WO2022201755A1 - Électrolyte solide, batterie tout solide, procédé de fabrication d'électrolyte solide, et procédé de fabrication de batterie tout solide - Google Patents

Électrolyte solide, batterie tout solide, procédé de fabrication d'électrolyte solide, et procédé de fabrication de batterie tout solide Download PDF

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WO2022201755A1
WO2022201755A1 PCT/JP2022/000842 JP2022000842W WO2022201755A1 WO 2022201755 A1 WO2022201755 A1 WO 2022201755A1 JP 2022000842 W JP2022000842 W JP 2022000842W WO 2022201755 A1 WO2022201755 A1 WO 2022201755A1
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solid electrolyte
solid
electrode
mol
state battery
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PCT/JP2022/000842
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English (en)
Japanese (ja)
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織茂洋子
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太陽誘電株式会社
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/447—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on phosphates, e.g. hydroxyapatite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • 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

Definitions

  • the present invention relates to a solid electrolyte, an all-solid battery, a method for producing a solid electrolyte, and a method for producing an all-solid battery.
  • oxide-based solid electrolyte that is stable in the atmosphere rather than a sulfide-based solid electrolyte that generates toxic gas even when exposed to the atmosphere.
  • oxide-based solid electrolytes are required to be sintered at a high temperature in order to develop ionic conduction and form a good interface with the electrode active material. In high-temperature sintering, interdiffusion reaction between the solid electrolyte and the electrode active material poses a problem.
  • a Li--La--Zr--O-based compound having a garnet-type structure or an element-substituted product thereof, a Li--Al--Ti--P--O system having a NASICON-type crystal structure, or a Li--Al--Ge-- PO-based compounds, Li-La-Ti-O-based compounds having a perovskite crystal structure, and the like are known.
  • Li-Ta-P-O-based compounds have also been reported, but all of them require heat treatment (firing) at relatively high temperatures, and there is concern about interdiffusion reactions when forming interfaces with electrode active materials. .
  • Patent Document 1 an oxide crystal is used as a first lithium ion conductor and mixed with a second lithium ion conductor, which is a glass material that can be sintered at 600 ° C. or lower, to obtain a lithium ion conductor of 600 ° C. or lower. High lithium ion conductivity is obtained at the sintering temperature of .
  • Patent Document 1 it is proposed that a solid electrolyte having high lithium ion conductivity can be obtained by heat-treating a first lithium ion conductor and a second lithium ion conductor at 600° C. or lower.
  • the heat treatment is performed at a relatively low temperature of 600° C. or less, and if it is desired to further densify the electrolyte layer and the solid electrolyte layer or reduce the interfacial resistance between both layers, heat treatment at a higher temperature is required. Therefore, the reaction due to the diffusion of both components is a matter of concern.
  • interdiffusion reaction of lithium is particularly likely to occur, and there are concerns about changes in the crystal structure of the solid electrolyte with high crystallinity and high ion conductivity and a decrease in ion conductivity.
  • the present invention has been made in view of the above problems, and an object of the present invention is to provide a solid electrolyte that exhibits high ion conductivity and that can be fired at a low temperature, an all-solid battery, a method for producing a solid electrolyte, and a method for producing an all-solid battery.
  • the solid electrolyte according to the present invention is an oxide-type solid electrolyte containing Li, Ta, and P, the ratio of Li content to 1 mol of P is 0.5 mol or more and 0.95 mol or less, and the result of XRD measurement It is characterized by being confirmed to have a crystal structure belonging to a monoclinic system.
  • the Ta/P molar ratio may be 1.7 or more and 2.3 or less.
  • An all-solid-state battery according to the present invention includes any one of the solid electrolytes according to the present invention as a first solid electrolyte, and a lithium-containing material having a sintering initiation temperature lower than that of the first solid electrolyte as a second solid electrolyte.
  • a first electrode including a solid electrolyte layer and an electrode active material and formed on a first main surface of the solid electrolyte layer; and a first electrode including an electrode active material and facing the first main surface of the solid electrolyte layer. and second electrodes formed on the two main surfaces.
  • a plurality of units may be stacked, with the solid electrolyte layer, the first electrode, and the second electrode forming one unit.
  • one of the first electrode and the second electrode may contain a positive electrode active material, and the other may contain a negative electrode active material.
  • the average crystal grain size of the first solid electrolyte in the solid electrolyte layer may be 1 ⁇ m or more and 20 ⁇ m or less.
  • the lithium-containing material includes Li—Ge—P—O based compounds, Li—Zr—P—O based compounds, Li—P—O based compounds, Li—B—O based compounds, Li— Si—O based compound, Li—Ge—Zr—P—O based compound, Li—Si—B—O based compound, Li—Al—Ge—P—O based compound, Li—La—Zr—P—O based It may be at least one of compounds and Li--Al--P--O based compounds.
  • a solid electrolyte according to the present invention from a raw material containing Li, Ta, and P, and having a Li content of 0.5 mol or more and 0.95 mol or less per 1 mol of P, at a temperature of 950 ° C. or more and 1300 ° C. or less, It is characterized by synthesizing an oxide-type solid electrolyte that is confirmed to have a crystal structure attributed to a monoclinic crystal by XRD measurement results.
  • the method for producing an all-solid-state battery according to the present invention contains Li, Ta, and P, the Li content relative to 1 mol of P is 0.5 mol or more and 0.95 mol or less, and the result of XRD measurement is that it is a monoclinic crystal.
  • a powder of a lithium-containing material having a sintering start temperature lower than that of the first solid electrolyte powder is used as a second solid electrolyte powder.
  • the firing temperature in the firing step may be 500°C or higher and 900°C or lower.
  • the present invention it is possible to provide a solid electrolyte that exhibits high ion conductivity and that can be fired at a low temperature, an all-solid battery, a method for producing a solid electrolyte, and a method for producing an all-solid battery.
  • FIG. 1 is a schematic cross-sectional view of an all-solid-state battery according to an embodiment
  • FIG. 4 is a schematic cross-sectional view of another all-solid-state battery
  • It is a figure which illustrates the flow of the manufacturing method of an all-solid-state battery.
  • It is a figure which illustrates a lamination process.
  • FIG. 10 is a diagram illustrating the flow of another method for manufacturing an all-solid-state battery;
  • FIG. 1(a) is a schematic cross-sectional view showing the basic structure of an all-solid-state battery 100.
  • the all-solid battery 100 has a structure in which a solid electrolyte layer 30 is sandwiched between a first electrode 10 and a second electrode 20 .
  • the first electrode 10 is formed on the first main surface of the solid electrolyte layer 30 and has a structure in which the first electrode layer 11 and the first current collector layer 12 are laminated.
  • a first electrode layer 11 is provided.
  • the second electrode 20 is formed on the second main surface of the solid electrolyte layer 30, has a structure in which a second electrode layer 21 and a second current collector layer 22 are laminated, and is provided on the solid electrolyte layer 30 side. A second electrode layer 21 is provided.
  • one of the first electrode 10 and the second electrode 20 is used as a positive electrode, and the other is used as a negative electrode.
  • the first electrode 10 is used as a positive electrode
  • the second electrode 20 is used as a negative electrode.
  • the solid electrolyte layer 30 is mainly composed of a solid electrolyte having ionic conductivity. As illustrated in FIG. 1B, the solid electrolyte of the solid electrolyte layer 30 has a structure in which a plurality of first solid electrolyte particles 31 and a plurality of second solid electrolyte particles 32 are mixed.
  • the first solid electrolyte particles 31 are oxide crystals containing Li, Ta, and P, such as Li--Ta--P--O compounds.
  • XRD X-ray diffraction
  • the first solid electrolyte particles 31 are confirmed to have a monoclinic crystal structure.
  • the first solid electrolyte particles 31 are LiTa 2 PO 8 based compounds.
  • the second solid electrolyte particles 32 are a lithium-containing material and have a sintering initiation temperature lower than that of the first solid electrolyte particles 31 .
  • the first solid electrolyte particles 31 have a Li-poor structure instead of having a Li:Ta:P molar ratio of 1:2:1. That is, in the first solid electrolyte particles 31, the ratio of the Li content to 1 mol of P is less than 1 mol. Since the first solid electrolyte particles 31 have the Li-poor structure, the monoclinic crystal structure is easily stabilized. Therefore, even if it is mixed with a lithium-containing material that can be sintered at a low temperature and fired, the reaction between the two components is suppressed, and a heterogeneous phase that can become a high-resistance component is less likely to be formed at the interface between the two, resulting in high ionic conductivity. As described above, the solid electrolyte layer 30 exhibits high ion conductivity and can be fired at a low temperature.
  • the ratio of the Li content to 1 mol of P is 0.5 mol or more, preferably 0.6 or more, and more preferably 0.7 or more.
  • the ratio of the Li content to 1 mol of P in the first solid electrolyte particles 31 is 0.95 or less, preferably 0.9 or less, and more preferably 0.8 or less.
  • the Ta/P molar ratio is preferably 1.7 or more, more preferably 1.8 or more, and even more preferably 1.9 or more.
  • the Ta/P molar ratio is preferably 2.3 or less, more preferably 2.2 or less, and even more preferably 2.1 or less.
  • the average crystal grain size of the first solid electrolyte particles 31 is small, the densification of the solid electrolyte layer is hindered, and the filling rate of the first solid electrolyte cannot be increased. It may not be possible to fully demonstrate it. Therefore, it is preferable to set a lower limit for the average crystal grain size of the first solid electrolyte particles 31 .
  • the average crystal grain size of the first solid electrolyte particles 31 is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, and even more preferably 3 ⁇ m or more.
  • the average crystal grain size of the first solid electrolyte particles 31 is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, and even more preferably 7 ⁇ m or less.
  • the average crystal grain size of the first solid electrolyte particles 31 is, for example, the horizontal or vertical Ferret diameter of 50 first solid electrolyte particles 31 specified by EDS mapping in the cross section of the solid electrolyte layer 30. It can be measured by measuring the length and calculating the average value.
  • the ratio of the first solid electrolyte particles 31 in the solid electrolyte layer 30 is high, it may become difficult to bake the solid electrolyte layer 30 at a sufficiently low temperature. Therefore, it is preferable to set an upper limit for the ratio of the first solid electrolyte particles 31 in the solid electrolyte layer 30 .
  • the area ratio of the first solid electrolyte particles 31 is preferably 70% or less, more preferably 60% or less, and even more preferably 50% or less.
  • the ratio of the second solid electrolyte particles 32 in the solid electrolyte layer 30 is high, there is a risk that sufficiently high ion conduction cannot be obtained. Therefore, it is preferable to set an upper limit for the ratio of the second solid electrolyte particles 32 in the solid electrolyte layer 30 .
  • the area ratio of the second solid electrolyte particles 32 is preferably 80% or less, more preferably 70% or less, and 60% or less. More preferred.
  • the area ratio between the first solid electrolyte particles 31 and the second solid electrolyte particles 32 is preferably 20:80 to 70:30, more preferably 30:70 to 60:40. is more preferred, and 40:60 to 50:50 is even more preferred.
  • the area ratio between the first solid electrolyte particles 31 and the second solid electrolyte particles 32 in the cross section of the solid electrolyte layer 30 can be measured, for example, by observing the cross section with an SEM and performing EDS elemental mapping analysis.
  • the second solid electrolyte particles 32 are not particularly limited as long as they contain lithium and have a sintering start temperature lower than that of the first solid electrolyte particles 31 .
  • the second solid electrolyte particles 32 are Li—Ge—P—O based compounds, Li—Zr—P—O based compounds, Li—P—O based compounds, Li—BO based compounds, Li—Si—
  • One or a plurality of O-based compounds may be used, or these elements may be combined, and these may contain Al, Y, La, and the like.
  • Li—Ge—Zr—P—O based compounds Li—Si—B—O based compounds, Li—Al—Ge—P—O based compounds, Li—La—Zr—P—O based compounds, Li—Al A —PO-based compound or the like may be used.
  • Li--Al--Ge--P--O compounds are preferably used as the second solid electrolyte particles 32 from the viewpoint of ion conductivity.
  • the thickness of the solid electrolyte layer 30 is, for example, in the range of 2 ⁇ m to 25 ⁇ m, in the range of 4 ⁇ m to 20 ⁇ m, and in the range of 6 ⁇ m to 15 ⁇ m.
  • the positive electrode active material of the first electrode 10 is not particularly limited. 7 ) 4 etc. are mentioned.
  • the negative electrode active material of the second electrode 20 prior art in secondary batteries can be referred to as appropriate. compounds such as
  • a solid electrolyte having ionic conductivity, a conductive material (conductive aid) such as carbon or metal, and the like are further added.
  • a conductive material such as carbon or metal, and the like.
  • an electrode layer paste can be obtained by uniformly dispersing a binder and a plasticizer in water or an organic solvent.
  • the metal of the conductive aid include Pd, Ni, Cu, Fe, and alloys containing these.
  • the first current collector layer 12 and the second current collector layer 22 are mainly composed of a conductive material.
  • a conductive material for example, metal, carbon, or the like can be used as the conductive material of the first current collector layer 12 and the second current collector layer 22 .
  • FIG. 2 is a schematic cross-sectional view of a stacked all-solid-state battery 100a in which a plurality of battery units are stacked.
  • the all-solid-state battery 100a includes a laminated chip 60 having a substantially rectangular parallelepiped shape.
  • the first external electrode 40a and the second external electrode 40b are provided so as to be in contact with two side surfaces of the four surfaces other than the top surface and the bottom surface of the stacking direction end.
  • the two side surfaces may be two adjacent side surfaces or two side surfaces facing each other.
  • the first external electrode 40a and the second external electrode 40b are provided so as to be in contact with two side surfaces (hereinafter referred to as two end surfaces) facing each other.
  • a plurality of first collector layers 12 and a plurality of second collector layers 22 are alternately laminated. Edges of the plurality of first current collector layers 12 are exposed on the first end face of the laminated chip 60 and are not exposed on the second end face. Edges of the plurality of second current collector layers 22 are exposed on the second end surface of the laminated chip 60 and are not exposed on the first end surface. Thereby, the first current collector layer 12 and the second current collector layer 22 are alternately connected to the first external electrode 40a and the second external electrode 40b.
  • a first electrode layer 11 is laminated on the first collector layer 12 .
  • a solid electrolyte layer 30 is laminated on the first electrode layer 11 .
  • the solid electrolyte layer 30 extends from the first external electrode 40a to the second external electrode 40b.
  • a second electrode layer 21 is laminated on the solid electrolyte layer 30 .
  • a second collector layer 22 is laminated on the second electrode layer 21 .
  • Another second electrode layer 21 is laminated on the second collector layer 22 .
  • Another solid electrolyte layer 30 is laminated on the second electrode layer 21 .
  • the solid electrolyte layer 30 extends from the first external electrode 40a to the second external electrode 40b.
  • a first electrode layer 11 is laminated on the solid electrolyte layer 30 .
  • the first current collector layer 12 and the two first electrode layers 11 sandwiching it are regarded as one electrode
  • the second current collector layer 22 and the two second electrode layers 21 sandwiching it are regarded as one electrode.
  • the laminated chip 60 can be said to have a structure in which a plurality of internal electrodes and a plurality of solid electrolyte layers are alternately laminated.
  • the all-solid-state battery 100a does not have to have a collector layer.
  • the first current collector layer 12 and the second current collector layer 22 may not be provided.
  • only the first electrode layer 11 constitutes the first electrode 10
  • only the second electrode layer 21 constitutes the second electrode 20 .
  • FIG. 4 is a diagram illustrating the flow of the method for manufacturing the all-solid-state battery 100a.
  • powder of the solid electrolyte that constitutes the solid electrolyte layer 30 is prepared.
  • the raw material powder of the first solid electrolyte particles 31 is synthesized, for example, by a solid-phase synthesis method.
  • Li 3 PO 4 , Ta 2 O 5 and NH 4 H 2 PO 4 are mixed in a molar ratio of 0.4:1.4:1 and heat-treated at about 900° C. in air.
  • LiOH.H 2 O is added to the reactant so that Li is in excess and mixed, and the main heat treatment is performed at 950 ° C. to 1300 ° C. to obtain an XRD measurement.
  • a Li--Ta--P--O-based compound is synthesized so that the results confirm that it has a crystal structure belonging to the monoclinic system.
  • the ratio of Li content to 1 mol of P in the synthesized Li--Ta--P--O compound is set to 0.50 mol or more and 0.95 mol or less.
  • the Li--Ta--P--O compound is pulverized to a desired particle size with a wet ball mill.
  • a vitreous precursor which is a lithium-containing material and has a sintering initiation temperature lower than that of the first solid electrolyte particles 31 is obtained by a conventional melting and quenching method.
  • a conventional melting and quenching method Li 2 CO 3 , Al 2 O 3 , GeO 2 and P 2 O 5 as raw materials are mixed to form a glass melt at 1400° C., and the glass is produced by casting, and the desired particles are obtained by a dry ball mill. Grind to diameter.
  • Solid electrolyte 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.
  • 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 solid electrolyte green sheet By applying the obtained solid electrolyte paste, a solid electrolyte green sheet can be produced.
  • the coating method is not particularly limited, and a slot die method, a reverse coating method, a gravure coating method, a bar coating method, a doctor blade method, or the like can be used.
  • the particle size distribution after wet pulverization can be measured, for example, using a laser diffraction measurement device using a laser diffraction scattering method.
  • an internal electrode paste for producing the above-described first electrode layer 11 and second electrode layer 21 is produced.
  • an internal electrode paste can be obtained by uniformly dispersing a conductive aid, an electrode active material, a solid electrolyte material, a binder, a plasticizer, and the like in water or an organic solvent.
  • the solid electrolyte material the solid electrolyte paste described above may be used.
  • Pd, Ni, Cu, Fe, alloys containing these, various carbon materials, and the like may further be used as conductive aids.
  • each internal electrode paste may be prepared separately.
  • a current collector paste for manufacturing the above-described first current collector layer 12 and second current collector layer 22 is prepared.
  • a current collector paste can be obtained by uniformly dispersing Pd powder, carbon black, plate-like graphite carbon, a binder, a dispersant, a plasticizer, and the like in water or an organic solvent.
  • an external electrode paste for producing the first external electrode 40a and the second external electrode 40b is prepared.
  • an external electrode paste can be obtained by uniformly dispersing a conductive material, an electrode active material, a solid electrolyte, a binder, a plasticizer, and the like in water or an organic solvent.
  • a laminate process As illustrated in FIG. 5A, on one surface of a solid electrolyte green sheet 51, an internal electrode paste 52, a current collector paste 53, and an internal electrode paste 52 are printed.
  • a reverse pattern 54 is printed on a region of the solid electrolyte green sheet 51 where the internal electrode paste 52 and the current collector paste 53 are not printed. As the reverse pattern 54, the same one as the solid electrolyte green sheet 51 can be used.
  • a laminate is obtained by stacking a plurality of solid electrolyte green sheets 51 alternately after printing, and crimping a cover sheet 55 in which a plurality of solid electrolyte green sheets are bonded together from above and below in the stacking direction.
  • a substantially rectangular parallelepiped laminate is obtained so that pairs of the internal electrode paste 52 and the current collector paste 53 are alternately exposed on the two end surfaces of the laminate.
  • an external electrode paste 56 is applied to each of the two end faces by a dipping method or the like and dried. Thereby, a molding for forming the all-solid-state battery 100a is obtained.
  • the firing conditions include, without particular limitation, an oxidizing atmosphere or a non-oxidizing atmosphere and a maximum temperature of preferably 500°C to 900°C, more preferably 600°C to 800°C.
  • a step of holding below the maximum temperature in an oxidizing atmosphere may be provided to sufficiently remove the binder until the maximum temperature is reached.
  • reoxidation treatment may be performed.
  • the step of applying the current collector paste 53 in the step of FIG. 5(a) may be omitted.
  • FIG. 6 is a flowchart illustrating the manufacturing method in this case.
  • the external electrode paste 56 is not applied in the stacking process, and the external electrode paste 56 is applied to the two end faces of the laminated chip 60 obtained in the firing process and baked. Thereby, the first external electrode 40a and the second external electrode 40b can be formed.
  • Li-poor powder is used as the raw material powder synthesized for the first solid electrolyte particles 31 .
  • the monoclinic crystal structure is easily stabilized. Therefore, even if it is mixed with a lithium-containing material that can be sintered at a low temperature and fired, the reaction between the two components is suppressed, and a heterogeneous phase that can become a high-resistance component is less likely to be formed at the interface between the two, resulting in high ionic conductivity.
  • the solid electrolyte layer 30 exhibiting high ionic conductivity can be fired at a low temperature.
  • a Li—Ta—P—O compound and a Li—Al—Ge—P—O glass precursor having a non-stoichiometric composition were ground and mixed in a weight ratio of 30:70. It was pelletized with a uniaxial press so as to have a thickness of 0.5 mm, and fired at a top temperature of 650°C.
  • the ion conductivity of the sintered body was 6.0 ⁇ 10 ⁇ 5 S/cm.
  • the cross section was observed by SEM, and EDS elemental mapping analysis was performed, the area ratio of the Li—Ta—P—O compound and the Li—Al—Ge—P—O compound was approximately It was 20:80. No reaction product was observed at the particle interface between these compounds.
  • a Li—Ta—P—O compound and a Li—Al—Ge—P—O glass precursor having a non-stoichiometric composition were ground and mixed in a weight ratio of 30:70. It was pelletized with a uniaxial press so as to have a thickness of 0.5 mm, and fired at a top temperature of 650°C.
  • the ion conductivity of the sintered body was 8.0 ⁇ 10 ⁇ 5 S/cm.
  • the cross section was observed by SEM, and EDS elemental mapping analysis was performed, the area ratio of the Li—Ta—P—O compound and the Li—Al—Ge—P—O compound was approximately It was 20:80. No reaction product was observed at the particle interface between these compounds.
  • Example 3 a crystalline Li--Ta--P--O compound was synthesized and pulverized in the same manner as in Example 1.
  • a Li—Ta—P—O compound and a Li—Al—Ge—P—O glass precursor having a non-stoichiometric composition were ground and mixed in a weight ratio of 30:70. It was pelletized with a uniaxial press so as to have a thickness of 0.5 mm, and fired at a top temperature of 650°C.
  • the ion conductivity of the sintered body was 2.0 ⁇ 10 ⁇ 5 S/cm.
  • the cross section was observed by SEM, and EDS elemental mapping analysis was performed, the area ratio of LiTa 2 PO 8 and the Li—Al—Ge—P—O compound was approximately 20:80. rice field. No reaction product was observed at the particle interface between these compounds.
  • a Li—Ta—P—O compound and a Li—Al—Ge—P—O glass precursor having a non-stoichiometric composition were ground and mixed in a weight ratio of 30:70. It was pelletized with a uniaxial press so as to have a thickness of 0.5 mm, and fired at a top temperature of 650°C.
  • the ion conductivity of the sintered body was 8.5 ⁇ 10 ⁇ 5 S/cm.
  • the cross section was observed by SEM, and EDS elemental mapping analysis was performed, the area ratio of LiTa 2 PO 8 and the Li—Al—Ge—P—O compound was approximately 20:80. rice field. No reaction product was observed at the particle interface between these compounds.
  • Example 5 a crystalline Li--Ta--P--O compound was synthesized and pulverized in the same manner as in Example 4.
  • a Li—Ta—P—O compound and a Li—Al—Ge—P—O glass precursor having a non-stoichiometric composition were ground and mixed in a weight ratio of 30:70. It was pelletized with a uniaxial press so as to have a thickness of 0.5 mm, and fired at a top temperature of 650°C.
  • the ion conductivity of the sintered body was 5.3 ⁇ 10 ⁇ 5 S/cm.
  • the cross section was observed by SEM, and EDS elemental mapping analysis was performed, the area ratio of LiTa 2 PO 8 and the Li—Al—Ge—P—O compound was approximately 20:80. rice field. No reaction product was observed at the particle interface between these compounds.
  • a Li—Ta—P—O compound and a Li—Al—Ge—P—O glass precursor having a non-stoichiometric composition were ground and mixed in a weight ratio of 30:70. It was pelletized with a uniaxial press so as to have a thickness of 0.5 mm, and fired at a top temperature of 650°C.
  • the ion conductivity of the sintered body was 9.1 ⁇ 10 ⁇ 5 S/cm.
  • the cross section was observed by SEM, and EDS elemental mapping analysis was performed, the area ratio of LiTa 2 PO 8 and the Li—Al—Ge—P—O compound was approximately 20:80. rice field. No reaction product was observed at the particle interface between these compounds.
  • Example 7 a crystalline Li--Ta--P--O compound was synthesized and pulverized in the same manner as in Example 1.
  • Li--Ta--P--O compound and the non-stoichiometric Li--Al--Ge--P--O-based glassy precursor material are ground and mixed in a weight ratio of 30:70, 2 wt % of Li 3 PO 4 was added to the Li—Al—Ge—P—O based glassy precursor (LAGP-g).
  • LAGP-g Li—Al—Ge—P—O based glassy precursor
  • the ion conductivity of the sintered body was 9.2 ⁇ 10 ⁇ 5 S/cm.
  • the cross section was observed by SEM, and EDS elemental mapping analysis was performed, the area ratio of LiTa 2 PO 8 and the Li—Al—Ge—P—O compound was approximately 20:80. rice field. No reaction product was observed at the particle interface between these compounds.
  • a Li—Ta—P—O compound and a Li—Al—Ge—P—O glass precursor having a non-stoichiometric composition were ground and mixed in a weight ratio of 30:70. It was pelletized with a uniaxial press so as to have a thickness of 0.5 mm, and fired at a top temperature of 650°C.
  • the ionic conductivity of the sintered body was 5.0 ⁇ 10 ⁇ 6 S/cm.
  • the cross section was observed by SEM, and EDS elemental mapping analysis was performed, the area ratio of LiTa 2 PO 8 and the Li—Al—Ge—P—O compound was approximately 20:80. rice field. A reaction product was formed at the particle interface between these compounds.
  • a Li—Ta—P—O compound and a Li—Al—Ge—P—O glass precursor having a non-stoichiometric composition were ground and mixed in a weight ratio of 30:70. It was pelletized with a uniaxial press so as to have a thickness of 0.5 mm, and fired at a top temperature of 650°C.
  • the ionic conductivity of the sintered body was 8.0 ⁇ 10 ⁇ 6 S/cm.
  • the cross section was observed by SEM, and EDS elemental mapping analysis was performed, the area ratio of LiTa 2 PO 8 and the Li—Al—Ge—P—O compound was approximately 20:80. rice field. A reaction product was formed at the particle interface between these compounds.
  • Table 1 shows the results of Examples 1 to 7 and Comparative Examples 1 and 2.

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Abstract

Cet électrolyte solide est un électrolyte solide de type oxyde contenant Li, Ta, et P, et est caractérisé en ce que : le rapport de la teneur en Li à 1 mole de P est de 0,5 à 0,95 mole, inclus; et, un résultat de mesure XRD confirme la présence d'une structure cristalline appartenant à un cristal monoclinique.　
PCT/JP2022/000842 2021-03-26 2022-01-13 Électrolyte solide, batterie tout solide, procédé de fabrication d'électrolyte solide, et procédé de fabrication de batterie tout solide WO2022201755A1 (fr)

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WO2023243327A1 (fr) * 2022-06-15 2023-12-21 国立研究開発法人産業技術総合研究所 Corps fritté d'oxyde et procédé de production d'un corps fritté d'oxyde

Citations (3)

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Publication number Priority date Publication date Assignee Title
WO2016157751A1 (fr) * 2015-03-31 2016-10-06 ソニー株式会社 Conducteur au lithium-ion, couche d'électrolyte solide, électrode, batterie et dispositif électronique
JP2020140963A (ja) * 2019-02-22 2020-09-03 Tdk株式会社 固体電解質、並びに全固体二次電池及びその製造方法
JP2020194773A (ja) * 2019-05-24 2020-12-03 三星電子株式会社Ｓａｍｓｕｎｇ Ｅｌｅｃｔｒｏｎｉｃｓ Ｃｏ．，Ｌｔｄ． 固体伝導体、その製造方法、それを含む固体電解質、及び電気化学素子

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Publication number Priority date Publication date Assignee Title
WO2016157751A1 (fr) * 2015-03-31 2016-10-06 ソニー株式会社 Conducteur au lithium-ion, couche d'électrolyte solide, électrode, batterie et dispositif électronique
JP2020140963A (ja) * 2019-02-22 2020-09-03 Tdk株式会社 固体電解質、並びに全固体二次電池及びその製造方法
JP2020194773A (ja) * 2019-05-24 2020-12-03 三星電子株式会社Ｓａｍｓｕｎｇ Ｅｌｅｃｔｒｏｎｉｃｓ Ｃｏ．，Ｌｔｄ． 固体伝導体、その製造方法、それを含む固体電解質、及び電気化学素子

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023243327A1 (fr) * 2022-06-15 2023-12-21 国立研究開発法人産業技術総合研究所 Corps fritté d'oxyde et procédé de production d'un corps fritté d'oxyde

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