Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
  • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
  • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
  • H01M10/0562—Solid materials
• • H—ELECTRICITY
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  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/058—Construction or manufacture
  • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
• • H—ELECTRICITY
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  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
• • H—ELECTRICITY
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  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/10—Primary casings; Jackets or wrappings
  • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
  • H01M50/109—Primary casings; Jackets or wrappings characterised by their shape or physical structure of button or coin shape
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/10—Primary casings; Jackets or wrappings
  • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
  • H01M50/117—Inorganic material
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
  • H01M50/431—Inorganic material
• • H—ELECTRICITY
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  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
  • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/50—Current conducting connections for cells or batteries
  • H01M50/543—Terminals
  • H01M50/545—Terminals formed by the casing of the cells
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/50—Current conducting connections for cells or batteries
  • H01M50/543—Terminals
  • H01M50/547—Terminals characterised by the disposition of the terminals on the cells
  • H01M50/548—Terminals characterised by the disposition of the terminals on the cells on opposite sides of the cell
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/50—Current conducting connections for cells or batteries
  • H01M50/543—Terminals
  • H01M50/564—Terminals characterised by their manufacturing process
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
  • H01M2010/4292—Aspects relating to capacity ratio of electrodes/electrolyte or anode/cathode
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M2300/00—Electrolytes
  • H01M2300/0017—Non-aqueous electrolytes
  • H01M2300/0065—Solid electrolytes
  • H01M2300/0068—Solid electrolytes inorganic
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M2300/00—Electrolytes
  • H01M2300/0017—Non-aqueous electrolytes
  • H01M2300/0065—Solid electrolytes
  • H01M2300/0068—Solid electrolytes inorganic
  • H01M2300/0071—Oxides
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M2300/00—Electrolytes
  • H01M2300/0088—Composites
  • H01M2300/0094—Composites in the form of layered products, e.g. coatings
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries

Definitions

• the present invention relates to an all-solid-state battery.
• all-solid-state batteries generally have lower lithium-ion conductivity than lithium-ion secondary batteries using organic electrolytes.
• the all-solid-state battery has higher internal resistance and lower charge/discharge rate characteristics than a lithium-ion secondary battery using an organic electrolyte. Therefore, in order to reduce the internal resistance, it was necessary to design the battery structure so that the active material layer and the solid electrolyte layer were thin. As a result, the proportion of the active material responsible for the capacity of the all-solid-state battery in the all-solid-state battery is small, and the discharge capacity per unit volume is small. ⁇ 2020/175632 2 (:171? 2020/008075
• Patent Document 1 discloses that a polyanion compound is used for each of a positive electrode active material, a negative electrode active material, and a solid electrolyte of an all-solid battery, and a polyanion constituting each of the positive electrode active material, the negative electrode active material, and the solid electrolyte. It is described that the element group (X) that becomes According to Patent Document 1, by sharing the element group (X) that becomes polyanion, the mutual ion conductivity of the positive electrode, the negative electrode, and the solid electrolyte layer is improved, and the extraction of a large current and the charge/discharge cycle are improved. It is said that the characteristics are improved.
• Patent Document 1 Japanese Unexamined Patent Publication No. 20 07 _ 25 8 16 5
• the present invention has been made to solve the above problems, and provides an all-solid-state battery having an improved electronic conductivity of an active material forming the all-solid-state battery and having an excellent discharge capacity per unit volume.
• the purpose is to
• the all-solid-state battery according to the first aspect includes a positive electrode current collector layer, a positive electrode active material layer, a solid electrolyte layer, a negative electrode active material layer, and a negative electrode current collector layer,
• the positive electrode active material layer includes a positive electrode active material
• the negative electrode active material layer includes a negative electrode active material, ⁇ 2020/175632 3 (:171? 2020/008075
• the negative electrode active material contains, as a main component, a compound represented by the following general formula ().
• the thickness of the negative electrode active material layer is in the range of 2 or more and 100 or less.
• the positive electrode active material may be configured to include a compound represented by the following general formula (II) as a main component.
• the weight of the positive electrode active material contained in the positive electrode active material layer and the weight ratio of the negative electrode active material contained in the negative electrode active material layer may satisfy the following formula (2).
• the solid electrolyte layer contains a solid electrolyte, and the solid electrolyte contains titanium aluminum phosphate lithium, lithium zirconium phosphate, and garnet-type zircon as main components. It may be configured to include any one of the acid salts.
• an area 3 1 of a portion of the negative electrode active material layer that is in contact with the solid electrolyte layer and an area 3 1 of a portion of the positive electrode active material layer that is in contact with the solid electrolyte layer 3 It may be configured such that the relationship with 2 satisfies the following formula (3).
• a first intermediate layer is provided between the positive electrode active material layer and the solid electrolyte layer, and between the negative electrode active material layer and the solid electrolyte layer. It may be configured to include the second intermediate layer.
• the two middle layers are each! It may be configured to include at least one element selected from the group consisting of _ Shi-hachi, Te-cho, V, "and.
• FIG. 1 A schematic cross-sectional view showing a configuration of an all-solid-state battery according to an embodiment of the present invention.
• the all-solid-state battery 1 includes a laminated body 20 in which a positive electrode 30 and a negative electrode 40 are laminated via a solid electrolyte layer 50.
• the positive electrode 30 has a positive electrode current collector layer 3 1 and a positive electrode active material layer 3 2.
• the negative electrode 40 has a negative electrode current collector layer 41 and a negative electrode active material layer 42.
• a margin layer 80 is formed on the same plane as the positive electrode 30 and the negative electrode 40.
• the laminated body 20 is a hexahedron, and has two end faces (first end face 21 and second end face 2 2) and two side faces (first side face and second side face) formed as faces parallel to the stacking direction.
• the positive electrode collector layer 31 is exposed on the first end face 21 and the negative electrode collector layer 41 is exposed on the second end face 22.
• the first side surface is the right side surface when viewed from the first end surface 21 side with the top surface 25 facing upward
• the second side surface is the left side surface when viewed from the first end surface 21 side with the top surface 25 facing up.
• the first end face 21 and the second end face 22 face each other, and the first side face and the second side face face face each other.
• the positive electrode current collector layer 31 and the negative electrode current collector layer 41 are also exposed on part of the first side surface and the second side surface.
• a positive electrode external electrode 60 which is electrically connected to the positive electrode current collector layer 31, is attached so as to cover the first end face 21 side of the laminate 20. Note that this electrical connection was made by connecting the positive electrode external electrode 60 to the positive electrode current collector layer 3 1 of the positive electrode 30 exposed on the first end face 21 of the laminate 20, the first side face, and the second side face. It is made by connecting.
• a negative electrode external electrode 70 electrically connected to the negative electrode current collector layer 41 is provided so as to cover the second end face 22 side of the laminate 20. Note that this electrical connection was made such that the negative electrode external electrode 70 was connected to the negative electrode current collector layer 41 of the negative electrode 40 exposed on the second end face 22 of the laminate 20, the first side face, and the second side face. It is made by connecting.
• the margin layer 80 of the all-solid-state battery 1 of the present embodiment is provided in order to eliminate the step between the solid electrolyte layer 50 and the positive electrode 30 and the step between the solid electrolyte layer 50 and the negative electrode 40. Can be provided. Therefore, the margin layer 80 is formed in a region other than the positive electrode 30 and the negative electrode 40, which exists on the same plane as the positive electrode 30 and the negative electrode 40. The presence of such a margin layer 80 eliminates the step between the solid electrolyte layer and the positive electrode and the negative electrode. ⁇ 2020/175632 6 ⁇ (:171? 2020/008075
• the distance from the positive electrode 30 and the negative electrode 40 of the margin layer 80 to the first end face 21 of the stack 20, the first side face, and the second side face is 10 to 1 000. Preferably.
• the outer layer 90 can be provided on each of the uppermost surface and the lowermost surface of the laminate 20.
• the thickness of the outer layer 90 is preferably, for example, 10 to 1000
• the solid electrolyte layer 50 contains a solid electrolyte.
• the solid electrolyte used for the solid electrolyte layer 50 of the all-solid-state battery 1 of the present embodiment may contain lithium titanium aluminum phosphate.
• Lithium titanium aluminum phosphate is preferably 1- ⁇ 1 +2 8 I 2 2 12 _ 2 ( ⁇ 4 ) 3 (0 £ 0.6).
• the solid electrolyte layer 50 may include a solid electrolyte other than lithium aluminum aluminum phosphate. For example, 1_ 1 3 + 21 3 1 Bok 21 ⁇ 4 (0. 4 £ z 1 £ 0. 6), 1_ 1 3. 4 ⁇ . 4 Rei_6_rei. 6 ⁇ 4, phosphate germanium lithium (1- 1 ⁇
• the solid electrolyte contains titanium aluminum phosphate, phosphorus, or phosphorus as main components. It is preferable to include at least one of lithium zirconate oxide and garnet-type zirconate salt
• the main component means that the solid electrolyte contains 50% by volume or more, preferably 60% by volume or more. means.
• the negative electrode active material layer 42 contains a negative electrode active material.
• the negative electrode active material used in the negative electrode active material layer 42 of the all-solid-state battery 1 of the present embodiment is a compound represented by the following general formula ( ⁇ ) as a main component (hereinafter, this compound will be referred to as "I- )” ⁇ 2020/175632 7 ⁇ (:171? 2020/008075
• main component means that the negative electrode active material contains 50% by volume or more, preferably 60% by volume or more.
• 3 1, ⁇ 1, ⁇ 1 and 1 are respectively 2.8 1 ⁇ 5, ⁇ 6 £b ⁇ £. ⁇ .1 £ ⁇ 1 £ 1.4, 0 £6 ⁇ £0.
• the thickness of the negative electrode active material layer 42 is preferably 2 to 100.
• the electron conductivity of the negative electrode active material layer 42 is improved by using "I-Cho (negative)" as the negative electrode active material and setting the thickness of the negative electrode active material layer 42 within the above range.
• the negative electrode active material layer 42 is thinned. Also, the addition of a conductive additive in the negative electrode active material layer 42 has been studied. In this case, it was difficult to increase the proportion of the active material responsible for the electric capacity of the all-solid-state battery 1 in the all-solid-state battery, and it was difficult to increase the discharge capacity per unit volume.
• I-cho (negative) is, for example, conventionally used as a negative electrode active material or a positive electrode active material.
• !_ I 3 2 ( ⁇ 4 ) 3 It is equivalent to the V replaced by a pallet or a pallet and eight pallets.
• Ding is an element that is more likely to become divalent ions than V. For this reason, “!_ Ding (negative)” tends to have oxygen deficiency in the crystal lattice, and electrons that become free due to the oxygen deficiency are generated, so the negative electrode active material (“Ding (negative)”) itself. Can have high electron conductivity.
• the atomic ratio (substitution amount) 1 of the eight points of "!_ Ding (negative)" is 0 £ 1 £ 0.7.
• the structure of "!_ Ding (negative)” becomes stable, and! _ ⁇ Ion conductivity tends to improve because the concentration of ions can be increased.
• the replacement amount of I increases too much, the structure of “1_chome (negative)” becomes unstable, and in addition, it is responsible for the discharge capacity.
• the discharge capacity may decrease.
• the atomic ratio (substitution amount) 1 of the Eight Hachijo is 0 £ 1 £ 0.7.
• I a value that can be obtained by desorption and insertion.
• the atomic ratio of V of "I-Ding (negative)" is 1 and the atomic ratio of Ding is (substitution amount) ⁇ 1, and the atomic ratio of 8 I (substitution amount) 1 is ( ⁇ 1 + ⁇ 11)
• X be X, and 0 1 1 be 3, we can express as follows.
• I-cho (negative) includes a compound represented by the following formula (I)'.
• the electron conductivity of the negative electrode active material layer 42 is improved, and the chemical reaction in the negative electrode active material layer 42 is smoothly performed. Therefore, the negative electrode active material layer 42 can be thickened. In addition, the amount of the conductive auxiliary agent in the negative electrode active material layer 42 can be reduced. Therefore, the proportion of the negative electrode active material, which is responsible for the electric capacity of the all-solid-state battery 1, in the all-solid-state battery 1 can be increased, and the discharge capacity per unit volume of the all-solid-state battery 1 can be improved.
• the ratio can be increased. Therefore, the discharge capacity per unit volume of the all-solid-state battery 1 can be effectively improved.
• the positive electrode active material layer 32 contains a positive electrode active material.
• the positive electrode active material used in the positive electrode active material layer 32 of the all-solid-state battery 1 of the present embodiment is a compound represented by the following general formula (II) as a main component (hereinafter, this compound is referred to as “I- )” may be referred to as)).
• the main component means that the positive electrode active material contains 50% by volume or more, preferably 60% by volume or more.
• the atomic ratio of V of "I-Ding (correct)" is 2 and the atomic ratio of Ding is (substitution amount) 02, and the atomic ratio of 8 I (substitution amount) 2 is (O 2 + O 12) So, and then ⁇ 12, it can be expressed as
• ⁇ 2 ( ⁇ 2 + ⁇ 12) 62 y b
• the positive electrode active material layer 32 is the main component of the negative electrode active material layer 42, “!_ Ding (negative)”. It is preferable to include "I-cho (correct)" containing the same element as.
• the positive electrode active material layer 32 and the negative electrode active material layer 42 may include a positive electrode active material and a negative electrode active material other than “I-V D (positive)” and “!_V D (negative)”.
• it preferably contains a transition metal oxide or a transition metal composite oxide.
• lithium manganese composite oxide! - ⁇ 2 1 ⁇ x3 1 ⁇ 3 ⁇ 3 0 3 (0.8 £ X 3 £ 1, Ma Co s Lithium cobaltate (1_ 1 ⁇ ⁇ ⁇ 2 ), Lithium dichelate (1- ⁇ 1 ⁇ 1 ⁇ 2 ), lithium manganese spinel (1_ ⁇ 1 ⁇ / ⁇ 2 ⁇ 4 ), and the general formula: 1_ ⁇ 4 ⁇ ⁇ 1 ⁇ /1
• ⁇ 4 ⁇ 2 (Father 4 + So 4 40 ⁇ 4 1, 0 ⁇ x4 ⁇ 1, ⁇ £74 £ 1, ⁇ £ 24 £ 1) Lithium vanadium compound (!_ ⁇ 2 ⁇ 5 ), olivine type!- ⁇ 1 ⁇ /16 ⁇ 4 (However, IV!
• ⁇ is ⁇ ⁇ , 1 ⁇ 1 I, IV! ⁇ , 6, IV! 9, 1 ⁇ 1 ⁇ , 7 ⁇ , 8 I, "one or more elements selected from ,! _ ⁇ Excess solid solution positive electrode!- I 2 Mn 0 3 -L Lithium titanate (1 _ 1 5 ⁇ 12
• the active materials forming the positive electrode active material layer 32 or the negative electrode active material layer 42 and the compounds in the positive electrode active material layer 32 and the compounds in the negative electrode active material layer 42 are not distinguished.
• a compound showing a more noble potential can be used as a positive electrode active material
• a compound showing a more noble potential can be used as a negative electrode active material.
• the same compound may be used for the positive electrode active material layer 32 and the negative electrode active material layer 42 as long as the compound has both lithium ion release and lithium ion storage at the same time.
• the volume of the positive electrode active material contained in the positive electrode active material layer 32 (3 V and the volume V of the negative electrode active material contained in the negative electrode active material layer 42 are set so as to satisfy the following formula (1). ing.
• the volume of the positive electrode active material contained in the positive electrode active material layer 32 (3 V and the volume V of the negative electrode active material contained in the negative electrode active material layer 42 are, for example, 3 1/ 1 (scanning electron microscope ) Can be calculated from the 3M IV! image taken in.
• volume 8 V volume 8 V can be measured, for example, as follows: The all-solid-state battery is disassembled and the number of negative electrode active material layers 42 ! ⁇ 1 and the number of positive electrode active material layers 32 ⁇ 2020/175632 11 ⁇ (:171? 2020/008075
• the area 31 of the portion of the negative electrode active material layer 42 in contact with the solid electrolyte layer 50 (the surface parallel to the laminated surface in which the negative electrode active material layer 42 and the solid electrolyte layer 50 are in contact) is measured.
• the area 31 is calculated by measuring the vertical and horizontal lengths of the plane parallel to the laminated surface of the negative electrode active material layer 42, and multiplying the obtained vertical and horizontal lengths.
• the area 32 of the portion of the positive electrode active material layer 32 in contact with the solid electrolyte layer 50 (the surface parallel to the laminated surface in which the positive electrode active material layer 32 and the solid electrolyte layer 50 contact) is measured.
• the thickness 1:1 of the negative electrode active material layer 42 is measured.
• the thickness 1:1 is measured using a 3M IV! image of a cross section perpendicular to the laminated surface of the negative electrode active material layer 42.
• the negative electrode active material layer 42 is embedded in a resin and polished to expose the cross section of the negative electrode active material layer 42. It can be obtained by using and observing.
• the thickness 12 of the positive electrode active material layer 32 is measured.
• the ratio 1 of the negative electrode active material in the negative electrode active material layer 42 is calculated.
• a ratio of 1 is calculated by binarizing the 3-day IV! image into the negative electrode active material and other parts by image processing.
• the ratio 2 of the positive electrode active material in the positive electrode active material layer 32 is calculated.
• the volume-based content of the positive electrode active material contained in the positive electrode active material layer 32 is 40 to 1
• the volume-based content of the negative electrode active material contained in the negative electrode active material layer 42 is preferably 40 to 100%, and more preferably 70 to 100%.
• the weight (mass) of the positive electrode active material contained in the positive electrode active material layer 32 and the weight (mass) of the negative electrode active material contained in the negative electrode active material layer 42 satisfy the following formula (2). Is preferred.
• the weight of the negative electrode active material contained in the negative electrode active material layer 42 can be calculated, for example, by multiplying the above-described volume 8 V by the density of the negative electrode active material.
• the density of the negative electrode active material can be obtained, for example, from the composition and crystal structure of the negative electrode active material.
• the composition of the negative electrode active material is, for example, an energy dispersive X-ray analysis method (Mix XX), a fluorescent X-ray analysis method ( ⁇ [3 ⁇ 4), a laser ablation I ⁇ mass spectrometry (!_ 81 ⁇ ⁇ ?1 1 ⁇ /1 3) can be used for measurement.
• the crystal structure for example, the X-ray diffraction method (B[[guchi]) can be used.
• Weight of positive electrode active material contained in positive electrode active material layer 32 Can be measured in the same manner as the above weight.
• the plates 1, 0 1 and 1 are the atomic ratios of V, D, and E of the negative electrode active material represented by the general formula (I).
• Slags 1, 0, 1 and 1 for example, are obtained by analyzing the composition of the negative electrode active material, and This can be obtained by calculating the atomic ratio of _ I, V, Ding I, and 8 I, and finding the atomic ratio of V, Ding, and Eighty-eighth when (phosphorus) is 3.
• Tables 2, 22, and 2 are the atomic ratios of V, D, and I of the positive electrode active material represented by the general formula (II). Slags 2, 0 2 and 0 12 can be obtained in the same manner as 1, 0 1 and 0 11 above.
• Shi-Ding (negative)! -Design capacity per unit weight of Ding (correct) has the following characteristics.
• 1_chome (negative) is charged by changing the valence of Vc along with the change in the valence of V during charging (when charging 1_c ion). Therefore, the design capacity of the negative electrode active material per unit weight does not change for 1 _ (negative).
• 1_ Ding? (Positive) requires a change in the valence of V during charging (1_ ion desorption), and the amount of V decreases due to the replacement of the hinge. This makes L y J P (positive)! -The amount of desorbed ions decreases, and the design capacity of the positive electrode active material per unit weight decreases.
• the design capacity of the negative electrode active material per unit weight is (1 ⁇ 1+01)/ + ⁇
• design capacity of the positive electrode active material per unit weight is represented by 62 / (spoon 2 + ⁇ 2 + Rei_12) XI 32 [Rei_1 eight 11/9.
• the material forming the positive electrode current collector layer and the negative electrode current collector layer of the all-solid-state battery of the present embodiment it is preferable to use a material having a high conductivity, for example, silver, palladium, gold, platinum, aluminum, copper. It is preferable to use nickel or the like. In particular, copper is more preferable because it hardly reacts with lithium aluminum aluminum phosphate and has an effect of reducing the internal resistance of the all-solid-state battery.
• the material forming the electrode current collector layer may be the same for the positive electrode and the negative electrode, or may be different.
• the positive electrode current collector layer 3 1 and the negative electrode current collector layer 41 of the all-solid-state battery 1 of the present embodiment preferably include a positive electrode active material and a negative electrode active material, respectively.
• the positive electrode current collector layer 3 1 and the negative electrode current collector layer 4 1 contain the positive electrode active material and the negative electrode active material, respectively, the positive electrode current collector layer 3 1 and the positive electrode active material layer 32 and the negative electrode current collector layer 32 are collected. It is desirable because the adhesion between the body layer 41 and the negative electrode active material layer 42 is improved.
• the ratio of the positive electrode active material and the negative electrode active material in the positive electrode current collector layer and the negative electrode current collector layer of the present embodiment is not particularly limited as long as it functions as a current collector, but the positive electrode current collector and the positive electrode current collector
• the volume ratio of the active material, or the negative electrode current collector and the negative electrode active material is preferably in the range of 90/10 to 70/30.
• the material composing the margin layer preferably contains, for example, the same material as the solid electrolyte layer, lithium aluminum aluminum phosphate. Therefore, titanium aluminum phosphate lithium! _ I 1 + ⁇ I ,7 I 2 _, ( ⁇ 4 ) 3 (0 £ ⁇ £ 0.
• the solid electrolyte layer may contain a solid electrolyte material other than lithium aluminum lithium aluminum phosphate.
• a solid electrolyte material other than lithium aluminum lithium aluminum phosphate.
• the outer layer 90 contains lithium titanium aluminum phosphate. It is preferable that the lithium aluminum lithium phosphate is 1 — 2 + 2 8: 2 ( 4 ) 3 (0 £ 0.6). It may also contain a solid electrolyte material other than titanium aluminum phosphate lithium or a glassy material. For example, the solid electrolyte material is 1_ ⁇ 3 + 21 3 ⁇ ⁇ ⁇ (0.4 £ ⁇ ⁇ 02020/175632 15 ⁇ (: 17 2020 /008075
• the positive electrode external electrode 60 and the negative electrode external electrode 70 mainly contain at least one kind of conductive metal such as 8 I, 89 I, O I, I, I. Further, in order to improve the adhesiveness with the laminate 20, it is preferable to contain a glass material or a resin component.
• Positive electrode active material 1- ⁇ ⁇ . 2 I ( ⁇ 4 ) 3 and negative electrode active material!- ⁇ 31 ⁇ 131 ⁇ . 1 eight 1 ( ⁇ 4) 3 can be prepared in the following manner.
• the production method is not limited to the above solid-phase synthesis, and liquid phase synthesis using a water-soluble salt such as nitrate, acetate, and oxalate, or a glass molten salt method can be used.
• the all-solid-state battery 1 of this embodiment can be manufactured by the following procedure. Materials used for each of the positive electrode current collector layer 31, the positive electrode active material layer 32, the solid electrolyte layer 50, the negative electrode current collector layer 41, the negative electrode active material layer 42, the outer layer 90, and the margin layer 80. ⁇ 2020/175632 16 ⁇ (:171? 2020/008075
• the method for forming a paste is not particularly limited, but for example, a paste can be obtained by mixing the powder of each of the above materials with a vehicle.
• the vehicle is a general term for a medium in a liquid phase, and includes a solvent, a binder and the like.
• the binder contained in the paste for molding the green sheet or the printed layer is not particularly limited, but polyvinyl acetal resin, cellulose resin, acrylic resin, urethane resin, vinyl acetate resin, polyvinyl alcohol resin, etc. should be used.
• the slurry can include at least one of these resins.
• the paste may include a plasticizer.
• the type of plasticizer is not particularly limited, but dioctyl phthalate, diisononyl phthalate, and other ester phthalates may also be used.
• a positive electrode current collector layer paste, a positive electrode active material layer paste, a solid electrolyte layer paste, a negative electrode active material layer paste, a negative electrode current collector layer paste, an outer layer A paste and a margin layer paste are prepared.
• the method for producing the solid electrolyte green sheet is not particularly limited, and a known method such as a doctor blade method, a die coater, a comma coater, or a gravure coater can be adopted.
• the positive electrode active material layer 32, the positive electrode current collector layer 31 and the positive electrode active material layer 32 are sequentially printed and laminated by screen printing on the solid electrolyte green sheet to form a positive electrode layer.
• screen printing is performed in a region other than the positive electrode layer using the margin layer paste to form the margin layer 80, and the positive electrode layer unit is formed. Create.
• the negative electrode layer unit can also be prepared in the same manner as the positive electrode layer unit, and screen printing is performed on the solid electrolyte green sheet in a region other than the negative electrode layer using a margin layer paste.
• the margin layer 80 is formed, and the negative electrode layer unit is manufactured. ⁇ 2020/175632 17 ⁇ (:171? 2020/008075
• the positive electrode layer unit and the negative electrode layer unit may be alternately stacked so that one ends thereof do not coincide with each other, and laminated, and an outer layer 90 may be provided if necessary.
• a laminated substrate is manufactured by laminating the outer layers 90.
• the outer layer 90 can be made of the same material as the solid electrolyte layer 50, and a green sheet for solid electrolyte can be used.
• the outer layer substrate prepared above is applied to a substrate such as polyethylene terephthalate (Mending) in a desired thickness and dried if necessary, An outer layer green sheet is prepared. Then, the outer layer 90 can be provided by laminating using the outer layer green sheet.
• a substrate such as polyethylene terephthalate (Mending)
• An outer layer green sheet is prepared. Then, the outer layer 90 can be provided by laminating using the outer layer green sheet.
• the manufacturing method is to manufacture a parallel-type all-solid-state battery
• the manufacturing method for the series-type all-solid-state battery is such that one end of the positive electrode layer and one end of the negative electrode layer are aligned, that is, It may be stacked without offsetting.
• the produced laminated substrates can be collectively pressed by a die press, a hot water isotropic press ⁇ ), a cold water isotropic press ( ⁇ I), a hydrostatic press, etc. to improve the adhesion. It is preferable to apply pressure while heating, and for example, it can be performed at 40 to 95°.
• the produced laminated substrate can be cut into an unfired all-solid-state battery laminated body using a dicing device.
• the laminated body 20 is manufactured by removing and firing the uncalcined laminated body of the all-solid-state battery.
• De Bi and calcination can be performed fired at 6 0 0 ° ⁇ ⁇ 1 1 0 0 ° ⁇ temperature under a nitrogen atmosphere.
• the holding time for de-baking and firing is, for example, 0.1 to 6 hours.
• the all-solid-state battery 1 can be produced by providing the laminated body 20 with the positive electrode external electrode 60 and the negative electrode external electrode 70.
• the positive electrode external electrode 60 and the negative electrode external electrode 70 are provided at one end of the positive electrode current collector layer 31 extending on one side surface of the stacked body 20 and the negative electrode current collector extending on one side surface of the stacked body 20. Each is connected to one end of layer 41. Therefore, a pair of positive electrode external electrode 60 and negative electrode external electrode 70 are formed so as to sandwich one side surface of the laminated body.
• Examples of the method for forming the external electrode 60 and the negative electrode external electrode 70 include a sputtering method, a screen printing method, a dip coating method and the like.
• a screen printing method and the dip coating method an external electrode base containing metal powder, a resin, and a solvent is prepared and formed as the positive electrode external electrode 60 and the negative electrode external electrode 70.
• a baking process for removing the solvent, and a plating treatment for forming terminal electrodes on the surfaces of the positive electrode external electrode 60 and the negative electrode external electrode 70 are performed.
• the sputtering method the external electrode and the terminal electrode can be formed directly, so that the baking process and the plating process are unnecessary.
• the all-solid-state battery 1 may be sealed in, for example, a coin cell in order to improve moisture resistance and impact resistance.
• the sealing method is not particularly limited, and for example, the laminated body after firing may be sealed with a resin. Further, an insulator pace Bok having an insulating material such as I 2 ⁇ 3 applied or dip coating around the laminate may be sealed by heat-treating the insulating base paste.
• the negative electrode active material layer 42 is represented by the above general formula (I)! -Since the negative polarity is included, the electron conductivity of the negative electrode active material layer is improved, and the chemical reaction in the negative electrode active material layer is smoothly performed. Then, by setting the thickness of the negative electrode active material layer 42 within the range of 2 or more and 100 or less, the conductive auxiliary agent in the negative electrode active material can be effectively reduced, and the activity that contributes to the capacity of the all-solid-state battery 1 can be achieved. The proportion of the substance in the all-solid-state battery can be increased. Therefore, the discharge capacity per unit volume of the all solid battery 1 can be improved.
• the relationship between the volume ⁇ 3 V of the positive electrode active material contained in the positive electrode active material layer 32 and the volume V of the negative electrode active material contained in the negative electrode active material layer 42 is shown. Since the above formula (1) is satisfied, the capacity balance of the positive electrode active material and the negative electrode active material is less likely to be lost, and the discharge capacity per unit volume of the all-solid-state battery 1 is less likely to decrease.
• the positive electrode active material layer 32 is represented by the above general formula (II)! -If it contains a positive (positive), the excess active material of the positive electrode active material layer and the negative electrode active material layer, which is an extra volume not related to the discharge capacity, can be reduced, ⁇ 2020/175632 19 ⁇ (:171? 2020/008075
• the discharge capacity per unit volume of the all-solid-state battery 1 can be further improved.
• the weight of the positive electrode active material contained in the positive electrode active material layer 32 When the relationship with the weight of the negative electrode active material contained in the negative electrode active material layer 42 satisfies the above expression (2), the surplus active material in the positive electrode active material layer 3 2 and the negative electrode active material layer 4 2 occupies The volume is reduced and the discharge capacity per unit volume is improved.
• the solid electrolyte contains any one of lithium titanium aluminum phosphate, lithium zirconium phosphate, and garnet-type zirconate as a main component, these substances are electronic. Since the resistance is high, the solid electrolyte layer 50 can be made thin. As a result, the volume of the portion that does not contribute to the discharge capacity is reduced, so that the discharge capacity per unit volume of the all-solid-state battery 1 is improved.
• the area 3 1 of the part in contact with 0 and the area 3 2 of the part of the positive electrode active material layer 3 2 in contact with the solid electrolyte layer 50 satisfy the above formula (3), it can be charged at the time of charging. It is possible to facilitate the insertion reaction of the ⁇ into the negative electrode active material.
• the arrangement of the active material in the all-solid-state battery 1 extends to the side exterior portion, and the thickness of the negative electrode active material layer can be reduced. As a result, the discharge capacity per unit volume of the all-solid-state battery 1 can be improved.
• a first intermediate layer may be provided between the positive electrode active material layer 32 and the solid electrolyte layer 50, and a second intermediate layer may be provided between the negative electrode active material layer 42 and the solid electrolyte layer 50.
• the first intermediate layer and the second intermediate layer are respectively! _ It is preferable to contain at least one element selected from the group consisting of shihachi, gyo, V, "and.
• 11 2 hundred 3 and 2 ⁇ 5 and Ding 1 ⁇ 2 and 1 ⁇ 11-1 4 1 to 1 2? ⁇ 4 and with the departure material 1 to 6 hours in a ball mill After mixing and dehydration and drying, the obtained powder was calcined at 850 ° for 2 hours in a nitrogen-hydrogen mixed gas.
• the calcined product was wet-milled with a ball mill and then dehydrated and dried to obtain a positive electrode active material powder.
• the composition of the produced powder is -. ⁇ 5 chome ⁇ 5 ( ⁇ 4) is 3, was confirmed using X-ray diffraction apparatus.
• the calcined product was wet-milled with a ball mill and then dehydrated and dried to obtain a negative electrode active material powder. It was confirmed using an X-ray diffractometer that the composition of the powder thus prepared was !- 3 3 (( 4 ) 3 ).
• Bast for the positive electrode active material layer is! _ ⁇ 5 chome ⁇ 5 ( ⁇ 4) powder 1 00 parts of 3, and ethylcellulose 1 5 ⁇ 6 as a binder, Jihidorota as solvent -.
• the base for the negative electrode active material layer is! - powder 1 0 0 parts of ⁇ 3 chome ⁇ ( ⁇ 4) 3, and ethylcellulose 1 5 ⁇ 6 as Ba Indah, dihydro terpinyl neo as solvent - adding and Le 6 5 parts, mixed and dispersed to the cathode
• An active material layer paste and a negative electrode active material layer paste were prepared.
• trioctahedral ⁇ 3 chome ⁇ I 7 ( ⁇ 4) 3 was used.
• the production method is 1_ ⁇ 3 and 8 1 2 0 3 and Ding 1 0 2 and 1 ⁇ 1 1 ⁇ 1 4 1 ⁇ 1 2 0 4 as starting materials, and wet mixing was performed for 16 hours in a ball mill. Then, it was dehydrated and dried, and then the obtained powder was calcined in the atmosphere at 800°C for 2 hours. After calcination, wet pulverization was performed for 16 hours with a ball mill, and then dehydration drying was performed to obtain a solid electrolyte powder.
• the composition of the produced powder! -.. ⁇ trioctahedral I ⁇ 3 7 ⁇ 7 ( ⁇ 4) is 3, was confirmed using X-ray diffraction device (say yes [3 ⁇ 4 port).
• the paste for a solid electrolyte layer was formed by a doctor blade method using a knife film as a base material to obtain a sheet for a solid electrolyte layer having a thickness of 15.
• the outer layer is the best! -. ⁇ trioctahedral ⁇ 3 chome ⁇ ( ⁇ 4) 3 powder, ethanol 1 0 0 parts as a solvent, and wet-mixed in a ball mill by adding 1 0 0 parts of toluene, followed by polyvinyl butyral system Binder 1 6 parts and benzyl butyl phthalate 4.8 parts were further added and mixed to prepare a margin layer paste.
• thermosetting type external electrode paste Silver powder, epoxy resin, and solvent were mixed and dispersed to prepare a thermosetting type external electrode paste.
• a positive electrode active material layer (first positive electrode active material) having a thickness of 2.5 was formed by screen printing so that the thickness of the positive electrode active material layer after firing was 2.0. Layer) and dried at 80 ° C for 10 minutes. Then, a positive electrode current collector layer having a thickness of 5 was formed thereon by screen printing, and dried at 80° for 10 minutes. On top of that, use screen printing to create a thickness of 2.
• a positive electrode active material layer (referred to as a second positive electrode active material layer) 5 was formed again and dried at 80 ° C. for 10 minutes to prepare a positive electrode layer on the solid electrolyte layer sheet.
• a margin layer paste is printed by screen printing on the outer periphery of one end of the positive electrode layer so that the height is approximately flush with the positive electrode layer, and at 80° ⁇ for 10 minutes. Dried. Then, the knife film was peeled off to obtain a sheet of the positive electrode layer unit.
• a negative electrode active material layer having a thickness of 2.5 was formed by screen printing so that the negative electrode active material layer had a thickness of 2.0 after firing.
• the first negative electrode active material layer (Referred to as the first negative electrode active material layer) was formed and dried at 80 ° C. for 10 minutes.
• a negative electrode current collector layer having a thickness of 5 was formed thereon by screen printing, and dried at 80° ⁇ for 10 minutes. On top of that, use screen printing to create a thickness of 2.
• a negative electrode active material layer (referred to as a second negative electrode active material layer) 5 was formed again and dried at 80 ° for 10 minutes to prepare a negative electrode layer on the solid electrolyte layer sheet.
• a margin layer paste is printed by screen printing on the outer periphery of one end of the negative electrode layer so as to be substantially flush with the negative electrode layer, and at 80° ⁇ for 10 minutes. Dried. Then, the knife film was peeled off to obtain a sheet of the negative electrode layer unit.
• a positive electrode layer unit and a negative electrode layer unit were alternately laminated so that one end of each did not coincide, and a plurality of layers were prepared so that the positive electrode and the negative electrode of the all-solid-state battery would each have 25 layers. Further, a plurality of solid electrolyte sheets were laminated as outer layers on both main surfaces of the laminated substrate to provide 500 outer layers. This was thermocompression-bonded by a die press, and then cut to produce an unfired all-solid-state battery laminate. Then, the laminated body was de-baked to obtain a laminated body of an all-solid-state battery.
• the debye temperature was raised to 700°C in the reducing atmosphere at a temperature rising rate of 60 ° 0/hr, and the temperature was maintained for 5 hours, and naturally cooled and taken out.
• the firing the firing temperature 7 5 0 ° at a heating rate 2 0 0 ° 0 / time nitrogen was heated to ⁇ , and held at that temperature for 2 hours, taken out after the natural cooling.
• the external electrode paste was applied to the end faces of the laminated body of the all-solid-state battery and heat-cured at 150 ° C. for 30 minutes to form a pair of external electrodes. With the above, an all-solid-state battery according to Example 1 was manufactured.
• the thicknesses of the positive electrode active material layer and the negative electrode active material layer were 5.0 0 1 (Example 2), 1 0 0! (Example 3), and 2 0 0, respectively. (Example 4), 5 0 ⁇ ⁇ ! (Example 5), 7000! (Example 6), ( ⁇ 2020/175632 24 ⁇ (:171? 2020 /008075
• Example 7 Example 1 was repeated except that the print application amounts of the positive electrode active material layer and the negative electrode active material layer in screen printing were adjusted in the production of the positive electrode layer unit and the negative electrode layer unit as described in Example 7). An all-solid-state battery was manufactured in the same manner as.
• the negative electrode active materials were produced so that the respective plates 1 and 0 1 were as shown in Table 1. Then, in the production of the positive electrode layer unit and the negative electrode layer unit, printing of the positive electrode active material layer and the negative electrode active material layer by screen printing was performed so that the thickness of the positive electrode active material layer and the negative electrode active material layer became 10.
• An all-solid-state battery was manufactured in the same manner as in Example 1 except that the coating amount was adjusted.
• the positive electrode active material layer and the negative electrode active material layer were made to have a thickness of 1.0, respectively.
• An all-solid-state battery was produced in the same manner as in Example 1 except that the printing coating amounts of the material layer and the negative electrode active material layer were adjusted.
• the all-solid-state battery according to Comparative Example 2 was prepared by preparing the positive electrode active material and the negative electrode active material so that the positive electrode active material and the negative electrode active material were as shown in Table 1 below. Was produced. Then, in the production of the positive electrode layer unit and the negative electrode layer unit, the positive electrode active material layer and the negative electrode active material layer were printed and applied by screen printing so that the thickness of the positive electrode active material layer and the negative electrode active material layer became 10. An all-solid-state battery was produced in the same manner as in Example 1 except that the amount was adjusted.
• the all-solid-state batteries according to Comparative Examples 3 to 6 were prepared using the positive electrode active material and the negative electrode active material so that the positive electrode active material and the negative electrode active material were as shown in Table 1. And a negative electrode active material. Then, in the production of the positive electrode layer unit and the negative electrode layer unit, the thicknesses of the positive electrode active material layer and the negative electrode active material layer were 1-0 (Comparative example 3), 2.01 (Comparative example 4), and 5.0, respectively. 01 (Comparative example 5), ⁇ 2020/175632 25 ⁇ (:171? 2020 /008075
• a solid-state battery was prepared in the same manner as in Example 1 except that the print application amounts of the positive electrode active material layer and the negative electrode active material layer in screen printing were adjusted so that the result was 10 (Comparative Example 6). did.
• the all-solid-state batteries produced in this example and comparative examples can be evaluated for the following battery characteristics.
• the weight of the negative electrode active material was calculated by multiplying the volume V obtained as described above by the density of the negative electrode active material.
• the weight ⁇ of the positive electrode active material was calculated by multiplying the volume ⁇ V obtained as described above by the density of the positive electrode active material.
• the discharge capacities of the all-solid-state batteries manufactured in this example and the comparative example can be evaluated, for example, under the following charging/discharging conditions.
• the charging and discharging conditions are as follows: under the environment of 70 ° ⁇ , the maximum current is 500, and the constant voltage charging ( ⁇ charging) is performed for 5 hours so that the battery voltage becomes 1.6, and then the constant current of 20 8 is used.
• the battery was discharged to the battery voltage ( ⁇ 3 (3 discharges). Under the above conditions, the discharge capacity was defined as the capacity at ⁇ 3 (3 discharges, and the value obtained by dividing this by the volume of the all-solid-state battery was used as the unit volume. The discharge capacity per unit was 111 8 11 /!_.
• Table 1 shows the composition of the positive electrode active material of the all-solid-state batteries according to Examples 1 to 10 and Comparative Examples 1 to 6 (32, ⁇ 2, ⁇ 2, And volume (3 and weight ⁇ , composition of negative electrode active material (31, ⁇ 1, ⁇ 1, 1) and volume V, weight and thickness 1), ⁇ ⁇ // ⁇ /, [3 ⁇ 4, and per unit volume The result of the discharge capacity of is shown.
• the all-solid-state batteries according to Examples 11 to 18 were prepared so that, in the production of the positive electrode active material and the negative electrode active material, the slag 2, 0 2, 2 and the sill 1, 0 1, 1 are as shown in Table 2.
• a positive electrode active material and a negative electrode active material were produced.
• the positive electrode active material layer and the negative electrode active material layer were applied by screen printing by printing so that the thickness of the positive electrode active material layer and the negative electrode active material layer became 10.
• An all-solid-state battery was produced in the same manner as in Example 1 except that the amount was adjusted, and the obtained all-solid-state battery was evaluated.
• the all-solid-state battery according to Comparative Example 7 was prepared so that the positive electrode active material and the negative electrode active material were prepared so that the slags 2, 0 2, 2 and the sill 1, 0 1, 1 are as shown in Table 2.
• a negative electrode active material was produced.
• printing of the positive electrode active material layer and the negative electrode active material layer by screen printing was performed so that the thickness of the positive electrode active material layer and the negative electrode active material layer became 10.
• An all-solid-state battery was prepared in the same manner as in Example 1 except that the coating amount was adjusted, and the obtained all-solid-state battery was evaluated.
• the weight of the positive electrode active material contained in the positive electrode active material layer per one all-solid-state battery was measured in the production of the positive electrode layer unit and the negative electrode layer unit.
• the target amount of the positive electrode active material is multiplied by the value obtained by dividing the total area of the positive electrode active material layer contained in one all-solid-state battery by the printing area to be applied by screen printing. It was divided by the ratio of the polar active material to calculate the coating amount of the positive electrode active material layer required for screen printing. In order to obtain this value, the coating amount of the paste for the positive electrode active material layer in printing the positive electrode active material layer in screen printing was adjusted by changing the mesh type of the screen and the number of times of printing.
• the weight of the negative electrode active material contained in the negative electrode active material layer ⁇ / ⁇ / is 7.0 0.019, so that the negative electrode active material contained in one all-solid-state battery is the target negative electrode active material amount.
• the amount of coating was calculated.
• the coating amount of the negative electrode active material layer paste in the printing of the negative electrode active material layer by screen printing was adjusted so that this value was obtained by changing the mesh type of the screen and the number of times of printing. Otherwise, an all-solid-state battery was produced in the same manner as in Example 1, and the obtained all-solid-state battery was evaluated.
• All-solid-state cell according to Example 2 5-3 in work made of a positive electrode active material and the anode active material, the positive electrode active material! _ ⁇ 3 1. 5 chome ⁇ . 5 ( ⁇ 4) 3 to produce As a negative electrode active material, 1 to 3 parts (90 4 ) 3 was prepared and used for the positive electrode active material layer and the negative electrode active material layer. Then, in the production of the positive electrode layer unit and the negative electrode layer unit, the weight of the positive electrode active material contained in the positive electrode active material layer for each all-solid-state battery. Multiply the target positive electrode active material amount by the value obtained by dividing the total area of the positive electrode active material layer contained in one all-solid-state battery by the printing area to be applied by screen printing to obtain the value shown in 3.
• the amount of the positive electrode active material layer paste required for screen printing was calculated by dividing by the ratio of the positive electrode active material in the positive electrode active material layer paste. Adjust the positive electrode active material in the positive electrode active material layer by screen printing so that this value is obtained. ⁇ 2020/175632 31 ⁇ (: 171? 2020/008075
• the coating amount of the substance layer paste was adjusted by changing the mesh type of the screen and the number of times of printing. Similarly, the total amount of the negative electrode active material layer contained in one all-solid-state battery is set to the target amount of negative electrode active material so that the weight of the negative electrode active material contained in the negative electrode active material layer is 10019. Multiply the value by dividing by the printing area to be applied by screen printing, and then divide by the ratio of the negative electrode active material in the negative electrode active material layer paste to calculate the coating amount of the negative electrode active material layer paste required for screen printing. did. In order to obtain this value, the coating amount of the negative electrode active material layer paste in the printing of the negative electrode active material layer by screen printing was adjusted by changing the mesh type of the screen and the number of times of printing. Except for that, an all-solid-state battery was manufactured in the same manner as in Example 1, and the obtained all-solid-state battery was evaluated.
• Table 3 shows the composition and volume 0 V and weight 0 of the positive electrode active material of the all-solid-state batteries of Examples 19 to 30 and the all-solid-state batteries of Comparative Example 7 and the negative electrode active material. Composition and volume V and weight and thickness, And the result of discharge capacity per unit volume is shown.
• the all-solid-state batteries according to Examples 31 to 36 were prepared as a solid electrolyte by the following method. ( ⁇ 4 ) 3 was used. What is the manufacturing method?
• an all solid state battery was prepared in the same manner as in Example 1 except that the positive electrode active material layer and the negative electrode active material layer were as shown in Table 4. The prepared all-solid-state battery was evaluated.
• Table 4 shows the composition and volume ⁇ V and weight ⁇ of the positive electrode active material of all solid state batteries according to Examples 31 to 36, the composition and volume V and weight and thickness of the negative electrode active material, ⁇ /8, 8, And the result of the discharge capacity per unit volume is shown.
• the positive electrode active material layer and the negative electrode active material layer are as shown in Table 5, and in the production of the laminate, the firing temperature is 10 except that the 0 ° ⁇ , the same procedure as in example 1 to produce a laminated all-solid battery total solid body batteries were evaluated all-solid.
• the stacked all-solid-state battery according to each of Examples 37 to 42 has a larger discharge capacity per unit volume and is more excellent.
• All-solid-state battery of Example 43 to 48 as a solid electrolyte, the produced by the following method -.. Using ⁇ 15 ⁇ 0 15 "85 ( ⁇ 4) 3 and its manufacturing method, 1_ 1 1 ⁇ 1_Rei 3 and ⁇ (1 ⁇ 1_Rei 3) 3 and 1 ⁇ ⁇ (1 ⁇ 1_Rei 3) 2 - as 61-1 2 ⁇ 1 ⁇ 11-1 4 1-1 2 ⁇ 4 starting materials, These were dissolved in water to prepare an aqueous solution, dehydrated and dried, and then the obtained powder was calcined in the air at 1000°° for 2 hours.After calcination, wet milling was performed in a ball mill for 16 hours.
• the solid electrolyte powder was obtained by drying.
• the composition of the produced powder is !- ⁇ 15 ⁇ ⁇ . 15 " 85 ( ⁇ 4 ) 3 " in the X-ray diffractometer ( ⁇ [3 ⁇ 4 ⁇ ) Is used to confirm.
• the positive electrode active material layer and the negative electrode active material layer are as shown in Table 6, and in the production of the laminate, the firing temperature is 1 000 ° C .
• An all-solid-state battery was manufactured in the same manner as in Example 1 except that the result was evaluated as ⁇ and the obtained all-solid-state battery was evaluated.
• Table 6 shows the composition and volume ⁇ V and weight ⁇ of the positive electrode active material of all solid state batteries according to Examples 43 to 48, the composition and volume V and weight and thickness of the negative electrode active material, ⁇ /8, 8, and units. The result of the discharge capacity per volume is shown.

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