WO2023047839A1 - All-solid-state battery, and method for manufacturing same - Google Patents

All-solid-state battery, and method for manufacturing same Download PDF

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Publication number
WO2023047839A1
WO2023047839A1 PCT/JP2022/030821 JP2022030821W WO2023047839A1 WO 2023047839 A1 WO2023047839 A1 WO 2023047839A1 JP 2022030821 W JP2022030821 W JP 2022030821W WO 2023047839 A1 WO2023047839 A1 WO 2023047839A1
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electrode layer
electrode
width
solid
layer
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PCT/JP2022/030821
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French (fr)
Japanese (ja)
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原田智宏
渡辺剛基
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太陽誘電株式会社
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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
    • H01M10/052—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/531—Electrode connections inside a battery casing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/543—Terminals
    • H01M50/547—Terminals characterised by the disposition of the terminals on the cells
    • H01M50/548—Terminals characterised by the disposition of the terminals on the cells on opposite sides of the cell
    • 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.
  • All-solid-state batteries are manufactured by stacking multiple layers of electrode paste for electrode layers and green sheets for solid electrolyte layers and firing them. At this time, the all-solid-state battery may warp due to the difference in thermal contraction rate between the electrode layer and the solid electrolyte layer.
  • the present invention has been made in view of the above problems, and an object of the present invention is to suppress the occurrence of warpage in an all-solid-state battery.
  • a plurality of each of a first electrode layer, a solid electrolyte layer, and a second electrode layer are laminated along a first direction, and the first electrode layer is exposed.
  • a laminate having a first surface and a second surface from which the second electrode layer is exposed; and a first electrode layer provided on the first surface and connected to the first electrode layer. and a second external electrode provided on the second surface and connected to the second electrode layer, wherein the first electrode layer is connected to the first external electrode and a second portion extending along a second direction from the first external electrode toward the second external electrode, wherein the first direction and the second external electrode are aligned.
  • a first width of the first portion along a third direction intersecting each of the directions is greater than a second width of the second portion.
  • the second electrode layer has a third portion connected to the second external electrode and a fourth portion extending along the second direction.
  • a third width along the third direction of the three portions may be greater than a fourth width of the fourth portion.
  • the all-solid-state battery has a region where the first electrode layer and the second electrode layer overlap when viewed from the first direction, and the first electrode layer and the second electrode in the region T1/T2 ⁇ 1 may be satisfied, where T1 is the thickness of any one of the layers, and T2 is the thickness of the solid electrolyte layer in the region.
  • the first width may be 1.01 times or more the second width
  • the third width may be 1.01 times or more the fourth width
  • the first width may be 1.02 times or more the second width
  • the third width may be 1.02 times or more the fourth width
  • the first width may be 1.05 times or more the second width
  • the third width may be 1.05 times or more the fourth width
  • the laminate further has a third surface parallel to each of the first direction and the second direction and from which the solid electrolyte layer is exposed, (D2 ⁇ D1) ⁇ 0.1 ⁇ D2, where D1 is the distance between the portion and the third surface, and D2 is the distance between the second portion and the third surface.
  • the all-solid-state battery further includes a first current collector layer sandwiched between the two first electrode layers and a second current collector layer sandwiched between the two second electrode layers.
  • a plurality of each of a first electrode layer, a solid electrolyte layer, and a second electrode layer are laminated along a first direction, and the first electrode layer is exposed.
  • the first electrode layer includes a first portion connected to the first external electrode and a second electrode layer extending along a second direction from the first external electrode toward the second external electrode.
  • a first width of the first portion along a third direction intersecting each of the first direction and the second direction is a second width of the second portion; is wider than the width of
  • FIG. 1 is an external view of an all-solid-state battery
  • FIG. FIG. 2 is a cross-sectional view taken along line II of FIG. 1
  • 2 is a cross-sectional view taken along line II-II of FIG. 1
  • FIG. FIG. 4 is a plan view of the first electrode layer and its surroundings; 4 is an enlarged cross-sectional view of a first electrode layer
  • FIG. FIG. 4 is a plan view of the second electrode layer and its surroundings
  • 4 is an enlarged cross-sectional view of a second electrode layer
  • FIG. FIG. 3 is a perspective view showing the positional relationship of each electrode layer in the laminate
  • FIG. 4 is a plan view of the first electrode layer and the second electrode layer viewed from the first direction; 3 is a flow chart of a method for manufacturing an all-solid-state battery according to the present embodiment; FIG. 4 is a plan view of a first electrode layer and its surroundings according to a comparative example; FIG. 4 is a plan view of a second electrode layer and its surroundings according to a comparative example; FIG. 5 is a perspective view showing the positional relationship of each electrode layer in a laminate according to a comparative example;
  • FIG. 1 is an external view of an all-solid-state battery 100.
  • the all-solid-state battery 100 includes a rectangular parallelepiped laminated chip 70 and external electrodes 40 a and 40 b provided on two opposing surfaces of the laminated chip 70 .
  • FIG. 2 is a cross-sectional view along line II in FIG.
  • the laminated chip 70 includes a laminated body 60 in which a plurality of solid electrolyte layers 11, first electrode layers 12, and second electrode layers 14 are laminated along the first direction Z. have.
  • the laminate 60 has a first surface 60a and a second surface 60b parallel to the first direction Z. Note that each of the first surface 60a and the second surface 60b is also a surface perpendicular to the second direction Y. As shown in FIG. The second direction Y is perpendicular to the first direction Z and is the direction from the first external electrode 40a to the second external electrode 40b.
  • a first external electrode 40a is provided on the first surface 60a, and the first electrode layer 12 is connected to the first external electrode 40a.
  • a second external electrode 40b is provided on the second surface 60b, and the second electrode layer 14 is connected to the second external electrode 40b.
  • Both the first electrode layer 12 and the second electrode layer 14 are conductive layers containing both a positive electrode active material and a negative electrode active material.
  • the positive electrode active material is not particularly limited, a material having an olivine crystal structure is used as the positive electrode active material here. Examples of such positive 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 As an electrode active material having an olivine type crystal structure, there is, for example, LiCoPO4 containing Co.
  • a phosphate or the like in which the transition metal Co is replaced in this chemical formula may also be used.
  • the ratio of Li and PO4 can vary depending on the valence. Co, Mn, Fe, Ni, etc. may be used as the transition metal.
  • the negative electrode active material includes, for example, titanium oxide, lithium-titanium composite oxide, lithium-titanium composite phosphate, carbon, and vanadium lithium phosphate.
  • each of the first electrode layer 12 and the second electrode layer 14 functions as both a positive electrode and a negative electrode. Also, it can withstand actual use without malfunctioning in short-circuit inspection.
  • the present embodiment is not limited to this, and by forming a positive electrode layer as the first electrode layer 12 and forming a negative electrode layer as the second electrode layer 13, the all-solid-state battery 100 has polarity.
  • an oxide-based solid electrolyte material or a conductive aid such as carbon or metal may be added to these electrode layers.
  • the metal of the conductive aid include Pd, Ni, Cu, and Fe.
  • alloys of these metals may be used as conductive aids.
  • the layer structures of the first electrode layer 12 and the second electrode layer 14 are not particularly limited.
  • the first electrode layer 12 is formed on both main surfaces of the first current collector layer 12b made of a conductive material, thereby turning the first current collector layer 12b into a first collector layer 12b. It may be sandwiched by one electrode layer 12 .
  • the second electrode layers 14 is sandwiched between the second electrode layers 14. good too.
  • the solid electrolyte layer 11 there is a phosphate-based solid electrolyte having a NASICON structure.
  • Phosphate-based solid electrolytes having the NASICON structure have high ionic conductivity and are chemically stable in the atmosphere.
  • the phosphate-based solid electrolyte is not particularly limited, a phosphate containing lithium is used here.
  • the phosphate is based on, for example, a composite lithium phosphate salt with Ti (LiTi 2 (PO 4 ) 3 ), and a trivalent compound such as Al, Ga, In, Y, or La to increase the Li content. It is a salt in which a transition metal is partially substituted.
  • Such salts include Li 1+x Al x Ge 2-x (PO 4 ) 3 , Li 1+x Al x Zr 2-x (PO 4 ) 3 and Li 1+x Al x Ti 2-x (PO 4 ) 3 .
  • Li--Al--M--PO 4 system phosphate M is Ge, Ti, Zr, etc.).
  • a Li—Al—Ge—PO 4 -based phosphate to which a transition metal contained in the phosphate in the first electrode layer 12 is added in advance may be used as the material for the solid electrolyte layer 11 .
  • the first electrode layer 12 contains a phosphate containing either Co or Li
  • the Li—Al—Ge—PO 4 -based phosphate to which Co is previously added is used as the solid electrolyte layer 11. may be contained in Thereby, it is possible to suppress the elution of the transition metal from the first electrode layer 12 to the solid electrolyte layer 11 .
  • FIG. 3 is a cross-sectional view along line II-II in FIG. As illustrated in FIG. 3, the laminate 60 has a third surface 60c and a fourth surface 60d parallel to the first direction Z and the second direction Y, respectively.
  • the laminate 60 has a fifth surface 60e and a sixth surface 60f perpendicular to the first direction Z.
  • the fifth surface 60e is an upper surface that faces upward when the all-solid-state battery 100 is mounted on the wiring substrate.
  • the sixth surface 60f is the lower surface that is the lower side during mounting.
  • the outermost layer of laminate 60 is solid electrolyte layer 11, and the surfaces of solid electrolyte layer 11 define the third to sixth surfaces 60c to 60f, respectively.
  • a moisture-proof layer 80 is provided on each surface of the third to sixth surfaces 60c to 60f.
  • the moisture-proof layer 80 is a layer of inorganic oxide containing silicon, and serves to protect the laminate 60 from moisture in the atmosphere. Any one of B, Bi, Zn, Ba, Li, P, Sn, Pb, Mg, and Na may be added to the moisture-proof layer 80 .
  • FIG. 4 is a plan view of the first electrode layer 12 and its surroundings. As shown in FIG. 4, the first electrode layer 12 has a first portion 12x connected to the first external electrode 40a and a second portion 12x extending along the second direction Y from the first portion 12x. and a portion 12y.
  • the first width W1 of the first portion 12x along the third direction X perpendicular to each of the first direction Z and the second direction Y is the second width along the third direction X. It is wider than the second width W2 of the portion 12y. As a result, the first electrode layer 12 becomes substantially T-shaped in plan view.
  • W1 ⁇ 1.01 ⁇ W2 W1 ⁇ 1.01 ⁇ W2.
  • concentration of stress on the corners of the all-solid-state battery 100 can be suppressed, and warping can be suppressed more effectively.
  • FIG. 5 is an enlarged cross-sectional view of the first electrode layer 12.
  • the distance between the first portion 12x of the first electrode layer 12 and the third surface 60c is D1
  • the distance between the second portion 12y of the first electrode layer 12 and the third surface 60c is D1.
  • the interval is D2.
  • these intervals D1 and D2 satisfy (D2-D1) ⁇ 0.1 ⁇ D2. Thereby, it is possible to suppress the occurrence of warping in the all-solid-state battery 100 due to the difference in contraction rate between the first electrode layer 12 and the solid electrolyte layer 11 .
  • FIG. 6 is a plan view of the second electrode layer 14 and its surroundings. As shown in FIG. 4, the second electrode layer 14 has a third portion 14x connected to the second external electrode 40b and a fourth portion 14x extending along the second direction Y from the third portion 14x. and a portion 14y.
  • a third width W3 of the third portion 14x along the third direction X is wider than a fourth width W4 of the fourth portion 14y along the third direction X.
  • the second electrode layer 14 becomes substantially T-shaped in plan view.
  • concentration of stress on the corners of the all-solid-state battery 100 can be suppressed, and warping can be suppressed more effectively.
  • FIG. 7 is an enlarged cross-sectional view of the second electrode layer 14.
  • the distance between the third portion 14x of the second electrode layer 14 and the third surface 60c is D3, and the distance between the fourth portion 14y of the second electrode layer 14 and the third surface 60c is D3.
  • the interval is D4.
  • these intervals D3 and D4 satisfy (D4-D3) ⁇ 0.1 ⁇ D4. Thereby, it is possible to suppress the occurrence of warpage in the all-solid-state battery 100 due to the difference in contraction rate between the second electrode layer 14 and the solid electrolyte layer 11 .
  • the third portion 14x is exposed on the third surface 60c, the third portion 14x and the second external electrode 40b are in close contact with each other, and the second electrode layer 14 and the second external electrode 40b are brought into close contact with each other. The adhesion strength of is increased.
  • FIG. 8 is a perspective view showing the positional relationship between the electrode layers 12 and 14 in the laminate 60.
  • the first portion 12x of the first electrode layer 12 is exposed on the first surface 60a and the third portion 14x of the second electrode layer 14 is exposed on the second surface 60b. .
  • FIG. 9 is a plan view of the first electrode layer 12 and the second electrode layer 14 viewed from the first direction Z.
  • the first portion 12x of the first electrode layer 12 and the third portion 14x of the second electrode layer 14 overlap each other in the region R.
  • the thickness of either the first electrode layer 12 or the second electrode layer 14 in the region R is T1
  • the thickness T2 of the solid electrolyte layer 11 in the region R is T1/ T2 ⁇ 1.
  • T1/T2 ⁇ 10 More preferably, T1/T2 ⁇ 50.
  • T1/T2 ⁇ 10 More preferably, T1/T2 ⁇ 50.
  • the film thickness of the first electrode layer 12 is set to 2 ⁇ m to 100 ⁇ m, more preferably 5 ⁇ m to 50 ⁇ m.
  • the film thickness of the second electrode layer 14 is 2 ⁇ m to 100 ⁇ m, preferably 5 ⁇ m to 50 ⁇ m. By adopting this range, it is possible to prevent a decrease in capacity due to thinning of the electrode layers 12 and 14 and to prevent a decrease in stacking accuracy due to thickening of the electrode layers 12 and 14 .
  • the film thickness of the solid electrolyte layer 11 is 2 ⁇ m to 50 ⁇ m, preferably 5 ⁇ m to 25 ⁇ m.
  • the first width W1 is wider than the second width W2
  • the area of the first electrode layer 12 exposed on the first surface 60a is increases. Therefore, even if there is a difference in thermal contraction rate between the solid electrolyte layer 11 and the first electrode layer 12 when the stacked body 60 after firing is cooled, the first portion widely present in the first portion 12x Since the electrode layer 12 acts to suppress the contraction of the solid electrolyte layer 11, the first portion 12x and the laminate 60 in the vicinity thereof are less likely to warp.
  • the third width W3 is wider than the fourth width W4
  • the area of the second electrode layer 14 exposed on the second surface 60b is increased.
  • the second electrode layer 14 widely present in the third portion 14x Since the electrode layer 14 acts to suppress contraction of the solid electrolyte layer 11, the third portion 14x and the laminate 60 in the vicinity thereof are less likely to warp.
  • first portion 12x and the third portion 14x having the wide width increase the strength of the laminate 60 in the vicinity of the first surface 60a and the second surface 60b, the mechanical strength of the all-solid-state battery 100 is increased. can also be increased.
  • FIG. 10 is a flowchart of the method for manufacturing an all-solid-state battery according to this embodiment.
  • powder of the phosphate-based solid electrolyte that constitutes the solid electrolyte layer 11 is prepared.
  • the powder of the phosphate-based solid electrolyte that constitutes the solid electrolyte layer 11 can be produced by mixing raw materials and additives and using a solid-phase synthesis method or the like.
  • a desired average particle size can be obtained by dry pulverizing the obtained powder.
  • a planetary ball mill using 5 mm ⁇ ZrO 2 balls is used to adjust the desired average particle size.
  • Additives include sintering aids.
  • a sintering aid for example, Li—B—O based compounds, Li—Si—O based compounds, Li—C—O based compounds, Li—SO based compounds, and Li—P—O based compounds. Any glass component can be used.
  • the obtained powder is uniformly dispersed in an aqueous solvent or an organic solvent together with a binder, a dispersant, a plasticizer, etc., and wet pulverized to obtain a solid electrolyte slurry having a desired average particle size.
  • 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.
  • a green sheet for the solid electrolyte layer 11 is obtained by applying the solid electrolyte paste.
  • 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.
  • Electrode layer paste preparation step Next, an electrode layer paste for forming the first electrode layer 12 and the second electrode layer 14 is prepared.
  • a positive electrode active material, a negative electrode active material, and a solid electrolyte material are highly dispersed in a bead mill or the like to prepare a ceramic paste consisting only of ceramic particles.
  • a carbon paste containing carbon particles such as carbon black may be prepared, and the carbon paste may be kneaded with the ceramic paste.
  • an electrode layer paste is printed on one main surface of the green sheet.
  • 150 printed green sheets are stacked alternately and cut into a predetermined size by a dicer to obtain a laminate 60 .
  • the uppermost layer and the lowermost layer of the laminate 60 are green sheets.
  • the laminate 60 is fired in a firing atmosphere containing oxygen.
  • the oxygen partial pressure in the firing atmosphere is preferably 2 ⁇ 10 ⁇ 13 atm or less.
  • the first external electrode 40a and the second external electrode 40b are formed by applying a metal paste to each surface 60a, 60b of the laminate 60 and baking it.
  • the first external electrode 40a and the second external electrode 40b may be formed by sputtering or plating.
  • the film thickness of the first electrode layer 12 after firing is 14 ⁇ m
  • the film thickness of the second electrode layer 14 is 10 ⁇ m
  • the film thickness of the solid electrolyte layer 11 after baking is 8 ⁇ m.
  • the third to sixth surfaces 60c to 60f of the laminate 60 are coated with dibutyl ether or a solution obtained by dissolving tetraalkoxysilane in a dibutyl ether-based solvent. Thereafter, the moisture-proof layer 80 is obtained by heating the solution to a temperature of about 100.degree. C. to 150.degree. With the above, the basic structure of the all-solid-state battery 100 is completed.
  • An all-solid-state battery was produced according to this embodiment.
  • Each parameter W1 to W4 and D1 to D4 shown in FIGS. D3) 0.7 ⁇ D4.
  • both the first electrode layer 12 and the second electrode layer 14 have a thickness difference from the solid electrolyte layer 11, but each electrode layer can suppress the shrinkage of the solid electrolyte layer 11 during firing. , no warpage was observed.
  • FIG. 11 is a plan view of a first electrode layer 12 and its periphery according to a comparative example. As shown in FIG. 11, in the comparative example, the first electrode layer 12 has a rectangular shape in plan view.
  • the first electrode layer 12 cannot suppress the contraction of the solid electrolyte layer 11 in the vicinity of the first surface 60a, and the laminate 60 is warped. occur.
  • FIG. 12 is a plan view of the second electrode layer 14 and its surroundings according to the comparative example.
  • the second electrode layer 14 according to the comparative example has a rectangular shape in plan view, like the first electrode layer 12 . Therefore, the laminated body 60 is warped for the same reason as the first electrode layer 12 in FIG.
  • FIG. 13 is a perspective view showing the positional relationship of each electrode layer in a laminate according to a comparative example. As shown in FIG. 13, in the comparative example, the first electrode layer 12 is exposed on the first surface 60a, and the second electrode layer 14 is exposed on the second surface 60b.

Abstract

This all-solid-state battery comprises a stacked body in which a plurality of each of a first electrode layer, a solid electrolyte layer, and a second electrode layer are stacked in a first direction, and which has a first surface in which the first electrode layer is exposed, and a second surface in which the second electrode layer is exposed, a first external electrode which is provided on the first surface and which is connected to the first electrode layer, and a second external electrode which is provided on the second surface and which is connected to the second electrode layer, characterized in that: the first electrode layer includes a first part connected to the first external electrode, and a second part which extends in a second direction from the first external electrode toward the second external electrode; and a first width of the first part in a third direction intersecting both the first direction and the second direction is greater than a second width of the second part.

Description

全固体電池とその製造方法All-solid-state battery and manufacturing method thereof
　本発明は、全固体電池とその製造方法に関する。 The present invention relates to an all-solid-state battery and its manufacturing method.
　近年、二次電池が様々な分野で利用されている。電解液を用いた二次電池には電解液の漏液等の問題がある。そこで、固体電解質を備え、他の構成要素も固体で構成した全固体電池の開発が行われている（特許文献１～４参照）。 In recent years, secondary batteries have been used in various fields. A secondary battery using an electrolytic solution has problems such as leakage of the electrolytic solution. Therefore, development of all-solid-state batteries in which solid electrolytes are provided and other constituent elements are also solid (see Patent Documents 1 to 4) is underway.
特開平６－２３１７９６号公報JP-A-6-231796 特開２０１１－２１６２３５号公報JP 2011-216235 A 特開２０１５－２２０１０６号公報JP 2015-220106 A 特開２０２０－１６６９８０号公報Japanese Unexamined Patent Application Publication No. 2020-166980
　全固体電池は、電極層用の電極ペーストと、固体電解質層用のグリーンシートとを複数積層し、それらを焼成することで作製される。このとき、電極層と固体電解質層の各々の熱収縮率の差に起因して全固体電池に反りが生じることがある。 All-solid-state batteries are manufactured by stacking multiple layers of electrode paste for electrode layers and green sheets for solid electrolyte layers and firing them. At this time, the all-solid-state battery may warp due to the difference in thermal contraction rate between the electrode layer and the solid electrolyte layer.
　本発明は上記課題に鑑みなされたものであり、全固体電池に反りが発生するのを抑制することを目的とする。 The present invention has been made in view of the above problems, and an object of the present invention is to suppress the occurrence of warpage in an all-solid-state battery.
　本発明に係る全固体電池は、第１の電極層、固体電解質層、及び第２の電極層の各々が第１の方向に沿って複数積層され、前記第１の電極層が表出する第１の面と、前記第２の電極層が表出する第２の面とを備えた積層体と、前記第１の面に設けられ、かつ前記第１の電極層に接続された第１の外部電極と、前記第２の面に設けられ、かつ前記第２の電極層に接続された第２の外部電極とを有し、前記第１の電極層は、前記第１の外部電極に接続された第１の部分と、前記第１の外部電極から前記第２の外部電極に向かう第２の方向に沿って延びる第２の部分とを有し、前記第１の方向と前記第２の方向の各々と交叉する第３の方向に沿った前記第１の部分の第１の幅が前記第２の部分の第２の幅よりも広いことを特徴とする。 In the all-solid-state battery according to the present invention, a plurality of each of a first electrode layer, a solid electrolyte layer, and a second electrode layer are laminated along a first direction, and the first electrode layer is exposed. a laminate having a first surface and a second surface from which the second electrode layer is exposed; and a first electrode layer provided on the first surface and connected to the first electrode layer. and a second external electrode provided on the second surface and connected to the second electrode layer, wherein the first electrode layer is connected to the first external electrode and a second portion extending along a second direction from the first external electrode toward the second external electrode, wherein the first direction and the second external electrode are aligned. A first width of the first portion along a third direction intersecting each of the directions is greater than a second width of the second portion.
　上記全固体電池において、前記第２の電極層は、前記第２の外部電極に接続された第３の部分と、前記第２の方向に沿って延びる第４の部分とを有し、前記第３の部分の前記第３の方向に沿った第３の幅が前記第４の部分の第４の幅よりも広くてもよい。 In the all-solid-state battery described above, the second electrode layer has a third portion connected to the second external electrode and a fourth portion extending along the second direction. A third width along the third direction of the three portions may be greater than a fourth width of the fourth portion.
　上記全固体電池において、前記第１の方向から見て前記第１の電極層と前記第２の電極層とが重なる領域を有し、前記領域における前記第１の電極層と前記第２の電極層のいずれかの膜厚をＴ１、前記領域における前記固体電解質層の膜厚をＴ２としたときに、Ｔ１／Ｔ２≧１となってもよい。 The all-solid-state battery has a region where the first electrode layer and the second electrode layer overlap when viewed from the first direction, and the first electrode layer and the second electrode in the region T1/T2≧1 may be satisfied, where T1 is the thickness of any one of the layers, and T2 is the thickness of the solid electrolyte layer in the region.
　上記全固体電池において、前記第１の幅は、前記第２の幅の１．０１倍以上であり、前記第３の幅は、前記第４の幅の１．０１倍以上でもよい。 In the all-solid-state battery, the first width may be 1.01 times or more the second width, and the third width may be 1.01 times or more the fourth width.
　上記全固体電池において、前記第１の幅は、前記第２の幅の１．０２倍以上であり、前記第３の幅は、前記第４の幅の１．０２倍以上でもよい。 In the all-solid-state battery, the first width may be 1.02 times or more the second width, and the third width may be 1.02 times or more the fourth width.
　上記全固体電池において、前記第１の幅は、前記第２の幅の１．０５倍以上であり、前記第３の幅は、前記第４の幅の１．０５倍以上でもよい。 In the all-solid-state battery, the first width may be 1.05 times or more the second width, and the third width may be 1.05 times or more the fourth width.
　上記全固体電池において、前記積層体は、前記第１の方向と前記第２の方向の各々に平行であり、かつ前記固体電解質層が表出する第３の面を更に有し、前記第１の部分と前記第３の面との間隔をＤ１、前記第２の部分と前記第３の面との間隔をＤ２としたときに、（Ｄ２－Ｄ１）≧０．１×Ｄ２でもよい。 In the above all-solid-state battery, the laminate further has a third surface parallel to each of the first direction and the second direction and from which the solid electrolyte layer is exposed, (D2−D1)≧0.1×D2, where D1 is the distance between the portion and the third surface, and D2 is the distance between the second portion and the third surface.
　上記全固体電池において、二つの前記第１の電極層に挟まれた第１の集電体層と、二つの前記第２の電極層に挟まれた第２の集電体層とを更に有してもよい。 The all-solid-state battery further includes a first current collector layer sandwiched between the two first electrode layers and a second current collector layer sandwiched between the two second electrode layers. You may
　本発明に係る全固体電池の製造方法は、第１の電極層、固体電解質層、及び第２の電極層の各々が第１の方向に沿って複数積層され、前記第１の電極層が表出する第１の面と、前記第２の電極層が表出する第２の面とを備えた積層体を形成する工程と、前記積層体を焼成する工程と、前記第１の面に、前記第１の電極層に接続された第１の外部電極を形成する工程と、前記第２の面に、前記第２の電極層に接続された第２の外部電極を形成する工程とを有し、前記第１の電極層は、前記第１の外部電極に接続された第１の部分と、前記第１の外部電極から前記第２の外部電極に向かう第２の方向に沿って延びる第２の部分とを有し、前記第１の方向と前記第２の方向の各々と交叉する第３の方向に沿った前記第１の部分の第１の幅が前記第２の部分の第２の幅よりも広いことを特徴とする。 In the method for manufacturing an all-solid-state battery according to the present invention, a plurality of each of a first electrode layer, a solid electrolyte layer, and a second electrode layer are laminated along a first direction, and the first electrode layer is exposed. forming a laminate having a first surface exposed and a second surface exposed by the second electrode layer; firing the laminate; forming a first external electrode connected to the first electrode layer; and forming a second external electrode connected to the second electrode layer on the second surface. and the first electrode layer includes a first portion connected to the first external electrode and a second electrode layer extending along a second direction from the first external electrode toward the second external electrode. a first width of the first portion along a third direction intersecting each of the first direction and the second direction is a second width of the second portion; is wider than the width of
　本発明によれば、全固体電池に反りが発生するのを抑制することができる。 According to the present invention, it is possible to suppress the occurrence of warpage in the all-solid-state battery.
全固体電池の外観図である。1 is an external view of an all-solid-state battery; FIG. 図１のI－I線に沿う断面図である。FIG. 2 is a cross-sectional view taken along line II of FIG. 1; 図１のII－II線に沿う断面図である。2 is a cross-sectional view taken along line II-II of FIG. 1; FIG. 第１の電極層とのその周囲の平面図である。FIG. 4 is a plan view of the first electrode layer and its surroundings; 第１の電極層の拡大断面図である。4 is an enlarged cross-sectional view of a first electrode layer; FIG. 第２の電極層とのその周囲の平面図である。FIG. 4 is a plan view of the second electrode layer and its surroundings; 第２の電極層の拡大断面図である。4 is an enlarged cross-sectional view of a second electrode layer; FIG. 積層体における各電極層の位置関係を示す斜視図である。FIG. 3 is a perspective view showing the positional relationship of each electrode layer in the laminate; 第１の方向から見た第１の電極層と第２の電極層の平面図である。FIG. 4 is a plan view of the first electrode layer and the second electrode layer viewed from the first direction; 本実施形態に係る全固体電池の製造方法のフローチャートである。3 is a flow chart of a method for manufacturing an all-solid-state battery according to the present embodiment; 比較例に係る第１の電極層とのその周囲の平面図である。FIG. 4 is a plan view of a first electrode layer and its surroundings according to a comparative example; 比較例に係る第２の電極層とのその周囲の平面図である。FIG. 4 is a plan view of a second electrode layer and its surroundings according to a comparative example; 比較例に係る積層体における各電極層の位置関係を示す斜視図である。FIG. 5 is a perspective view showing the positional relationship of each electrode layer in a laminate according to a comparative example;
（実施形態）
　図１は、全固体電池１００の外観図である。図１に例示するように、全固体電池１００は、直方体形状を有する積層チップ７０と、積層チップ７０の対向する２つの面に設けられた外部電極４０ａ、４０ｂとを備える。 (embodiment)
FIG. 1 is an external view of an all-solid-state battery 100. FIG. As illustrated in FIG. 1 , the all-solid-state battery 100 includes a rectangular parallelepiped laminated chip 70 and external electrodes 40 a and 40 b provided on two opposing surfaces of the laminated chip 70 .
　図２は、図１のI－I線に沿う断面図である。図２に例示するように、積層チップ７０は、固体電解質層１１、第１の電極層１２、及び第２の電極層１４の各々を第１の方向Ｚに沿って複数積層した積層体６０を有する。 FIG. 2 is a cross-sectional view along line II in FIG. As illustrated in FIG. 2, the laminated chip 70 includes a laminated body 60 in which a plurality of solid electrolyte layers 11, first electrode layers 12, and second electrode layers 14 are laminated along the first direction Z. have.
　積層体６０は、第１の方向Ｚに平行な第１の面６０ａと第２の面６０ｂとを有する。なお、第１の面６０ａと第２の面６０ｂの各々は第２の方向Ｙに垂直な面でもある。第２の方向Ｙは、第１の方向Ｚに垂直であり、第１の外部電極４０ａから第２の外部電極４０ｂに向かう方向である。 The laminate 60 has a first surface 60a and a second surface 60b parallel to the first direction Z. Note that each of the first surface 60a and the second surface 60b is also a surface perpendicular to the second direction Y. As shown in FIG. The second direction Y is perpendicular to the first direction Z and is the direction from the first external electrode 40a to the second external electrode 40b.
　また、第１の面６０ａには第１の外部電極４０ａが設けられており、第１の電極層１２が第１の外部電極４０ａと接続される。一方、第２の面６０ｂには第２の外部電極４０ｂが設けられており、第２の電極層１４が第２の外部電極４０ｂと接続される。 A first external electrode 40a is provided on the first surface 60a, and the first electrode layer 12 is connected to the first external electrode 40a. On the other hand, a second external electrode 40b is provided on the second surface 60b, and the second electrode layer 14 is connected to the second external electrode 40b.
　また、第１の電極層１２と第２の電極層１４は、いずれも正極活物質と負極活物質の両方を含む導電層である。正極活物質は特に限定されないが、ここではオリビン型結晶構造をもつ材料を正極活物質として使用する。このような正極活物質としては、例えば遷移金属とリチウムとを含むリン酸塩がある。オリビン型結晶構造は、天然のカンラン石（ｏｌｉｖｉｎｅ）が有する結晶であり、Ｘ線回折において判別することができる。 Both the first electrode layer 12 and the second electrode layer 14 are conductive layers containing both a positive electrode active material and a negative electrode active material. Although the positive electrode active material is not particularly limited, a material having an olivine crystal structure is used as the positive electrode active material here. Examples of such positive 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.
　オリビン型結晶構造をもつ電極活物質としては、例えばＣｏを含むＬｉＣｏＰＯ４等がある。この化学式において遷移金属のＣｏが置き換わったリン酸塩等を用いてもよい。ここで、価数に応じてＬｉやＰＯ４の比率は変動し得る。なお、遷移金属として、Ｃｏ，Ｍｎ，Ｆｅ，Ｎｉなどを用いてもよい。 As an electrode active material having an olivine type crystal structure, there is, for example, LiCoPO4 containing Co. A phosphate or the like in which the transition metal Co is replaced in this chemical formula may also be used. Here, the ratio of Li and PO4 can vary depending on the valence. Co, Mn, Fe, Ni, etc. may be used as the transition metal.
　また、負極活物質としては、例えばチタン酸化物、リチウムチタン複合酸化物、リチウムチタン複合リン酸塩、カーボン、及びリン酸バナジウムリチウムのいずれかがある。 In addition, the negative electrode active material includes, for example, titanium oxide, lithium-titanium composite oxide, lithium-titanium composite phosphate, carbon, and vanadium lithium phosphate.
　このように第１の電極層１２と第２の電極層１４の各々に正極活物質と負極活物質の両方を使用することにより各電極層１２、１４の類似性が高まる。その結果、第１の電極層１２と第２の電極層１４の各々が正極としても負極としても機能するようになり、全固体電池１００の端子の取り付けを正負逆にしてしまった場合であっても、短絡検査において誤作動せずに実使用に耐えられる。なお、本実施形態はこれに限定されず、第１の電極層１２として正極層を形成し、かつ第２の電極層１３として負極層を形成することにより、全固体電池１００に極性を持たせてもよい。 By using both the positive electrode active material and the negative electrode active material in each of the first electrode layer 12 and the second electrode layer 14 in this manner, the similarity between the electrode layers 12 and 14 is enhanced. As a result, each of the first electrode layer 12 and the second electrode layer 14 functions as both a positive electrode and a negative electrode. Also, it can withstand actual use without malfunctioning in short-circuit inspection. Note that the present embodiment is not limited to this, and by forming a positive electrode layer as the first electrode layer 12 and forming a negative electrode layer as the second electrode layer 13, the all-solid-state battery 100 has polarity. may
　更に、第１の電極層１２と第２の電極層１４を作製する際に、これらの電極層に酸化物系固体電解質材料や、カーボンや金属等の導電助剤を添加してもよい。導電助剤の金属としては、例えばＰｄ、Ｎｉ、Ｃｕ、及びＦｅのいずれかがある。更に、これらの金属の合金を導電助剤として使用してもよい。 Furthermore, when the first electrode layer 12 and the second electrode layer 14 are produced, an oxide-based solid electrolyte material or a conductive aid such as carbon or metal may be added to these electrode layers. Examples of the metal of the conductive aid include Pd, Ni, Cu, and Fe. Furthermore, alloys of these metals may be used as conductive aids.
　また、第１の電極層１２と第２の電極層１４の層構造は特に限定されない。例えば、点線円内に示すように、導電性材料からなる第１の集電体層１２ｂの両主面に第１の電極層１２を形成することにより、第１の集電体層１２ｂを第１の電極層１２で挟むようにしてもよい。同様に、導電性材料からなる第２の集電体層１４ｂの両主面に第２の電極層１４を形成することにより、第２の集電体１４ｂを第２の電極層１４で挟むようにしてもよい。 Also, the layer structures of the first electrode layer 12 and the second electrode layer 14 are not particularly limited. For example, as shown in the dotted line circle, the first electrode layer 12 is formed on both main surfaces of the first current collector layer 12b made of a conductive material, thereby turning the first current collector layer 12b into a first collector layer 12b. It may be sandwiched by one electrode layer 12 . Similarly, by forming the second electrode layers 14 on both main surfaces of the second current collector layer 14b made of a conductive material, the second current collector 14b is sandwiched between the second electrode layers 14. good too.
　一方、固体電解質層１１の材料としては、例えばＮＡＳＩＣＯＮ構造を有するリン酸塩系固体電解質がある。ＮＡＳＩＣＯＮ構造を有するリン酸塩系固体電解質は、高いイオン導電率を有すると共に、大気中で化学的に安定である。リン酸塩系固体電解質は特に限定されないが、ここではリチウムを含んだリン酸塩を使用する。当該リン酸塩は、例えばＴｉとの複合リン酸リチウム塩（ＬｉＴｉ２（ＰＯ４）３）をベースとし、Ｌｉ含有量を増加させるためにＡｌ，Ｇａ，Ｉｎ，Ｙ，Ｌａなどの３価の遷移金属に一部置換させた塩である。そのような塩としては、Ｌｉ１＋ｘＡｌｘＧｅ２－ｘ（ＰＯ４）３、Ｌｉ１＋ｘＡｌｘＺｒ２－ｘ（ＰＯ４）３、及びＬｉ１＋ｘＡｌｘＴｉ２－ｘ（ＰＯ４）３等のＬｉ－Ａｌ－Ｍ－ＰＯ４系リン酸塩（Ｍは、Ｇｅ，Ｔｉ，Ｚｒ等）がある。 On the other hand, as a material of the solid electrolyte layer 11, for example, there is a phosphate-based solid electrolyte having a NASICON structure. Phosphate-based solid electrolytes having the NASICON structure have high ionic conductivity and are chemically stable in the atmosphere. Although the phosphate-based solid electrolyte is not particularly limited, a phosphate containing lithium is used here. The phosphate is based on, for example, a composite lithium phosphate salt with Ti (LiTi 2 (PO 4 ) 3 ), and a trivalent compound such as Al, Ga, In, Y, or La to increase the Li content. It is a salt in which a transition metal is partially substituted. Such salts include Li 1+x Al x Ge 2-x (PO 4 ) 3 , Li 1+x Al x Zr 2-x (PO 4 ) 3 and Li 1+x Al x Ti 2-x (PO 4 ) 3 . Li--Al--M--PO 4 system phosphate (M is Ge, Ti, Zr, etc.).
　また、第１の電極層１２中のリン酸塩に含まれる遷移金属を予め添加したＬｉ－Ａｌ－Ｇｅ－ＰＯ４系リン酸塩を固体電解質層１１の材料として用いてもよい。例えば、第１の電極層１２にＣｏとＬｉのいずれかを含むリン酸塩が含有される場合には、Ｃｏを予め添加したＬｉ－Ａｌ－Ｇｅ－ＰＯ４系リン酸塩を固体電解質層１１に含有させてもよい。これにより、第１の電極層１２から固体電解質層１１に遷移金属が溶出するのを抑制することができる。 Alternatively, a Li—Al—Ge—PO 4 -based phosphate to which a transition metal contained in the phosphate in the first electrode layer 12 is added in advance may be used as the material for the solid electrolyte layer 11 . For example, when the first electrode layer 12 contains a phosphate containing either Co or Li, the Li—Al—Ge—PO 4 -based phosphate to which Co is previously added is used as the solid electrolyte layer 11. may be contained in Thereby, it is possible to suppress the elution of the transition metal from the first electrode layer 12 to the solid electrolyte layer 11 .
　図３は、図１のII－II線に沿う断面図である。図３に例示するように、積層体６０は、第１の方向Ｚと第２の方向Ｙの各々に平行な第３の面６０ｃと第４の面６０ｄとを有する。 FIG. 3 is a cross-sectional view along line II-II in FIG. As illustrated in FIG. 3, the laminate 60 has a third surface 60c and a fourth surface 60d parallel to the first direction Z and the second direction Y, respectively.
　更に、積層体６０は、第１の方向Ｚに垂直な第５の面６０ｅと第６の面６０ｆとを有する。第５の面６０ｅは、配線基板に全固体電池１００を実装するときに上側となる上面である。また、第６の面６０ｆは、実装時に下側となる下面である。この例では積層体６０の最外層は固体電解質層１１であり、第３～第６の面６０ｃ～６０ｆの各々は固体電解質層１１の表面で画定される。 Furthermore, the laminate 60 has a fifth surface 60e and a sixth surface 60f perpendicular to the first direction Z. The fifth surface 60e is an upper surface that faces upward when the all-solid-state battery 100 is mounted on the wiring substrate. Also, the sixth surface 60f is the lower surface that is the lower side during mounting. In this example, the outermost layer of laminate 60 is solid electrolyte layer 11, and the surfaces of solid electrolyte layer 11 define the third to sixth surfaces 60c to 60f, respectively.
　更に、第３～第６の面６０ｃ～６０ｆの各々の表面には防湿層８０が設けられる。防湿層８０は、シリコンを含む無機酸化物の層であって、大気中の水分から積層体６０を保護する役割を担う層である。なお、Ｂ、Ｂｉ、Ｚｎ、Ｂａ、Ｌｉ、Ｐ、Ｓｎ、Ｐｂ、Ｍｇ、及びＮａのいずれかを防湿層８０に添加してもよい。 Furthermore, a moisture-proof layer 80 is provided on each surface of the third to sixth surfaces 60c to 60f. The moisture-proof layer 80 is a layer of inorganic oxide containing silicon, and serves to protect the laminate 60 from moisture in the atmosphere. Any one of B, Bi, Zn, Ba, Li, P, Sn, Pb, Mg, and Na may be added to the moisture-proof layer 80 .
　図４は、第１の電極層１２とのその周囲の平面図である。図４に示すように、第１の電極層１２は、第１の外部電極４０ａに接続された第１の部分１２ｘと、第１の部分１２ｘから第２の方向Ｙに沿って延びる第２の部分１２ｙとを有する。 FIG. 4 is a plan view of the first electrode layer 12 and its surroundings. As shown in FIG. 4, the first electrode layer 12 has a first portion 12x connected to the first external electrode 40a and a second portion 12x extending along the second direction Y from the first portion 12x. and a portion 12y.
　また、第１の方向Ｚと第２の方向Ｙの各々に垂直な第３の方向Ｘに沿った第１の部分１２ｘの第１の幅Ｗ１は、第３の方向Ｘに沿った第２の部分１２ｙの第２の幅Ｗ２よりも広い。これにより、第１の電極層１２は、平面視で概略Ｔ字型となる。 Also, the first width W1 of the first portion 12x along the third direction X perpendicular to each of the first direction Z and the second direction Y is the second width along the third direction X. It is wider than the second width W2 of the portion 12y. As a result, the first electrode layer 12 becomes substantially T-shaped in plan view.
　なお、この例ではＷ１≧１．０１×Ｗ２とする。これにより、第１の電極層１２と固体電解質層１１の各々の収縮率の差に起因して全固体電池１００に反りが発生するのを抑制することができる。また、より好ましくはＷ１≧１．０２×Ｗ２とし、更に好ましくはＷ１≧１．０５×Ｗ２とする。これにより、全固体電池１００の角に応力が集中するのを抑制でき、反りの発生を更に効果的に抑制することができる。 In this example, W1≧1.01×W2. Thereby, it is possible to suppress the occurrence of warping in the all-solid-state battery 100 due to the difference in contraction rate between the first electrode layer 12 and the solid electrolyte layer 11 . More preferably, W1≧1.02×W2, and even more preferably W1≧1.05×W2. As a result, concentration of stress on the corners of the all-solid-state battery 100 can be suppressed, and warping can be suppressed more effectively.
　図５は、第１の電極層１２の拡大断面図である。図５においては、第１の電極層１２の第１の部分１２ｘと第３の面６０ｃとの間隔をＤ１とし、第１の電極層１２の第２の部分１２ｙと第３の面６０ｃとの間隔をＤ２としている。本実施形態では、これらの間隔Ｄ１、Ｄ２が（Ｄ２－Ｄ１）≧０．１×Ｄ２を満たすようにする。これにより、第１の電極層１２と固体電解質層１１の各々の収縮率の差に起因して全固体電池１００に反りが発生するのを抑制することができる。より好ましくは（Ｄ２－Ｄ１）≧０．５×Ｄ２とし、更に好ましくは（Ｄ２－Ｄ１）≧１．０×Ｄ２、すなわち第１の部分１２ｘが第３の面６０ｃに露出するものとする。これにより、第１の電極層１２と固体電解質層１１の各々の収縮率の差に起因して全固体電池１００に反りが発生するのを効果的に抑制することができる。しかも、第１の部分１２ｘが第３の面６０ｃに露出することで、第１の部分１２ｘと第１の外部電極４０ａとが密着し、第１の電極層１２と第１の外部電極４０ａとの密着強度が高まる。 FIG. 5 is an enlarged cross-sectional view of the first electrode layer 12. FIG. In FIG. 5, the distance between the first portion 12x of the first electrode layer 12 and the third surface 60c is D1, and the distance between the second portion 12y of the first electrode layer 12 and the third surface 60c is D1. The interval is D2. In this embodiment, these intervals D1 and D2 satisfy (D2-D1)≧0.1×D2. Thereby, it is possible to suppress the occurrence of warping in the all-solid-state battery 100 due to the difference in contraction rate between the first electrode layer 12 and the solid electrolyte layer 11 . More preferably (D2−D1)≧0.5×D2, and even more preferably (D2−D1)≧1.0×D2, that is, the first portion 12x is exposed on the third surface 60c. Thereby, it is possible to effectively suppress the occurrence of warpage in the all-solid-state battery 100 due to the difference in contraction rate between the first electrode layer 12 and the solid electrolyte layer 11 . Moreover, since the first portion 12x is exposed on the third surface 60c, the first portion 12x and the first external electrode 40a are in close contact with each other, and the first electrode layer 12 and the first external electrode 40a are brought into close contact with each other. The adhesion strength of is increased.
　図６は、第２の電極層１４とのその周囲の平面図である。図４に示すように、第２の電極層１４は、第２の外部電極４０ｂに接続された第３の部分１４ｘと、第３の部分１４ｘから第２の方向Ｙに沿って延びる第４の部分１４ｙとを有する。 FIG. 6 is a plan view of the second electrode layer 14 and its surroundings. As shown in FIG. 4, the second electrode layer 14 has a third portion 14x connected to the second external electrode 40b and a fourth portion 14x extending along the second direction Y from the third portion 14x. and a portion 14y.
　また、第３の方向Ｘに沿った第３の部分１４ｘの第３の幅Ｗ３は、第３の方向Ｘに沿った第４の部分１４ｙの第４の幅Ｗ４よりも広い。これにより、第２の電極層１４は、平面視で概略Ｔ字型となる。なお、この例ではＷ３≧１．０１×Ｗ４とする。これにより、第２の電極層１４と固体電解質層１１の各々の収縮率の差に起因して全固体電池１００に反りが発生するのを抑制することができる。また、より好ましくはＷ３≧１．０２×Ｗ４とし、更に好ましくはＷ３≧１．０５×Ｗ４とする。これにより、全固体電池１００の角に応力が集中するのを抑制でき、反りの発生を更に効果的に抑制することができる。 A third width W3 of the third portion 14x along the third direction X is wider than a fourth width W4 of the fourth portion 14y along the third direction X. As a result, the second electrode layer 14 becomes substantially T-shaped in plan view. In this example, W3≧1.01×W4. Thereby, it is possible to suppress the occurrence of warpage in the all-solid-state battery 100 due to the difference in contraction rate between the second electrode layer 14 and the solid electrolyte layer 11 . More preferably, W3≧1.02×W4, and even more preferably W3≧1.05×W4. As a result, concentration of stress on the corners of the all-solid-state battery 100 can be suppressed, and warping can be suppressed more effectively.
　図７は、第２の電極層１４の拡大断面図である。図７においては、第２の電極層１４の第３の部分１４ｘと第３の面６０ｃとの間隔をＤ３とし、第２の電極層１４の第４の部分１４ｙと第３の面６０ｃとの間隔をＤ４としている。本実施形態では、これらの間隔Ｄ３、Ｄ４が（Ｄ４－Ｄ３）≧０．１×Ｄ４を満たすようにする。これにより、第２の電極層１４と固体電解質層１１の各々の収縮率の差に起因して全固体電池１００に反りが発生するのを抑制することができる。より好ましくは（Ｄ４－Ｄ３）≧０．５×Ｄ４とし、更に好ましくは（Ｄ４－Ｄ３）≧１．０×Ｄ４、すなわち第３の部分１４ｘが第３の面６０ｃに露出するものとする。これにより、第２の電極層１４と固体電解質層１１の各々の収縮率の差に起因して全固体電池１００に反りが発生するのを効果的に抑制することができる。しかも、第３の部分１４ｘが第３の面６０ｃに露出することで、第３の部分１４ｘと第２の外部電極４０ｂとが密着し、第２の電極層１４と第２の外部電極４０ｂとの密着強度が高まる。 7 is an enlarged cross-sectional view of the second electrode layer 14. FIG. In FIG. 7, the distance between the third portion 14x of the second electrode layer 14 and the third surface 60c is D3, and the distance between the fourth portion 14y of the second electrode layer 14 and the third surface 60c is D3. The interval is D4. In this embodiment, these intervals D3 and D4 satisfy (D4-D3)≧0.1×D4. Thereby, it is possible to suppress the occurrence of warpage in the all-solid-state battery 100 due to the difference in contraction rate between the second electrode layer 14 and the solid electrolyte layer 11 . More preferably, (D4-D3)≧0.5×D4, and even more preferably (D4-D3)≧1.0×D4, that is, the third portion 14x is exposed on the third surface 60c. Thereby, it is possible to effectively suppress the occurrence of warpage in the all-solid-state battery 100 due to the difference in contraction rate between the second electrode layer 14 and the solid electrolyte layer 11 . Moreover, since the third portion 14x is exposed on the third surface 60c, the third portion 14x and the second external electrode 40b are in close contact with each other, and the second electrode layer 14 and the second external electrode 40b are brought into close contact with each other. The adhesion strength of is increased.
　図８は、積層体６０における各電極層１２、１４の位置関係を示す斜視図である。図８に示すように、第１の電極層１２の第１の部分１２ｘは第１の面６０ａに露出し、第２の電極層１４の第３の部分１４ｘは第２の面６０ｂに露出する。 FIG. 8 is a perspective view showing the positional relationship between the electrode layers 12 and 14 in the laminate 60. FIG. As shown in FIG. 8, the first portion 12x of the first electrode layer 12 is exposed on the first surface 60a and the third portion 14x of the second electrode layer 14 is exposed on the second surface 60b. .
　図９は、第１の方向Ｚから見た第１の電極層１２と第２の電極層１４の平面図である。図９に示すように、第１の電極層１２の第１の部分１２ｘと、第２の電極層１４の第３の部分１４ｘは、領域Ｒにおいて相互に重なる。本実施形態では、領域Ｒにおける第１の電極層１２と第２の電極層１４のいずれかの膜厚をＴ１とし、当該領域Ｒにおける固体電解質層１１の膜厚Ｔ２としたときに、Ｔ１／Ｔ２≧１とする。このように固体電解質層１１の膜厚Ｔ２を小さくすることで、全固体電池において各電極層１２、１４が占める割合が増え、全固体電池の容量が増大する。更に好ましくは、Ｔ１／Ｔ２≧１０とし、より好ましくはＴ１／Ｔ２≧５０とする。これにより、固体電解質層１１の薄厚化に伴うショートやリーク電流の増大を防止しつつ、固体電解質層１１の厚膜化に伴う容量低下や応答性低下を防止できる。 9 is a plan view of the first electrode layer 12 and the second electrode layer 14 viewed from the first direction Z. FIG. As shown in FIG. 9, the first portion 12x of the first electrode layer 12 and the third portion 14x of the second electrode layer 14 overlap each other in the region R. As shown in FIG. In the present embodiment, when the thickness of either the first electrode layer 12 or the second electrode layer 14 in the region R is T1, and the thickness T2 of the solid electrolyte layer 11 in the region R is T1/ T2≧1. By reducing the film thickness T2 of the solid electrolyte layer 11 in this manner, the proportion of the electrode layers 12 and 14 in the all-solid battery increases, and the capacity of the all-solid battery increases. More preferably, T1/T2≧10, more preferably T1/T2≧50. As a result, it is possible to prevent a short circuit and an increase in leakage current due to the thinning of the solid electrolyte layer 11, and prevent a decrease in capacity and response due to an increase in the thickness of the solid electrolyte layer 11. FIG.
　一例として、本実施形態では、第１の電極層１２の膜厚を２μｍ～１００μｍ、より好ましくは５μｍ～５０μｍとする。また、第２の電極層１４の膜厚は２μｍ～１００μｍ、より好ましくは５μｍ～５０μｍである。この範囲を採用することで、各電極層１２、１４の薄厚化に伴う容量低下を防止し、かつ各電極層１２、１４の厚膜化に伴う積層精度の低下を防止できる。更に、固体電解質層１１の膜厚は２μｍ～５０μｍ、より好ましくは５μｍ～２５μｍである。この範囲を採用することで、固体電解質層１１の薄厚化に伴うショートやリーク電流の増大を防止しつつ、固体電解質層１１の厚膜化に伴う容量低下や応答性低下を防止できる。 As an example, in the present embodiment, the film thickness of the first electrode layer 12 is set to 2 μm to 100 μm, more preferably 5 μm to 50 μm. The film thickness of the second electrode layer 14 is 2 μm to 100 μm, preferably 5 μm to 50 μm. By adopting this range, it is possible to prevent a decrease in capacity due to thinning of the electrode layers 12 and 14 and to prevent a decrease in stacking accuracy due to thickening of the electrode layers 12 and 14 . Furthermore, the film thickness of the solid electrolyte layer 11 is 2 μm to 50 μm, preferably 5 μm to 25 μm. By adopting this range, it is possible to prevent a short circuit and an increase in leakage current due to the thinning of the solid electrolyte layer 11, and prevent a decrease in capacity and a decrease in responsiveness due to the thickening of the solid electrolyte layer 11.
　上記した本実施形態によれば、図４に示したように、第１の幅Ｗ１を第２の幅Ｗ２よりも広くするため、第１の面６０ａに露出する第１の電極層１２の面積が増大する。そのため、焼成後の積層体６０が冷却するときに固体電解質層１１と第１の電極層１２との間に熱収縮率に差が生じても、第１の部分１２ｘに広く存在する第１の電極層１２が固体電解質層１１の収縮を抑えるように作用するため、第１の部分１２ｘとその近傍の積層体６０に反りが発生し難くなる。 According to the present embodiment described above, as shown in FIG. 4, since the first width W1 is wider than the second width W2, the area of the first electrode layer 12 exposed on the first surface 60a is increases. Therefore, even if there is a difference in thermal contraction rate between the solid electrolyte layer 11 and the first electrode layer 12 when the stacked body 60 after firing is cooled, the first portion widely present in the first portion 12x Since the electrode layer 12 acts to suppress the contraction of the solid electrolyte layer 11, the first portion 12x and the laminate 60 in the vicinity thereof are less likely to warp.
　同様に、図６に示したように、第３の幅Ｗ３を第４の幅Ｗ４よりも広くするため、第２の面６０ｂに露出する第２の電極層１４の面積が増大する。その結果、焼成後の積層体６０が冷却するときに固体電解質層１１と第２の電極層１４との間に熱収縮率に差が生じても、第３の部分１４ｘに広く存在する第２の電極層１４が固体電解質層１１の収縮を抑えるように作用するため、第３の部分１４ｘとその近傍の積層体６０に反りが発生し難くなる。 Similarly, as shown in FIG. 6, since the third width W3 is wider than the fourth width W4, the area of the second electrode layer 14 exposed on the second surface 60b is increased. As a result, even if there is a difference in thermal shrinkage between the solid electrolyte layer 11 and the second electrode layer 14 when the laminated body 60 after firing is cooled, the second electrode layer 14 widely present in the third portion 14x Since the electrode layer 14 acts to suppress contraction of the solid electrolyte layer 11, the third portion 14x and the laminate 60 in the vicinity thereof are less likely to warp.
　しかも、幅が広い第１の部分１２ｘと第３の部分１４ｘにより、第１の面６０ａと第２の面６０ｂの近傍における積層体６０の強度が高まるため、全固体電池１００の機械的強度を高めることもできる。 Moreover, since the first portion 12x and the third portion 14x having the wide width increase the strength of the laminate 60 in the vicinity of the first surface 60a and the second surface 60b, the mechanical strength of the all-solid-state battery 100 is increased. can also be increased.
　次に、本実施形態に係る全固体電池の製造方法について説明する。図１０は、本実施形態に係る全固体電池の製造方法のフローチャートである。 Next, a method for manufacturing an all-solid-state battery according to this embodiment will be described. FIG. 10 is a flowchart of the method for manufacturing an all-solid-state battery according to this embodiment.
　（セラミック原料粉末作製工程）
　まず、上述の固体電解質層１１を構成するリン酸塩系固体電解質の粉末を作製する。例えば、原料と添加物とを混合し、固相合成法などを用いることにより、固体電解質層１１を構成するリン酸塩系固体電解質の粉末を作製することができる。得られた粉末を乾式粉砕することにより、所望の平均粒径に調整することができる。例えば、５ｍｍφのＺｒＯ２ボールを用いた遊星ボールミルで、所望の平均粒径に調整する。 (Ceramic raw material powder preparation process)
First, powder of the phosphate-based solid electrolyte that constitutes the solid electrolyte layer 11 is prepared. For example, the powder of the phosphate-based solid electrolyte that constitutes the solid electrolyte layer 11 can be produced by mixing raw materials and additives and using a solid-phase synthesis method or the like. A desired average particle size can be obtained by dry pulverizing the obtained powder. For example, a planetary ball mill using 5 mmφ ZrO 2 balls is used to adjust the desired average particle size.
　添加物には焼結助剤が含まれる。焼結助剤として、例えば、Ｌｉ－Ｂ－Ｏ系化合物、Ｌｉ－Ｓｉ－Ｏ系化合物、Ｌｉ－Ｃ－Ｏ系化合物、Ｌｉ－Ｓ－Ｏ系化合物，及びＬｉ－Ｐ－Ｏ系化合物のいずれかのガラス成分を使用し得る。 Additives include sintering aids. As a sintering aid, for example, Li—B—O based compounds, Li—Si—O based compounds, Li—C—O based compounds, Li—SO based compounds, and Li—P—O based compounds. Any glass component can be used.
　（グリーンシート作製工程）
　次に、得られた粉末を、結着材、分散剤、及び可塑剤等と共に、水性溶媒又は有機溶媒に均一に分散させて、湿式粉砕を行うことにより所望の平均粒径を有する固体電解質スラリを得る。このとき、ビーズミル、湿式ジェットミル、各種混錬機、高圧ホモジナイザーなどを用いることができ、粒度分布の調整と分散とを同時に行うことができる観点からビーズミルを用いることが好ましい。 (Green sheet manufacturing process)
Next, the obtained powder is uniformly dispersed in an aqueous solvent or an organic solvent together with a binder, a dispersant, a plasticizer, etc., and wet pulverized to obtain a solid electrolyte slurry having a desired average particle size. 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.
　そして、得られた固体電解質スラリにバインダを添加して固体電解質ペーストを得る。固体電解質ペーストを塗工することにより、固体電解質層１１用のグリーンシートが得られる。塗工方法は特に限定されず、スロットダイ方式、リバースコート方式、グラビアコート方式、バーコート方式、ドクターブレード方式などを用いることができる。湿式粉砕後の粒度分布は、例えば、レーザ回折散乱法を用いたレーザ回折測定装置を用いて測定することができる。 Then, a binder is added to the obtained solid electrolyte slurry to obtain a solid electrolyte paste. A green sheet for the solid electrolyte layer 11 is obtained by applying the solid electrolyte paste. 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.
　（電極層用ペースト作製工程）
　次に、第１の電極層１２と第２の電極層１４とを作製するための電極層用ペーストを作製する。例えば、正極活物質、負極活物質、及び固体電解質材料をビーズミル等で高分散化し、セラミックス粒子のみからなるセラミックスペーストを作製する。また、カーボンブラック等のカーボン粒子を含むカーボンペーストを作製し、セラミックスペーストにカーボンペーストを混錬してもよい。 (Electrode layer paste preparation step)
Next, an electrode layer paste for forming the first electrode layer 12 and the second electrode layer 14 is prepared. For example, a positive electrode active material, a negative electrode active material, and a solid electrolyte material are highly dispersed in a bead mill or the like to prepare a ceramic paste consisting only of ceramic particles. Alternatively, a carbon paste containing carbon particles such as carbon black may be prepared, and the carbon paste may be kneaded with the ceramic paste.
　（積層工程）
　次に、グリーンシートの一方の主面に電極層用ペーストを印刷する。次いで、印刷後の複数のグリーンシートを交互にずらして１５０枚積層し、それをダイサーで所定のサイズにカットすることで積層体６０を得る。なお、その積層体６０の最上層と最下層はグリーンシートとなる。 (Lamination process)
Next, an electrode layer paste is printed on one main surface of the green sheet. Next, 150 printed green sheets are stacked alternately and cut into a predetermined size by a dicer to obtain a laminate 60 . The uppermost layer and the lowermost layer of the laminate 60 are green sheets.
　（焼成工程）
　次に、酸素を含む焼成雰囲気中で積層体６０を焼成する。電極層用ペーストに含まれるカーボン材料の消失を抑制するために、焼成雰囲気の酸素分圧を２×１０－１３ａｔｍ以下とすることが好ましい。一方、リン酸塩系固体電解質の融解を抑制するために酸素分圧を５×１０－２２ａｔｍ以上とすることが好ましい。 (Baking process)
Next, the laminate 60 is fired in a firing atmosphere containing oxygen. In order to suppress disappearance of the carbon material contained in the electrode layer paste, the oxygen partial pressure in the firing atmosphere is preferably 2×10 −13 atm or less. On the other hand, it is preferable to set the oxygen partial pressure to 5×10 −22 atm or more in order to suppress melting of the phosphate-based solid electrolyte.
　その後、積層体６０の各面６０ａ、６０ｂに金属ペーストを塗布してそれを焼き付けることにより第１の外部電極４０ａと第２の外部電極４０ｂを形成する。なお、スパッタ法やめっき法で第１の外部電極４０ａと第２の外部電極４０ｂを形成してもよい。 After that, the first external electrode 40a and the second external electrode 40b are formed by applying a metal paste to each surface 60a, 60b of the laminate 60 and baking it. Alternatively, the first external electrode 40a and the second external electrode 40b may be formed by sputtering or plating.
　なお、焼成後の第１の電極層１２の膜厚は１４μｍであり、第２の電極層１４の膜厚は１０μｍである。また、焼成後の固体電解質層１１の膜厚は８μｍである。 The film thickness of the first electrode layer 12 after firing is 14 μm, and the film thickness of the second electrode layer 14 is 10 μm. Moreover, the film thickness of the solid electrolyte layer 11 after baking is 8 μm.
　（塗布工程）
　次に、積層体６０の第３～第６の面６０ｃ～６０ｆにジブチルエーテル又はジブチルエーテル系の溶媒にテトラアルコキシシランを溶解させた溶液を塗布する。その後、その溶液を１００℃～１５０℃程度の温度に加熱することにより防湿層８０を得る。以上により、全固体電池１００の基本構造が完成する。 (Coating process)
Next, the third to sixth surfaces 60c to 60f of the laminate 60 are coated with dibutyl ether or a solution obtained by dissolving tetraalkoxysilane in a dibutyl ether-based solvent. Thereafter, the moisture-proof layer 80 is obtained by heating the solution to a temperature of about 100.degree. C. to 150.degree. With the above, the basic structure of the all-solid-state battery 100 is completed.
　本実施形態に従って全固体電池を作製した。図４～図７に示した各パラメータＷ１～Ｗ４及びＤ１～Ｄ４を、Ｗ１＝１．１×Ｗ２、Ｗ３＝１．１×Ｗ４、（Ｄ２－Ｄ１）＝０．７×Ｄ２、（Ｄ４－Ｄ３）＝０．７×Ｄ４となるようにした。作製した全固体電池チップは第１の電極層１２、第２の電極層１４ともに固体電解質層１１と厚み差があるものの、焼成においてそれぞれの電極層が固体電解質層１１の収縮を抑えることができ、反りがみられなかった。 An all-solid-state battery was produced according to this embodiment. Each parameter W1 to W4 and D1 to D4 shown in FIGS. D3)=0.7×D4. In the fabricated all-solid battery chip, both the first electrode layer 12 and the second electrode layer 14 have a thickness difference from the solid electrolyte layer 11, but each electrode layer can suppress the shrinkage of the solid electrolyte layer 11 during firing. , no warpage was observed.
　（比較例）
　図１１は、比較例に係る第１の電極層１２とのその周囲の平面図である。図１１に示すように、比較例においては第１の電極層１２は平面視で矩形状である。 (Comparative example)
FIG. 11 is a plan view of a first electrode layer 12 and its periphery according to a comparative example. As shown in FIG. 11, in the comparative example, the first electrode layer 12 has a rectangular shape in plan view.
　そのため、図４の本実施形態と比較して、比較例では第１の面６０ａの近傍における固体電解質層１１の収縮を第１の電極層１２で抑えることができず、積層体６０に反りが生じてしまう。 Therefore, compared with the present embodiment shown in FIG. 4, in the comparative example, the first electrode layer 12 cannot suppress the contraction of the solid electrolyte layer 11 in the vicinity of the first surface 60a, and the laminate 60 is warped. occur.
　図１２は、比較例に係る第２の電極層１４とのその周囲の平面図である。図１２に示すように、比較例に係る第２の電極層１４は、第１の電極層１２と同様に平面視で矩形状である。そのため、図１１の第１の電極層１２と同じ理由によって積層体６０に反りが生じてしまう。 FIG. 12 is a plan view of the second electrode layer 14 and its surroundings according to the comparative example. As shown in FIG. 12 , the second electrode layer 14 according to the comparative example has a rectangular shape in plan view, like the first electrode layer 12 . Therefore, the laminated body 60 is warped for the same reason as the first electrode layer 12 in FIG.
　図１３は、比較例に係る積層体における各電極層の位置関係を示す斜視図である。図１３に示すように、比較例においては第１の面６０ａに第１の電極層１２が露出し、第２の面６０ｂに第２の電極層１４が露出する。 FIG. 13 is a perspective view showing the positional relationship of each electrode layer in a laminate according to a comparative example. As shown in FIG. 13, in the comparative example, the first electrode layer 12 is exposed on the first surface 60a, and the second electrode layer 14 is exposed on the second surface 60b.
　以上、本発明の実施形態について詳述したが、本発明は係る特定の実施形態に限定されるものではなく、特許請求の範囲に記載された本発明の要旨の範囲内において、種々の変形・変更が可能である。 Although the embodiments of the present invention have been described in detail above, the present invention is not limited to such specific embodiments, and various modifications and variations can be made within the scope of the gist of the present invention described in the claims. Change is possible.

Claims (9)

  1. 　第１の電極層、固体電解質層、及び第２の電極層の各々が第１の方向に沿って複数積層され、前記第１の電極層が表出する第１の面と、前記第２の電極層が表出する第２の面とを備えた積層体と、
    　前記第１の面に設けられ、かつ前記第１の電極層に接続された第１の外部電極と、
    　前記第２の面に設けられ、かつ前記第２の電極層に接続された第２の外部電極とを有し、
    　前記第１の電極層は、前記第１の外部電極に接続された第１の部分と、前記第１の外部電極から前記第２の外部電極に向かう第２の方向に沿って延びる第２の部分とを有し、
    　前記第１の方向と前記第２の方向の各々と交叉する第３の方向に沿った前記第１の部分の第１の幅が前記第２の部分の第２の幅よりも広いことを特徴とする全固体電池。     Each of a first electrode layer, a solid electrolyte layer, and a second electrode layer is laminated along a first direction, and a first surface where the first electrode layer is exposed; a laminate comprising a second surface from which the electrode layer is exposed;
    a first external electrode provided on the first surface and connected to the first electrode layer;
    a second external electrode provided on the second surface and connected to the second electrode layer;
    The first electrode layer has a first portion connected to the first external electrode and a second portion extending along a second direction from the first external electrode toward the second external electrode. having a part and
    A first width of the first portion along a third direction crossing each of the first direction and the second direction is wider than a second width of the second portion. All-solid-state battery.
  2. 　前記第２の電極層は、前記第２の外部電極に接続された第３の部分と、前記第２の方向に沿って延びる第４の部分とを有し、
    　前記第３の部分の前記第３の方向に沿った第３の幅が前記第４の部分の第４の幅よりも広いことを特徴とする請求項１に記載の全固体電池。     the second electrode layer has a third portion connected to the second external electrode and a fourth portion extending along the second direction;
    2. The all-solid-state battery according to claim 1, wherein a third width of said third portion along said third direction is wider than a fourth width of said fourth portion.
  3. 　前記第１の方向から見て前記第１の電極層と前記第２の電極層とが重なる領域を有し、前記領域における前記第１の電極層と前記第２の電極層のいずれかの膜厚をＴ１、前記領域における前記固体電解質層の膜厚をＴ２としたときに、Ｔ１／Ｔ２≧１となることを特徴とする請求項２に記載の全固体電池。 a region where the first electrode layer and the second electrode layer overlap when viewed from the first direction, and a film of either the first electrode layer or the second electrode layer in the region; 3. The all-solid-state battery according to claim 2, wherein T1/T2≧1, where T1 is the thickness and T2 is the film thickness of the solid electrolyte layer in the region.
  4. 　前記第１の幅は、前記第２の幅の１．０１倍以上であり、
    　前記第３の幅は、前記第４の幅の１．０１倍以上であることを特徴とする請求項２又は請求項３に記載の全固体電池。     The first width is 1.01 times or more the second width,
    4. The all-solid-state battery according to claim 2, wherein the third width is 1.01 times or more the fourth width.
  5. 　前記第１の幅は、前記第２の幅の１．０２倍以上であり、
    　前記第３の幅は、前記第４の幅の１．０２倍以上であることを特徴とする請求項２又は請求項３に記載の全固体電池。     The first width is 1.02 times or more the second width,
    4. The all-solid-state battery according to claim 2, wherein the third width is 1.02 times or more the fourth width.
  6. 　前記第１の幅は、前記第２の幅の１．０５倍以上であり、
    　前記第３の幅は、前記第４の幅の１．０５倍以上であることを特徴とする請求項２又は請求項３に記載の全固体電池。     The first width is 1.05 times or more the second width,
    4. The all-solid-state battery according to claim 2, wherein the third width is 1.05 times or more the fourth width.
  7. 　前記積層体は、前記第１の方向と前記第２の方向の各々に平行であり、かつ前記固体電解質層が表出する第３の面を更に有し、
    　前記第１の部分と前記第３の面との間隔をＤ１、前記第２の部分と前記第３の面との間隔をＤ２としたときに、（Ｄ２－Ｄ１）≧０．１×Ｄ２であることを特徴とする請求項２乃至請求項４のいずれか１項に記載の全固体電池。     The laminate further has a third surface parallel to each of the first direction and the second direction and from which the solid electrolyte layer is exposed,
    When the distance between the first portion and the third surface is D1, and the distance between the second portion and the third surface is D2, (D2−D1)≧0.1×D2. The all-solid-state battery according to any one of claims 2 to 4, characterized in that there is a
  8. 　二つの前記第１の電極層に挟まれた第１の集電体層と、
    　二つの前記第２の電極層に挟まれた第２の集電体層とを更に有することを特徴とする請求項１乃至請求項５のいずれか１項に記載の全固体電池。     a first current collector layer sandwiched between the two first electrode layers;
    The all-solid-state battery according to any one of claims 1 to 5, further comprising a second current collector layer sandwiched between the two second electrode layers.
  9. 　第１の電極層、固体電解質層、及び第２の電極層の各々が第１の方向に沿って複数積層され、前記第１の電極層が表出する第１の面と、前記第２の電極層が表出する第２の面とを備えた積層体を形成する工程と、
    　前記積層体を焼成する工程と、
    　前記第１の面に、前記第１の電極層に接続された第１の外部電極を形成する工程と、
    　前記第２の面に、前記第２の電極層に接続された第２の外部電極を形成する工程とを有し、
    　前記第１の電極層は、前記第１の外部電極に接続された第１の部分と、前記第１の外部電極から前記第２の外部電極に向かう第２の方向に沿って延びる第２の部分とを有し、
    　前記第１の方向と前記第２の方向の各々と交叉する第３の方向に沿った前記第１の部分の第１の幅が前記第２の部分の第２の幅よりも広いことを特徴とする全固体電池の製造方法。     Each of a first electrode layer, a solid electrolyte layer, and a second electrode layer is laminated along a first direction, and a first surface where the first electrode layer is exposed; forming a laminate having a second surface from which the electrode layer is exposed;
    a step of firing the laminate;
    forming on the first surface a first external electrode connected to the first electrode layer;
    forming on the second surface a second external electrode connected to the second electrode layer;
    The first electrode layer has a first portion connected to the first external electrode and a second portion extending along a second direction from the first external electrode toward the second external electrode. having a part and
    A first width of the first portion along a third direction crossing each of the first direction and the second direction is wider than a second width of the second portion. A method for manufacturing an all-solid-state battery.
PCT/JP2022/030821 2021-09-27 2022-08-12 All-solid-state battery, and method for manufacturing same WO2023047839A1 (en)

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JP2000151325A (en) * 1998-11-13 2000-05-30 Sumitomo Metal Ind Ltd Stacked chip-type noise filter and its manufacture
JP2019204911A (en) * 2018-05-25 2019-11-28 日本特殊陶業株式会社 Method for manufacturing power storage device
WO2020145226A1 (en) * 2019-01-10 2020-07-16 Tdk株式会社 All-solid battery
WO2021125337A1 (en) * 2019-12-19 2021-06-24 株式会社村田製作所 Solid-state battery

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Publication number Priority date Publication date Assignee Title
JP2000151325A (en) * 1998-11-13 2000-05-30 Sumitomo Metal Ind Ltd Stacked chip-type noise filter and its manufacture
JP2019204911A (en) * 2018-05-25 2019-11-28 日本特殊陶業株式会社 Method for manufacturing power storage device
WO2020145226A1 (en) * 2019-01-10 2020-07-16 Tdk株式会社 All-solid battery
WO2021125337A1 (en) * 2019-12-19 2021-06-24 株式会社村田製作所 Solid-state battery

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