WO2022102271A1 - Batterie entièrement solide - Google Patents

Batterie entièrement solide Download PDF

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Publication number
WO2022102271A1
WO2022102271A1 PCT/JP2021/036177 JP2021036177W WO2022102271A1 WO 2022102271 A1 WO2022102271 A1 WO 2022102271A1 JP 2021036177 W JP2021036177 W JP 2021036177W WO 2022102271 A1 WO2022102271 A1 WO 2022102271A1
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Prior art keywords
electrode layer
positive electrode
negative electrode
layers
layer
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PCT/JP2021/036177
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English (en)
Japanese (ja)
Inventor
佐藤宇人
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太陽誘電株式会社
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Priority to JP2022561317A priority Critical patent/JPWO2022102271A1/ja
Publication of WO2022102271A1 publication Critical patent/WO2022102271A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • 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.
  • the small all-solid-state battery mounted on the wiring board or the like has a small capacity, and there is room for improvement in that the capacity is increased.
  • the present invention has been made in view of the above problems, and an object thereof is to increase the capacity of an all-solid-state battery.
  • a plurality of each of a positive electrode layer containing a positive electrode active material, a solid electrolyte layer, and a negative electrode layer containing a negative electrode active material are laminated, and the first surface on which the positive electrode layer is exposed and the above-mentioned
  • a laminate provided with a second surface on which the negative electrode layer is exposed, a first external electrode provided on the first surface and connected to the positive electrode layer, and provided on the second surface. It also has a second external electrode connected to the negative electrode layer, and the number of layers of the positive electrode layer is different from the number of layers of the negative electrode layer.
  • the positive electrode capacity determined by the ratio of the positive electrode active material in the positive electrode layer and the theoretical capacity per unit weight of the positive electrode active material is the ratio of the negative electrode active material in the negative electrode layer.
  • the number of layers of the negative electrode layer is larger than the number of layers of the positive electrode layer, and the positive electrode capacity is smaller than the negative electrode capacity. In some cases, the number of layers of the negative electrode layer may be smaller than the number of layers of the positive electrode layer.
  • a plurality of layers of either one of the positive electrode layer and the negative electrode layer and one layer of the other may be alternately laminated.
  • each of the plurality of layers may be thinner than the other one layer.
  • the laminate has a third surface that is different from each of the first surface and the second surface and is parallel to each of the positive electrode layer and the negative electrode layer.
  • a cover layer that covers the third surface and a marker that is provided on the cover layer and distinguishes the first external electrode from the second external electrode may be further provided.
  • the first distance between the marker and the first external electrode and the second distance between the marker and the second external electrode may be different.
  • the shape of the marker may be asymmetric with respect to a straight line perpendicular to the direction from the first external electrode to the second external electrode.
  • the capacity of the all-solid-state battery can be increased.
  • FIG. 1 is a schematic cross-sectional view showing the basic structure of the all-solid-state battery 100.
  • the all-solid-state battery 100 has a laminate 60 in which a plurality of solid electrolyte layers 11, positive electrode layers 12, and negative electrode layers 14 are laminated.
  • the solid electrolyte layer 11 is interposed between the positive electrode layer 12 and the negative electrode layer 14.
  • the positive electrode layer 12 is formed by laminating the first electrode layer 12c on both main surfaces of the first current collector layer 12b made of a conductive material.
  • the material of the first electrode layer 12c is not particularly limited as long as it is a conductive layer containing a positive electrode active material.
  • a material having an olivine-type crystal structure is used as the positive electrode active material. Examples of such a positive electrode active material include a phosphate containing a transition metal and lithium.
  • the olivine-type crystal structure is a crystal of natural olivine and can be discriminated by X-ray diffraction.
  • Examples of the electrode active material having an olivine type crystal structure include LiCoPO 4 containing Co.
  • a phosphate or the like in which the transition metal Co is replaced may be used.
  • the ratio of Li and PO 4 may fluctuate depending on the valence.
  • Co, Mn, Fe, Ni and the like may be used as a transition metal.
  • the negative electrode layer 14 is formed by laminating the second electrode layer 14c on both main surfaces of the second current collector layer 14b made of a conductive material.
  • the material of the second electrode layer 14c is not particularly limited as long as it is a conductive layer containing a negative electrode active material.
  • any one of titanium oxide, lithium titanium composite oxide, lithium titanium composite phosphate, carbon, and vanadium lithium phosphate is used as the negative electrode active material.
  • the second electrode layer 14c may contain an electrode active material having an olivine-type crystal structure. This makes it possible to increase the discharge capacity and increase the action potential associated with the discharge.
  • an oxide-based solid electrolyte material or a conductive auxiliary agent such as carbon or metal may be added to these electrode layers.
  • a conductive auxiliary agent such as carbon or metal
  • the metal of the conductive auxiliary agent include any of Pd, Ni, Cu, and Fe. Further, alloys of these metals may be used as a conductive auxiliary agent.
  • the positive electrode layer 12 is composed of the first current collector layer 12b and the two first electrode layers 12c, but only the first single-layer current collector layer 12b containing the positive electrode active material. May form the positive electrode layer 12 with.
  • the negative electrode layer 14 may be formed only by the second current collector layer 14b of a single layer containing the negative electrode active material.
  • the 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 a NASICON structure have high ionic conductivity and are chemically stable in the atmosphere.
  • the phosphate-based solid electrolyte is not particularly limited, but a phosphate containing lithium is used here.
  • the phosphate is based on, for example, a lithium complex phosphate salt with Ti (LiTi 2 (PO 4 ) 3 ), and is trivalent such as Al, Ga, In, Y, La in order to increase the Li content. It is a salt partially substituted with a transition metal.
  • 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 , etc.
  • Li-Al-M - PO4 phosphate (M is Ge, Ti, Zr, etc.).
  • a Li-Al-Ge - PO4 phosphate having a transition metal contained in the phosphate in the first electrode layer 12c added in advance may be used as a material for the solid electrolyte layer 11.
  • the first electrode layer 12c contains a phosphate containing either Co or Li
  • the Li-Al-Ge - PO4 phosphate to which Co is added in advance is added to the solid electrolyte layer 11. May be contained in.
  • Such a laminated body 60 has a first surface 60a and a second surface 60b parallel to the stacking direction Z of the positive electrode layer 12 and the negative electrode layer 14. Of these, the solid electrolyte layer 11 and the positive electrode layer 12 are exposed on the first surface 60a.
  • a first external electrode 40a is further provided on the first surface 60a, and the positive electrode layer 12 is connected to the first external electrode 40a.
  • the second surface 60b faces the first surface 60a, and the solid electrolyte layer 11 and the negative electrode layer 14 are exposed.
  • a second external electrode 40b is provided on the second surface 60b, and the negative electrode layer 14 is connected to the second external electrode 40b.
  • the laminated body 60 has a third surface 60c and a fourth surface 60d parallel to each of the positive electrode layer 12 and the negative electrode layer 14.
  • the third surface 60c is an upper surface that becomes an upper surface when the all-solid-state battery 100 is mounted on the wiring board.
  • the fourth surface 60d is a lower surface which is a lower surface at the time of mounting.
  • a cover layer 19 for protecting the positive electrode layer 12 and the negative electrode layer 14 from the atmosphere is formed on each of the third surface 60c and the fourth surface 60d.
  • the material of the cover layer 19 is not particularly limited, but the same material as the solid electrolyte layer 11 can be used as the material of the cover layer 19.
  • a visible marker 70 for distinguishing the first external electrode 40a and the second external electrode 40b is provided on the cover layer 19.
  • the thickness of the marker 70 is not particularly limited, but in the present embodiment, it is, for example, about 5 ⁇ m to 20 ⁇ m. As a result, it is possible to prevent the marker 70 from cracking or peeling off when the marker 70 is fired. Further, the marker 70 may be connected to either the first external electrode 40a or the second external electrode 40b, or may not be connected to both the external electrodes 40a and 40b.
  • the marker 70 has a color different from that of the cover layer 19 so that the marker 70 can be easily recognized visually or by a camera.
  • the cover layer 19 is white
  • carbon is added to the marker 70 to make the color black, so that a clear difference in brightness is generated between the marker 70 and the cover layer 19, which can be visually observed with a camera. It becomes easy to visually recognize the marker 70. If the marker 70 can be visually recognized without adding carbon, it is not necessary to add carbon to the marker 70.
  • the marker 70 is made of a material different from that of the cover layer 19 and the external electrodes 40a and 40b.
  • the marker 70 may be formed of a material different from that of the positive electrode layer 12 and the negative electrode layer 14.
  • FIG. 2 is a top view of the all-solid-state battery 100. As shown in FIG. 2, in the present embodiment, the marker 70 is moved toward the first external electrode 40a in a top view, so that the marker 70 points to the first external electrode 40a. In this case, the distance L1 between the first external electrode 40a and the marker 70 is shorter than the distance L2 between the second external electrode 40b and the marker 70.
  • the marker 70 may be separated from the external electrodes 40a and 40b by setting each of the intervals L1 and L2 to a value larger than 0.
  • the shape of the marker 70 is a rectangle symmetrical with respect to the straight line P perpendicular to the direction X from the first external electrode 40a to the second external electrode 40b.
  • FIG. 3 is a cross-sectional view of the laminated body 60 before forming the first external electrode 40a and the second external electrode 40b.
  • the number of layers of the negative electrode layer 14 is n
  • the number of layers of the positive electrode layer 12 is n + 1, and the positive electrode layer 12 and the negative electrode layer 14, respectively.
  • the number of layers is different.
  • the number of layers of the positive electrode layer 12 can be increased and the capacity of the all-solid-state battery 100 can be increased as compared with the case where the number of layers of the positive electrode layer 12 is the same as that of the negative electrode layer 14.
  • the capacity on the positive electrode side becomes too large as compared with the negative electrode side, and an imbalance in capacity occurs between the positive electrode side and the negative electrode side.
  • the theoretical capacity per unit weight of the positive electrode active material is cp (Ah / g), and the density of the positive electrode active material is ⁇ p ( g / cm 3 ). Further, the thickness of the positive electrode layer 12 is T p (cm), and the area is Sp (cm 2 ). Further, the ratio of the area occupied by the positive electrode active material in the positive electrode layer 12 is defined as Ap (%).
  • the positive electrode capacity C p (Ah / g) per one positive electrode layer 12 is c p ⁇ ⁇ p ⁇ T p ⁇ Sp ⁇ Ap .
  • the thickness Tp of the positive electrode layer 12 is not particularly limited, but is, for example, 10 ⁇ m to 20 ⁇ m.
  • the theoretical capacity per unit weight of the negative electrode active material is cn (Ah / g), and the density of the negative electrode active material is ⁇ n ( g / cm 3 ).
  • the thickness of the negative electrode layer 14 is T n (cm), and the area is Sn (cm 2 ). Further, the ratio of the area occupied by the negative electrode active material in the negative electrode layer 14 is defined as An (%).
  • the negative electrode capacity C n (Ah / g) per one negative electrode layer 14 is cn ⁇ ⁇ n ⁇ T n ⁇ Sn ⁇ An .
  • the thickness Tn of the negative electrode layer 14 is not particularly limited, but is, for example, 10 ⁇ m to 20 ⁇ m.
  • the ratio Ann is the ratio of the cross section of the negative electrode layer 14 parallel to the stacking direction Z (see FIG. 1) observed by SEM-EDS mapping, and the element peculiar to the negative electrode active material appearing in the cross section occupies the cross section. Can be calculated by specifying.
  • the positive electrode capacity C p thus obtained is smaller than the negative electrode capacity C n , the number of layers of the negative electrode layer 14 is smaller than the number of layers of the positive electrode layer 12 as shown in FIG.
  • the difference in capacitance on the side becomes small, and the imbalance between the capacitance on the positive electrode side and the capacitance on the negative electrode side can be reduced.
  • FIG. 4 is a cross-sectional view of the laminated body 60 when the number of layers of the negative electrode layer 14 is larger than the number of layers of the positive electrode layer 12 in this way.
  • the positive electrode layer 12 and the negative electrode so that the difference ⁇ C between the total value C p_all of the positive electrode capacities C p of all the positive electrode layers 12 and the total value C n_all of the negative electrode capacities C n of all the negative electrode layers 14 is as small as possible.
  • the number of each layer of the layer 14 may be adjusted. For example, by adjusting the number of layers of the positive electrode layer 12 and the negative electrode layer 14 so that ⁇ C is ⁇ 15% or less, more preferably ⁇ 5% or less of C p_all , the capacitance on the positive electrode side and the negative electrode side can be adjusted. The imbalance may be reduced.
  • the number of layers of the positive electrode layer 12 is larger than the number of layers of the negative electrode layer 14, it is possible to impart the effect of improving the capacity change, so-called charge / discharge cycle characteristics, when charging / discharging is repeated. ..
  • the marker 70 when the marker 70 is formed on the cover layer 19 as in the present embodiment, the marker 70 is exposed, so that the marker 70 may be peeled off due to an impact from the outside or the like. In this case, the marker 70 cannot be visually recognized by a camera or visual inspection, and the first external electrode 40a and the second external electrode 40b cannot be distinguished from each other.
  • the marker 70 is peeled off in this way, the number of layers of the positive electrode layer 12 exposed on the first surface 60a and the number of layers exposed on the second surface 60b before the external electrodes 40a and 40b are formed.
  • the polarity can be distinguished by visually recognizing the difference in the number of layers of the negative electrode layer 14 by a person or a camera.
  • FIG. 5 is a cross-sectional view of the laminated body 60 when the two negative electrode layers 14 are paired. In this case, the two negative electrode layers 14 and the one positive electrode layer 12 are alternately laminated.
  • the number of layers of the positive electrode layer 12 is n
  • the number of layers of the negative electrode layer 14 becomes 2n, which is twice that number.
  • the difference in the number of layers of the negative electrode layer 14 displayed on the surface 60b of No. 2 is larger than that in the case of FIG. As a result, it becomes easy for a person or a camera to discriminate the difference in the number of layers between the positive electrode layer 12 and the negative electrode layer 14, and it becomes easy to discriminate the polarity of the all-solid-state battery 100.
  • the negative electrode layer 14 is thinner than the positive electrode layer 12.
  • the thickness T p of the positive electrode layer 12 is 20 ⁇ m to 30 ⁇ m
  • the thickness T n of the negative electrode layer 14 is 5 ⁇ m to 10 ⁇ m.
  • the two negative electrode layers 14 are paired, but the two positive electrode layers 12 may be paired as shown in the cross-sectional view of FIG. Further, three or more positive electrode layers 12 and one negative electrode layer 14 may be alternately laminated, or three or more negative electrode layers 14 and one positive electrode layer 12 may be alternately laminated.
  • FIG. 7 is a top view showing another example of the all-solid-state battery.
  • the marker 70 points to the second external electrode 40b by the marker 70 by making the interval L2 smaller than the interval L1 and moving the marker 70 toward the second external electrode 40b.
  • FIG. 8 is a top view showing another example of the all-solid-state battery.
  • a triangular marker 70 is provided at substantially the center of the all-solid-state battery 100 when viewed from above. Then, by pointing the apex 70a of the marker 70 toward the first external electrode 40a, the marker 70 points to the first external electrode 40a.
  • the shape of the marker 70 is asymmetric with respect to the straight line P perpendicular to the direction X from the first external electrode 40a to the second external electrode 40b. Due to such asymmetry, a person or a camera can discriminate between the first external electrode 40a and the second external electrode 40b.
  • the positive electrode layer 12 is the n + 1 layer and the negative electrode layer 14 is the n layer, so that the number of layers of the positive electrode layer 12 and the negative electrode layer 14 is different. I did it. Therefore, the number of layers of the positive electrode layer 12 can be increased and the capacity of the all-solid-state battery 100 can be increased as compared with the case where the number of layers of the positive electrode layer 12 and the negative electrode layer 14 are both n layers.
  • the marker 70 is provided on the all-solid-state battery 100, the first external electrode 40a and the second external electrode 40b can be discriminated by visually recognizing the marker 70 with a camera or visually. Therefore, it is possible to prevent the all-solid-state battery 100 from being mounted on the wiring board with the opposite polarity, and it is possible to prevent the malfunction of the electronic device and the heat generation accident.
  • the polarity of the all-solid-state battery 100 can be determined.
  • FIG. 9 is a flowchart of a method for manufacturing an all-solid-state battery according to the present embodiment.
  • a phosphate-based solid electrolyte powder constituting the above-mentioned solid electrolyte layer 11 is prepared.
  • a phosphate-based solid electrolyte powder constituting the solid electrolyte layer 11 can be produced.
  • the obtained powder can be adjusted to a desired average particle size by dry-grinding.
  • a planetary ball mill using a 5 mm ⁇ ZrO 2 ball is used to adjust the particle size to a desired average particle size.
  • Additives include sintering aids.
  • the sintering aid for example, any of 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. That 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, and the like, and wet pulverization is performed 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 the bead mill from the viewpoint that the particle size distribution can be adjusted and dispersed at the same time.
  • 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 can be obtained.
  • the green sheet for the cover layer 19 can be manufactured in the same manner.
  • the coating method is not particularly limited, and a slot die method, a reverse coat method, a gravure coat method, a bar coat method, a doctor blade method and the like can be used.
  • the particle size distribution after wet grinding can be measured, for example, by using a laser diffraction measuring device using a laser diffraction scattering method.
  • a paste for an electrode layer for forming the first electrode layer 12c and the second electrode layer 14c is prepared.
  • the electrode active material and the solid electrolyte material are highly dispersed by a bead mill or the like to prepare a ceramic paste consisting of only 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.
  • a current collector paste for producing the above-mentioned first current collector layer 12b and the second current collector layer 14b is produced.
  • a paste for a current collector can be obtained by uniformly dispersing Pd powder, a binder, a dispersant, a plasticizer, or the like in water or an organic solvent.
  • a marker paste for producing the above-mentioned marker 70 is produced.
  • a paste for a marker is produced by kneading carbon particles such as carbon black with ceramic particles.
  • the paste for the electrode layer, the paste for the current collector, and the paste for the electrode layer are printed on one main surface of the green sheet in this order.
  • the laminated body 60 is obtained by alternately shifting and laminating the plurality of printed green sheets.
  • a plurality of green sheets for the cover layer 19 are laminated on each of the third surface 60c and the fourth surface 60d of the laminated body 60, and the paste for the marker 70 is printed on the uppermost green sheet. do.
  • the laminated body 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 oxygen partial pressure is preferably 5 ⁇ 10-22 atm or more.
  • a metal paste is applied to each of the surfaces 60a and 60b of the laminated body 60 and baked to form a first external electrode 40a and a second external electrode 40b.
  • the first external electrode 40a and the second external electrode 40b may be formed by a sputtering method or a plating method. From the above, the basic structure of the all-solid-state battery 100 is completed.
  • Example 1 Co 3 O 4 , Li 2 CO 3 , ammonium dihydrogen phosphate, Al 2 O 3 , and GeO 2 are mixed, and a predetermined amount of Co is contained as a solid electrolyte material powder.
  • Li 1.3 Al 0.3 Ge 1.7 ( PO 4 ) 3 was prepared by a solid phase synthesis method. The obtained powder was pulverized to prepare a solid electrolyte slurry. A binder was added to the obtained slurry to obtain a solid electrolyte paste, and a green sheet was prepared.
  • LiCoPO 4 Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 containing a predetermined amount of Co was synthesized by the solid phase synthesis method in the same manner as described above, and wet-mixed and dispersed to prepare a slurry. A binder and Pd paste were added to prepare a paste for an electrode layer.
  • the paste for the electrode layer, the paste for the current collector, and the paste for the electrode layer were each printed to a thickness of 2 ⁇ m by a screen printing method.
  • Five printed green sheets were laminated by shifting the electrodes to the left and right so as to be pulled out, to prepare a laminated body 60. Of the five green sheets, three are green sheets for the positive electrode layer 12, and the remaining two are green sheets for the negative electrode layer 14.
  • a plurality of green sheets were attached as cover layers 19 above and below the laminated body 60. Further, the marker 70 was printed on the green sheet on the uppermost layer. Then, the green sheet was crimped by a hot pressure press, and the laminated body 60 was cut into a predetermined size by a dicer.
  • the cut laminate 60 was heat-treated at 300 ° C. or higher and 500 ° C. or lower to degreas, and then heat-treated at 900 ° C. or lower to be sintered.
  • Example 2 Two of the five green sheets were used as green sheets for the positive electrode layer 12, and the remaining three sheets were used as green sheets for the negative electrode layer 14. Other than this, it is the same as that of the first embodiment.
  • Example 3 Nine green sheets were laminated to prepare a laminated body 60. Three of the nine green sheets were used as green sheets for the positive electrode layer 12, and the remaining six sheets were used as green sheets for the negative electrode layer 14. Further, by laminating two green sheets for each of the six negative electrode layers 14, a structure was obtained in which the two negative electrode layers 14 and the one positive electrode layer 12 were alternately laminated as shown in FIG. .. Other than this, it is the same as that of the first embodiment.
  • a laminated body 60 was produced by laminating four green sheets. Two of the four green sheets were used as green sheets for the positive electrode layer 12, and the remaining two sheets were used as green sheets for the negative electrode layer 14. Other than this, it is the same as that of the first embodiment.
  • the capacities of the all-solid-state batteries were examined for Examples 1 to 3 and Comparative Example 1. Further, when the marker 70 is peeled off, the polarity of the all-solid-state battery is determined by the difference between the number of layers of the positive electrode layer 12 exposed on the first surface 60a and the number of layers of the negative electrode layer 14 exposed on the second surface 60b. I also investigated whether it could be determined. The results are shown in Table 1.
  • the larger of the positive electrode capacity and the negative electrode capacity indicates which of the above-mentioned positive electrode capacity C p and negative electrode capacity C n is larger.
  • the polarity is discriminated based on the difference between the number of layers of the positive electrode layer 12 expressed on the first surface 60a and the number of layers of the negative electrode layer 14 expressed on the second surface 60b. If it can be done, it is marked as " ⁇ ”, and if it cannot be done, it is marked as " ⁇ ".
  • Comparative Example 1 since the number of layers of the positive electrode layer 12 and the negative electrode layer 14 is the same, the “polarity discrimination by appearance” is “x”. Further, in Comparative Example 1, the total number of layers of the positive electrode layer 12 and the negative electrode layer 14 was smaller than that of Examples 1 to 3, so that the capacity was “ ⁇ ”. As a result, the "comprehensive evaluation" of Comparative Example 1 was "x".

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Abstract

Batterie entièrement solide, caractérisée en ce qu'elle comprend : un corps multicouche qui s'obtient par empilement d'une pluralité de couches d'électrode positive contenant chacune un matériau actif d'électrode positive, d'une pluralité de couches d'électrolyte solide et d'une pluralité de couches d'électrode négative contenant chacune un matériau actif d'électrode négative, et qui présente une première surface où une des couches d'électrode positive est exposée et une seconde surface où une des couches d'électrode négative est exposée; une première électrode externe qui est disposée sur la première surface et est connectée à la couche d'électrode positive; et une seconde électrode externe qui est disposée sur la seconde surface et est connectée à la couche d'électrode négative. Cette batterie entièrement solide est également caractérisée en ce que le nombre des couches d'électrode positive est différent du nombre des couches d'électrode négative.　
PCT/JP2021/036177 2020-11-11 2021-09-30 Batterie entièrement solide WO2022102271A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005251632A (ja) * 2004-03-05 2005-09-15 Matsushita Electric Ind Co Ltd チップ型電池
WO2018087970A1 (fr) * 2016-11-08 2018-05-17 株式会社村田製作所 Batterie solide, procédé de fabrication d'une batterie solide, bloc-batterie, véhicule, système de stockage d'électricité, outil électrique et appareil électronique
WO2019176945A1 (fr) * 2018-03-14 2019-09-19 株式会社村田製作所 Batterie et son procédé de fabrication, carte de circuit imprimé, dispositif électronique et véhicule électrique

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005251632A (ja) * 2004-03-05 2005-09-15 Matsushita Electric Ind Co Ltd チップ型電池
WO2018087970A1 (fr) * 2016-11-08 2018-05-17 株式会社村田製作所 Batterie solide, procédé de fabrication d'une batterie solide, bloc-batterie, véhicule, système de stockage d'électricité, outil électrique et appareil électronique
WO2019176945A1 (fr) * 2018-03-14 2019-09-19 株式会社村田製作所 Batterie et son procédé de fabrication, carte de circuit imprimé, dispositif électronique et véhicule électrique

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