WO2022131301A1 - 固体電池、及び、固体電池の製造方法 - Google Patents

固体電池、及び、固体電池の製造方法 Download PDF

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Publication number
WO2022131301A1
WO2022131301A1 PCT/JP2021/046318 JP2021046318W WO2022131301A1 WO 2022131301 A1 WO2022131301 A1 WO 2022131301A1 JP 2021046318 W JP2021046318 W JP 2021046318W WO 2022131301 A1 WO2022131301 A1 WO 2022131301A1
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Prior art keywords
negative electrode
solid
state battery
layer
electrode layer
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PCT/JP2021/046318
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English (en)
French (fr)
Japanese (ja)
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奨平 川島
裕介 伊東
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Toyota Motor Corp
Panasonic Holdings Corp
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Toyota Motor Corp
Panasonic Holdings Corp
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Priority to US18/255,140 priority Critical patent/US20240021894A1/en
Priority to CN202180080242.4A priority patent/CN116529912A/zh
Priority to JP2022570042A priority patent/JP7578722B2/ja
Priority to EP21906662.8A priority patent/EP4266430A4/en
Publication of WO2022131301A1 publication Critical patent/WO2022131301A1/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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44—Methods for charging or discharging
    • H01M10/445—Methods for charging or discharging in response to gas pressure
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44—Methods for charging or discharging
    • H01M10/446—Initial charging measures
    • 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
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • 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

  • This application relates to solid-state batteries.
  • the battery when manufacturing an all-solid-state battery, the battery is assembled and then charged. At this time, from the viewpoint of improving the battery performance, there is a technique of charging the battery while applying a predetermined pressure to the battery.
  • Patent Document 1 discloses a technique of applying a restraining pressure of 0.1 MPa to 10 MPa in a constant voltage charging step of an all-solid-state battery from the viewpoint of improving cycle characteristics.
  • Patent Document 2 describes a technique for charging a battery laminate with an initial charging voltage while restraining a constant pressure in the stacking direction of the layers constituting the unit battery from the viewpoint of suppressing deterioration of the all-solid-state battery and improving the energy density. It has been disclosed.
  • Patent Document 3 from the viewpoint of improving the contact state of the solid / solid interface and improving the charge / discharge performance under atmospheric pressure, the battery laminate is sealed in a bag-shaped container and then under a predetermined pressure.
  • a technique for performing pre-charging / discharging at least once is disclosed.
  • the inventors do not promote fusion of the negative electrode active material if the binding pressure of the battery in the initial charging step is low, and charge / discharge during actual use. It was found that the rate of increase in the resistance increase rate was extremely high.
  • the present application is a solid-state battery having a laminate including a positive electrode layer, a solid electrolyte layer, and a negative electrode layer containing an alloy-based negative electrode active material as one means for solving the above-mentioned problems, and the present application is a solid-state battery having a laminate direction of the negative electrode layer.
  • Disclosed is a solid-state battery in which the voids are greater than 36% by volume of the total voids of the negative electrode layer.
  • the ratio of the voids in the stacking direction to the total voids of the negative electrode layer may be 55% by volume or more and 100% by volume or less.
  • the alloy-based negative electrode active material may contain silicon.
  • silicon may be particles.
  • the particle size D50 of the silicon particles can be set to 1 ⁇ m or less.
  • silicon may be a thin film.
  • the solid electrolyte layer may contain a sulfide solid electrolyte.
  • the negative electrode layer further has a negative electrode current collector, and the negative electrode current collector may have a surface roughness Rz of 0.8 ⁇ m or more and 4.0 ⁇ m or less.
  • a preparatory step for preparing a laminated body including a positive electrode layer, a solid electrolyte layer, and a negative electrode layer, and a first time of restraining the laminated body in the laminating direction to form a laminated body The initial charging step of performing constant current and constant voltage charging is provided, and in the initial charging step, the restraining pressure of the laminated body at the start of charging is 30 MPa or more, and the restraining pressure of the laminated body at the end of charging is 40 MPa or more.
  • a method for manufacturing a solid-state battery is provided, and in the initial charging step, the restraining pressure of the laminated body at the start of charging is 30 MPa or more, and the restraining pressure of the laminated body at the end of charging is 40 MPa or more.
  • the laminate may be constrained with a restraining pressure of 10 MPa or less after the initial filling step.
  • the negative electrode layer may contain an alloy-based negative electrode active material, and the alloy-based negative electrode-forming material may contain silicon.
  • silicon may be particles.
  • the particle size D50 of the silicon particles can be set to 1 ⁇ m or less.
  • silicon may be a thin film.
  • the solid electrolyte layer may contain a sulfide solid electrolyte.
  • the negative electrode layer may further have a negative electrode current collector, and the negative electrode current collector may have a surface roughness Rz of 0.8 ⁇ m or more and 4.0 ⁇ m or less.
  • FIG. 1 is a flowchart of the manufacturing method 10.
  • FIG. 2 is a cross-sectional image (test A1) of the negative electrode layer including the negative electrode mixture layer.
  • FIG. 3 is a cross-sectional image (test A7) of the negative electrode layer including the negative electrode thin film layer.
  • FIG. 4 is a diagram showing the relationship between the restraint pressure at the end of the initial charge and the relative resistance increase rate for the tests A1 to A3 and the tests B1 and B2.
  • FIG. 5 is a diagram showing the relationship between Rz and the relative resistance increase rate for tests A11 to A13 and tests B11 and B12.
  • the method for manufacturing a solid-state battery of the present disclosure will be described with reference to the method S10 for manufacturing an all-solid-state battery according to one embodiment (hereinafter, may be simply referred to as “manufacturing method S10”).
  • the solid-state battery means a battery containing a solid electrolyte
  • the all-solid-state battery means a solid-state battery containing no liquid-based material.
  • FIG. 1 shows a flowchart of the manufacturing method S10. As shown in FIG. 1, the manufacturing method S10 includes a preparation step S11 and an initial charging step S12. Hereinafter, each step will be described.
  • the preparation step S11 is a step of preparing a laminate in which a positive electrode layer, a solid electrolyte layer, and a negative electrode layer containing an alloy-based negative electrode active material are laminated in this order.
  • Positive electrode layer includes a positive electrode mixture layer. Further, the positive electrode layer may be provided with a positive electrode current collector on the surface opposite to the surface on the side where the solid electrolyte layer is laminated.
  • the positive electrode mixture layer contains a positive electrode active material.
  • the positive electrode active material is not particularly limited as long as it is a positive electrode active material that can be used in a lithium ion all-solid-state battery.
  • lithium cobalt oxide, lithium cobalt cobalt oxide (NCA-based active material), LiNi 1/3 Co 1/3 Mn 1/3 O2 , lithium manganate, spinel-based lithium compounds and the like can be mentioned.
  • the particle size of the positive electrode active material is not particularly limited, but is, for example, in the range of 5 ⁇ m or more and 50 ⁇ m or less.
  • the content of the positive electrode active material in the positive electrode mixture layer is, for example, in the range of 50% by weight or more and 99% by weight or less. Further, the surface of the positive electrode active material may be coated with an oxide layer such as a lithium niobate layer, a lithium titanate layer, or lithium phosphate.
  • the "particle size” in the present specification means the particle size (D50) at an integrated value of 50% in the volume-based particle size distribution measured by the laser diffraction / scattering method.
  • the positive electrode mixture layer may optionally include a solid electrolyte.
  • the solid electrolyte include an oxide solid electrolyte and a sulfide solid electrolyte.
  • a sulfide solid electrolyte is preferable.
  • the oxide solid electrolyte include Li 7 La 3 Zr 2 O 12 , Li 7-x La 3 Zr 1-x Nb x O 12 , Li 7-3 x La 3 Zr 2 Al x O 12 , Li 3 x La 2/3 .
  • Examples of the sulfide solid electrolyte include Li 3 PS 4 , Li 2 S-P 2 S 5 , Li 2 S-SiS 2 , LiI-Li 2 S-SiS 2 , LiI-Si 2 S-P 2 S 5 , Li 2 SP 2 S 5 -LiI-LiBr, LiI-Li 2 SP 2 S 5 , LiI-Li 2 SP 2 O 5 , LiI-Li 3 PO 4 -P 2 S 5 , Li 2 S -P 2 S 5 -GeS 2 and the like can be mentioned.
  • the content of the solid electrolyte in the positive electrode mixture layer is not particularly limited, but is, for example, in the range of 1% by weight or more and 50% by weight or less.
  • the positive electrode mixture layer may optionally be provided with a conductive auxiliary agent.
  • the conductive agent include carbon materials such as acetylene black, ketjen black, and vapor phase carbon fiber (VGCF), and metal materials such as nickel, aluminum, and stainless steel.
  • the content of the conductive auxiliary agent in the positive electrode mixture layer is not particularly limited, but is, for example, in the range of 0.1% by weight or more and 10% by weight or less.
  • the positive electrode mixture layer may optionally be provided with a binder (binding material).
  • a binder binder
  • the binder include butadiene rubber (BR), butylene rubber (IIR), acrylate butadiene rubber (ABR), polyvinylidene fluoride (PVdF), polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP) and the like. ..
  • the content of the binder in the positive electrode mixture layer is not particularly limited, but is, for example, in the range of 0.1% by weight or more and 10% by weight or less.
  • the thickness of the positive electrode mixture layer is not particularly limited, and may be appropriately set according to the desired battery performance.
  • the range is 0.1 ⁇ m or more and 1 mm or less.
  • the positive electrode current collector is arranged on the surface opposite to the surface on which the solid electrolyte layer of the positive electrode mixture layer is laminated.
  • the material of the positive electrode current collector is not particularly limited, and a known material can be appropriately selected depending on the intended purpose. For example, Cu, Ni, Cr, Au, Pt, Ag, Al, Fe, Ti, Zn, Co, stainless steel and the like can be mentioned.
  • the thickness of the positive electrode current collector is not particularly limited, and may be appropriately set according to the desired battery performance. For example, the range is 0.1 ⁇ m or more and 1 mm or less.
  • the method for producing the positive electrode layer is not particularly limited, and the positive electrode layer can be produced by a known method.
  • the positive electrode layer can be manufactured by mixing the materials constituting the positive electrode mixture layer together with a solvent to form a slurry, applying the slurry to the base material or the positive electrode current collector, and drying the slurry.
  • Solid electrolyte layer contains a solid electrolyte.
  • the type of solid electrolyte the same type as the solid electrolyte used for the positive electrode layer can be used.
  • the solid electrolyte layer may contain, for example, a sulfide solid electrolyte.
  • the sulfide solid electrolyte is relatively soft and easily absorbs the volume change in the construction of the negative electrode structure in the initial activation.
  • the content of the solid electrolyte in the solid electrolyte layer is, for example, in the range of 50% by weight or more and 99% by weight or less.
  • the solid electrolyte layer may optionally be provided with a binder (binding material).
  • a binder binder
  • the type of binder the same type as the binder used for the positive electrode layer can be used.
  • the content of the binder in the solid electrolyte layer is not particularly limited, but is, for example, in the range of 0.1% by weight or more and 10% by weight or less.
  • the method for producing the solid electrolyte layer is not particularly limited, and the solid electrolyte layer can be produced by a known method.
  • a solid electrolyte layer can be produced by mixing the materials constituting the solid electrolyte layer together with a solvent to form a slurry, applying the slurry to the substrate, and drying the slurry.
  • Negative electrode layer includes a negative electrode mixture layer or a negative electrode thin film layer. Further, the negative electrode layer may be provided with a negative electrode current collector on the surface opposite to the surface on the side where the solid electrolyte layer is laminated.
  • the negative electrode mixture layer contains an alloy-based negative electrode active material.
  • the alloy-based negative electrode active material is a metal element that can be bonded to Li, and specifically, Si, Sn, Al, Mg, C, Al, Ge, Sb, In, Cu, Mn, or oxides thereof. ..
  • it is Si or Sn or an oxide thereof. More preferably, it is Si or Si oxide.
  • the negative electrode active material is preferably in the form of particles, and the particle size is more preferably 1 ⁇ m or less. The smaller the particle size of the negative electrode active material, the more the inert interface (the interface between the negative electrode active material and the negative electrode active material) in the negative electrode mixture layer, while the inert interface due to the fusion between the negative electrode active materials by charging.
  • the effect of reducing the deactivating interface is remarkably increased when the particle size of the negative electrode active material is 1 ⁇ m or less, and as a result, an increase in the resistance increase rate can be suppressed.
  • the content of the negative electrode active material in the negative electrode mixture layer is, for example, in the range of 30% by weight or more and 90% by weight or less.
  • the negative electrode mixture layer may optionally include a solid electrolyte.
  • a solid electrolyte the same type as the solid electrolyte used for the positive electrode layer can be used.
  • the content of the solid electrolyte in the negative electrode mixture layer is not particularly limited, but is, for example, in the range of 10% by weight or more and 70% by weight or less.
  • the negative electrode mixture layer may optionally be provided with a conductive auxiliary agent.
  • a conductive auxiliary agent the same kind as the conductive auxiliary agent used for the positive electrode layer can be used.
  • the content of the conductive auxiliary agent in the negative electrode mixture layer is not particularly limited, but is, for example, in the range of 0.1% by weight or more and 20% by weight or less.
  • the negative electrode mixture layer may optionally be provided with a binder (binding material).
  • a binder the same kind of binder as the conductive auxiliary agent used for the positive electrode layer can be used.
  • the content of the binder in the negative electrode mixture layer is not particularly limited, but is, for example, in the range of 0.1% by weight or more and 10% by weight or less.
  • the thickness of the negative electrode mixture layer is not particularly limited, and may be appropriately set according to the desired battery performance.
  • the range is 0.1 ⁇ m or more and 1 mm or less.
  • the negative electrode thin film layer is a thin film containing an alloy-based negative electrode active material.
  • the content of the alloy-based negative electrode active material in the negative electrode thin film layer is preferably 90% by weight or more, more preferably 95% by weight or more, and particularly preferably 100% by weight (consisting of the alloy-based negative electrode active material). ..
  • the above-mentioned types of alloy-based negative electrode active materials can be used.
  • the thickness of the negative electrode thin film layer is not particularly limited. For example, it is in the range of 1 ⁇ m or more and 10 ⁇ m or less. From the viewpoint of ensuring the energy density, the lower limit is set to 1 ⁇ m. Further, the upper limit is set to 10 ⁇ m in consideration of the battery performance and the expansion coefficient due to charge / discharge.
  • the negative electrode current collector is a member arranged on the surface of the negative electrode mixture layer or the negative electrode thin film layer on the side opposite to the surface on which the solid electrolyte layer is laminated.
  • the material constituting the negative electrode current collector can be appropriately selected from known materials according to the purpose. For example, Cu, Ni, Cr, Au, Pt, Ag, Al, Fe, Ti, Zn, Co, stainless steel and the like can be mentioned.
  • the thickness of the negative electrode current collector is not particularly limited, and may be appropriately set according to the desired battery performance. For example, the range is 0.1 ⁇ m or more and 1 mm or less.
  • the negative electrode current collector has a surface roughness of at least 0.8 ⁇ m or more at the maximum height Rz of JIS B 0601: 2013 (ISO 4287: 1997) on the side in contact with the negative electrode mixture layer or the negative electrode thin film layer. It is preferably 0 ⁇ m or less.
  • the method for producing the negative electrode layer is not particularly limited, and the negative electrode layer can be produced by a known method.
  • the materials constituting the negative electrode mixture layer are mixed with a solvent to form a slurry, and the slurry is applied to a base material or a negative electrode current collector and dried. This makes it possible to manufacture a negative electrode layer including a negative electrode mixture layer.
  • the negative electrode layer including the negative electrode thin film layer is manufactured, for example, the negative electrode layer including the negative electrode thin film layer can be manufactured by sputtering the negative electrode active material onto the base material or the negative electrode current collector. Sputtering conditions can be appropriately set according to the thickness of the negative electrode thin film layer and the like.
  • the laminated body is a laminated body in which a positive electrode layer, a solid electrolyte layer, and a negative electrode layer containing an alloy-based active material are laminated in this order.
  • the capacity ratio of the negative electrode layer to the positive electrode layer is preferably 5 or less.
  • the "capacity ratio" is a value calculated from the theoretical capacity (mAh) of the negative electrode layer / the theoretical capacity (mAh) of the positive electrode layer.
  • the softness of the negative electrode active material changes by occluding Li during charging.
  • the method of laminating the positive electrode layer, the solid electrolyte layer, and the negative electrode layer is not particularly limited, and a known method can be adopted.
  • a positive electrode layer, a solid electrolyte layer, and a negative electrode layer are separately prepared, and the positive electrode layer and the solid electrolyte layer are laminated by pressing at a predetermined pressure, and the negative electrode layer is opposite to the positive electrode layer of the solid electrolyte layer.
  • a laminated body can be produced by laminating by pressing on the side surface with a predetermined pressure.
  • a slurry constituting the positive electrode layer, the solid electrolyte layer and the negative electrode layer is separately prepared, and the positive electrode layer, the solid electrolyte layer and the negative electrode layer are laminated in this order and dried to prepare a laminated body. Can be done.
  • Initial charging process S12 The initial charging step S12 is a step performed after the preparation step S11, and the laminate produced in the preparation step S11 is constrained in the stacking direction to perform the initial constant current constant voltage charging of the battery. Further, in the initial charging step S12, the restraining pressure of the laminated body at the start of charging is 30 MPa or more, and the restraining pressure at the end of charging is 40 MPa or more.
  • the conditions for initial constant current and constant voltage charging are not particularly limited and may be the same as before. That is, it may be appropriately set according to the battery performance of the laminated body.
  • the restraining pressure of the laminated body at the start of charging may be 30 MPa or more. It is preferably 40 MPa or more. On the other hand, it may be 70 MPa or less in consideration of the durability of the laminated body. Further, the restraining pressure of the laminated body at the end of charging may be 40 MPa or more. It is preferably 50 MPa or more. On the other hand, it may be 80 MPa or less in consideration of the durability of the laminated body.
  • the negative electrode active material expands by occluding Li by charging, the restraining pressure at the end of charging becomes larger than that at the start of charging. Therefore, it is premised that the restraining pressure of the laminated body at the end of charging is larger than the restraining pressure of the laminated body at the start of charging.
  • an all-solid-state battery manufactured using the laminated body is subjected to initial charging by applying a large restraining pressure to the laminated body in the initial charging step as compared with normal use. It is possible to suppress an increase in the resistance increase rate. More specifically, by performing the first charge under the conditions that the restraint pressure at the start of charging is 30 MPa or more and the restraint pressure at the end of charging is 40 MPa or more, the relative resistance increase rate is lowered, that is, the deterioration of the battery laminate due to durability is prevented. It can be suppressed.
  • the active material is grown in the thickness direction in which the restraining pressure is applied. This is very important.
  • the inert interface (the interface between the negative electrode active material and the negative electrode active material) is reduced, and the negative electrode active material is rearranged in the negative electrode layer.
  • voids in the negative electrode layer that are generated when the negative electrode active material is contracted (for example, during discharge) are likely to be generated in the stacking direction. Voids in the stacking direction are less likely to interfere with electron paths and ion paths. Therefore, the arrangement of the voids generated in the negative electrode layer can be controlled by the initial charging step, and as a result, the increase in the resistance increase rate can be suppressed.
  • the above effect becomes more remarkable.
  • the above-mentioned restraint enhances the adhesion between the negative electrode current collector and the layer containing the negative electrode active material, and at the same time.
  • the laminate may be constrained with a restraining pressure of 10 MPa or less. Further, after the initial charging step S12, a step of accommodating the laminated body in a case provided with terminals necessary for the battery such as electrodes may be provided.
  • An all-solid-state battery which is one embodiment of the solid-state battery manufactured by the method for manufacturing a solid-state battery of the present disclosure, comprises a laminate in which a positive electrode layer, a solid electrolyte layer, and a negative electrode layer are laminated in this order, and a negative electrode is provided.
  • the ratio of the voids in the stacking direction to the total voids existing in the layer can be made larger than 36% by volume. More preferably, it is 55% by volume or more. On the other hand, the upper limit is 100% by volume.
  • the "void in the stacking direction” means that the direction of the major axis of the void is 45 ° or less with respect to the stacking direction, the length of the major axis is 0.5 ⁇ m or more, and the length of the minor axis is 2 ⁇ m. It means the following voids.
  • the major axis is 45 ° or more with respect to the horizontal plane, the length thereof is 0.5 ⁇ m or more, and the length of the minor axis is 2 ⁇ m, with the direction seen from the upper and lower surfaces as the horizontal plane with respect to the stacking direction.
  • the following are defined as vertical cracks, and the volume ratio of the voids in the stacking direction to the volume of all voids is calculated as the vertical crack ratio (volume%).
  • the voids in the stacking direction are less likely to obstruct the electron path and ion path in the negative electrode layer than other voids. Therefore, according to the all-solid-state battery of the present disclosure in which the ratio (vertical cracking ratio) of the voids in the stacking direction in the negative electrode layer is larger than 36% by volume, preferably 55% by volume or more, the increase in the resistance increase rate is suppressed. be able to. In particular, even in the case of silicon having a large expansion and contraction, it is possible to suppress an increase in resistance during cycling.
  • Test 3.1 Test on binding force 3.1.1. Preparation of Laminates Laminates for evaluation according to Tests A1 to A7 and Tests B1 to B5 were prepared as follows.
  • negative electrode layer including negative electrode mixture layer
  • Negative electrode mixture containing powdered Si particles, sulfide-based solid electrolyte (Li 2 SP 2 S 5 ), vapor-phase growth method carbon fiber, PVdF-based binder, and butyl butyrate as raw materials.
  • the particle size of the Si particles is as shown in Tables 2 to 4.
  • the weight ratio of the powdered Si particles: the sulfide-based solid electrolyte: the vapor-phase growth method carbon fiber: the PVdF-based binder in the negative electrode slurry is 47.0: 44.6: 7.0: 1.4. It was adjusted.
  • This negative electrode slurry was applied onto a negative electrode current collector foil (Ni foil) by a blade method, and this was dried on a hot plate for 30 minutes at 100 ° C. to obtain a negative electrode layer.
  • Negative Electrode Layer including Negative Electrode Thin Film As the negative electrode current collector, an electrolytic copper foil whose surface was roughened by precipitating copper by an electrolytic method was used. A Si thin film was formed on the surface of the negative electrode current collector using an RF sputtering device to obtain a negative electrode layer.
  • Table 1 shows the formation conditions of the Si thin film.
  • the thickness of the Si thin film was calculated by calculating the areal density of Si by inductively coupled plasma emission spectrometry and dividing the value of this areal density by the true density of Si (2.3 gcm -3 ).
  • the Si content in the negative electrode layer was 95% by mass or more.
  • a solid electrolyte slurry is prepared by stirring a solid electrolyte mixture containing a sulfide-based solid electrolyte (Li 2 SP 2 S 5 ), PVdF-based binder, and butyl butyrate as raw materials with an ultrasonic disperser. did.
  • the weight ratio of the sulfide-based solid electrolyte: PVdF-based binder in the solid electrolyte slurry was adjusted to be 99.6: 0.4.
  • This solid electrolyte slurry was applied onto an Al foil by a blade method and dried on a hot plate for 30 minutes at 100 ° C. to obtain a peelable solid electrolyte layer.
  • the prepared negative electrode layer and the solid electrolyte layer were laminated so that the mixed material surfaces overlapped with each other or the thin film surface and the mixed material surface overlapped with each other. After pressing with a roll press machine at a press pressure of 50 kN / cm and a temperature of 160 ° C., the Al foil of the solid electrolyte layer was peeled off to obtain a negative electrode laminate A. Further, a solid electrolyte layer was further laminated on the solid electrolyte layer side of the negative electrode laminate A so that the mixture surface overlapped.
  • the prepared positive electrode laminate and negative electrode laminate B were laminated so that the mixed material surfaces overlapped.
  • This laminate was pressed with a flat uniaxial press at a press pressure of 200 MPa and a temperature of 120 ° C. to obtain a laminate.
  • the volume ratio of the negative electrode layer to the positive electrode layer of the produced laminate is shown in Tables 2 to 5.
  • the major axis is 45 ° or more with respect to the horizontal plane, the length thereof is 0.5 ⁇ m or more, and the length of the minor axis is 2 ⁇ m, with the direction seen from the upper and lower surfaces as the horizontal plane with respect to the stacking direction.
  • the following are defined as vertical cracks, and the volume ratio of the voids in the stacking direction to the volume of all voids is calculated as the vertical crack ratio (volume%).
  • FIG. 2 shows a cross-sectional image (test A1) of the negative electrode including the negative electrode mixture layer.
  • FIG. 3 shows a cross-sectional image (test A7) of the negative electrode including the negative electrode thin film layer.
  • the laminated body was charged with a constant current up to 1 / 10C and 3.0V, and then charged with a constant voltage up to 3.0V and a final current of 1 / 100C to adjust the charging state.
  • a current of 8.2 mAh / cm 2 was passed through the laminated body whose charge state was adjusted for 10 seconds, and the voltage change before and after that was divided by the current value to obtain resistance. This resistance value was taken as the resistance value after durability.
  • the resistance increase rate was calculated from the following formula.
  • the relative resistance increase rate is calculated with the resistance increase rate of the test B1 as a reference (100%).
  • the relative resistance increase rate is calculated based on the resistance increase rate of the test B5 (100%). The small rate of increase in relative resistance indicates that deterioration of the battery laminate due to durability is suppressed.
  • the results are shown in Tables 2 to 5.
  • Resistance increase rate (%) resistance value after durability ( ⁇ ) / initial resistance value ( ⁇ ) x 100
  • Tables 2 to 4 are the results of test examples of the laminated body including the negative electrode layer including the negative electrode mixture layer.
  • Table 2 is a test example in which the particle size of the negative electrode active material and the volume ratio of the laminated body are fixed, while the restraining pressure at the start of charging and the restraining pressure at the end of charging are changed.
  • FIG. 4 shows the relationship between the restraint pressure at the end of the initial charge and the relative resistance increase rate. From Table 2 and FIG.
  • the restraint pressure at the start of charging is 30 MPa or more and the restraint pressure at the end of electricity is 40 MPa or more with respect to the test B1 and the test B2 generally applied at the restraint pressure of 10 MPa to 20 MPa in the initial charge.
  • Tests A1 to A3 conducted under the above conditions an increase in the vertical cracking rate and a decrease in the relative resistance increase rate were confirmed. From this result, it can be seen that the deterioration of the laminated body due to the durability test is suppressed in the tests A1 to A3 as compared with the tests B1 and B2.
  • Table 3 shows the results of changing the volume ratio of the laminated body while fixing the particle size of the negative electrode active material, the restraining pressure at the start of charging, and the restraining pressure at the end of charging. From Table 3, it can be seen that the relative resistance increase rate decreases in the range where the capacity ratio is 5 or less, that is, the deterioration of the laminated body due to the durability test is suppressed.
  • the softness of Si used as the alloy-based negative electrode active material changes by occluding Li. Therefore, the reason why the relative resistance increase rate decreased in the range where the capacity ratio was 5 or less is that by setting the capacity ratio to 5 or less, it was possible to reach the softness at which LiSis are likely to bind to each other during charging. it is conceivable that.
  • Table 4 shows the results of changing the particle size of the negative electrode active material while fixing the capacity ratio of the laminate, the restraining pressure at the start of charging, and the restraining pressure at the end of charging. From Table 4, it can be seen that the relative resistance increase rate is reduced under the condition that the particle size of the negative electrode active material is 1 ⁇ m or less, that is, the deterioration of the battery laminate due to durability is suppressed. This is because the smaller the particle size of the negative electrode active material, the more the interface between the negative electrode active material and the negative electrode active material in the negative electrode. When an active material having a particle size of 1 ⁇ m or less is used, the active material It is shown that the effect of reducing the inert interface by fusion between them is large.
  • Table 5 shows the results of a test example of a laminated body using a negative electrode layer including a negative electrode thin film layer. From Table 5, even when the first charge is performed using such a laminated body under the conditions that the restraint pressure at the start of charging is 30 MPa and the restraint pressure at the end of charging is 50 MPa, the vertical cracking rate increases and the relative It has been confirmed that the resistance increase rate has decreased, and it can be seen that the deterioration of the battery laminate by the durability test is suppressed. In particular, in test A7, it can be seen that the vertical crack rate is 100%.
  • Laminates Laminates for evaluation according to Test A11 to Test A16 and Test B11 to Test B14 were prepared as follows.
  • Negative Electrode Layer (Negative Electrode Layer with Negative Electrode Mixture Layer) Powdered Si particles, sulfide-based solid electrolyte (Li 2 SP 2 S 5 ), vapor-phase growth method carbon fiber, PVdF-based binder, butyl butyrate are used as raw materials.
  • a negative electrode slurry was prepared by stirring the containing negative electrode mixture with an ultrasonic disperser.
  • the weight ratio of the powdered Si particles: the sulfide-based solid electrolyte: the vapor-phase growth method carbon fiber: the PVdF-based binder in the negative electrode slurry is 46.8: 44.4: 7.0: 1.4. It was adjusted.
  • This negative electrode slurry is applied to a metal foil having Rz shown in Tables 6 and 7 as a negative electrode current collector by a blade method, and this is dried on a hot plate for 30 minutes at 100 ° C. to obtain a negative electrode.
  • a negative electrode layer having a material layer was obtained.
  • Negative Electrode Layer (Negative Electrode Layer with Negative Electrode Thin Film Layer) A Ni foil having Rz shown in Table 8 was used as a negative electrode current collector. A Si thin film was formed on the surface of the negative electrode current collector using an RF sputtering device to obtain a negative electrode layer. The conditions for forming the Si thin film are the same as those in Table 1 above.
  • the laminated body was charged with a constant current up to 1 / 10C and 3.0V, and then charged with a constant voltage up to 3.0V and a final current of 1 / 100C to adjust the charging state.
  • a current of 8.2 mAh / cm 2 was passed through the laminated body whose charge state was adjusted for 10 seconds, and the voltage change before and after that was divided by the current value to obtain resistance. This resistance value was taken as the resistance value after durability.
  • the resistance increase rate was calculated from the following formula.
  • the relative resistance increase rate is calculated with the resistance increase rate of the test A11 as a reference (100%).
  • the relative resistance increase rate is calculated based on the resistance increase rate of the test A16 (100%). The small rate of increase in relative resistance indicates that deterioration of the battery laminate due to durability is suppressed.
  • the results are shown in Tables 6-8.
  • Resistance increase rate (%) resistance value after durability ( ⁇ ) / initial resistance value ( ⁇ ) x 100
  • the adhesion between the negative electrode mixture and the negative electrode current collector is low, peeling occurs at the interface between the negative electrode mixture and the negative electrode current collector, and the expansion of the negative electrode mixture in the plane direction is suppressed. It is probable that the cracking could not be controlled because it could not be done, and the resistance increase rate increased. Further, when Rz is larger than 4.0 ⁇ m, the difference in thickness between the valley and the peak in the roughened portion of the negative electrode current collector is large, and the local facing capacitance ratio in the valley and the local facing capacitance ratio in the peak. It is probable that the resistance increase rate increased due to the occurrence of deviation and causing uneven reaction.
  • the surface roughness Rz of the negative electrode current collector is 0.8 ⁇ m or more as in the above mixture.

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2024013898A (ja) * 2022-07-21 2024-02-01 マクセル株式会社 全固体二次電池用負極、全固体二次電池及びその製造方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12537216B2 (en) * 2022-08-17 2026-01-27 Ford Global Technologies, Llc Multi-layer all solid-state battery coating
CN116449243B (zh) * 2023-04-20 2026-04-14 星恒电源股份有限公司 一种电池性能改善方法、装置、存储介质及电子设备
DE102024109077A1 (de) * 2024-03-28 2025-10-02 Bayerische Motoren Werke Aktiengesellschaft Elektrochemische feststoffspeicherzelle und verfahren zum herstellen einer elektrochemischen feststoffspeicherzelle

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005285651A (ja) * 2004-03-30 2005-10-13 Sanyo Electric Co Ltd リチウム二次電池
JP2006155959A (ja) * 2004-11-25 2006-06-15 Sony Corp 負極および電池
JP2010272210A (ja) 2009-05-19 2010-12-02 Hitachi Zosen Corp 全固体二次電池の製造方法
JP2014107163A (ja) * 2012-11-28 2014-06-09 Toyota Motor Corp 全固体リチウム二次電池の製造方法
JP2016018704A (ja) * 2014-07-09 2016-02-01 トヨタ自動車株式会社 全固体電池
JP2016081790A (ja) 2014-10-20 2016-05-16 トヨタ自動車株式会社 全固体二次電池の製造方法
JP2019091547A (ja) * 2017-11-10 2019-06-13 トヨタ自動車株式会社 全固体電池の製造方法
JP2019192338A (ja) * 2018-04-18 2019-10-31 トヨタ自動車株式会社 全固体電池
JP2019192563A (ja) * 2018-04-27 2019-10-31 トヨタ自動車株式会社 全固体電池およびその製造方法
US20200136178A1 (en) * 2018-10-30 2020-04-30 Samsung Electronics Co., Ltd. All-solid secondary battery and method for preparing all-solid secondary battery
JP2020107389A (ja) 2018-12-25 2020-07-09 株式会社Ｓｏｋｅｎ 全固体電池の製造方法
JP2020177904A (ja) * 2019-04-17 2020-10-29 トヨタ自動車株式会社 全固体電池用負極

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI311384B (en) * 2004-11-25 2009-06-21 Sony Corporatio Battery and method of manufacturing the same
JP2008117785A (ja) * 2005-08-02 2008-05-22 Matsushita Electric Ind Co Ltd リチウム二次電池用負極およびその製造方法
JP5718476B2 (ja) * 2012-06-27 2015-05-13 古河電気工業株式会社 リチウムイオン二次電池用電解銅箔、リチウムイオン二次電池の負極電極及びリチウムイオン二次電池
JP6123642B2 (ja) * 2013-11-08 2017-05-10 トヨタ自動車株式会社 全固体電池の充電システム
US10122010B2 (en) * 2014-07-11 2018-11-06 Semiconductor Energy Laboratory Co., Ltd. Secondary battery and electronic device including the same
JP6172083B2 (ja) * 2014-08-04 2017-08-02 トヨタ自動車株式会社 リチウム固体二次電池およびその製造方法
US20190145765A1 (en) * 2017-11-15 2019-05-16 Uber Technologies, Inc. Three Dimensional Object Detection
US10985407B2 (en) * 2017-11-21 2021-04-20 Samsung Electronics Co., Ltd. All-solid-state secondary battery including anode active material alloyable with lithium and method of charging the same

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005285651A (ja) * 2004-03-30 2005-10-13 Sanyo Electric Co Ltd リチウム二次電池
JP2006155959A (ja) * 2004-11-25 2006-06-15 Sony Corp 負極および電池
JP2010272210A (ja) 2009-05-19 2010-12-02 Hitachi Zosen Corp 全固体二次電池の製造方法
JP5557471B2 (ja) * 2009-05-19 2014-07-23 日立造船株式会社 全固体二次電池の製造方法
JP2014107163A (ja) * 2012-11-28 2014-06-09 Toyota Motor Corp 全固体リチウム二次電池の製造方法
JP2016018704A (ja) * 2014-07-09 2016-02-01 トヨタ自動車株式会社 全固体電池
JP2016081790A (ja) 2014-10-20 2016-05-16 トヨタ自動車株式会社 全固体二次電池の製造方法
JP2019091547A (ja) * 2017-11-10 2019-06-13 トヨタ自動車株式会社 全固体電池の製造方法
JP2019192338A (ja) * 2018-04-18 2019-10-31 トヨタ自動車株式会社 全固体電池
JP2019192563A (ja) * 2018-04-27 2019-10-31 トヨタ自動車株式会社 全固体電池およびその製造方法
US20200136178A1 (en) * 2018-10-30 2020-04-30 Samsung Electronics Co., Ltd. All-solid secondary battery and method for preparing all-solid secondary battery
JP2020107389A (ja) 2018-12-25 2020-07-09 株式会社Ｓｏｋｅｎ 全固体電池の製造方法
JP2020177904A (ja) * 2019-04-17 2020-10-29 トヨタ自動車株式会社 全固体電池用負極

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4266430A4

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2024013898A (ja) * 2022-07-21 2024-02-01 マクセル株式会社 全固体二次電池用負極、全固体二次電池及びその製造方法

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