WO2023127283A1 - Batterie à électrolyte entièrement solide et procédé de production de celle-ci - Google Patents

Batterie à électrolyte entièrement solide et procédé de production de celle-ci Download PDF

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WO2023127283A1
WO2023127283A1 PCT/JP2022/040464 JP2022040464W WO2023127283A1 WO 2023127283 A1 WO2023127283 A1 WO 2023127283A1 JP 2022040464 W JP2022040464 W JP 2022040464W WO 2023127283 A1 WO2023127283 A1 WO 2023127283A1
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solid electrolyte
layer
solid
state battery
particle size
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PCT/JP2022/040464
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English (en)
Japanese (ja)
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織茂洋子
伊藤大悟
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太陽誘電株式会社
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • 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 battery and its manufacturing method.
  • the cover layer is desirably composed of a material that does not interdiffuse with the solid electrolyte layer during firing
  • a material with the same composition as the solid electrolyte layer is used for the cover layer material.
  • the laminated all-solid-state battery in addition to the cover layer and the solid electrolyte layer, a large number of layers mainly composed of different materials are laminated, such as the positive electrode layer, the negative electrode layer, and the reverse pattern layer. If such a stacked all-solid-state battery is to be fired all at once, there is a concern that delamination may occur due to differences in shrinkage behavior of each layer.
  • Patent Document 3 a moisture-proof layer is provided in contact with the laminate in order to suppress the decrease in battery capacity due to the reaction between the active material contained in the electrode layer and moisture.
  • a moisture-proof layer is provided by using a method such as spray coating or dip coating after baking the laminate, and the moisture-proof property of the laminate before forming the moisture-proof layer is not guaranteed.
  • the present invention has been made in view of the above problems, and an object of the present invention is to provide an all-solid-state battery that is capable of suppressing delamination during batch firing and that includes a moisture-proof cover layer, and a method for manufacturing the same. .
  • the all-solid-state battery according to the present invention has a laminated structure in which a solid electrolyte layer and an electrode layer containing an electrode active material are alternately laminated, and at least one of the upper surface and the lower surface of the laminated structure in the lamination direction. and a cover layer containing an oxide-based solid electrolyte and a filler material having a sintering temperature higher than that of the oxide-based solid electrolyte and insulating properties.
  • the volume ratio of the filler material to the oxide-based solid electrolyte may be 10 vol% or more.
  • the filler material may have a conductivity including electronic conductivity and ionic conductivity of 10 ⁇ 8 S/cm or less.
  • the filler material may be alumina or SiO2 glass.
  • the shape of the filler material may have an average cross-sectional circularity of 0.6 or more.
  • the D50% particle size of the filler material may be 0.5 ⁇ m or more and 8 ⁇ m or less.
  • the particle size distribution of the solid electrolyte of the other layer is between D0% particle size and D10% particle size in the particle size distribution of the solid electrolyte of one layer.
  • there is a D100% particle size in the particle size distribution of the solid electrolyte in the other layer between D90% particle size and D100% particle size in the particle size distribution of the solid electrolyte in the one layer.
  • the oxide-based solid electrolyte of the cover layer may be a solid electrolyte having a NASICON-type crystal structure.
  • the main component of the solid electrolyte layer may be a solid electrolyte having a NASICON-type crystal structure.
  • the oxide-based solid electrolyte of the cover layer may have the same composition as the main component of the solid electrolyte layer.
  • the oxide-based solid electrolyte of the cover layer may be a glass material.
  • the electrode layer may contain an oxide-based solid electrolyte having ion conductivity.
  • a method for manufacturing an all-solid-state battery according to the present invention comprises a laminate in which a solid electrolyte green sheet containing a solid electrolyte powder and an internal electrode pattern containing an electrode active material powder are alternately laminated on the top surface and the bottom surface in the stacking direction.
  • a preparation step and a firing step of firing the ceramic laminate are included.
  • the sintering temperature of the oxide-based solid electrolyte powder of the cover sheet is lower than the sintering temperature in the sintering step, and the sintering temperature of the filler material is lower than the sintering temperature in the sintering step. higher than the temperature.
  • an all-solid-state battery that is capable of suppressing interrelated delamination during batch firing and that includes a moisture-proof cover layer, and a method for manufacturing the same.
  • FIG. 1 is a schematic cross-sectional view showing the basic structure of an all-solid-state battery
  • FIG. 1 is a schematic cross-sectional view of a stacked all-solid-state battery
  • FIG. 3 is a schematic cross-sectional view of another stacked all-solid-state battery
  • 4 is a schematic cross-sectional view of a cover layer
  • FIG. It is a figure which illustrates the flow of the manufacturing method of an all-solid-state battery.
  • (a) and (b) are figures which illustrate a lamination process.
  • FIG. 1 is a schematic cross-sectional view showing the basic structure of an all-solid-state battery 100.
  • the all-solid-state battery 100 has a structure in which a solid electrolyte layer 30 is sandwiched between a first internal electrode 10 (first electrode layer) and a second internal electrode 20 (second electrode layer). have.
  • First internal electrode 10 is formed on the first main surface of solid electrolyte layer 30 .
  • the second internal electrode 20 is formed on the second main surface of the solid electrolyte layer 30 .
  • one of the first internal electrode 10 and the second internal electrode 20 is used as a positive electrode, and the other is used as a negative electrode.
  • the first internal electrode 10 is used as a positive electrode layer
  • the second internal electrode 20 is used as a negative electrode layer.
  • the solid electrolyte layer 30 has a NASICON-type crystal structure and is mainly composed of an oxide-based solid electrolyte having ionic conductivity.
  • the solid electrolyte of the solid electrolyte layer 30 is, for example, an oxide-based solid electrolyte having lithium ion conductivity.
  • the solid electrolyte is, for example, a phosphate-based solid electrolyte.
  • a phosphate-based solid electrolyte having a NASICON-type crystal structure has the property of having high electrical conductivity and being stable in the atmosphere.
  • a phosphate-based solid electrolyte is, for example, a phosphate containing lithium.
  • the phosphate is not particularly limited, but examples thereof include a composite lithium phosphate with Ti (eg, LiTi 2 (PO 4 ) 3 ).
  • Ti can be partially or wholly substituted with tetravalent transition metals such as Ge, Sn, Hf, and Zr.
  • tetravalent transition metals such as Ge, Sn, Hf, and Zr.
  • trivalent transition metals such as Al, Ga, In, Y and La. More specifically, for example, Li 1+x Al x Ge 2-x (PO 4 ) 3 , Li 1+x Al x Zr 2-x (PO 4 ) 3 , Li 1+x Al x Ti 2-x (PO 4 ) 3 etc.
  • the Li—Al—Ge—PO 4 -based material pre-added with Co is used as the solid electrolyte layer 30. is preferably included in In this case, the effect of suppressing the elution of the transition metal contained in the electrode active material into the electrolyte can be obtained.
  • first internal electrode 10 and the second internal electrode 20 contain a transition element other than Co and a phosphate containing Li
  • a Li—Al—Ge—PO 4 -based material to which the transition metal has been previously added is used. It is preferably included in the solid electrolyte layer 30 .
  • the first internal electrode 10 used as a positive electrode contains a material having an olivine crystal structure as an electrode active material.
  • the second internal electrode 20 also preferably contains the electrode active material. Examples of such electrode active materials include phosphates containing transition metals and lithium.
  • the olivine type crystal structure is a crystal of natural olivine and can be identified by X-ray diffraction.
  • LiCoPO4 containing Co can be used as a typical example of an electrode active material having an olivine-type crystal structure.
  • a phosphate or the like in which the transition metal Co is replaced in this chemical formula can also be used.
  • the ratio of Li and PO4 can vary depending on the valence. Co, Mn, Fe, Ni, etc. are preferably used as transition metals.
  • An electrode active material having an olivine-type crystal structure acts as a positive electrode active material in the first internal electrode 10 that acts as a positive electrode.
  • the electrode active material acts as a positive electrode active material.
  • the second internal electrode 20 also contains an electrode active material having an olivine-type crystal structure, the second internal electrode 20 acting as a negative electrode has not been completely clarified, but the negative electrode active material is Effects such as an increase in discharge capacity and an increase in operating potential associated with discharge, which are presumed to be based on the formation of a partial solid solution state with a substance, are exerted.
  • each electrode active material preferably contains the same or different Contains good transition metals. “They may be the same or different” means that the electrode active materials contained in the first internal electrode 10 and the second internal electrode 20 may contain the same type of transition metal, or may contain different types of transition metals. of transition metals may be included.
  • the first internal electrode 10 and the second internal electrode 20 may contain only one kind of transition metal, or may contain two or more kinds of transition metals.
  • the first internal electrode 10 and the second internal electrode 20 contain transition metals of the same kind. More preferably, both electrodes contain the same electrode active material in chemical composition.
  • the compositional similarity of both internal electrode layers increases. Even if the polarity of the terminal of the all-solid-state battery 100 is reversed, depending on the application, it can withstand actual use without malfunction.
  • the second internal electrode 20 contains a negative electrode active material.
  • the negative electrode active material By including the negative electrode active material in only one electrode, it becomes clear that the one electrode acts as a negative electrode and the other electrode acts as a positive electrode. Both electrodes may contain a known negative electrode active material.
  • the negative electrode active material of the electrode prior art in secondary batteries can be appropriately referred to, for example, titanium oxide, lithium titanium composite oxide, lithium titanium composite phosphate, carbon, compounds such as vanadium lithium phosphate is mentioned.
  • a solid electrolyte having ion conductivity, a conductive material (conductive aid), and the like are added.
  • an internal electrode paste can be obtained by uniformly dispersing a binder and a plasticizer in water or an organic solvent.
  • a carbon material or the like may be contained as a conductive aid.
  • a metal may be contained as a conductive aid. Examples of the metal of the conductive aid include Pd, Ni, Cu, Fe, alloys containing these, and the like.
  • the solid electrolyte contained in the first internal electrode 10 and the second internal electrode 20 can be the same as the main component solid electrolyte of the solid electrolyte layer 30, for example.
  • the thickness of the solid electrolyte layer 30 is, for example, 5 ⁇ m or more and 30 ⁇ m or less, 7 ⁇ m or more and 25 ⁇ m or less, and 10 ⁇ m or more and 20 ⁇ m or less.
  • the thickness of the first internal electrode 10 and the second internal electrode 20 is, for example, 5 ⁇ m or more and 50 ⁇ m or less, 7 ⁇ m or more and 45 ⁇ m or less, or 10 ⁇ m or more and 40 ⁇ m or less.
  • the thickness of each layer can be measured, for example, as an average value of ten different thicknesses of one layer.
  • FIG. 2 is a schematic cross-sectional view of a stacked all-solid-state battery 100a in which a plurality of battery units are stacked.
  • the all-solid-state battery 100a includes a laminated chip 60 having a substantially rectangular parallelepiped shape.
  • the first external electrode 40a and the second external electrode 40b are provided so as to be in contact with two side surfaces of the four surfaces other than the top surface and the bottom surface of the stacking direction end.
  • the two side surfaces may be two adjacent side surfaces or two side surfaces facing each other.
  • the first external electrode 40a and the second external electrode 40b are provided so as to be in contact with two side surfaces (hereinafter referred to as two end surfaces) facing each other.
  • the all-solid-state battery 100a a plurality of first internal electrodes 10 and a plurality of second internal electrodes 20 are alternately stacked with solid electrolyte layers 30 interposed therebetween. Edges of the plurality of first internal electrodes 10 are exposed on the first end surface of the laminated chip 60 and are not exposed on the second end surface. Edges of the plurality of second internal electrodes 20 are exposed on the second end surface of the laminated chip 60 and are not exposed on the first end surface. Thereby, the first internal electrode 10 and the second internal electrode 20 are alternately connected to the first external electrode 40a and the second external electrode 40b.
  • the solid electrolyte layer 30 extends from the first external electrode 40a to the second external electrode 40b.
  • the all-solid-state battery 100a has a structure in which a plurality of battery units are stacked.
  • a cover layer 50 is laminated on the upper surface of the laminated structure of the first internal electrode 10 , the solid electrolyte layer 30 and the second internal electrode 20 .
  • the cover layer 50 is in contact with the uppermost internal electrode (either one of the first internal electrode 10 and the second internal electrode 20 ) and is in contact with a portion of the solid electrolyte layer 30 .
  • a cover layer 50 is also laminated on the lower surface of the laminated structure.
  • the cover layer 50 is in contact with the lowermost internal electrode (either one of the first internal electrode 10 and the second internal electrode 20 ) and is in contact with a portion of the solid electrolyte layer 30 .
  • the first internal electrode 10 and the second internal electrode 20 may have collector layers.
  • the first collector layer 11 may be provided inside the first internal electrode 10 .
  • a second collector layer 21 may be provided in the second internal electrode 20 .
  • the first current collector layer 11 and the second current collector layer 21 are mainly composed of a conductive material.
  • metal, carbon, or the like can be used as the conductive material of the first current collector layer 11 and the second current collector layer 21 .
  • a stacked all-solid-state battery such as the all-solid-state battery 100a in FIGS. 2 and 3 has a large number of layers mainly composed of different materials. delamination may occur. Moreover, in order to suppress a decrease in battery capacity due to a reaction between the electrode active material contained in the electrode layer and moisture, it is required that the stacked all-solid-state battery be provided with moisture resistance. Therefore, the cover layer 50 according to the present embodiment has a structure capable of suppressing delamination during batch firing and having moisture resistance.
  • FIG. 4 is a diagram schematically showing a cross section of the cover layer 50.
  • the cover layer 50 includes an oxide-based solid electrolyte 50a and a filler material 50b having a sintering temperature higher than that of the solid electrolyte 50a and insulating properties.
  • particles of the solid electrolyte 50a and particles of the filler material 50b are randomly dispersed.
  • the solid electrolyte 50a contained in the cover layer 50 is sintered together with the solid electrolyte 50a contained in the solid electrolyte layer 30 and the electrode layer with which the cover layer 50 is in contact. High adhesion to the solid electrolyte layer 30 and the electrode layer that are in contact can be obtained. Thereby, delamination can be suppressed.
  • the filler material 50b contained in the cover layer 50 is higher than the sintering temperature of the solid electrolyte 50a, the filler material 50b is not sintered and grains do not grow during batch firing. of the particle morphology is retained. As a result, the in-plane shrinkage of the cover layer 50 is suppressed, and delamination can be controlled by suppressing or absorbing the stress or strain due to the difference in shrinkage behavior of each layer.
  • the cover layer 50 achieves moisture resistance.
  • the cover layer 50 according to the present embodiment can suppress delamination during batch firing and achieve moisture resistance.
  • alumina Al 2 O 3
  • SiO 2 glass SiO 2 glass
  • ZrO 2 zirconium oxide
  • the filler material 50b alumina (Al 2 O 3 ), SiO 2 glass, ZrO 2 or the like can be used as the filler material 50b.
  • the filler particles may form agglomerates, which may cause voids during batch firing with the solid electrolyte 50a. Therefore, it is preferable to set a lower limit for the D50% particle size of the filler material 50b.
  • the D50% particle diameter of the filler material 50b is preferably 0.5 ⁇ m or more, more preferably 1.0 ⁇ m or more, and even more preferably 2.0 ⁇ m or more.
  • the particle size of the filler material 50b can be measured using a particle size distribution measuring device using a laser diffraction/scattering method in the powder stage, and can be measured by image analysis from an SEM image after firing.
  • the D50% particle size of the filler material 50b is preferably 8 ⁇ m or less, more preferably 6 ⁇ m or less, and even more preferably 4 ⁇ m or less.
  • the filler material 50b preferably has an irregular shape. If the particles of the filler material 50b existing on the surface in contact with the solid electrolyte layer 30 and the electrode layer are spherical, they will come into contact with the solid electrolyte layer 30 and the electrode layer by point contact. This is because the frequency of surface contact with the solid electrolyte layer 30 and the electrode layer is increased, and the adhesion is further improved.
  • the irregular shape here means that the shape of the filler material 50b has an average circularity of 0.6 or more in cross section.
  • the ratio of the filler material 50b is preferably 10 vol% or more, more preferably 20 vol% or more. Preferably, it is more preferably 30 vol % or more.
  • the volume ratio the cross section of the all-solid-state battery 100 is FIB-processed and then observed with an SEM. Build a three-dimensional structure by image processing. Since the filler material 50b and the glass material have a clear contrast ratio in the SEM image, the volume ratio of the filler material 50b can be calculated based on the contrast.
  • the cover layer 50 if the amount of the filler material 50b is large, the amount of the solid electrolyte 50a will be small, and there is a risk that sufficient adhesion cannot be obtained. Therefore, it is preferable to set an upper limit to the amount of the filler material 50b in the cover layer 50 .
  • the ratio of the filler material 50b is preferably 80 vol% or less, more preferably 70 vol% or less. It is preferably 65 vol % or less, and more preferably 65 vol % or less.
  • the filler material 50b preferably has sufficient insulation.
  • the conductivity including electronic conductivity and ionic conductivity of the filler material 50b is preferably 10 ⁇ 8 S/cm or less, more preferably 10 ⁇ 12 S/cm or less, and 10 ⁇ 14 S/cm or less. cm or less is more preferable.
  • the solid electrolyte 50a includes an oxide-based solid electrolyte that is the main component of the solid electrolyte layer 30, an oxide-based solid electrolyte that is included in the first internal electrode 10, and an oxide-based solid electrolyte that is included in the second internal electrode 20. It preferably has a common structure with the oxide-based solid electrolyte contained.
  • the solid electrolyte 50a preferably has a NASICON crystal structure.
  • the solid electrolyte 50 a preferably has the same composition as the oxide-based solid electrolyte that is the main component of the solid electrolyte layer 30 .
  • the solid electrolyte 50a is preferably made of a glass material.
  • the solid electrolyte 50 a in the cover layer 50 and the particle size distribution of the oxide-based solid electrolyte in the solid electrolyte layer 30 are approximately the same, the softening timing of the solid electrolyte particles in each layer is aligned during batch firing. Sintering between layers becomes easier to progress. Therefore, in the cover layer 50 , the solid electrolyte 50 a preferably has a particle size distribution similar to that of the oxide-based solid electrolyte, which is the main component in the solid electrolyte layer 30 .
  • the D0% particle size in the particle size distribution of the solid electrolyte in one layer exists, and the solid electrolyte in one layer
  • the same degree of particle size distribution is defined as a state in which the D100% particle size in the particle size distribution of the solid electrolyte in the other layer exists between the D90% particle size and the D100% particle size in the particle size distribution of .
  • the thickness of the cover layer 50 is, for example, 5 ⁇ m or more and 100 ⁇ m or less, 10 ⁇ m or more and 85 ⁇ m or less, or 15 ⁇ m or more and 70 ⁇ m or less.
  • the thickness of the cover layer 50 can be measured, for example, as an average value of ten different thicknesses of one layer.
  • FIG. 5 is a diagram illustrating the flow of the method for manufacturing the all-solid-state battery 100a.
  • raw material powder for the solid electrolyte layer that constitutes the solid electrolyte layer 30 described above is prepared.
  • raw material powder of an oxide-based solid electrolyte can be produced by mixing raw materials, additives, and the like and using a solid-phase synthesis method or the like.
  • a desired average particle size For example, a planetary ball mill using 5 mm ⁇ ZrO 2 balls is used to adjust the desired average particle size.
  • raw material powder of ceramics that constitutes the cover layer 50 is prepared.
  • raw material powder for the cover layer can be produced by mixing raw materials, additives, and the like and using a solid-phase synthesis method or the like.
  • the raw material powder includes the raw material powder of the solid electrolyte 50a and the raw material powder of the filler material 50b.
  • a desired average particle size For example, a planetary ball mill using 5 mm ⁇ ZrO 2 balls is used to adjust the desired average particle size.
  • an internal electrode paste for producing the above-described first internal electrodes 10 and second internal electrodes 20 are individually produced.
  • an internal electrode paste can be obtained by uniformly dispersing a conductive aid, an electrode active material, a solid electrolyte material, a sintering aid, a binder, a plasticizer, and the like in water or an organic solvent.
  • the solid electrolyte material the solid electrolyte paste described above may be used.
  • a carbon material or the like is used as the conductive aid.
  • a metal may be used as the conductive aid. Examples of the metal of the conductive aid include Pd, Ni, Cu, Fe, alloys containing these, and the like. Pd, Ni, Cu, Fe, alloys containing these, and various carbon materials may also be used.
  • Examples of sintering aids for internal electrode paste include Li—B—O compounds, Li—Si—O compounds, Li—C—O compounds, Li—S—O compounds, Li—P—O
  • a glass component such as any one or more of the glass components such as base compounds is included.
  • an external electrode paste for producing the first external electrode 40a and the second external electrode 40b is prepared.
  • an external electrode paste can be obtained by uniformly dispersing a conductive material, a glass frit, a binder, a plasticizer, and the like in water or an organic solvent.
  • a solid electrolyte slurry having a desired average particle size is prepared by uniformly dispersing the raw material powder for the solid electrolyte layer in an aqueous solvent or an organic solvent together with a binder, a dispersant, a plasticizer, etc., followed by wet pulverization. get At this time, a bead mill, a wet jet mill, various kneaders, a high-pressure homogenizer, or the like can be used, and it is preferable to use a bead mill from the viewpoint of being able to simultaneously adjust the particle size distribution and disperse.
  • a binder is added to the obtained solid electrolyte slurry to obtain a solid electrolyte paste.
  • the solid electrolyte green sheet 51 can be produced.
  • the coating method is not particularly limited, and a slot die method, a reverse coating method, a gravure coating method, a bar coating method, a doctor blade method, or the like can be used.
  • the particle size distribution after wet pulverization can be measured, for example, using a laser diffraction measurement device using a laser diffraction scattering method.
  • an internal electrode paste 52 is printed on one surface of a solid electrolyte green sheet 51 .
  • a reverse pattern 53 is printed on a region of the solid electrolyte green sheet 51 where the internal electrode paste 52 is not printed.
  • the reverse pattern 53 the same one as the solid electrolyte green sheet 51 can be used.
  • a plurality of solid electrolyte green sheets 51 after printing are alternately shifted and laminated.
  • the laminate is obtained by crimping the cover sheets 54 from above and below in the lamination direction. In this case, in the laminate, the internal electrode paste 52 for the first internal electrode 10 is exposed on one end surface, and the internal electrode paste 52 for the second internal electrode 20 is exposed on the other end surface.
  • the cover sheet 54 can be formed by coating the raw material powder for the cover layer in the same manner as in the solid electrolyte green sheet production process.
  • the cover sheet 54 is formed thicker than the solid electrolyte green sheet 51 . The thickness may be increased during coating, or may be increased by stacking a plurality of coated sheets.
  • the external electrode paste 55 is applied to each of the two end faces by a dipping method or the like and dried. Thereby, a molding for forming the all-solid-state battery 100a is obtained.
  • the firing conditions are oxidizing atmosphere or non-oxidizing atmosphere, and the maximum temperature is preferably 400° C. to 1000° C., more preferably 500° C. to 900° C., without any particular limitation.
  • a step of holding below the maximum temperature in an oxidizing atmosphere may be provided to sufficiently remove the binder until the maximum temperature is reached. In order to reduce process costs, it is desirable to bake at as low a temperature as possible. After firing, reoxidation treatment may be performed. Through the above steps, the all-solid-state battery 100a is produced.
  • the internal electrode paste, the current collector paste containing a conductive material, and the internal electrode paste are sequentially laminated to form current collector layers in the first internal electrode 10 and the second internal electrode 20. can be formed.
  • the solid electrolyte 50a included in the cover layer 50 is sintered together with the solid electrolyte layer 30 and the solid electrolyte included in the electrode layer with which the cover layer 50 is in contact. Therefore, high adhesion between the cover layer 50 and the contacting solid electrolyte layer 30 and electrode layer can be obtained. Thereby, delamination can be suppressed.
  • the filler material 50b contained in the cover layer 50 is higher than the sintering temperature of the solid electrolyte 50a, the filler material 50b is not sintered and grains do not grow during batch firing. of the particle morphology is retained. As a result, in-plane shrinkage of the cover layer 50 is suppressed, shape change of the cover layer 50 is suppressed, and delamination can be suppressed.
  • the cover layer 50 achieves moisture resistance.
  • the sintering temperature of the raw material powder of the solid electrolyte 50a is preferably lower than the sintering temperature in the sintering process, and the sintering temperature of the filler material 50b is preferably higher than the sintering temperature in the sintering process. In this case, the sintering of the solid electrolyte 50a improves the adhesion of the cover layer 50 and maintains the particle form of the filler material 50b.
  • Example 1 Alumina having an irregular shape and a D50% particle size of 3 ⁇ m was used as the filler material.
  • Li--Al--Ge--P--O glass (hereinafter referred to as LAGP-g), which is a solid electrolyte obtained by melt quenching, was pulverized with a wet ball mill to a D50% particle size of 1.5 ⁇ m.
  • a filler material and a solid electrolyte were mixed at a volume ratio of 70:30, and uniformly dispersed in water or an organic solvent together with a binder, a dispersant and a plasticizer to obtain a slurry.
  • the resulting slurry was coated to produce a cover sheet having the desired thickness.
  • a ceramic laminate was obtained by arranging cover sheets on the uppermost layer and the lowermost layer of the laminate of solid electrolyte green sheets on which each electrode was printed and pressing them. This ceramic laminate was degreased by heat treatment and fired.
  • LAGP-g which is a solid electrolyte obtained by a melt quenching method, was pulverized by a wet ball mill to a D50% particle size of 1.5 ⁇ m before use.
  • a filler material and a solid electrolyte were mixed at a volume ratio of 70:30, and uniformly dispersed in water or an organic solvent together with a binder, a dispersant and a plasticizer to obtain a slurry.
  • the resulting slurry was coated to produce a cover sheet having the desired thickness.
  • a ceramic laminate was obtained by arranging cover sheets on the uppermost layer and the lowermost layer of the laminate of solid electrolyte green sheets on which each electrode was printed and pressing them. This ceramic laminate was degreased by heat treatment and fired.
  • Example 3 Alumina having an irregular shape and a D50% particle size of 3 ⁇ m was used as the filler material.
  • LAGP-g which is a solid electrolyte obtained by a melt quenching method, was pulverized by a wet ball mill to a D50% particle size of 1.5 ⁇ m before use.
  • a filler material and a solid electrolyte were mixed at a volume ratio of 20:80, and uniformly dispersed in water or an organic solvent together with a binder, a dispersant and a plasticizer to obtain a slurry.
  • the resulting slurry was coated to produce a cover sheet having the desired thickness.
  • a ceramic laminate was obtained by arranging cover sheets on the uppermost layer and the lowermost layer of the laminate of solid electrolyte green sheets on which each electrode was printed and pressing them. This ceramic laminate was degreased by heat treatment and fired.
  • Example 4 Spherical alumina having a D50% particle size of 3 ⁇ m was used as the filler material.
  • LAGP-g which is a solid electrolyte obtained by a melt quenching method, was pulverized by a wet ball mill to a D50% particle size of 1.5 ⁇ m before use.
  • a filler material and a solid electrolyte were mixed at a volume ratio of 70:30, and uniformly dispersed in water or an organic solvent together with a binder, a dispersant and a plasticizer to obtain a slurry.
  • the resulting slurry was coated to produce a cover sheet having the desired thickness.
  • a ceramic laminate was obtained by arranging cover sheets on the uppermost layer and the lowermost layer of the laminate of solid electrolyte green sheets on which each electrode was printed and pressing them. This ceramic laminate was degreased by heat treatment and fired.
  • Example 5 Alumina having an irregular shape and a D50% particle size of 3 ⁇ m was used as the filler material.
  • LAGP-g which is a solid electrolyte obtained by a melt quenching method, was pulverized by a wet ball mill to a D50% particle size of 1.5 ⁇ m before use.
  • a filler material and a solid electrolyte were mixed at a volume ratio of 30:70, and uniformly dispersed in water or an organic solvent together with a binder, a dispersant and a plasticizer to obtain a slurry.
  • the resulting slurry was coated to produce a cover sheet having the desired thickness.
  • a ceramic laminate was obtained by arranging cover sheets on the uppermost layer and the lowermost layer of the laminate of solid electrolyte green sheets on which each electrode was printed and pressing them. This ceramic laminate was degreased by heat treatment and fired.
  • Example 6 Alumina having an irregular shape and a D50% particle size of 3 ⁇ m was used as the filler material.
  • LAGP-g which is a solid electrolyte obtained by a melt quenching method, was pulverized by a wet ball mill to a D50% particle size of 1.5 ⁇ m before use.
  • a filler material and a solid electrolyte were mixed at a volume ratio of 10:90, and uniformly dispersed in water or an organic solvent together with a binder, a dispersant and a plasticizer to obtain a slurry.
  • the resulting slurry was coated to produce a cover sheet having the desired thickness.
  • a ceramic laminate was obtained by arranging cover sheets on the uppermost layer and the lowermost layer of the laminate of solid electrolyte green sheets on which each electrode was printed and pressing them. This ceramic laminate was degreased by heat treatment and fired.
  • LAGP-g which is a solid electrolyte obtained by a melting and quenching method, is pulverized with a wet ball mill to a D50% particle size of 1.5 ⁇ m, and uniformly dispersed in water or an organic solvent together with a binder, dispersant, plasticizer, etc.
  • a slurry was obtained by The resulting slurry was coated to produce a cover sheet having the desired thickness. That is, no filler material was used.
  • a ceramic laminate was obtained by arranging cover sheets on the uppermost layer and the lowermost layer of the laminate of solid electrolyte green sheets on which each electrode was printed and pressing them. This ceramic laminate was degreased by heat treatment and fired.
  • the LAGP-g in the cover layer was sintered with the LAGP-g in each electrode layer and solid electrolyte layer, and the adhesion itself between the cover layer and the electrode layer and between the cover layer and the solid electrolyte layer was secured.
  • the cover layer does not contain a filler material, the cover layer is strongly shrunk in the in-plane direction due to the heat treatment, making it difficult to maintain the shape.
  • a slurry was obtained by uniformly dispersing alumina having an irregular shape with a D50% particle size of 3 ⁇ m in water or an organic solvent together with a binder, a dispersant, a plasticizer, and the like. The resulting slurry was coated to produce a cover sheet having the desired thickness. That is, no solid electrolyte was used.
  • a ceramic laminate was obtained by arranging cover sheets on the uppermost layer and the lowermost layer of the laminate of solid electrolyte green sheets on which each electrode was printed and pressing them. This ceramic laminate was degreased by heat treatment and fired.
  • the cover layer did not shrink even after heat treatment, and the adhesion between each electrode layer and the solid electrolyte layer could not be obtained.
  • Adhesion test For Examples 1 to 4 and Comparative Examples 1 and 2, the adhesion of the cover layer was evaluated. Specifically, a peeling resistance test was conducted to determine the adhesion of the cover layer. The peeling resistance test was performed by attaching an adhesive tape to the cover layer and rapidly peeling it off. As a result, if there was no deposit on the tape, it was determined that the adhesion was good. If a small amount of adhering matter adhered to the tape, the adhesion was determined to be somewhat good ( ⁇ ). Adhesion was determined to be poor "x" when most adhered to the tape. Table 1 shows the results.
  • Comparative Examples 1 and 2 were judged to have poor moisture resistance "x". As for Comparative Example 1, this is probably because the cover layer did not contain an insulating filler material. As for Comparative Example 2, the cover layer did not contain a solid electrolyte, and thus good adhesion was not obtained. On the other hand, in Examples 1 to 4, the moisture resistance was judged to be good “ ⁇ ” or somewhat good “ ⁇ ”. It is considered that this is because the cover layer with the adhesion property contained an insulating filler material. The reason why the adhesion of Examples 1, 2, and 4 was better than that of Example 3 is considered to be that the volume ratio of the filler material to the solid electrolyte in the cover layer was 30 vol% or more. be done.

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Abstract

Une batterie à électrolyte entièrement solide selon la présente invention comprend : une structure multicouche dans laquelle des couches d'électrolyte solide et des couches d'électrode contenant un matériau actif d'électrode sont empilées en alternance; et une couche de couverture qui est disposée sur la surface supérieure et/ou la surface inférieure de la structure multicouche dans la direction d'empilement. En ce qui concerne cette batterie entièrement solide, la couche de couverture contient un électrolyte solide à base d'oxyde et un matériau de charge qui a des propriétés isolantes, tout en ayant une température de frittage qui est supérieure à la température de frittage de l'électrolyte solide à base d'oxyde.　
PCT/JP2022/040464 2021-12-28 2022-10-28 Batterie à électrolyte entièrement solide et procédé de production de celle-ci WO2023127283A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011198692A (ja) * 2010-03-23 2011-10-06 Namics Corp リチウムイオン二次電池及びその製造方法
JP2019087347A (ja) * 2017-11-02 2019-06-06 太陽誘電株式会社 全固体電池
JP2019087348A (ja) * 2017-11-02 2019-06-06 太陽誘電株式会社 全固体電池
WO2019181909A1 (fr) * 2018-03-19 2019-09-26 Tdk株式会社 Batterie entièrement solide
JP2020166965A (ja) * 2019-03-28 2020-10-08 太陽誘電株式会社 全固体電池
JP2022135581A (ja) * 2021-03-05 2022-09-15 太陽誘電株式会社 全固体電池及びその製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011198692A (ja) * 2010-03-23 2011-10-06 Namics Corp リチウムイオン二次電池及びその製造方法
JP2019087347A (ja) * 2017-11-02 2019-06-06 太陽誘電株式会社 全固体電池
JP2019087348A (ja) * 2017-11-02 2019-06-06 太陽誘電株式会社 全固体電池
WO2019181909A1 (fr) * 2018-03-19 2019-09-26 Tdk株式会社 Batterie entièrement solide
JP2020166965A (ja) * 2019-03-28 2020-10-08 太陽誘電株式会社 全固体電池
JP2022135581A (ja) * 2021-03-05 2022-09-15 太陽誘電株式会社 全固体電池及びその製造方法

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