WO2025062763A1 - 固体電解質材料、電極および固体電池 - Google Patents

固体電解質材料、電極および固体電池 Download PDF

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WO2025062763A1
WO2025062763A1 PCT/JP2024/021474 JP2024021474W WO2025062763A1 WO 2025062763 A1 WO2025062763 A1 WO 2025062763A1 JP 2024021474 W JP2024021474 W JP 2024021474W WO 2025062763 A1 WO2025062763 A1 WO 2025062763A1
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solid electrolyte
solid
positive electrode
negative electrode
active material
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French (fr)
Japanese (ja)
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裕介 森野
洋樹 三田
大輔 伊藤
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Murata Manufacturing Co Ltd
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Murata Manufacturing Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/10—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances sulfides
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • 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

Definitions

  • the present disclosure relates to a solid electrolyte material, as well as an electrode and a solid-state battery that include the solid electrolyte material.
  • secondary batteries are being developed as a power source that is small, lightweight, and capable of achieving high energy density.
  • These secondary batteries have a positive electrode, a negative electrode, and an electrolyte housed inside an exterior member.
  • Patent Document 1 proposes a sulfide solid electrolyte material that can improve the charge/discharge characteristics of batteries.
  • Patent Document 2 proposes solid electrolyte composite particles made of a solid electrolyte with low grain boundary resistance, excellent ionic conductivity, and high density.
  • a solid electrolyte material includes solid electrolyte particles and a coating portion provided on the surface of the solid electrolyte particles, the coating portion including Li2 +x (OH) 1-xY (0 ⁇ x ⁇ 1) (wherein Y is chlorine, bromine, or iodine).
  • a coating portion is provided on the surface of the solid electrolyte particle, so that the solid electrolyte particle is protected from the outside air and moisture. Therefore, even if the solid electrolyte particle contains sulfide, for example, the generation of hydrogen sulfide can be suppressed. Since the coating portion contains Li 2+x (OH) 1-x Y (0 ⁇ x ⁇ 1) (wherein Y is chlorine, bromine, or iodine), a decrease in ion conductivity can be prevented. Therefore, excellent performance can be achieved.
  • FIG. 1 is a schematic cross-sectional view illustrating an example of a configuration of a solid electrolyte material according to an embodiment of the present disclosure.
  • FIG. 2 is a schematic cross-sectional view showing an example of the configuration of a solid-state battery using the solid electrolyte material shown in FIG.
  • FIG. 3 is a schematic cross-sectional view showing an enlarged portion of the positive electrode active material layer of the solid-state battery shown in FIG.
  • Solid-state battery refers to a battery whose components are solid.
  • the "solid-state battery” in the present disclosure is a laminated solid-state battery in which multiple layers are laminated. The multiple layers are made of, for example, a sintered body.
  • the "solid-state battery” in the present disclosure includes not only secondary batteries that can be repeatedly charged and discharged, but also primary batteries that can only be discharged.
  • solid-state batteries have a solid electrolyte, they generally have better high-temperature resistance and higher safety than batteries using liquid electrolytes. In other words, solid-state batteries do not require the use of flammable solvents contained in liquid electrolytes, so they are less likely to catch fire than batteries using liquid electrolytes. Furthermore, solid-state batteries are expected to have a longer life because the volume expansion of the battery caused by the decomposition of the liquid electrolyte is suppressed.
  • sulfide solid electrolyte materials As a solid electrolyte material that affects the performance of such solid-state batteries, sulfide solid electrolyte materials have attracted attention because they have high ionic conductivity at room temperature and do not require a high-temperature sintering process (i.e., they can be processed at low temperatures). However, sulfide solid electrolyte materials have the potential to react with moisture in the air, for example, to generate hydrogen sulfide.
  • Patent Document 1 proposes a sulfide solid electrolyte material in which an oxide layer containing an oxide of a sulfide material is provided on the surface of the sulfide solid electrolyte particle. That is, Patent Document 1 reports a technology related to a surface treatment in which some of the S (sulfur) atoms on the surface of the sulfide solid electrolyte particle are replaced with O (oxygen) atoms.
  • Patent Document 1 it is considered that the generation of hydrogen sulfide from the sulfide solid electrolyte particle cannot be suppressed completely when the amount of sulfur atoms on the surface of the sulfide solid electrolyte particle replaced with oxygen atoms is small.
  • the amount of sulfur atoms on the surface of the sulfide solid electrolyte particle replaced with oxygen atoms is large, there is a risk that the ion conductivity will decrease due to an increase in oxide on the surface of the sulfide solid electrolyte particle.
  • Patent Document 2 proposes solid electrolyte composite particles in which the surfaces of the base particles are coated with a coating layer.
  • the coating layer include oxo-oxides ( LiNbO3 ) and lithium salts (LiCl, LiBr, LiI, LiOH).
  • LiNbO3 oxo-oxides
  • LiI LiOH
  • the coating layer is an oxo-oxide, it has poor flexibility, and the bonding between the solid electrolyte composite particles is weakened.
  • lithium halides and lithium hydroxide are non-conductors, so the lithium ion conductivity of the coating layer is low. For this reason, it is thought that the ion conductivity at the interface between the solid electrolyte composite particles decreases.
  • FIG. 1 is a cross-sectional schematic diagram showing a schematic configuration example of a solid electrolyte material SE.
  • the solid electrolyte material SE has a solid electrolyte particle 1 and a coating portion 2.
  • the coating portion 2 is provided on the surface of the solid electrolyte particle 1.
  • the solid electrolyte material SE includes a plurality of solid electrolyte particles 1.
  • the coating portion 2 is provided so as to cover the surface of each of the plurality of solid electrolyte particles 1. As shown in FIG.
  • a plurality of coating portions 2 covering adjacent plurality of solid electrolyte particles 1 may be connected to each other and integrated. Note that, for convenience, in FIG. 1, the entire surface of the solid electrolyte particle 1 is described as being covered by the coating portion 2, but a gap or an opening may be provided in a part of the coating portion 2. That is, it is sufficient that the coating portion 2 is provided so as to cover at least a part of the surface of each of the plurality of solid electrolyte particles 1.
  • the solid electrolyte particle 1 is a particle of a solid electrolyte capable of conducting ions such as lithium ions or sodium ions.
  • the solid electrolyte constituting the solid electrolyte particle 1 include lithium-containing phosphate compounds having a Nasicon structure, oxides having a perovskite structure, and oxides having a garnet structure or a garnet-like structure.
  • the lithium-containing phosphate compounds having a Nasicon structure include Li x My (PO 4 ) 3 (1 ⁇ x ⁇ 2, 1 ⁇ y ⁇ 2, M is at least one selected from the group consisting of Ti, Ge, Al, Ga, and Zr).
  • lithium-containing phosphate compounds having a Nasicon structure examples include Li 1.2 Al 0.2 Ti 1.8 (PO 4 ) 3 , etc.
  • oxides having a perovskite structure examples include La 0.55 Li 0.35 TiO 3 , etc.
  • An example of the oxide having garnet type or garnet type similar structure is Li7La3Zr2O12 .
  • the solid electrolyte capable of conducting sodium ions for example, the sodium - containing phosphate compound having Nasicon type structure, the oxide having perovskite type structure, the oxide having garnet type or garnet type similar structure, etc. can be mentioned.
  • NaxMy ( PO4 ) 3 (1 ⁇ x ⁇ 2, 1 ⁇ y ⁇ 2, M is at least one selected from the group consisting of Ti, Ge, Al, Ga and Zr) can be mentioned.
  • the solid electrolyte particle 1 may be a particle of a sulfide solid electrolyte containing a sulfide.
  • the sulfide solid electrolyte constituting the solid electrolyte particle 1 may be a lithium salt Li-M-S containing S (sulfur) (M is, for example, at least one of P (phosphorus), Sn (tin), Ge (germanium), and Si (silicon)).
  • the sulfide solid electrolyte constituting the solid electrolyte particle 1 may be a lithium salt Li-M-S-X further containing a halogen element (M is, for example, at least one of P (phosphorus), Sn (tin), Ge (germanium), and Si (silicon), and X is, for example, at least one of Cl (chlorine), F (fluorine), Br (bromine), and I (iodine)).
  • M is, for example, at least one of P (phosphorus), Sn (tin), Ge (germanium), and Si (silicon
  • X is, for example, at least one of Cl (chlorine), F (fluorine), Br (bromine), and I (iodine)).
  • examples of the sulfide solid electrolyte include Li6PS5Cl , Li6PS5Cl0.5Br0.5 , Li4SnS4 , and Li4.5SnS4I0.5 .
  • the sulfide solid electrolyte may be Li7PS6 having an argyrodite structure, a material obtained by substituting a part of it (such as Li6PS5Cl or Li6PS5Br ), or Li10GeP2S12 having a lithicon structure, or a material obtained by substituting a part of it (such as Li10SiP2S12 or Li9.54Si1.74P1.44S11.7Cl0.3 ) .
  • diffuse reflectance IR spectroscopy or Raman spectroscopy can be performed on the solid electrolyte material SE of this embodiment to detect OH groups contained in the coating portion 2 attached to the surface of the solid electrolyte particle 1.
  • X-ray diffraction XRD
  • composition analysis can be performed on the solid electrolyte particle 1 and the coating portion 2 by energy dispersive X-ray spectroscopy (TEM-EDX).
  • a solid electrolyte particle 1 having a predetermined median diameter is prepared.
  • the solid electrolyte particle 1 includes a solid electrolyte containing Cl (chlorine), Br (bromine), or I (iodine)
  • the solid electrolyte particle 1 is put into an electric furnace, and N2 (nitrogen gas) or Ar (argon gas) with a dew point temperature controlled to -60 to -40°C is passed through for 1 hour, and then the solid electrolyte particle 1 is heated for 1 hour at a temperature of 150°C in an N2 (nitrogen gas) or Ar (argon gas) atmosphere.
  • the solid electrolyte material SE can be manufactured by the following procedure. First, the solid electrolyte particle 1 having a predetermined median size is prepared, and then LiY (wherein Y is Cl (chlorine), Br (bromine), or I (iodine)) is added to the surface of the solid electrolyte particle 1 by performing mechanical milling or solution spraying.
  • the coating portion 2 containing Li 2+x (OH) 1-x Y (wherein Y is Cl (chlorine), Br (bromine), or I (iodine)) is formed on the surface of the solid electrolyte particle 1 by performing the same process as described in the above (1.2.1), and the solid electrolyte material SE of this embodiment is obtained.
  • the solid electrolyte material SE can be manufactured by the following procedure. First, LiY (where Y is Cl (chlorine), Br (bromine), or I (iodine)) is mixed with LiOH to prepare a mixture, and then the mixture is heat-treated to synthesize Li 2+x (OH) 1-x Y. Next, the synthesized Li 2+x (OH) 1-x Y is added to the surface of the solid electrolyte particle 1 by performing mechanical milling or solution spraying.
  • the coating portion 2 is provided on the surface of the solid electrolyte particle 1. Therefore, the solid electrolyte particle 1 is protected from the outside air and moisture, and the environmental resistance of the solid electrolyte particle 1 is improved. Therefore, even if the solid electrolyte particle 1 is made of a sulfide solid electrolyte containing sulfide, for example, the generation of hydrogen sulfide (H2S) due to the reaction between sulfur and hydrogen can be suppressed.
  • H2S hydrogen sulfide
  • the solid electrolyte particle 1 by forming the solid electrolyte particle 1 from a sulfide solid electrolyte, it is possible to manufacture the solid electrolyte material SE at room temperature without using a high-temperature sintering process. Furthermore, high ionic conductivity can be ensured.
  • the coating portion 2 contains Li 2+x (OH) 1-x Y (where Y is chlorine, bromine, or iodine), the decrease in ionic conductivity of the solid electrolyte material due to the provision of the coating portion 2 can be suppressed. Furthermore, since the coating portion 2 contains Li 2+x (OH) 1-x Y (where Y is chlorine, bromine, or iodine), it has excellent flexibility.
  • the solid electrolyte material SE of this embodiment can achieve excellent performance, such as excellent ionic conductivity and excellent processability.
  • the covering portion 2 is provided, so that it is possible to prevent contact between, for example, LCO (lithium cobalt oxide) as a positive electrode material or LTO as a negative electrode material, and the sulfide solid electrolyte constituting the solid electrolyte particle 1, and to avoid decomposition of the sulfide solid electrolyte constituting the solid electrolyte particle 1. Therefore, the solid electrolyte material SE of one embodiment of the present disclosure is suitable as a constituent material for solid batteries.
  • LCO lithium cobalt oxide
  • FIG. 2 is a schematic cross-sectional view showing a typical configuration of the solid-state battery 100.
  • the solid-state battery 100 has a laminated structure in which a positive electrode 10, a solid electrolyte layer 20, and a negative electrode 30 are laminated in this order.
  • the negative electrode 30 has a negative electrode current collector 31 and a negative electrode active material layer 32.
  • the solid-state battery 100 may have a structure in which a unit in which the positive electrode 10, the solid electrolyte layer 20, the negative electrode 30, and the solid electrolyte layer 20 are laminated in this order is regarded as one unit, and a plurality of units are repeatedly laminated.
  • the positive electrode 10 is an electrode layer including at least a positive electrode active material.
  • the positive electrode 10 includes a positive electrode current collector 11 and a positive electrode active material layer 12.
  • the positive electrode collector 11 is, for example, a metal foil.
  • the material of the positive electrode collector 11 may be one metal (single metal) selected from the group consisting of Al (aluminum), Cu (copper), Mg (magnesium), Ti (titanium), Fe (iron), Co (cobalt), Ni (nickel), Zn (zinc), Ge (germanium), In (indium), Au (gold), Pt (platinum), Ag (silver) and Pd (palladium), or an alloy containing two or more metal elements selected from the above group.
  • the positive electrode collector 11 may also be a sintered body. This is to enable the solid-state battery 100 to be formed by integral firing, or to reduce the internal resistance of the positive electrode collector 11.
  • the positive electrode collector 11 may contain a conductive additive and a sintering additive.
  • the shape of the positive electrode collector 11 can be, for example, a plate, a foil, or a mesh.
  • the surface of the positive electrode collector 11 can be smooth or can have projections and recesses.
  • the positive electrode active material layer 12 contains a positive electrode active material as a main component.
  • the positive electrode active material contained in the positive electrode active material layer 12 is a material that is involved in the absorption and release of ions in the solid-state battery 100 and the transfer of electrons to and from an external circuit. Ions move between the positive electrode 10 and the negative electrode 30 via the solid electrolyte (i.e., ion conduction).
  • the absorption and release of ions in the positive electrode active material is accompanied by the oxidation or reduction of the positive electrode active material. Electrons or holes for such an oxidation-reduction reaction are transferred to the positive electrode 10 or the negative electrode 30, thereby allowing charging and discharging to proceed.
  • the positive electrode active material layer 12 is a layer that can absorb and release, for example, lithium ions, sodium ions, protons (H + ), potassium ions (K + ), magnesium ions (Mg 2+ ), aluminum ions (Al 3+ ), silver ions (Ag + ), fluoride ions (F ⁇ ), or chloride ions (Cl ⁇ ).
  • the solid-state battery 100 is an all-solid-state secondary battery in which charging and discharging are performed by the above-mentioned ions moving between the positive electrode 10 and the negative electrode 30 via the solid electrolyte.
  • the positive electrode active material contained in the positive electrode 10 may be at least one selected from the group consisting of a lithium-containing phosphate compound having a Nasicon structure, a lithium-containing phosphate compound having an olivine structure, a lithium-containing layered oxide, and a lithium-containing oxide having a spinel structure.
  • a lithium-containing phosphate compound having a Nasicon structure is Li 3 V 2 (PO 4 ) 3.
  • An example of a lithium-containing phosphate compound having an olivine structure is Li 3 Fe 2 (PO 4 ) 3 , LiFePO 4 , LiMnPO 4 , LiFe 0.6 Mn 0.4 PO 4 , etc.
  • lithium -containing layered oxides examples include LiCoO2 , LiCo1 /3Ni1 / 3Mn1 / 3O2 , LiCo0.8Ni0.15Al0.05O2 , etc.
  • lithium-containing oxides having a spinel structure examples include LiMn2O4 , LiNi0.5Mn1.5O4 , etc.
  • examples of the positive electrode active material capable of absorbing and releasing sodium ions include at least one selected from the group consisting of sodium-containing phosphate compounds having a Nasicon structure, sodium-containing phosphate compounds having an olivine structure, sodium-containing layered oxides, and sodium-containing oxides having a spinel structure.
  • the positive electrode active material layer 12 contains the solid electrolyte material SE described in the first embodiment above.
  • FIG. 2 is a cross-sectional schematic diagram showing the positive electrode active material particles 12P and the solid electrolyte material SE contained in the positive electrode active material layer 12 of the positive electrode 10.
  • the positive electrode active material particles 12P are particles made of the above-mentioned positive electrode active material, and a part of them is in contact with the solid electrolyte material SE. That is, the positive electrode active material particles 12P are in contact with the coating portion 2.
  • a part of the solid electrolyte material SE may be in contact with the positive electrode current collector 11 near the interface between the positive electrode active material layer 12 and the positive electrode current collector 11. There are multiple voids in the solid electrolyte material SE.
  • the solid electrolyte layer 20 includes the solid electrolyte material SE described in the first embodiment.
  • the solid electrolyte material SE is a material that can conduct ions, such as lithium ions, between the positive electrode 10 and the negative electrode 30.
  • the negative electrode 30 is an electrode layer including at least a negative electrode active material.
  • the negative electrode 30 has a negative electrode current collector 31 and a negative electrode active material layer 32.
  • the negative electrode current collector 31 is, for example, a metal foil such as copper foil.
  • the negative electrode current collector 31 may be a sintered body. This is to reduce the internal resistance of the negative electrode current collector 31.
  • the negative electrode current collector 31 may include a conductive assistant and a sintering assistant.
  • the negative electrode active material layer 32 includes a negative electrode active material as a main component. The negative electrode active material will be described in detail later.
  • the negative electrode active material layer 32 may further include the solid electrolyte material SE described in the first embodiment.
  • the negative electrode active material layer 32 has a plurality of negative electrode active material particles made of a negative electrode active material, and a portion of each of the plurality of negative electrode active material particles is in contact with the solid electrolyte material SE.
  • the negative electrode active material contained in the negative electrode 30, like the positive electrode active material contained in the positive electrode 10, is a material that participates in the absorption and release of ions in the solid-state battery 100 and in the transfer of electrons to and from an external circuit. Ions move between the positive electrode 10 and the negative electrode 30 through the solid electrolyte layer 20 (i.e., ion conduction). The absorption and release of ions in the negative electrode active material is accompanied by the oxidation or reduction of the negative electrode active material. Electrons or holes for such an oxidation-reduction reaction are transferred to the positive electrode 10 or the negative electrode 30, so that charging and discharging proceeds.
  • the negative electrode active material can absorb and release, for example, lithium ions, sodium ions, protons (H + ), potassium ions (K + ), magnesium ions (Mg 2+ ), aluminum ions (Al 3+ ), silver ions (Ag + ), fluoride ions (F ⁇ ), or chloride ions (Cl ⁇ ).
  • the negative electrode active material contained in the negative electrode 30 may be, for example, at least one selected from the group consisting of an oxide containing at least one element selected from the group consisting of Ti, Si, Sn, Cr, Fe, Nb, and Mo, a graphite-lithium compound, a lithium alloy, a lithium-containing phosphate compound having a Nasicon structure, a lithium-containing phosphate compound having an olivine structure, and a lithium-containing oxide having a spinel structure.
  • An example of a lithium alloy is Li-Al, etc.
  • An example of a lithium-containing phosphate compound having a Nasicon structure is Li 3 V 2 (PO 4 ) 3 , LiTi 2 (PO 4 ) 3 , etc.
  • An example of a lithium-containing phosphate compound having an olivine structure is Li 3 Fe 2 (PO 4 ) 3 , LiCuPO 4 , etc.
  • An example of a lithium-containing oxide having a spinel structure is Li 4 Ti 5 O 12, etc.
  • the negative electrode active material capable of absorbing and releasing sodium ions may be at least one selected from the group consisting of sodium-containing phosphate compounds having a Nasicon structure, sodium-containing phosphate compounds having an olivine structure, and sodium-containing oxides having a spinel structure.
  • the positive electrode 10 is prepared. Specifically, a plurality of positive electrode active material particles 12P having a predetermined median diameter are prepared. The plurality of positive electrode active material particles 12P may be coated with an ion conductive material such as LiNbO3 using a rolling fluidized coating device. Next, the plurality of positive electrode active material particles 12P and the solid electrolyte material SE are kneaded in a predetermined volume ratio (e.g., 5:5) to prepare a positive electrode active material mixture. Next, a positive electrode current collector 11 is prepared, and the positive electrode active material mixture is applied to the surface of the positive electrode current collector 11, and then pressure-molded using a press to obtain a positive electrode active material layer 12. In this manner, the positive electrode 10 is obtained.
  • a predetermined volume ratio e.g., 5:5
  • the negative electrode 30 is produced. Specifically, a negative electrode active material mixture is produced by kneading a plurality of negative electrode active material particles and a solid electrolyte material SE at a predetermined volume ratio (for example, 5:5). Next, a negative electrode current collector 31 is prepared, and the above-mentioned negative electrode active material mixture is applied to the surface of the negative electrode current collector 31. Thereafter, the negative electrode active material mixture applied to the negative electrode current collector 31 is pressure-molded using a press machine, thereby forming a negative electrode active material layer 32 on the negative electrode current collector 31. In this manner, the negative electrode 30 is obtained.
  • a negative electrode active material mixture is produced by kneading a plurality of negative electrode active material particles and a solid electrolyte material SE at a predetermined volume ratio (for example, 5:5).
  • a negative electrode current collector 31 is prepared, and the above-mentioned negative electrode active material mixture is applied to the surface of the negative electrode current collector 31. Thereafter, the
  • the positive electrode 10, the solid electrolyte layer 20, and the negative electrode 30 are stacked in this order to produce a laminate, which is then compressed using a press to produce the solid-state battery 100.
  • the solid electrolyte material SE described in the first embodiment is used. Therefore, excellent performance can be realized, such as excellent ion conductivity and excellent processability.
  • the coating portion 2 is provided on the surface of the solid electrolyte particle 1, for example, in the positive electrode 10, contact between the positive electrode active material and the solid electrolyte particle 1 can be prevented, and decomposition of the sulfide solid electrolyte constituting the solid electrolyte particle 1 can be avoided. Therefore, the solid-state battery 100 of this embodiment can obtain high reliability.
  • Example 1 As described below, the solid-state battery of the present disclosure shown in FIG. 2 was fabricated, and then the battery characteristics were evaluated.
  • an Al (aluminum) foil having a thickness of 12 ⁇ m was prepared as a positive electrode current collector.
  • LCO lithium cobalt oxide
  • Li 6 PS 5 Cl having a median diameter D50 of 0.3 ⁇ m was put into an electric furnace as a solid electrolyte particle having a predetermined median diameter, and N 2 (nitrogen gas) or Ar (argon gas) with a dew point temperature controlled to ⁇ 60 to ⁇ 40° C. was passed through for 1 hour. After that, the solid electrolyte particles were heated at a temperature of 150° C.
  • the above-mentioned plurality of positive electrode active material particles and the above-mentioned solid electrolyte material were kneaded at a volume ratio of 5:5 to prepare a positive electrode active material mixture.
  • the above-mentioned positive electrode active material mixture was applied to the surface of the positive electrode current collector, and then the positive electrode active material layer was formed by pressure molding at a pressure of 98 MPa using a press machine, thereby obtaining a positive electrode.
  • the thickness of the positive electrode active material layer was set to 60 ⁇ m.
  • a Cu (copper) foil having a thickness of 12 ⁇ m was prepared as the negative electrode current collector.
  • graphite having a median diameter D50 of 12 ⁇ m was prepared as a plurality of negative electrode active material particles.
  • a plurality of negative electrode active material particles and the same solid electrolyte material solid electrolyte material in which the solid electrolyte particles are Li 6 PS 5 Cl and the coating portion is Li 2 OHCl as the solid electrolyte material used in the preparation of the positive electrode were kneaded at a volume ratio of 5:5 to prepare a negative electrode active material mixture.
  • the above-mentioned negative electrode active material mixture was applied to the surface of the negative electrode current collector, and then the negative electrode active material layer was formed by pressure molding at a pressure of 98 MPa using a press machine, thereby obtaining a negative electrode.
  • the thickness of the negative electrode active material layer was set to 55 ⁇ m.
  • a solid electrolyte layer made of the same solid electrolyte material (solid electrolyte material in which the solid electrolyte particles are Li 6 PS 5 Cl and the coating portion is Li 2 OHCl) as the solid electrolyte material used in the preparation of the negative electrode was attached to the negative electrode obtained as described above, and then pressure molding at 98 MPa and pressure molding at 588 MPa were performed in sequence using a press to form a laminate of the negative electrode and the solid electrolyte layer.
  • the battery characteristics of the solid battery of Example 1 were evaluated, and the results shown in Table 1 were obtained.
  • the positive electrode discharge capacity [mAh/g] and the negative electrode discharge capacity [mAh/g] were measured when the solid battery of Example 1 was discharged at a rate of 0.5C under a room temperature environment.
  • 1C is the magnitude of the current calculated by multiplying the mass [g] of the active material introduced as the electrode of the solid battery by the theoretical capacity [mAh/g].
  • the ion conductivity [mS/cm] of the solid battery of Example 1 and the amount of hydrogen sulfide (H 2 S) generated at a humidity of 70% were measured. Note that the details of the test conditions are as follows.
  • the discharge capacity of the solid positive electrode half cell was defined as 1C based on the theoretical capacity of LCO of 150 mAh/g, and the discharge capacity was obtained by charging at 1C to 3.63 V (4.25 V in terms of Li potential vs. Li+/Li) at 0.1C and then discharging at 0.5C to 2.38 V (3.0 V in terms of Li+/Li).
  • Negative electrode The discharge capacity of the solid negative electrode half cell was defined as 1C based on the theoretical capacity of graphite, 372 mAh/g, and was measured by charging at 0.1C to -0.57V (0.05V vs.
  • a humidified air atmosphere at 23° C. and relative humidity of 70% was prepared inside a 2 L container, and 300 mg of each solid electrolyte and a hydrogen sulfide concentration meter were placed inside the container, and the cumulative amount of hydrogen sulfide generated [cc/g] over the course of one hour was recorded.
  • Example 2 As shown in Table 1, a solid-state battery of Example 2 was fabricated in the same manner as in Example 1, except that Li6PS5Cl0.5Br0.5 was used as the solid electrolyte particles and a coating portion made of Li2OH (Cl,Br) was formed. Thereafter, the battery characteristics of the solid-state battery of Example 2 were evaluated in the same manner as in Example 1. The results are also shown in Table 1.
  • Example 3 As shown in Table 1, except that Li4SnS4 was used as the solid electrolyte particles and a coating portion made of Li2OHI was formed, a solid battery of Example 3 was fabricated in the same manner as in Example 1. Thereafter, the battery characteristics of the solid battery of Example 3 were evaluated in the same manner as in Example 1. The results are also shown in Table 1.
  • Example 4 As shown in Table 1, except that Li4.5SnS4I0.5 was used as the solid electrolyte particles and a coating portion made of Li2OHI was formed, a solid battery of Example 4 was fabricated in the same manner as in Example 1. Thereafter, the battery characteristics of the solid battery of Example 4 were evaluated in the same manner as in Example 1. The results are also shown in Table 1.
  • the coating portion can protect the solid electrolyte particles from outside air and moisture without impairing the ion conductivity, and the environmental resistance of the solid electrolyte particles can be improved.
  • both the positive electrode active material layer 12 and the negative electrode active material layer 32 contain the solid electrolyte material SE, but the present disclosure is not limited to this.
  • only one of the positive electrode active material layer 12 or the negative electrode active material layer 32 may contain the solid electrolyte material SE.
  • the present disclosure may take the following forms.
  • Solid electrolyte particles a coating portion provided on a surface of the solid electrolyte particle, the coating portion containing Li 2+x (OH) 1-x Y (0 ⁇ x ⁇ 1) (wherein Y is chlorine, bromine, or iodine); and
  • ⁇ 2> The solid electrolyte material according to ⁇ 1> above, wherein the solid electrolyte particles contain a sulfide.
  • ⁇ 3> The solid electrolyte material according to ⁇ 1> above, wherein the solid electrolyte particles contain Li (lithium) and S (sulfur).
  • ⁇ 4> The solid electrolyte material according to ⁇ 3> above, wherein the solid electrolyte particles further contain a halogen element.
  • ⁇ 5> The solid electrolyte material according to any one of ⁇ 1> to ⁇ 4> above , wherein the solid electrolyte particles contain Li6PS5Cl , Li6PS5Cl0.5Br0.5 , Li4SnS4 , or Li4.5SnS4I0.5 .
  • the median diameter of the solid electrolyte particles is 0.1 ⁇ m or more and 20 ⁇ m or less
  • Solid electrolyte particles a coating portion including Li 2+x (OH) 1-x Y (wherein Y is chlorine, bromine, or iodine) and provided on a surface of the solid electrolyte particle; and an active material in contact with the covering portion.

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PCT/JP2024/021474 2023-09-20 2024-06-13 固体電解質材料、電極および固体電池 Pending WO2025062763A1 (ja)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018003333A1 (ja) * 2016-07-01 2018-01-04 三井金属鉱業株式会社 リチウム二次電池用硫化物系固体電解質
JP2019050182A (ja) * 2017-09-08 2019-03-28 パナソニックＩｐマネジメント株式会社 硫化物固体電解質材料及びそれを用いた電池
JP2020064832A (ja) * 2018-10-19 2020-04-23 三菱瓦斯化学株式会社 固体電解質材料およびその成形体
WO2021033424A1 (ja) * 2019-08-22 2021-02-25 日本特殊陶業株式会社 蓄電デバイス用電極および蓄電デバイス
WO2021124812A1 (ja) * 2019-12-20 2021-06-24 キヤノンオプトロン株式会社 イオン伝導性固体及び全固体電池
JP2023121067A (ja) * 2022-02-18 2023-08-30 三井金属鉱業株式会社 電極合剤、及びそれを用いた電極スラリー並びに電池

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018003333A1 (ja) * 2016-07-01 2018-01-04 三井金属鉱業株式会社 リチウム二次電池用硫化物系固体電解質
JP2019050182A (ja) * 2017-09-08 2019-03-28 パナソニックＩｐマネジメント株式会社 硫化物固体電解質材料及びそれを用いた電池
JP2020064832A (ja) * 2018-10-19 2020-04-23 三菱瓦斯化学株式会社 固体電解質材料およびその成形体
WO2021033424A1 (ja) * 2019-08-22 2021-02-25 日本特殊陶業株式会社 蓄電デバイス用電極および蓄電デバイス
WO2021124812A1 (ja) * 2019-12-20 2021-06-24 キヤノンオプトロン株式会社 イオン伝導性固体及び全固体電池
JP2023121067A (ja) * 2022-02-18 2023-08-30 三井金属鉱業株式会社 電極合剤、及びそれを用いた電極スラリー並びに電池

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