z < 1.1), etc., are composite metal oxides.

[0028] Lithium-free positive electrode active materials can also be used as the positive electrode active material. These positive electrode active materials can be used by first placing metallic lithium or a negative electrode active material doped with lithium ions in the negative electrode layer and then starting the battery by discharging. Examples of such positive electrode active materials include lithium-free metal oxides (MnO2, V2O5, etc.), lithium-free metal sulfides (MoS2, etc.), and lithium-free fluorides (FeF3, VF3, etc.).

[0029] 2 is an example of an enlarged cross-sectional view schematically illustrating the inside of the positive electrode active material layer 1B, in which the conductive additive is omitted.

[0030] The positive electrode active material layer 1B contains positive electrode active materials AM1 and AM2 and solid electrolytes SE1 and SE2 inside. In Fig. 2, the solid electrolytes SE1 and SE2 are in contact with the positive electrode active materials AM1 and AM2, for example.

[0031] The solid electrolyte SE2 is a mesh-like solid electrolyte. The cross-sectional shape of the solid electrolyte SE2, cut perpendicularly to the in-plane direction of the positive electrode active material layer 1B, is mesh-like. The solid electrolyte SE2 has, for example, a shape in which a plurality of fibrous solid electrolytes are overlapped. Therefore, the plurality of fibrous solid electrolytes are, for example, integrated. That is, the solid electrolyte SE2 has, for example, a plurality of fibrous portions P1. For example, the fibers of each of the plurality of fibrous portions P1 branch and merge with adjacent fibers. Thus, in the positive electrode active material layer 1B according to this embodiment, the plurality of fibrous portions P1 of the solid electrolyte SE2 branch and merge, so that the solid electrolyte SE2 has a mesh portion P2 surrounded by the plurality of fibrous portions P1. The mesh-like solid electrolyte has a nest-like structure.

[0032] The mesh portion P2 is formed by a plurality of fibrous portions P1 in the cross section of the positive electrode active material layer 1B, or The mesh portion P2 is a region enclosed by the plurality of fibrous portions P1 and the positive electrode active materials AM1, AM2, and / or the solid electrolyte SE1. Note that the mesh portion P2 is a region enclosed by the plurality of fibrous portions P1 in a two-dimensional observation, but does not necessarily need to be enclosed by the plurality of fibrous portions P1 in a three-dimensional observation.

[0033] When solid electrolyte SE2 is observed using a scanning electron microscope (SEM), the brightness of the multiple fibrous portions P1 is higher than the brightness of the mesh-like portion P2. In the SEM cross-sectional image, the mesh-like portion P2 can be confirmed as a void, and the interior is thought to be filled with a substance other than solid electrolyte SE2 (e.g., vacuum).

[0034] The average diameter of each fiber in the plurality of fibrous portions P1 is, for example, 5 nm or more and 30 nm or less, and may be 10 nm or more or 20 nm or less. Here, the average diameter of each fiber in the plurality of fibrous portions P1 is the average diameter of each fiber in a cross section perpendicular to the in-plane direction of the positive electrode active material layer 1B. The average diameter of each fiber in the plurality of fibrous portions P1 can be measured by the following procedure.

[0035] First, a cross section perpendicular to the in-plane direction of the positive electrode active material layer 1B is observed using a scanning electron microscope. Next, the brightness of the network solid electrolyte SE2 is binarized and classified into a fibrous portion P1 with a brightness above a threshold and a mesh portion P2 with a brightness below the threshold (hereinafter, the binarized image is referred to as a binarized image). Next, the maximum length of each fiber in the direction with the smallest aspect ratio of the multiple fibrous portions P1 is taken as the diameter of each fiber, and 10 fibers with the largest diameter are selected. Next, the diameters of the selected 10 fibers are averaged to determine the average diameter.

[0036] The average area of the mesh portion P2 is, for example, 70 nm 2 More than 8000nm 2 less than 70nm 2 More than 3000nm 2 Below 500nm 2 More than 8000nm 2Here, the average area of the mesh portion P2 is measured by the following procedure.

[0037] First, a cross-section of the positive electrode active material layer 1B containing the mesh-like solid electrolyte SE2 is observed using an SEM to obtain a binarized image. Next, ten mesh portions P2 in the field of view are selected in descending order of area, and their areas are calculated. Next, the average area of the ten selected mesh portions (mesh portion areas) is calculated, and this is defined as the average mesh portion area.

[0038] When the brightness of the reticulated solid electrolyte SE2 in a scanning electron microscope image is binarized, for example, when the image is expressed as an 8-bit (256-level) black-and-white image, a brightness of 100 can be used as the threshold. When determining the average diameter and average area of the mesh portions, fibers with large diameters and mesh portions with large areas are selected from within the same field of view. The magnification of the SEM can be, for example, about 100,000 times.

[0039] The solid electrolytes SE1 and SE2 contained in the positive electrode active material layer 1B are, for example, compounds represented by the following formula (1): The solid electrolytes SE1 and SE2 are made of, for example, the same material. Li 2+a E 1-b G b D c X d ···(1) (0≦a<1.5, 0≦b<0.5, 0≦c≦5.0, 0 <d≦6.1)

[0040] In the above formula (1), E is at least one element selected from the group consisting of Al, Sc, Y, Zr, Hf, and lanthanoids. Lanthanoids are La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. When the solid electrolyte contains the element E, the potential window of the solid electrolyte is widened. E preferably contains Sc or Zr, and particularly preferably Zr. When E contains Sc or Zr, the ionic conductivity of the solid electrolyte is increased.

[0041] In the above formula (1), G is at least one element selected from the group consisting of Na, K, Rb, Cs, Mg, Ca, Sr, Ba, B, Si, Al, Ti, Cu, Sc, Y, Zr, Nb, Ag, In, Sn, Sb, Hf, Ta, W, Au, and Bi. When the solid electrolyte contains the element G, the amount of lithium ions, which are carrier ions, increases or decreases, thereby increasing the ionic conductivity.

[0042] In the above formula (1), D is at least one group selected from the group consisting of CO3, SO4, BO3, PO4, NO3, SiO3, OH, and O2. If the covalent bond between D and E is strong, the ionic bond between E and X will also be strong. For this reason, it is presumed that E in the compound is difficult to reduce, resulting in a compound with a wide potential window on the reduction side.

[0043] In the above formula (1), X is at least one element selected from the group consisting of F, Cl, Br, and I. X has a large ionic radius per valence. When the solid electrolyte contains X, the conductivity of lithium ions in the solid electrolyte increases. In order to increase the ionic conductivity of the solid electrolyte, X preferably contains Cl. In order to improve the balance between the oxidation resistance and reduction resistance of the solid electrolyte, X preferably contains F. In order to increase the reduction resistance of the solid electrolyte, X preferably contains I. When the solid electrolyte contains D, the potential window on the reduction side of the solid electrolyte becomes wider.

[0044] In this embodiment, a positive electrode active material layer 1B containing a solid electrolyte, at least a part of which is a network portion, is obtained by mixing a positive electrode mixture with a solid electrolyte and processing the mixture by a predetermined method.

[0045] "Negative electrode" As shown in FIG. 1, the negative electrode layer 2 includes, for example, a negative electrode current collector 2A and a negative electrode active material layer 2B containing a negative electrode active material.

[0046] (Negative electrode current collector) The negative electrode current collector 2A is, for example, a current collector made of powder, foil, punching, or expansion. The negative electrode current collector 2A preferably has a high conductivity. For example, metals such as silver, palladium, gold, platinum, aluminum, copper, nickel, stainless steel, iron, and their alloys, or conductive resins may be used.

[0047] (Negative electrode active material layer) The negative electrode active material layer 2B is formed on one or both sides of the negative electrode current collector 2A. The negative electrode active material layer 2B contains a negative electrode active material and may further contain a conductive assistant, a binder, and a solid electrolyte as required. As the solid electrolyte, the same solid electrolyte as that contained in the solid electrolyte layer may be included. In this embodiment, the materials used to form the negative electrode active material layer 2B may be collectively referred to as the negative electrode mixture.

[0048] The negative electrode active material contained in the negative electrode active material layer 2B may be any compound that can occlude and release mobile ions, and known negative electrode active materials used in lithium ion secondary batteries can be used. The negative electrode active material is, for example, an alkali metal simple substance, an alkali metal alloy, carbon materials such as graphite (natural graphite, artificial graphite), carbon nanotubes, non-graphitizable carbon, graphitizable carbon, low-temperature fired carbon, etc., metals such as aluminum, silicon, tin, germanium and their alloys, etc., which can combine with metals such as alkali metals, SiO x (0 < x < 2), oxides such as iron oxide, titanium oxide, tin dioxide, etc., lithium metal oxides such as lithium titanate (Li4Ti5O 12 ) etc.

[0049] (Conductive assistant) The conductive assistant is not particularly limited as long as it can improve the electron conductivity in the positive electrode active material layer 1B and the negative electrode active material layer 2B, and known conductive assistants can be used. The conductive assistant is, for example, carbon-based materials such as graphite, carbon black, graphene, carbon nanotubes, etc., metals such as gold, platinum, silver, palladium, aluminum, copper, nickel, stainless steel, iron, etc., conductive oxides such as ITO, or mixtures thereof. The conductive assistant may be in the form of powder or fiber.

[0050] (binder) The binder bonds together various materials constituting the positive electrode current collector 1A and the positive electrode active material layer 1B, the positive electrode active material layer 1B and the solid electrolyte layer 3, the positive electrode active material layer 1B, the negative electrode current collector 2A and the negative electrode active material layer 2B, the negative electrode active material layer 2B and the solid electrolyte layer 3, and the negative electrode active material layer 2B.

[0051] The binder can be used within a range that does not impair the functions of the positive electrode active material layer 1B and the negative electrode active material layer 2B. If a binder is not required, it need not be contained. The content of the binder in the positive electrode active material layer 1B and the negative electrode active material layer 2B is, for example, 0.5 to 30% by volume of the positive electrode active material layer 1B and the negative electrode active material layer 2B. If the content of the binder is within this range, the resistance of the positive electrode active material layer 1B and the negative electrode active material layer 2B will be sufficiently low.

[0052] Any binder may be used as long as it is capable of forming the above-mentioned bonds, and examples thereof include fluororesins such as polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE). In addition to the above, binders such as cellulose, styrene-butadiene rubber, ethylene-propylene rubber, polyimide resin, and polyamide-imide resin may also be used. Furthermore, conductive polymers with electronic conductivity or ionic conductive polymers with ionic conductivity may also be used. Examples of conductive polymers with electronic conductivity include polyacetylene. In this case, the binder also functions as a conductive additive particle, so no conductive additive is required. Examples of ionic conductive polymers with ionic conductivity include those that conduct lithium ions, such as polymers (polyether-based polymers such as polyethylene oxide and polypropylene oxide, polyphosphazene, etc.) that are composited with a monomer of a polymer compound and a lithium salt or lithium-based alkali metal salt such as LiClO4, LiBF4, or LiPF6. The polymerization initiator used for the composite is, for example, a photopolymerization initiator or a thermal polymerization initiator that is compatible with the above-mentioned monomers. The properties required for the binder include oxidation / reduction resistance and good adhesiveness.

[0053] "Solid electrolyte layer" The solid electrolyte layer 3 is located between the positive electrode layer 1 and the negative electrode layer 2. The solid electrolyte layer 3 includes a solid electrolyte. The solid electrolyte is a substance (e.g., particles) that can move ions when an externally applied electric field is applied. For example, lithium ions move within the solid electrolyte when an externally applied electric field is applied. The solid electrolyte is also an insulator that inhibits the movement of electrons.

[0054] The solid electrolyte includes, for example, lithium. For the solid electrolyte layer 3, for example, the same material as the solid electrolyte contained in the positive electrode active material layer 1B can be used. Furthermore, the solid electrolyte contained in the solid electrolyte layer 3 may be a solid electrolyte different from the solid electrolyte contained in the positive electrode active material layer 1B.

[0055] The solid electrolyte may be, for example, a sulfide-based material, or may be, for example, a perovskite-type compound, a lithizone-type compound, a garnet-type compound, a nasicon-type compound, a thiolithizone-type compound, a glass compound, or a phosphate compound. 0.5 Li 0.5 TiO3 is an example of a perovskite compound. 14 Zn(GeO4)4 is an example of a lysicone-type compound. i7 La3Zr2O 12 is an example of a garnet-type compound. LiZr2(PO4)3, Li 1.3 Al 0.3 Ti 1.7 (PO4) 3、 Li 1.5 Al 0.5 Ge 1.5 (PO4)3, Li 1.55 Al 0.2 Zr 1.7 Si 0.25 P 9.75 O 12 , Li 1.4 Na 0.1 Zr 1.5 Al 0.5 (PO4)3, Li 1.4 Ca 0.25 Er 0.3 Zr1.7 (PO4) 3.2 , Li 1.4 Ca 0.25 Yb 0.3 Zr 1.7 (PO4) 3.2 is an example of a Nasicon-type compound. 3.25 Ge 0.25 P 0.75 S 4、 Li3PS4 is an example of a thiolisicone-type compound. Li2S-P2S 5、 Li2O-V2O5-SiO2 is an example of a glass compound. 3.5 Si 0.5 P 0.5 O4, Li 2.9 PO 3.3 N 0.46 is an example of a phosphate compound. The solid electrolyte may contain one or more of these compounds.

[0056] (action) In all-solid-state batteries, the electrode active material contained in the electrode active material layer repeatedly expands and contracts during charging and discharging. In conventional all-solid-state batteries, repeated expansion and contraction of the electrode active material can sometimes cause separation between the solid electrolyte and the electrode active material, and between the electrode active materials themselves, for example, at the interface between the electrode layer and the solid electrolyte layer. That is, spaces can sometimes be created between the solid electrolyte and the electrode active material, and between the electrode active materials themselves. As a result, conventional all-solid-state batteries can sometimes experience peeling or cracking of the electrode layer. That is, they have a problem of prone to deterioration in cycle characteristics. In addition, lithium ion conduction paths and electron conduction paths can be blocked, increasing interfacial resistance and deteriorating rate characteristics.

[0057] In an all-solid-state battery 100 including the cathode active material layer 1B according to this embodiment, even when the cathode active materials AM1 and AM2 repeatedly expand and contract, the network-like solid electrolyte SE2 absorbs stresses associated with the expansion and contraction of the cathode active materials AM1 and AM2 and strains due to volume changes in the all-solid-state battery 100. This prevents spaces from forming between the solid electrolytes SE1 and SE2 and the cathode active materials AM1 and AM2, and between the cathode active materials (AM1 and AM2). This prevents peeling and cracking of the electrode layer. Furthermore, it prevents interruption of the lithium ion conduction pathway or the electron conduction pathway, which can lead to an increase in interfacial resistance and a decrease in rate characteristics. In other words, the use of the electrode active material layer according to this embodiment allows for excellent cycle characteristics and rate characteristics to be obtained.

[0058] Furthermore, in the positive electrode active material layer 1B according to this embodiment, the mesh portions P2 of the mesh-like solid electrolyte SE2 are responsible for distortion due to volumetric changes in the all-solid-state battery 100. Increasing the voids between the solid electrolyte and the active material can also alleviate distortion due to volumetric changes in the all-solid-state battery 100. However, in this case, the greater the proportion of voids present, the fewer the lithium ion conduction paths and electron conduction paths, resulting in a smaller capacity of the all-solid-state battery 100. In contrast, the mesh-like solid electrolyte SE2 can ensure lithium ion conduction paths while also ensuring voids that alleviate volumetric changes.

[0059] The all-solid-state battery including the electrode active material layer according to this embodiment is not limited to the above example. For example, in the above example, the cathode active material layer 1B of the electrode active material layer contains at least a portion of a network-like solid electrolyte. However, the anode active material layer 2B of the electrode active material layer may contain at least a portion of a network-like solid electrolyte. The solid electrolyte contained in the anode active material layer 2B may be, for example, the same solid electrolyte as the solid electrolyte contained in the cathode active material layer 1B. The average diameter of the fibrous solid electrolyte in the anode active material layer 2B, the average area of the network portion, and the methods for determining them are the same as those in the example described above for the cathode active material layer 1B.

[0060] Even when only the negative electrode active material layer 2B contains a solid electrolyte at least partially in a mesh-like structure, the mesh-like solid electrolyte absorbs stress caused by expansion and contraction of the negative electrode active material and strain caused by volumetric changes in the all-solid-state battery, as in the case when only the positive electrode active material layer 1B contains a solid electrolyte at least partially in a mesh-like structure, and therefore excellent cycle characteristics and rate characteristics can be obtained.

[0061] An all-solid-state battery in which both the positive electrode active material layer 1B and the negative electrode active material layer 2B contain a solid electrolyte, at least a portion of which is network-like, can achieve particularly excellent cycle characteristics and rate characteristics. When the negative electrode active material layer 2B contains a solid electrolyte, at least a portion of which is network-like, the solid electrolyte may have the same structure as the solid electrolyte contained in the positive electrode active material layer 1B.

[0062] 1 illustrates an all-solid-state battery 100 having one each of a positive electrode layer 1, a negative electrode layer 2, and a solid electrolyte layer 3, but the all-solid-state battery according to this embodiment may have two or more of the positive electrode layer 1, the negative electrode layer 2, and the solid electrolyte layer 3. In this case, it is sufficient that at least one of the positive electrode active material layer or the negative electrode active material layer contains a solid electrolyte at least a portion of which is reticulated.

[0063] [Manufacturing method for all-solid-state batteries] Next, a method for manufacturing an all-solid-state battery according to this embodiment will be described. The all-solid-state battery can be manufactured using, for example, a powder molding method. First, a resin holder with a through hole in the center, a lower punch, and an upper punch are prepared. The diameter of the through hole in the resin holder is, for example, 12 mm, and the diameters of the lower punch and upper punch are, for example, 11.99 mm.

[0064] A lower punch is inserted from below the through-hole of the resin holder, and powdered positive electrode mixture, solid electrolyte, and negative electrode mixture are poured into the opening of the resin holder. Next, an upper punch is inserted on top of the poured powdered materials, and the resin holder is placed in a press and pressed. The pressing pressure is, for example, 20 kPa. When the solid electrolyte layer is formed only from the solid electrolyte contained in the positive electrode mixture and / or the negative electrode mixture, it is not necessary to add the solid electrolyte separately from the positive electrode mixture and the negative electrode mixture.

[0065] Examples of solid electrolytes that can be added to the positive electrode mixture include Li3YCl6, Li2ZrCl6, and Li2ZrSO4Cl6.

[0066] The powder material is pressed by an upper punch and a lower punch in a resin holder to form a compact in which the positive electrode active material layer 1B, the solid electrolyte layer 3, and the negative electrode active material layer 2B are laminated.

[0067] Next, the upper punch is removed, and the positive electrode current collector 1A and the upper punch are inserted in this order on top of the positive electrode active material layer 1B. The lower punch is also removed, and the negative electrode current collector 2A and the lower punch are inserted in this order on top of the negative electrode active material layer 2B. The positive electrode current collector 1A and the negative electrode current collector 2A are, for example, aluminum foil or copper foil with a diameter of 12 mm. Through the above procedure, a laminate 4 is obtained in which the positive electrode current collector 1A / positive electrode active material layer 1B / solid electrolyte layer 3 / negative electrode active material layer 2B / negative electrode current collector 2A are laminated in this order.

[0068] The laminate 4 may be made of a stainless steel disk and a Bakelite disk, each having four screw holes, stacked in the following order: stainless steel disk / Bakelite disk / upper punch / electricity storage element 10 / lower punch / Bakelite disk / stainless steel disk, and then fastened with four screws. This configuration improves the bonding strength between the upper punch and positive electrode current collector 1A, between the positive electrode current collector 1A and positive electrode active material 1B, between the lower punch and negative electrode current collector 2A, and between the negative electrode current collector 2A and negative electrode active material 2B. The energy storage element 10 may have a similar structure with a shape-retaining function.

[0069] Next, screws are inserted into the screw holes provided on the side surfaces of the upper punch and the lower punch, and the punch is inserted into the exterior body to which the external terminals 12, 14 are attached, and the screws attached to the side surfaces of the upper punch and the lower punch are connected to the external terminals 12, 14 with lead wires or the like. The battery is then housed in the exterior body 20. The exterior body 20 improves the weather resistance of the all-solid-state battery 100. Thereafter, the exterior body 20 may be heat-sealed except for one opening. Alternatively, the remaining opening may then be heat-sealed while the interior of the exterior body 20 is evacuated. In this manner, an all-solid-state battery is manufactured.

[0070] Next, the all-solid-state battery is subjected to two cycles of charging and discharging while applying pressure, followed by maintaining the temperature and time for aging treatment. The aging treatment can be performed under the following conditions, for example. By performing the aging treatment, defective products can be removed. Pressure can be applied to the all-solid-state battery by, for example, holding the all-solid-state battery between a hydraulic press (Shimazu Manufacturing Co., Ltd., model: SSP-10A) and charging and discharging the battery while applying pressure.

[0071] For example, charging the all-solid-state battery during aging treatment is performed at 0.1C, and the potential of the positive electrode is 4.3V (vsLi / Li + ) until the potential of the negative electrode reaches 0.1 V (vs Li / Li + ), and then constant voltage charging is performed until the current density reaches 0.05 C. That is, the charging voltage of the positive electrode is 4.3 V (vs Li / Li + ), and the negative electrode charging voltage was 0.1 V (vs Li / Li + ) can be achieved. For example, the discharge of the all-solid-state battery in the aging treatment is performed at 0.1 C until the potential of the positive electrode reaches 0.1 V (vs Li / Li + At this time, the pressure applied to the all-solid-state battery can be, for example, 5 kPa or more and 10 kPa or less.

[0072] Next, an aging treatment is performed by controlling the pressure, temperature, and time. The pressure during the aging treatment can be maintained at the same pressure applied to the all-solid-state battery during charging. The temperature during the aging treatment can be, for example, 70°C or higher and 85°C or lower. The time period for the aging treatment can be, for example, 30 minutes or higher and 90 minutes or lower. The conditions for the aging treatment can be changed as appropriate as long as an all-solid-state battery having an electrode active material layer at least a portion of which contains a network-like solid electrolyte can be produced.

[0073] Through the above steps, an all-solid-state battery 100 is manufactured in which at least a portion of the positive electrode active material layer 1B contains a network-like solid electrolyte.

[0074] In order to obtain an all-solid-state battery containing a network-like solid electrolyte in at least a part of the negative electrode active material layer 2B, for example, the charging voltage of the positive electrode is set to 4.2 V (vs Li / Li + ), and the charging voltage of the negative electrode is 0.05V (vs Li / Li + ) to 4.3 V (vs Li / Li). In order to manufacture an all-solid-state battery in which at least a portion of the positive electrode active material layer 1B and the negative electrode active material layer 2B contains a network-like solid electrolyte, for example, the charging voltage of the positive electrode may be changed to 4.3 V (vs Li / Li). + ), and the charging voltage of the negative electrode is 0.05V (vs Li / Li + ) simply change the charging conditions.

[0075] The method for manufacturing an all-solid-state battery according to the present embodiment can manufacture the all-solid-state battery according to the present embodiment through the above steps. The all-solid-state battery according to the present embodiment cannot be manufactured under manufacturing conditions in which the charging voltage is low during the manufacturing process or under conditions in which no pressure is applied during charging.

[0076] The above describes in detail one embodiment of the present invention with reference to the drawings. However, each configuration and combination thereof in the above embodiment is merely an example, and addition, omission, substitution, and other modifications of the configuration are possible within the scope that does not deviate from the gist of the present invention. [Example]

[0077] "Example 1" The all-solid-state battery of Example 1 was fabricated by the following procedure.

[0078] (Preparation of positive electrode mixture) A positive electrode active material, a conductive additive, and a solid electrolyte were prepared as a positive electrode mixture. The positive electrode active material, conductive additive, and solid electrolyte were weighed out to be 60 wt%, 5 wt%, and 40 wt%, respectively. Lithium cobalt oxide (LiCoO2) was used as the positive electrode active material. Acetylene black was used as the conductive additive. Li2ZrCl6 was used as the solid electrolyte.

[0079] (Preparation of negative electrode mixture) A negative electrode active material, a conductive additive, and a solid electrolyte were prepared as the negative electrode mixture. The negative electrode active material, conductive additive, and solid electrolyte were weighed out to be 60 wt%, 5 wt%, and 40 wt%, respectively. Lithium cobalt oxide (LiCoO2) was used as the negative electrode active material. Acetylene black was used as the conductive additive. Li2ZrCl6 was used as the solid electrolyte.

[0080] (Production of molded body) First, a resin holder with a 12 mm diameter through-hole in the center, a lower punch made of SKD11 material with a diameter of 11.99 mm, and an upper punch were prepared. The lower punch was inserted from below the through-hole of the resin holder, and the negative electrode mixture was poured into the open side of the resin holder. At this time, the negative electrode active material in the negative electrode mixture was positioned on the lower punch side, and the solid electrolyte was positioned on the open side. Next, the positive electrode mixture was poured into the resin holder. At this time, the solid electrolyte in the positive electrode mixture was positioned on the lower punch side, and the positive electrode active material was positioned on the open side.

[0081] Next, an upper punch was inserted, and a unit having the upper punch, a resin holder for accommodating the positive electrode mixture and the negative electrode mixture, and the lower punch was placed in a press and pressed at 20 kPa to produce a compact.

[0082] Next, the upper punch was removed, and a positive electrode current collector (aluminum foil, 12 mm in diameter, 15 μm in thickness) and the upper punch were inserted in this order on top of the positive electrode active material. The lower punch was also removed, and a negative electrode current collector (copper foil, 12 mm in diameter, 9 μm in thickness) and the lower punch were inserted in this order on top of the negative electrode active material layer to obtain a fourth unit.

[0083] Next, a 50 mm, 5 mm thick stainless steel disk and a Bakelite disk with four screw holes were prepared, and the battery elements were set as follows: stainless steel disk / Bakelite disk / fourth unit / Bakelite disk / stainless steel disk, and the fifth unit was created by tightening the four screws. Screws for connecting external terminals were inserted into the screw holes on the sides of the upper and lower punches.

[0084] The resulting energy storage element was then housed in an exterior case. An A4-sized aluminum laminate bag was prepared as the exterior case. Aluminum foil (4 mm wide, 40 mm long, 100 μm thick) wrapped with maleic anhydride-grafted polypropylene (PP) was attached to one side of the aluminum laminate opening as an external terminal, and nickel foil (4 mm wide, 40 mm long, 100 μm thick) was thermally bonded at a distance to prevent short-circuiting. The fourth unit was inserted into the aluminum laminate bag with the external terminal attached, and lead wires were connected between the screw on the side of the upper punch and the aluminum terminal extending inside the exterior case, and between the screw on the side of the lower punch and the nickel terminal extending inside the exterior case.

[0085] Next, the all-solid-state battery was charged while applying pressure using a charger / discharger SD8 (manufactured by Hokuto Denko Corporation). The pressure on the all-solid-state battery was 5 kPa. The all-solid-state battery was charged at a constant current of 0.1 C until the potential of the positive electrode reached 4.3 V (vs. Li / Li+) and the potential of the negative electrode reached 0.1 V (vs. Li / Li+), and then constant voltage was charged until the current density reached 0.05 C.

[0086] Next, an aging treatment was performed by adjusting the temperature and time while maintaining pressure on the all-solid-state battery. The temperature and time were set to 70°C for 45 minutes. The aging treatment was performed in two cycles. In this way, the all-solid-state battery of Example 1 was prepared.

[0087] (cross-sectional measurement) First, the positive electrode active material layer and the negative electrode active material layer of the fabricated all-solid-state battery were observed using an SEM (SEM observation conditions: accelerating voltage: 1 kV, emission current value: 2 μA, WD (sample stage height): 2 mm). Next, the obtained images were binarized as 8-bit (256 gradations) black-and-white images using image analysis software, ImageJ. At this time, a brightness of 100 was used as the threshold. The observed cross sections of the positive electrode active material layer and the negative electrode active material layer were cross sections perpendicular to the in-plane direction of each.

[0088] Next, the positive electrode active material layer and the negative electrode active material layer were each observed for the presence or absence of a network-like solid electrolyte. If a network-like solid electrolyte was confirmed, the average diameter of the multiple fibrous portions and the average area of the network portions were calculated based on the binarized image.

[0089] The average diameter of the multiple fibrous portions was calculated by taking the maximum length of each fiber in the multiple fibrous portions P1 in the direction with the smallest aspect ratio as the diameter of each fiber, selecting 10 fibers with the largest diameter, determining their respective diameters, and calculating the average of these.

[0090] The average area of the mesh portions was calculated by selecting 10 mesh portions P2 in the visual field in descending order of area, determining the area of each, and then calculating the average area.

[0091] (Battery evaluation: cycle characteristics) After discharge, the initial capacity and cycle characteristics of the all-solid-state battery of Example 1 were determined. The initial capacity and cycle characteristics were measured using a secondary battery charge / discharge tester. The voltage range was from 4.2 V to 0.1 V. First, a 0.2 C constant current charge was performed as a pre-treatment. Then, charge / discharge was performed to determine the cycle characteristics. Charging was performed at a constant current. Charging was performed at a current value of 0.1 C, and after reaching 4.2 V, it was terminated when the current value reached 50% of the 0.1 C current value. Discharging was performed under conditions of discharging at a current value of 0.1 C.

[0092] The cycle characteristics were evaluated as the capacity retention rate (%). The capacity retention rate (%) is the ratio of the discharge capacity after 100 cycles to the initial discharge capacity, where the discharge capacity at the first cycle is the initial discharge capacity. The capacity retention rate (%) is expressed by the following formula: Capacity retention rate (%) = ("Discharge capacity after 100 cycles" / "Discharge capacity at the first cycle") x 100

[0093] (Battery evaluation: discharge rate characteristics) The discharge rate characteristics of the all-solid-state battery of Example 1 were also evaluated. The discharge rate characteristics were determined as the ratio (%) of the discharge capacity at a discharge rate of 2C (a current value at which discharge ends in 30 minutes when constant current discharge is performed at 25°C) to the discharge capacity at a discharge rate of 2C (a current value at which discharge ends in 1 hour when constant current discharge is performed at 25°C) taken as 100%.

[0094] To evaluate the discharge rate characteristics, the fabricated cells were subjected to an initial charge / discharge cycle and the actual capacity of the fabricated cells was measured. Based on the actual capacity obtained, the current densities at discharge rates of 1C and 2C were determined.

[0095] After the initial charge / discharge, the battery was charged at a constant current of 0.2 C to 4.2 V, and then charged at a constant voltage of 0.05 C until the current density reached 0.05 C. After a 10-minute rest period, the battery was discharged at a constant current of 1 C to 0.1 V, and the discharge capacity at 1 C was measured. After the measurement, a 5-minute rest period was taken.

[0096] Thereafter, the battery was charged at a constant current of 0.2 C up to 4.2 V, and then charged at a constant voltage until the current density reached 0.05 C. After a 10-minute rest period, the battery was discharged at a constant current of 2 C down to 0.1 V, and the discharge capacity at 2 C was measured.

[0097] "Examples 2 to 4" Example 2 differs from Example 1 in that the aging treatment time is 45 minutes. Example 3 differs from Example 1 in that constant current charging of the all-solid-state battery was carried out until the potential of the positive electrode reached 4.2 V (vs. Li / Li+) and the potential of the negative electrode reached 0.05 V (vs. Li / Li+). That is, the charging voltage of the positive electrode was set to 4.2 V (vs. Li / Li+) and the charging voltage of the negative electrode was set to 0.05 V (vs. Li / Li+). Example 4 differs from Example 1 in that the charging voltages of the positive electrode and negative electrode were 4.2 V (vs Li / Li+) and 0.05 V (vs Li / Li+), respectively, and the aging treatment time was 45 minutes. In Examples 2 to 4, all-solid-state batteries were produced under the same conditions as in Example 1, and measurements similar to those in Example 1 were carried out.

[0098] "Examples 5 to 10" Example 5 differs from Example 1 in that the pressure when charging the all-solid-state battery was set to 10 kPa. Example 6 differs from Example 1 in that the pressure when charging the all-solid-state battery was 10 kPa, and the charging voltages of the positive electrode and negative electrode were 4.2 V (vs Li / Li+) and 0.05 V (vs Li / Li+), respectively. Example 7 differs from Example 1 in that the pressure when charging the all-solid-state battery was set to 10 kPa and the aging treatment time was set to 45 minutes. Example 8 differs from Example 1 in that the pressure when charging the all-solid-state battery was 10 kPa, the charging voltages of the positive electrode and negative electrode were 4.2 V (vs Li / Li+) and 0.05 V (vs Li / Li+), respectively, and the aging treatment time was 45 minutes. Example 9 differs from Example 1 in that the pressure when charging the all-solid-state battery was set to 10 kPa and the aging treatment time was set to 60 minutes. Example 10 differs from Example 1 in that the pressure when charging the all-solid-state battery was 10 kPa, the charging voltages of the positive electrode and negative electrode were 4.2 V (vs Li / Li+) and 0.05 V (vs Li / Li+), respectively, and the aging treatment time was 60 minutes. In Examples 5 to 10, all-solid-state batteries were produced under the same conditions as in Example 1, and measurements similar to those in Example 1 were carried out.

[0099] "Examples 11 to 20" Example 11 differs from Example 1 in that the pressure when charging the all-solid-state battery was 10 kPa, and the aging temperature was 80°C and the aging time was 60 minutes. The other conditions were the same as those of Example 1, and the all-solid-state battery was manufactured. Example 12 differs from Example 11 in that the aging treatment time was 15 minutes. Example 13 differs from Example 11 in that the aging treatment time was 30 minutes. Example 14 differs from Example 11 in that the aging treatment time was 90 minutes. Example 15 differs from Example 11 in that the aging treatment time was 120 minutes. In Examples 12 to 15, all-solid-state batteries were produced in the same manner as in Example 11 except for the above. In addition, the all-solid-state batteries of Examples 11 to 15 were subjected to the same measurements as in Example 1.

[0100] Example 16 differs from Example 1 in that the pressure when charging the all-solid-state battery was 10 kPa, the charging voltages of the positive electrode and negative electrode were 4.2 V (vs Li / Li+) and 0.05 V (vs Li / Li+), respectively, and the aging treatment temperature was 80°C and the aging treatment time was 60 minutes. All-solid-state batteries were manufactured under the same conditions as in Example 1. Example 17 differs from Example 16 in that the aging treatment temperature was 80° C. and the aging treatment time was 15 minutes. Example 18 differs from Example 16 in that the aging treatment time was 30 minutes. Example 19 differs from Example 16 in that the aging treatment time was 90 minutes. Example 20 differs from Example 16 in that the aging treatment time was 120 minutes. In Examples 17 to 20, all-solid-state batteries were produced under the same conditions as in Example 16. Furthermore, the all-solid-state batteries of Examples 16 to 20 were subjected to the same measurements as in Example 1.

[0101] "Examples 21 and 22" Example 21 differs from Example 1 in that the pressure when charging the all-solid-state battery was 10 kPa, the charging voltages of the positive electrode and negative electrode were 4.3 V (vs Li / Li+) and 0.05 V (vs Li / Li+), respectively, and the aging treatment temperature was 85°C and the aging treatment time was 60 minutes. All-solid-state batteries were manufactured under the same conditions as in Example 1. Example 22 differs from Example 21 in that the aging treatment time was 90 minutes. The other conditions were the same as in Example 21, and an all-solid-state battery was produced. The same measurements as in Example 1 were performed on the all-solid-state batteries of Examples 21 and 22.

[0102] "Comparative Example 1" Comparative Example 1 differs from Example 1 in that no pressure was applied when charging the all-solid-state battery, and that the charging voltages of the positive electrode and negative electrode were 4.0 V (vs. Li / Li+) and 0.5 V (vs. Li / Li+), respectively. Other conditions were the same as in Example 1, and an all-solid-state battery was produced, and measurements similar to those in Example 1 were carried out.

[0103] The conditions for Examples 1 to 22 and Comparative Example 1 are summarized in the following Table 1. The results for Examples 1 to 22 and Comparative Example 1 are summarized in Table 2.

[0104] [Table 1]

[0105] [Table 2]

[0106] As shown in Table 2, in the all-solid-state batteries of Examples 1, 2, 5, 7, and 22 to 15, a solid electrolyte having at least a partial network structure was confirmed in the positive electrode active material layer. Furthermore, in the all-solid-state batteries of Examples 3, 4, 6, 8, and 16 to 20, a solid electrolyte having at least a partial network structure was confirmed in the negative electrode active material layer. Furthermore, in the all-solid-state batteries of Examples 21 and 22, a solid electrolyte having at least a partial network structure was confirmed in both the positive electrode active material layer and the negative electrode active material layer. On the other hand, in Comparative Example 1, a solid electrolyte having at least a partial network structure was not confirmed in either the positive electrode active material layer or the negative electrode active material layer.

[0107] It was confirmed that Examples 1 to 22 had excellent cycle characteristics and rate characteristics compared to Comparative Example 1. In particular, Examples 5 to 22, in which the average diameter of the plurality of fibers of the network-like solid electrolyte contained in the electrode active material layer was in the range of 5 nm to 30 nm, exhibited particularly high cycle characteristics and rate characteristics. In addition, in Examples 5 to 22, in which the average area of the network portion contained in the electrode active material layer was 70 nm 2 More than 200nm 2 Particularly high cycle characteristics and rate characteristics were obtained in the following Examples 11 to 22. Furthermore, in Examples 21 and 22, in which both the positive electrode active material layer and the negative electrode active material layer had at least a portion of a network-like solid electrolyte, particularly high cycle characteristics and rate characteristics were obtained. [Explanation of symbols]

[0108] 1 Positive electrode layer 1A positive electrode current collector 1B Cathode active material layer 2. Negative electrode layer 2A negative electrode current collector 2B Negative electrode active material layer 3 Solid electrolyte layer 4 Laminate 10. Energy storage element 12,14 External terminals 20 Exterior body 100 solid state battery SE1,SE2 Solid electrolyte AM1,AM2 Positive electrode active material P1 Fibrous part P2 mesh part

Claims

1. An electrode active material layer including an active material and a solid electrolyte, At least a portion of the solid electrolyte is reticulated, The mesh-like portion of the solid electrolyte is made of a plurality of overlapping fibers, In an image obtained by observing a cross section perpendicular to the in-plane direction of the electrode active material layer with a scanning electron microscope, When the maximum length of each of the plurality of fibers in the direction in which the aspect ratio is small is defined as the diameter of the fiber, and the area of a mesh portion surrounded by the plurality of fibers or the plurality of fibers and the active material and / or the solid electrolyte is defined as a mesh portion area, Ten fibers selected from the plurality of fibers in order of diameter in the field of view have an average diameter of 5 nm or more and 30 nm or less, an electrode active material layer, wherein the average area of the ten mesh portion areas selected in descending order of mesh portion area is 70 nm 2 or more and 8000 nm 2 or less;

2. The solid electrolyte is represented by the following formula (1): Li ２＋ａ E １－ｂ G ｂ D ｃ X ｄ ・・・(1) (In formula (1), E is at least one element selected from the group consisting of Al, Sc, Y, Zr, Hf, and lanthanides; G is at least one element selected from the group consisting of Na, K, Rb, Cs, Mg, Ca, Sr, Ba, B, Si, Al, Ti, Cu, Sc, Y, Zr, Nb, Ag, In, Sn, Sb, Hf, Ta, W, Au, and Bi; D is CO ３ , S.O. ４ , B.O. ３ , P.O. ４ , NO ３ , SiO ３ , O.H., O. ２ and at least one group selected from the group consisting of X is at least one selected from the group consisting of F, Cl, Br, and I; 0≦a<1.5, 0≦b<0.5, 0≦c≦5.0, 0<d≦6.1) The electrode active material layer according to claim 1 .

3. An electrode comprising the electrode active material layer according to claim 1 or 2.

4. An all-solid-state battery comprising the electrode according to claim 3 .

5. A battery comprising: a positive electrode active material layer containing a positive electrode active material; and a negative electrode active material layer containing a negative electrode active material, The all-solid-state battery according to claim 4 , wherein the positive electrode active material layer and the negative electrode active material layer are the electrode active material layers.

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