WO2023188466A1 - 全固体二次電池 - Google Patents

全固体二次電池 Download PDF

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WO2023188466A1
WO2023188466A1 PCT/JP2022/036171 JP2022036171W WO2023188466A1 WO 2023188466 A1 WO2023188466 A1 WO 2023188466A1 JP 2022036171 W JP2022036171 W JP 2022036171W WO 2023188466 A1 WO2023188466 A1 WO 2023188466A1
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negative electrode
solid
electrode layer
secondary battery
state secondary
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English (en)
French (fr)
Japanese (ja)
Inventor
啓子 竹内
知子 中村
絢加 永冨
裕介 山口
翔太 鈴木
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TDK Corp
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TDK Corp
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Priority to JP2024511175A priority Critical patent/JPWO2023188466A1/ja
Priority to EP22935597.9A priority patent/EP4503234A4/en
Priority to CN202280092637.0A priority patent/CN118765453A/zh
Publication of WO2023188466A1 publication Critical patent/WO2023188466A1/ja
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    • 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
    • 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
    • H01M10/058—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
    • 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
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/626—Metals
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H01M4/662—Alloys
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to an all-solid-state secondary battery. This application claims priority based on Japanese Patent Application No. 2022-058998 filed in Japan on March 31, 2022, the contents of which are incorporated herein.
  • Lithium ion secondary batteries that serve as power sources for electronic devices to be smaller, lighter, thinner, and more reliable.
  • Lithium ion secondary batteries that are currently in general use have conventionally used an electrolyte (electrolyte) such as an organic solvent as a medium for moving ions.
  • electrolyte electrolyte
  • organic solvents and the like used in electrolytes are flammable substances, there is a need to further improve the safety of batteries.
  • Solid electrolytes for all-solid secondary batteries mainly include sulfide-based solid electrolytes and oxide-based solid electrolytes.
  • Sulfide-based solid electrolytes generate hydrogen sulfide when they react with water, so batteries must be manufactured in a glove box with a controlled dew point.
  • sulfide-based solid electrolytes are difficult to form into sheets, and there is a need for solid electrolytes that can be made thinner, which can contribute to making portable electronic devices smaller, lighter, thinner, and more multifunctional. Under these circumstances, the application of oxide-based solid electrolytes is expected.
  • LSPO Li 3+x Si x P 1-x O 4
  • Non-Patent Document 1 LSPO is known to be relatively stable to active materials even when sintered at high temperatures for densification.
  • Oxide-based solid electrolytes need to be sintered at high temperatures in order to be densified, but at that time, they may react with the active material and form a reaction layer with low ionic conductivity at the interface.
  • a method of utilizing the above-mentioned LSPO as a solid electrolyte has been studied.
  • Ag, AgPd alloy, AgPd alloy, and lithium titanate Li 4 Ti 5 It is expected that the use of a material containing O 12 ) will lead to the realization of an all-solid-state secondary battery in which it is difficult to form a reaction layer.
  • all-solid-state secondary batteries are required to have improved cycle characteristics.
  • the cycle characteristics of a stacked chip type all-solid-state secondary battery are degraded by expansion and contraction of the active material during charging and discharging, and cracks and peeling occur inside the electrode and at the interface with the solid electrolyte. In order to improve cycle characteristics, it is necessary to suppress these cracks and peeling.
  • LSPO is used as the solid electrolyte and a phase containing Ag is used as the negative electrode, such as Ag, AgPd alloy, AgPd alloy, and lithium titanate, there is a problem that the cycle characteristics are low.
  • the present invention was made in view of the above circumstances, and an object of the present invention is to provide an all-solid-state secondary battery in which stress caused by expansion and contraction of the negative electrode is alleviated and cycle characteristics can be improved.
  • the present invention provides the following means to solve the above problems.
  • An all-solid-state secondary battery includes a laminate including a positive electrode layer, a negative electrode layer, and a solid electrolyte layer between the positive electrode layer and the negative electrode layer,
  • the solid electrolyte layer includes a compound represented by the following formula (1)
  • the negative electrode layer includes a phase containing Ag
  • a plurality of voids are formed in the negative electrode layer
  • at least some of the voids is an all-solid-state secondary battery in which the first void is formed in contact with the phase containing Ag.
  • the first void may have a diameter of 0.01 ⁇ m or more and 3.0 ⁇ m or less.
  • the volume ratio of the first voids formed in contact with the Ag-containing phase in the negative electrode layer may be 1% or more and 10% or less.
  • the aspect ratio of the length of the void in the direction in which the negative electrode layer extends to the length of the first void in the stacking direction of the laminate is 3 or more. It may be.
  • At least part of the voids formed in contact with the Ag-containing phase are formed at the interface between the solid electrolyte layer and the Ag-containing phase. It may also be a second cavity.
  • the ratio of the second voids to the entire first voids may be 80 to 100%.
  • the negative electrode layer may be made of a phase containing the Ag.
  • the negative electrode layer is composed of a first phase composed of the Ag-containing phase and lithium titanate, and a second phase sandwiching the first phase in the stacking direction. two phases, and the negative electrode layer may have a third void in contact with an interface between the first phase and the second phase.
  • the third void may account for 50 to 100% of the entire first void.
  • FIG. 1 is a cross-sectional view schematically showing an all-solid-state secondary battery according to the present embodiment.
  • FIG. 2 is an enlarged cross-sectional view of the vicinity of the negative electrode layer of the all-solid-state secondary battery of FIG. 1.
  • FIG. 2 is an enlarged cross-sectional view of the vicinity of a negative electrode layer of an all-solid-state secondary battery according to a modification of FIG. 1.
  • FIG. 1 is a cross-sectional view schematically showing an all-solid-state secondary battery according to the present embodiment.
  • FIG. 2 is an enlarged cross-sectional view of the vicinity of the negative electrode layer of the all-solid-state secondary battery of FIG. 1.
  • FIG. 2 is an enlarged cross-sectional view of the vicinity of a negative electrode layer of an all-solid-state secondary battery according to a modification of FIG. 1.
  • FIG. 1 is a cross-sectional view schematically showing an all-solid-state secondary battery according to this embodiment.
  • FIG. 2 is an enlarged cross-sectional view of the vicinity of the negative electrode layer of the all-solid-state secondary battery of FIG. 1, and FIG. 2 also shows an enlarged view schematically showing the vicinity of one void. There is.
  • the all-solid-state secondary battery 10 shown in FIGS. 1 and 2 includes a laminate 4, a positive terminal 5, and a negative terminal 6.
  • the positive electrode terminal 5 and the negative electrode terminal 6 are in contact with opposing surfaces of the laminate 4, respectively.
  • the positive electrode terminal 5 and the negative electrode terminal 6 extend in a direction intersecting (orthogonal to) the laminated surface of the laminated body 4 .
  • the direction in which the negative electrode layer 2 extends is referred to as the x direction
  • the direction in which the laminate 4 is stacked is referred to as the z direction
  • the direction orthogonal to the x direction and the z direction is referred to as the y direction.
  • the laminate 4 includes a positive electrode layer 1 , a negative electrode layer 2 , and a solid electrolyte layer 3 sandwiched between the positive electrode layer 1 and the negative electrode layer 2 .
  • the laminate 4 is a sintered body in which a positive electrode layer 1 and a negative electrode layer 2 are laminated with a solid electrolyte layer 3 in between and sintered.
  • the number of positive electrode layers 1 and negative electrode layers 2 included in the laminate 4 may be one each, or two or more.
  • the solid electrolyte layer 3 is provided not only between the positive electrode layer 1 and the negative electrode layer 2, but also between the positive electrode layer 1 and the negative electrode terminal 6, and between the negative electrode layer 2 and the positive electrode terminal 5. be.
  • one end of the positive electrode layer 1 is connected to the positive electrode terminal 5.
  • the negative electrode layer 2 has one end connected to the negative electrode terminal 6.
  • the all-solid-state secondary battery 10 is charged or discharged by transferring ions between the positive electrode layer 1 and the negative electrode layer 2 via the solid electrolyte layer 3.
  • the present embodiment will be described using the stacked all-solid-state secondary battery 10 shown in FIG. 1 as an example.
  • the solid electrolyte layer 3 can move ions by an externally applied electric field.
  • the solid electrolyte layer 3 conducts lithium ions, for example, and inhibits the movement of electrons.
  • the solid electrolyte layer 3 includes LSPO represented by the following formula (1). Li 3+x Si x P 1-x O 4 (1) (In formula (1), x is a number satisfying 0 ⁇ x ⁇ 1.)
  • the solid electrolyte layer 3 preferably contains, for example, LSPO as a main component and is made of LSPO.
  • solid electrolyte layer 3 containing LSPO as a main component means that LSPO in solid electrolyte layer 3 is 80% by volume or more.
  • the positive electrode layer 1 includes, for example, a positive electrode current collector 1A and a positive electrode active material layer 1B. As shown in FIG. 1, the positive electrode active material layer 1B may be formed on both sides of the positive electrode current collector 1A, or may be formed only on one side.
  • the positive electrode current collector 1A is made of a material with high conductivity.
  • the positive electrode current collector 1A includes, for example, metals such as silver, palladium, gold, platinum, aluminum, copper, nickel, stainless steel, and iron, alloys thereof, and conductive materials such as conductive resin.
  • the positive electrode current collector 1A may contain, for example, a positive electrode active material such as lithium cobalt oxide (LiCoO 2 ) or a lithium vanadium compound (LiV 2 O 5 , Li 3 V 2 (PO 4 ) 3 , LiVOPO 4 ).
  • the positive electrode current collector 1A may be in the form of powder, foil, punching, or expanded.
  • the positive electrode active material layer 1B includes a positive electrode active material.
  • the positive electrode active material layer 1B may include a conductive aid and a solid electrolyte.
  • the positive electrode active material is not particularly limited as long as it is capable of reversibly releasing and inserting lithium ions and deintercalating and inserting lithium ions.
  • positive electrode active materials used in known lithium ion secondary batteries can be used.
  • the positive electrode active material is preferably one or more selected from, for example, composite transition metal oxides and transition metal composite oxides.
  • a positive electrode active material that does not contain lithium may be used as the positive electrode active material.
  • a positive electrode active material that does not contain lithium can be used by placing a negative electrode active material doped with metallic lithium and/or lithium ions in the negative electrode layer 2 in advance and starting the all-solid-state secondary battery 10 from discharging.
  • Examples of positive electrode active materials that do not contain lithium include metal oxides (MnO 2 , V 2 O 5 , etc.).
  • the conductive aid is not particularly limited as long as it improves the electron conductivity within the positive electrode active material layer 1B, and any known conductive aid can be used.
  • Examples of conductive aids include carbon-based materials such as graphite, carbon black, graphene, and carbon nanotubes, metals such as gold, platinum, silver, palladium, aluminum, copper, nickel, stainless steel, and iron, and ITO (indium tin oxide). conductive oxides, or mixtures thereof.
  • the conductive aid may be in the form of powder or fiber.
  • the solid electrolyte contained in the positive electrode active material layer 1B improves the ionic conductivity within the positive electrode active material layer 1B.
  • the solid electrolyte one kind or a mixture of two or more kinds of known solid electrolytes can be used. It is preferable to use the same compound as the compound constituting the solid electrolyte layer 3 as the solid electrolyte from the viewpoint of improving the adhesion between the solid electrolyte layer 3 and the positive electrode layer 1.
  • the negative electrode layer 2 shown in FIGS. 1 and 2 serves as a negative electrode current collector and a negative electrode active material layer.
  • the negative electrode layer 2 includes a phase 21 containing Ag, which is either Ag or an AgPd alloy, and may further include lithium titanate (Li 4 Ti 5 O 12 ).
  • the negative electrode layer 2 is made of a base material that exhibits a lower potential than the positive electrode active material. In the negative electrode layer 2, voids V are formed which are in contact with the phase 21 containing Ag.
  • the negative electrode layer 2 has, for example, a plurality of voids V.
  • the plurality of voids V are classified into first voids 41 which are voids in contact with the phase 21 containing Ag, and voids 42 which are not in contact with the phase 21 containing Ag.
  • the first void 41 is further classified into a second void 41a and a third void 41b.
  • the second void 41a is a void that is in contact with the interface between the solid electrolyte layer 3 and the phase 21 containing Ag.
  • the third void 41b is a void that is in contact with the interface between the first phase 21 (phase 21 containing Ag) and the second phase 22 composed of lithium titanate.
  • the relationship between the second void 41a and the third void 41b is basically mutually exclusive.
  • Each of the plurality of voids V is formed, for example, at a part of the interface between the Ag-containing phase 21 and the solid electrolyte of the solid electrolyte layer 3, and all the voids V are formed between the Ag-containing phase and the solid electrolyte, respectively. may be formed on a part of the interface. That is, each of the plurality of voids V exists, for example, in contact with a part of the interface of the phase 21 containing LSPO 31 and Ag, and all the voids V exist in contact with a part of the interface of the phase 21 containing LSPO 31 and Ag, respectively. It is preferable that it be in contact with. Further, when the negative electrode layer 2 contains lithium titanate, each of the plurality of voids V may be formed, for example, in a part of the interface between the phase containing Ag and the lithium titanate.
  • the volume ratio (porosity) of the voids V in the negative electrode layer 2 is, for example, 0.1% or more and 20% or less, preferably 1% or more and 10% or less, and preferably 1% or more and 5% or less. More preferred.
  • the volume ratio of the first voids 41 in the negative electrode layer 2 may be 1% or more and 10% or less, or may be 1% or more and 5% or less.
  • the ratio of the second voids to the entire first voids may be 80% or more and 100% or less.
  • the ratio of the third voids to the entire first voids may be 50% or more and 100% or less, or may be 80% or more and 100% or less.
  • the volume ratio of the voids V in the negative electrode layer 2 is calculated based on an electron microscope image. Specifically, the region of the void V in the negative electrode layer 2 is defined and its volume ratio is calculated by the following procedure.
  • a scanning electron microscope image of a cross section parallel to the stacking direction of the laminate 4 is obtained, and a region of the negative electrode layer 2 is defined based on the scanning electron microscope image.
  • the negative electrode layer 2 is considered to be a region between the two solid electrolyte layers in the scanning electron microscope image, and is defined by image analysis.
  • the area of the negative electrode layer 2 is calculated by image analysis.
  • the phase corresponding to the voids is separated from the phase corresponding to other regions by image processing that binarizes the scanning electron microscope image based on brightness. Binarization processing of a scanning electron microscope image is performed by creating a density histogram using the mode method, and using the density region of the valley that is the boundary between the target phase and other phases as a threshold value.
  • valleys are areas with low brightness in the scanning electron microscope image, and there is a peak with the lowest brightness, a peak with the next lowest brightness, and a peak with the lowest brightness.
  • the valley between them may be selected as the valley corresponding to the boundary, and the density value of the valley may be used as the threshold value.
  • the area with the darkest brightness is considered to be a void.
  • the total area of the voids in contact with an alloy such as AgPd or a metal such as Ag in the negative electrode layer 2 is calculated by image analysis.
  • the total area of the voids and the negative electrode layer is determined, for example, in the same scanning electron microscope image at a magnification of 1000 to 5000 times. In this way, by calculating the area of the negative electrode layer 2 and the area of the voids V, and dividing the area of the voids V by the area of the negative electrode layer 2, the volume ratio (porosity) of the voids V in the negative electrode layer 2 is calculated. Calculated.
  • the diameter of the void V is assumed to be a circle having the same area as the region whose lightness is equal to or less than a predetermined value and determined to be a void by the binarization process, and the diameter of the circle is set as the diameter of the void. Estimated to be the diameter of V.
  • the aspect ratio (L Vx /L Vz ) of the length L Vx of the void V in the direction in which the negative electrode layer 2 extends to the length L Vz of the void V in the stacking direction of the laminate 4 is, for example, 1 or more, and 3 or more. It is preferable that The aspect ratio of each void V is calculated by image analysis of a binarized electron microscope image using the same procedure as described above. That is, the length L Vx in the extending direction of the negative electrode layer 2 and the length L Vz in the stacking direction were calculated by image analysis of the void V defined by binarizing the electron microscope image. . Next, the length L Vz of each void V was divided by the length L Vzx to calculate the aspect ratio of each void V.
  • the aspect ratio of the void V is calculated for ten arbitrary voids V in the electron microscope image, and the arithmetic average thereof is calculated as the length L Vz of the void V in the stacking direction of the laminate 4.
  • the length L of the void V in the direction in which the negative electrode layer 2 extends relative to the length L is treated as the aspect ratio of Vx .
  • the voids V in the negative electrode layer 2 have an axial direction in the direction in which the negative electrode layer 2 extends.
  • the aspect ratio (L Vx /L Vz ) is a value larger than 1, and that the extending direction of the voids is approximately parallel to the extending direction of the negative electrode layer 2.
  • the plurality of voids V in the negative electrode layer 2 are connected to each other to form a network structure. Further, it is preferable that the voids V in the negative electrode layer 2 have the above-mentioned network structure and are in contact with the AgPd alloy particles in the x direction and the z direction. By having voids in such a structure, stress in various directions can be easily relaxed.
  • the negative electrode layer 2 may contain a conductive additive, a solid electrolyte, and the like.
  • the conductive aid improves the electron conductivity of the negative electrode layer 2.
  • the same material as the positive electrode active material layer 1B can be used.
  • solid electrolyte The solid electrolyte contained in the negative electrode layer 2 improves the ionic conductivity within the negative electrode layer 2.
  • the solid electrolyte one or a mixture of two or more of known solid electrolytes can be used.
  • the solid electrolyte may contain the same compound as the compound forming the solid electrolyte layer 3 described above.
  • the laminate 4 is produced.
  • the laminate 4 is produced, for example, by firing, and may be produced by either a simultaneous firing method or a sequential firing method.
  • the simultaneous firing method is a method in which the materials forming each layer are laminated and then fired all at once to produce the laminate 4.
  • the sequential firing method is a method in which firing is performed each time each layer is formed.
  • the simultaneous firing method allows the laminate 4 to be produced in fewer work steps than the sequential firing method.
  • the laminate 4 produced by the simultaneous firing method is denser than the laminate 4 produced by the sequential firing method.
  • a method for manufacturing the laminate 4 using the co-firing method will be described.
  • the materials of the positive electrode current collector 1A, the positive electrode active material layer 1B, the solid electrolyte layer 3, and the negative electrode layer 2 that constitute the laminate 4 are made into a paste, and a paste corresponding to the material of each layer is manufactured.
  • a plurality of voids are formed in the negative electrode layer 2 in contact with a phase containing Ag, and the following methods are used to control the amount, shape, and size of the voids. adopt.
  • an organic filler is added to the negative electrode active material and the amount thereof is changed.
  • the shape of the voids in the negative electrode layer 2 for example, the flatness of the organic filler is changed, and in order to obtain voids with a high aspect ratio, an organic filler with a high flatness is used.
  • the direction of the voids in the negative electrode can be controlled by, for example, arranging an organic filler in the in-plane direction during coating. Specifically, a doctor blade method is used, and the degree of orientation is controlled by coating speed and coating thickness.
  • the size of the voids in the negative electrode layer for example, the size of the organic filler to be added is controlled, and by using a large organic filler, the size of the voids is also increased.
  • the method of turning each material used for manufacturing the laminate 4 into a paste is not particularly limited, and for example, a method of obtaining a paste by mixing powders of each material in a vehicle can be used.
  • Vehicle here is a general term for a medium in a liquid phase.
  • the vehicle in this embodiment includes, for example, a solvent, a binder, and a plasticizer.
  • the solvent for example, dihydroterpineol can be used.
  • the binder for example, ethyl cellulose can be used.
  • green sheets corresponding to each layer constituting the laminate 4 are produced.
  • the green sheet is produced by applying a paste prepared for each material of each layer constituting the laminate 4 onto a base material such as a PET (polyethylene terephthalate) film, drying it as necessary, and applying the paste to the base material. It is obtained by a method of peeling from.
  • the method for applying the paste to the base material is not particularly limited, and for example, known methods such as screen printing, coating, transfer, and doctor blade methods can be used.
  • green sheets corresponding to each layer constituting the laminate 4 are stacked in a desired order and number of layers to produce a laminate sheet that becomes the laminate 4.
  • alignment, cutting, etc. are performed as necessary.
  • alignment is performed so that the end face of the positive electrode current collector 1A and the end face of the negative electrode layer 2 do not match, and Stack green sheets.
  • the green sheet that becomes the laminated sheet may be a positive electrode unit and a negative electrode unit that have been prepared in advance.
  • the positive electrode unit is a green sheet in which a solid electrolyte layer 3, a sheet to become the positive electrode active material layer 1B, a sheet to become the positive electrode current collector 1A, and a sheet to become the positive electrode active material layer 1B are laminated in this order.
  • the configuration of the negative electrode unit can be changed according to the desired negative electrode layer, but for example, a second negative electrode paste serving as a second phase containing lithium titanate as a main component, and a first negative electrode paste containing a phase containing Ag as a main component.
  • a green sheet is a green sheet in which a first negative electrode paste serving as a phase and a second negative electrode paste serving as a second phase containing lithium titanate as a main component are laminated in this order.
  • the laminated sheet that becomes the laminate 4 can be produced by a method in which the positive electrode unit and the negative electrode unit that becomes the negative electrode layer 2 are laminated via a solid electrolyte green sheet.
  • the produced laminated sheets are pressurized all at once to improve the adhesion of each layer and form a laminated body.
  • Pressure can be applied, for example, by a mold press, a hot water isostatic press (WIP), a cold water isostatic press (CIP), a hydrostatic press, or the like. It is preferable to pressurize while heating.
  • the heating temperature during pressurization can be, for example, 40 to 95°C.
  • the laminate obtained after pressurization is cut using a dicing device to form a laminate chip. Thereafter, the obtained laminated chip is fired. As a result, a laminate 4 made of a sintered body is obtained.
  • the binder removal and firing steps can be performed, for example, by placing the laminate on a ceramic table.
  • the binder removal and firing process can be, for example, a process of heating at 550° C. to 1100° C. in an air atmosphere.
  • the heating time (baking time) can be, for example, 0.1 to 10 hours.
  • the heating temperature and firing time in the binder removal and firing steps can be determined as appropriate depending on the composition of each layer constituting the laminate 4.
  • the sintered laminate 4 (sintered body) may be placed in a cylindrical container together with an abrasive such as alumina and polished by a method of polishing. Thereby, the corners of the laminate 4 can be chamfered.
  • the laminate 4 may be polished using sandblasting. Sandblasting is preferable because only a specific portion of the surface of the laminate 4 can be scraped.
  • a positive electrode terminal 5 and a negative electrode terminal 6 are formed on mutually opposing side surfaces of the produced laminate 4, respectively.
  • the positive electrode terminal 5 and the negative electrode terminal 6 are each formed by a method such as a sputtering method, a dipping method, a screen printing method, or a spray coating method.
  • the all-solid-state secondary battery 10 is manufactured by the above steps.
  • the solid electrolyte layer 3 contains LSPO
  • the negative electrode layer 2 contains the Ag-containing phase
  • the negative electrode layer 2 contains the Ag-containing phase.
  • FIG. 1 shows an all-solid-state secondary battery 10 in which the negative electrode layer 2 serves as both a negative electrode current collector and a negative electrode active material layer
  • an all-solid-state secondary battery 10 in which the negative electrode layer 2 has an independent negative electrode current collector and negative electrode active material, respectively is shown in FIG. It may also be a solid secondary battery.
  • Such an all-solid-state secondary battery may be fabricated, for example, in which negative-electrode active material layers are provided on both sides of the main surface of a negative-electrode current collector.
  • the all-solid-state secondary battery according to the above embodiment may have a configuration in which the negative electrode layer 2 has a laminated structure of a negative electrode active material layer and a negative electrode current collector.
  • the negative electrode layer 2 has a laminated structure of a negative electrode active material layer and a negative electrode current collector
  • the phase 21 containing Ag is included in the negative electrode active material layer, and voids V are formed so as to be in contact with the phase 21 containing Ag. has been done.
  • a phase 21 containing Ag may be further included in the negative electrode current collector, and a void V may be formed so as to be in contact with a part of the phase 21 containing Ag within the negative electrode current collector.
  • the first phase 21 may include a phase 21 containing Ag
  • the second phase 22 may include a lithium titanate.
  • FIG. 3 shows a cross-sectional view of an all-solid-state secondary battery that satisfies the above configuration, with the vicinity of the negative electrode layer enlarged.
  • the negative electrode layer has a structure in which, for example, in the z direction, a first phase 21 containing Ag is sandwiched between a second phase 22 such as lithium titanate, and the first phase 21 containing Ag is sandwiched between second phases 22 such as lithium titanate.
  • a void V is formed in contact with the interface between the second phase 22 and the second phase 22 .
  • first phase and the second phase may exist adjacent to each other in a layered manner, and the first phase may be arranged so that a part of the first phase is located closer to the solid electrolyte layer 3 than the second phase. Some regions of the phase may be located outside in the z direction with respect to the second phase, or voids may be formed in contact with the interface between the first phase and the second phase, and these may be combined. It may also have a different configuration.
  • configurations such as the amount of voids and the structure can be the same as those of the all-solid-state secondary battery 10 according to the embodiment described above.
  • the percentage of voids in contact with the AgPd alloy is preferably 50% or more. It is desirable that the voids V exist at the boundary between the Ag-containing phase 21 and lithium titanate, or at the boundary between the Ag-containing phase 21 and the solid electrolyte layer 3. If there are voids in other locations, the stress caused by expansion and contraction of the negative electrode cannot be alleviated, and no improvement in cycle characteristics is observed.
  • Example 1 (1) Preparation of solid electrolyte paste
  • a solid electrolyte paste was prepared according to the following procedure. Particles consisting of Li 3+x Si x P 1-x O 4 (x in formula (1) is 0.5), ethyl cellulose and dihydroterpineol were added to a ball mill and wet mixed to obtain a solid electrolyte paste. Ta.
  • Lithium cobalt oxide (LiCoO 2 ) powder, ethyl cellulose, and dihydroterpineol were added to a ball mill and wet mixed to prepare the positive electrode active material paste of Example 1.
  • a positive electrode unit serving as a positive electrode layer A positive electrode active material layer paste was applied to a thickness of 5 ⁇ m on a base material made of a PET (polyethylene terephthalate) film using screen printing, and dried at 80° C. for 5 minutes. On the dried positive electrode active material layer paste, a positive electrode current collector paste was applied to a thickness of 5 ⁇ m using screen printing, and dried at 80° C. for 5 minutes. On the dried positive electrode current collector paste, a positive electrode active material layer paste was applied to a thickness of 5 ⁇ m using screen printing, dried at 80° C. for 5 minutes, and then peeled off from the base material. As a result, a positive electrode unit was obtained in which the positive electrode active material layer, the positive electrode current collector layer, and the positive electrode active material layer were stacked in this order.
  • a negative electrode unit serving as a negative electrode layer A second negative electrode paste was applied to a thickness of 5 ⁇ m on a base material made of a PET (polyethylene terephthalate) film using screen printing, and dried at 80° C. for 5 minutes.
  • the first negative electrode paste was applied to a thickness of 5 ⁇ m using screen printing, and dried at 80° C. for 5 minutes.
  • a second negative electrode paste was applied to a thickness of 5 ⁇ m using screen printing, dried at 80° C. for 5 minutes, and then peeled off from the base material.
  • a negative electrode unit was obtained in which the second negative electrode layer, the first negative electrode layer, and the second negative electrode layer were laminated in this order.
  • Example 1 made of a sintered body.
  • the binder was removed by heat-treating the laminate at 500° C. for 10 hours in an air atmosphere. Firing was performed at 900° C. for 1 hour in an air atmosphere. De-buying and firing can be performed in one step.
  • a positive electrode terminal and a negative electrode terminal were formed on a pair of opposing side surfaces of the produced laminate by Au sputtering to obtain an all-solid-state secondary battery of Example 1.
  • the positive electrode terminal and the negative electrode terminal were formed such that the positive electrode terminal was connected to the positive electrode unit, and the negative electrode terminal was connected to the negative electrode unit, respectively.
  • Example 2 An all-solid-state secondary battery was produced in the same manner as in Example 1, except that the particle size of the polymer particles in the first negative electrode paste was changed to 0.005 ⁇ m.
  • Example 3 An all-solid-state secondary battery was produced in the same manner as in Example 1, except that the particle size of the polymer particles in the first negative electrode paste was changed to 0.05 ⁇ m.
  • Example 4 An all-solid-state secondary battery was produced in the same manner as in Example 1, except that the particle size of the polymer particles in the first negative electrode paste was changed to 1 ⁇ m.
  • Example 5 An all-solid-state secondary battery was produced in the same manner as in Example 1, except that the particle size of the polymer particles in the first negative electrode paste was changed to 5 ⁇ m.
  • Example 6 An all-solid-state secondary battery was produced in the same manner as in Example 1, except that the volume ratio of AgPd powder to polymer particles in the first negative electrode paste was changed to 99.9:0.1.
  • Example 7 An all-solid-state secondary battery was produced in the same manner as in Example 1, except that the volume ratio of AgPd powder to polymer particles in the first negative electrode paste was changed to 99:1.
  • Example 8 An all-solid-state secondary battery was produced in the same manner as in Example 1, except that the volume ratio of AgPd powder and polymer particles in the first negative electrode paste was changed to 90:10.
  • Example 9 An all-solid-state secondary battery was produced in the same manner as in Example 1, except that the volume ratio of AgPd powder and polymer particles in the first negative electrode paste was changed to 80:20.
  • Example 10 An all-solid-state secondary battery was produced in the same manner as in Example 1, except that the aspect ratio of the polymer particles in the first negative electrode paste was changed to 1:1.
  • Example 11 An all-solid-state secondary battery was produced in the same manner as in Example 1, except that the aspect ratio of the polymer particles in the first negative electrode paste was changed to 1:10.
  • Example 12 An all-solid-state secondary battery was produced in the same manner as in Example 1, except that the negative electrode layer was formed without using the second negative electrode paste. As a result of this change, the negative electrode layer in Examples 1 to 11 had a configuration substantially made of an AgPd alloy and lithium titanate, but was changed to a configuration substantially made of an AgPd alloy.
  • Example 13 An all-solid-state secondary battery was produced in the same manner as in Example 12, except that the aspect ratio of the polymer particles in the first negative electrode paste was changed to 1:10.
  • the negative electrode layer was substantially made of an AgPd alloy.
  • Example 14 An all-solid-state secondary battery was produced in the same manner as in Example 1, except that the volume ratio of AgPd powder to polymer particles in the first negative electrode paste was changed to 89:11.
  • Example 15 An all-solid-state secondary battery was produced in the same manner as in Example 1, except that the particle size of the polymer particles in the first negative electrode paste was changed to 0.01 ⁇ m.
  • Example 16 An all-solid-state secondary battery was produced in the same manner as in Example 1, except that the particle size of the polymer particles in the first negative electrode paste was changed to 3 ⁇ m.
  • Example 17 An all-solid-state secondary battery was produced in the same manner as in Example 1, except that the aspect ratio of the polymer particles in the first negative electrode paste was changed to 1:5.
  • Example 18 An all-solid-state secondary battery was produced in the same manner as in Example 12, except that the volume ratio of AgPd powder to polymer particles in the first negative electrode paste was changed to 99:1.
  • Example 19 An all-solid-state secondary battery was produced in the same manner as in Example 12, except that the volume ratio of AgPd powder and polymer particles in the first negative electrode paste was changed to 90:10.
  • Example 20 An all-solid-state secondary battery was produced in the same manner as in Example 12, except that the particle size of the polymer particles in the first negative electrode paste was changed to 0.01 ⁇ m.
  • Example 21 An all-solid-state secondary battery was produced in the same manner as in Example 12, except that the particle size of the polymer particles in the first negative electrode paste was changed to 3 ⁇ m.
  • the solid electrolyte paste was prepared by adding solid electrolyte particles consisting of Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 , ethyl cellulose and dihydroterpineol to a ball mill and wet-mixing them.
  • An all-solid-state secondary battery was produced in the same manner as Example 1.
  • the solid electrolyte paste was prepared by adding solid electrolyte particles consisting of Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 , ethyl cellulose and dihydroterpineol to a ball mill and wet-mixing them.
  • An all-solid-state secondary battery was produced in the same manner as Example 12.
  • the all-solid-state secondary battery whose initial capacity Q1 was determined was again subjected to constant current charging (CC charging) at a constant current of 100 ⁇ A until the battery voltage reached 3.9 V in an environment of 60°C.
  • the battery was discharged (CC discharge) until the battery voltage reached 0 V, and the above charging and discharging was counted as one cycle, and 1000 cycles of charging and discharging were performed. Thereafter, the discharge capacity Q2 after 1000 cycles of charging and discharging was determined. From the discharge capacities Q 1 and Q 2 thus determined, the capacity retention rate E after 1000 cycles was determined using the following formula. The results are shown in Table 1.
  • E (%) (Q 2 /Q 1 ) x 100
  • the negative electrode layer 2 sandwiched between the second phase 22 containing lithium titanate was sandwiched between the solid electrolyte layers 3.
  • the negative electrode layer was made of a material containing AgPd alloy as a main component, so that an all-solid-state secondary battery having the structure shown in FIG. 1 and FIG. 2 was composed of a phase 21 containing Ag.
  • the areas where the voids were formed were defined by binarizing these scanning electron microscope images using the mode method based on their brightness.
  • the region sandwiched between the solid electrolyte layers was used as a negative electrode layer.
  • most of the voids were in contact with AgPd.
  • Comparative Example 1 no voids were observed.
  • a void was formed in contact with a part of the interface between the first phase and the second phase, and in Examples 12 and 13, a part of the interface between the phase containing Ag and the solid electrolyte was formed.
  • a void was formed in contact with the
  • the area of the negative electrode layer and the area of the voids in the same scanning electron microscope image are determined by image analysis, and the area of the voids is calculated as the area of the negative electrode layer.
  • the porosity occupied by voids in the negative electrode layer was determined by dividing by the area, and was regarded as the volume percentage of voids in the negative electrode layer. Further, the arithmetic average of the areas of all the voids in this scanning electron microscope image was calculated, and the diameter of a circle having the same area as the arithmetic average was calculated.
  • the length of the void in the stacking direction of the laminate and the length of the void in the direction in which the negative electrode layer extends are measured, and the length of the void in the direction in which the negative electrode layer extends is calculated as the length of the void in the stacking direction of the laminate.
  • the aspect ratio of the void (L Vx /L Vz ) was calculated by dividing by the length.
  • Table 1 shows that the all-solid-state secondary battery has a solid electrolyte layer containing LSPO, a negative electrode layer containing Ag or an Ag alloy, and a void formed in a part of the interface between the LSPO and the Ag alloy. It was confirmed that Examples 1 to 13 can significantly improve cycle characteristics compared to the all-solid-state secondary battery of Comparative Example 1 in which voids are not formed in a part of the interface between LSPO and the phase containing Ag. It was done. In addition, Examples 1, 7, and 8 in which the porosity occupied by voids in the negative electrode layer is 1% or more and 10% or less are compared with Example 6, which is 0.05%, and Example 9, which is 20%. It was confirmed that high cycle characteristics could be obtained.
  • the porosity of the voids in the negative electrode layer is small, the stress caused by expansion and contraction due to charging and discharging of the negative electrode will not be sufficiently relaxed, and if there are many voids, the stress may cause the voids to connect with each other. ing.
  • the aspect ratio of the voids is larger than 1, and the electron microscope images show that many of the voids are in a direction substantially parallel to the direction in which the negative electrode layer extends. It was confirmed that it has an axial direction.
  • Negative electrode terminal 10 All-solid-state secondary battery V Gap L Vx Length of the gap in the extending direction of the negative electrode layer L Length of voids in the stacking direction of the Vz laminate 21 Phase containing Ag (first phase) 22 2nd phase 31 LSPO 41 First void 41a Second void 41b Third void 42 A void not in contact with the phase containing Ag

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JP2001068150A (ja) * 1999-08-30 2001-03-16 Kyocera Corp 全固体二次電池の製造方法
WO2007135790A1 (ja) * 2006-05-23 2007-11-29 Incorporated National University Iwate University 全固体二次電池
WO2008099468A1 (ja) * 2007-02-13 2008-08-21 Incorporated National University Iwate University 全固体二次電池
JP2011216234A (ja) * 2010-03-31 2011-10-27 Namics Corp リチウムイオン二次電池及びその製造方法
JP2022058998A (ja) 2017-04-21 2022-04-12 ソニーグループ株式会社 受信装置、及び情報処理方法

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JP2001068150A (ja) * 1999-08-30 2001-03-16 Kyocera Corp 全固体二次電池の製造方法
WO2007135790A1 (ja) * 2006-05-23 2007-11-29 Incorporated National University Iwate University 全固体二次電池
WO2008099468A1 (ja) * 2007-02-13 2008-08-21 Incorporated National University Iwate University 全固体二次電池
JP2011216234A (ja) * 2010-03-31 2011-10-27 Namics Corp リチウムイオン二次電池及びその製造方法
JP2022058998A (ja) 2017-04-21 2022-04-12 ソニーグループ株式会社 受信装置、及び情報処理方法

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Title
See also references of EP4503234A4
SOLID STATE IONICS, vol. 283, 2015, pages 109 - 114

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