WO2024195744A1 - 固体電解質電池 - Google Patents

固体電解質電池 Download PDF

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Publication number
WO2024195744A1
WO2024195744A1 PCT/JP2024/010367 JP2024010367W WO2024195744A1 WO 2024195744 A1 WO2024195744 A1 WO 2024195744A1 JP 2024010367 W JP2024010367 W JP 2024010367W WO 2024195744 A1 WO2024195744 A1 WO 2024195744A1
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solid electrolyte
negative electrode
molar ratio
less
electrolyte battery
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English (en)
French (fr)
Japanese (ja)
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洋平 野田
雅人 栗原
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TDK Corp
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TDK Corp
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Priority to JP2025508411A priority Critical patent/JPWO2024195744A1/ja
Priority to CN202480018658.7A priority patent/CN120937163A/zh
Publication of WO2024195744A1 publication Critical patent/WO2024195744A1/ja
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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
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • 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 invention relates to a solid electrolyte battery.
  • This application claims priority based on Japanese Patent Application No. 2023-043374, filed on March 17, 2023, the contents of which are incorporated herein by reference.
  • solid electrolytes include oxide-based solid electrolytes, sulfide-based solid electrolytes, complex hydride-based solid electrolytes, and halide-based solid electrolytes.
  • Patent Document 1 discloses a halide-based solid electrolyte containing Li, M, O, X, and A.
  • Patent Document 2 discloses a halide-based solid electrolyte containing a specific compound.
  • Halide-based solid electrolytes are said to have higher ionic conductivity than oxide-based solid electrolytes, sulfide-based solid electrolytes, complex hydride-based solid electrolytes, etc. However, when a halide-based solid electrolyte is used together with a negative electrode with a low potential of 0.8 V or less, the solid electrolyte is reduced, reducing the stability of the solid electrolyte battery.
  • This disclosure has been made in consideration of the above problems, and aims to provide a solid electrolyte battery in which the solid electrolyte is less susceptible to reduction and is highly stable.
  • a solid electrolyte battery includes a positive electrode, a negative electrode, and a solid electrolyte layer sandwiched between the positive electrode and the negative electrode.
  • the solid electrolyte layer includes a solid electrolyte containing Li, Zr, SO x, and one or more halogens.
  • a first region of the solid electrolyte layer in contact with the negative electrode contains P.
  • the solid electrolyte layer has a molar ratio of SO x to Zr of 0.25 to 3.0, a molar ratio of P to Zr of 0.02 to 0.6, and a molar ratio of halogen to Zr of 3.0 to 6.1.
  • the solid electrolyte layer may have a molar ratio of Li to Zr of 1.5 or more and 5.0 or less.
  • the solid electrolyte layer may have a molar ratio of SOx to Zr of 1.0 or more and 3.0 or less.
  • the solid electrolyte layer may have a molar ratio of P to Zr of 0.05 or more and 0.3 or less.
  • the first region may contain a phosphorus compound.
  • the phosphorus compound may include a phosphorus oxide.
  • the solid electrolyte layer may contain lithium oxide powder.
  • the negative electrode may have a negative electrode current collector and a negative electrode active material layer.
  • the negative electrode active material layer is between the negative electrode current collector and the solid electrolyte layer.
  • the negative electrode active material layer contains lithium metal.
  • the negative electrode may have a negative electrode current collector, and lithium metal may be precipitated between the negative electrode current collector and the solid electrolyte layer during charging, and the lithium metal may dissolve during discharging.
  • the negative electrode may have a negative electrode current collector and a negative electrode active material layer.
  • the negative electrode active material layer is between the negative electrode current collector and the solid electrolyte layer.
  • the negative electrode active material layer contains one or more selected from graphite, silicon, tin, and silver.
  • the negative electrode may include the solid electrolyte and P.
  • a molar ratio of SOx to Zr is 0.25 to 3.0
  • a molar ratio of P to Zr is 0.02 to 0.6
  • a molar ratio of halogen to Zr is 3.0 to 6.1.
  • the negative electrode may have a molar ratio of Li to Zr of 1.5 or more and 5.0 or less.
  • the negative electrode may have a molar ratio of SOx to Zr of 1.0 or more and 3.0 or less.
  • the negative electrode may have a molar ratio of P to Zr of 0.05 or more and 0.3 or less.
  • the negative electrode may contain a phosphorus compound.
  • the phosphorus compound may include a phosphorus oxide.
  • the negative electrode may contain lithium oxide powder.
  • the positive electrode may include the solid electrolyte and P.
  • a molar ratio of SOx to Zr is 0.25 to 3.0
  • a molar ratio of P to Zr is 0.02 to 0.6
  • a molar ratio of halogen to Zr is 3.0 to 6.1.
  • the solid electrolyte battery according to the above embodiment the solid electrolyte is not easily reduced and is stable.
  • FIG. 1 is a schematic cross-sectional view of a solid electrolyte battery according to an embodiment of the present invention.
  • FIG. 1 is a schematic cross-sectional view of a solid electrolyte battery 100 according to this embodiment.
  • the solid electrolyte battery 100 shown in FIG. 1 includes a power generating element 40 and an exterior body 50.
  • the exterior body 50 covers the periphery of the power generating element 40.
  • the power generating element 40 is connected to the outside through a pair of terminals 60, 62 connected to the power generating element 40.
  • a stacked type battery is shown in FIG. 1, a wound type battery may also be used.
  • the solid electrolyte battery 100 is used, for example, in a laminate battery, a square battery, a cylindrical battery, a coin battery, a button battery, etc. Although it is a solid battery, an organic component such as a liquid electrolyte may be detected.
  • the power generating element 40 includes a solid electrolyte layer 10, a positive electrode 20, and a negative electrode 30.
  • the power generating element 40 is charged or discharged by the exchange of ions between the positive electrode 20 and the negative electrode 30 via the solid electrolyte layer 10 and the exchange of electrons via an external circuit.
  • the solid electrolyte layer 10 is sandwiched between the positive electrode 20 and the negative electrode 30.
  • the solid electrolyte layer 10 includes a solid electrolyte that can move ions by an externally applied voltage.
  • the solid electrolyte conducts lithium ions and inhibits the movement of electrons.
  • the solid electrolyte layer 10 includes, for example, a solid electrolyte.
  • a solid electrolyte is a substance that can move ions by applying an external electric field. If the ionic conductivity of the solid electrolyte is high, the exchange of ions in the solid electrolyte battery becomes smoother, and the internal resistance becomes smaller.
  • the solid electrolyte may be in the form of a powder (particles) or a sintered body obtained by sintering the powder.
  • the solid electrolyte may also be a compact formed by compressing the powder, a compact formed by molding a mixture of the powder and a binder, or a coating formed by applying a paint containing the powder, a binder, and a solvent, and then heating to remove the solvent.
  • the solid electrolyte layer 10 may contain, in addition to the solid electrolyte, a binder, a compound, etc.
  • the binder may be the same as that used for the positive electrode 20 or the negative electrode 30.
  • the compound is a material originating from the raw material powder, such as Li2SO4 , ZrCl4 , P2O5 , or PCl5 .
  • the solid electrolyte layer 10 includes Li, Zr, SO x , one or more halogens, and P.
  • Li is a lithium ion.
  • Zr is a zirconium ion.
  • SO x is, for example, SO 3 , SO 4 , SO 5 , SO 3/2 , SO 2 , SO 5/2 , and SO 7/2 .
  • 1 mol of S 2 O 3 is counted as 2 mol of SO 1.5 .
  • the halogen is at least one ion selected from the group consisting of F, Cl, Br, and I.
  • P is a phosphorus ion.
  • the solid electrolyte layer 10 contains Li, Zr, SO x , one or more halogens, and P as main elements.
  • the main elements are the main elements confirmed in the composition analysis, excluding elements mixed as impurities.
  • the main elements are elements that are clearly detected in the composition analysis.
  • the composition analysis is performed, for example, by surface analysis using an electron probe microanalyzer (EPMA).
  • the composition analysis may be performed, for example, by energy dispersive X-ray spectroscopy (SEM-EDS) using a transmission electron microscope or inductively coupled plasma mass spectrometry (ICP-MS).
  • the main elements are, for example, elements that are responsible for the crystal structure of the solid electrolyte.
  • the molar fractions of Li, Zr, SO x , one or more halogens, and P are 90% or more of the total number of moles of the solid electrolyte layer 10.
  • Li, Zr, SO x , and one or more halogens are, for example, one of the constituent elements constituting the solid electrolyte.
  • the solid electrolyte may be crystalline or amorphous.
  • Li, Zr, SO x , and one or more halogens may be included as compounds originating from raw materials other than the solid electrolyte.
  • the solid electrolyte layer 10 may include a composition mainly composed of Li, S, and O as a different phase other than the solid electrolyte.
  • the composition mainly composed of Li, S, and O is, for example, Li 2 SO 4.
  • the composition mainly composed of Li, S, and O and the solid electrolyte may have, for example, an island-like relationship.
  • the composition mainly composed of Li, S, and O may be scattered in the solid electrolyte layer 10.
  • the solid electrolyte layer 10 may also include, for example, lithium oxide powder.
  • the content of the lithium oxide powder in solid electrolyte layer 10 may be, relative to the total mass of solid electrolyte layer 10, 0.1 mass % or more and 20 mass % or less, 1 mass % or more and 15 mass % or less, or 2 mass % or more and 12 mass % or less.
  • P may be included as one of the constituent elements of the solid electrolyte, or may be included as a phosphorus compound different from the solid electrolyte.
  • the phosphorus compound is, for example , a phosphorus oxide.
  • the phosphorus oxide is, for example, P2O5 .
  • the molar ratio of P to Zr may be 0.05 or more and 1.0 or less, 0.07 or more and 0.8 or less, or 0.1 or more and 0.6 or less.
  • the molar ratio of SO x to Zr is 0.25 or more and 3.0 or less, preferably 1.0 or more and 3.0 or less.
  • the molar ratio is determined, for example, by surface analysis using an electron probe microanalyzer (EPMA).
  • EPMA electron probe microanalyzer
  • Zr is an element that forms the framework of the solid electrolyte and defines the molar ratio of SO x to Zr. If the solid electrolyte layer 10 contains sulfate ions, the potential window on the reduction side of the solid electrolyte layer 10 becomes wider, so the molar ratio of SO x to Zr is preferably 0.25 or more, more preferably 1.0 or more.
  • the molar ratio of P to Zr is 0.02 or more and 0.6 or less, and preferably 0.05 or more and 0.3 or less.
  • the molar ratio is determined, for example, by surface analysis using an electron probe microanalyzer (EPMA).
  • EPMA electron probe microanalyzer
  • the molar ratio of halogen to Zr is 3.0 or more and 6.1 or less, and preferably 4.0 or more and 5.0 or less.
  • the molar ratio is determined, for example, by surface analysis using an electron probe microanalyzer (EPMA).
  • EPMA electron probe microanalyzer
  • the halogen is F
  • the solid electrolyte has sufficiently high ionic conductivity and excellent oxidation resistance.
  • the halogen is Cl
  • the solid electrolyte has high ionic conductivity and a good balance of oxidation resistance and reduction resistance.
  • the halogen is Br
  • the solid electrolyte has sufficiently high ionic conductivity and a good balance of oxidation resistance and reduction resistance.
  • the halogen is I
  • the solid electrolyte has high ionic conductivity.
  • the molar ratio of Li to Zr is 0.6 to 6.0, and preferably 1.5 to 5.0.
  • the Li content in the compound is within this range, the ionic conductivity of the solid electrolyte layer 10 is high.
  • the molar ratios of Zr, SO x , halogens, and Li in the solid electrolyte layer 10 are the molar ratios of these elements contained in the entire solid electrolyte layer 10.
  • area analysis such as EPMA
  • five surfaces at different positions in the thickness direction of the solid electrolyte layer 10 are area analyzed, and an average of these is determined.
  • the solid electrolyte layer 10 is divided into five equal parts in the thickness direction, and each of the 20 ⁇ m square regions that overlap as viewed from the thickness direction is used as the area analysis region.
  • the solid electrolyte contained in the solid electrolyte layer 10 is, for example, a halide-based solid electrolyte represented by Li a Zr(SO x ) b X c ... (1).
  • Formula (1) satisfies 0.6 ⁇ a ⁇ 6.0, 0.25 ⁇ b ⁇ 3.0, 3.0 ⁇ c ⁇ 6.1, and 0 ⁇ x ⁇ 4.0.
  • a is preferably 1.2 ⁇ a ⁇ 6.0, and more preferably 1.5 ⁇ a ⁇ 5.0.
  • b is preferably 1.0 ⁇ b ⁇ 3.0.
  • the solid electrolyte contained in the solid electrolyte layer 10 may be a compound represented by formula (1) in which a part of the compound is substituted with phosphorus.
  • the positive electrode 20 has a plate-shaped (foil-shaped) positive electrode collector 22 and a positive electrode active material layer 24.
  • the positive electrode active material layer 24 is in contact with at least one surface of the positive electrode collector 22.
  • the positive electrode collector 22 may be made of any electronically conductive material that is resistant to oxidation during charging and is not easily corroded.
  • the positive electrode collector 22 may be made of, for example, a metal such as aluminum, stainless steel, nickel, or titanium, or a conductive resin.
  • the positive electrode collector 22 may be in the form of a powder, foil, punching, or expanded material.
  • the positive electrode active material layer 24 contains a positive electrode active material, and optionally a solid electrolyte, a binder, and a conductive additive.
  • the positive electrode active material is not particularly limited as long as it is capable of reversibly absorbing and releasing lithium ions and inserting and removing them (intercalation and deintercalation), and any positive electrode active material used in known solid electrolyte batteries can be used.
  • positive electrode active materials include lithium-containing metal oxides and lithium-containing metal phosphates.
  • LiCoO2 lithium cobalt oxide
  • LiNiO2 lithium nickel oxide
  • LiMn2O4 lithium manganese spinel
  • composite metal oxides represented by the general formula LiNixCoyMnzO2 (x + y+ z 1 )
  • LiVOPO4 lithium vanadium compounds
  • Li3V2 ( PO4 ) 3 olivine-type LiMPO4 (wherein M represents at least
  • the positive electrode active material may not contain lithium.
  • positive electrode active materials include non-lithium-containing metal oxides (MnO 2 , V 2 O 5 , etc.), non-lithium-containing metal sulfides (MoS 2 , etc.), and non-lithium-containing fluorides (FeF 3 , VF 3 , etc.).
  • the negative electrode is doped with lithium ions in advance, or a negative electrode containing lithium ions is used.
  • the solid electrolyte contained in the positive electrode 20 is, for example, the same as the solid electrolyte contained in the solid electrolyte layer 10. If the solid electrolyte contained in the solid electrolyte layer 10, the positive electrode 20, and the negative electrode 30 is the same, the solid electrolyte battery 100 can be easily manufactured.
  • the solid electrolyte contained in the positive electrode 20 may be different from the solid electrolyte contained in the solid electrolyte layer 10, for example.
  • the positive electrode 20 may include, for example, Li, Zr, SO x , one or more halogens, and P.
  • the positive electrode 20 may include, for example, a solid electrolyte including Li, Zr, SO x , one or more halogens, and P.
  • P may be included as one of the constituent elements constituting the solid electrolyte, or may be included as another phosphorus compound different from the solid electrolyte.
  • the phosphorus compound is, for example, a phosphorus oxide.
  • the phosphorus oxide is, for example, P 2 O 5.
  • the positive electrode 20 may include, for example, lithium oxide powder.
  • the molar ratio of SO x to Zr is, for example, 0.25 to 3.0, preferably 1.0 to 3.0.
  • the molar ratio of P to Zr is, for example, 0.02 to 0.6, preferably 0.05 to 0.3.
  • the molar ratio of halogen to Zr is, for example, 3.0 to 6.1, preferably 4.0 to 5.0.
  • the molar ratio of Li to Zr is, for example, 0.6 to 6.0, preferably 1.5 to 5.0.
  • the content of the solid electrolyte in the positive electrode active material layer 24 is not particularly limited, but is preferably 1% by mass to 50% by mass, and more preferably 5% by mass to 30% by mass, based on the total mass of the positive electrode active material, solid electrolyte, conductive additive, and binder.
  • the binder bonds the positive electrode active material, the solid electrolyte, and the conductive additive to each other in the positive electrode active material layer 24, and also firmly bonds the positive electrode active material layer 24 to the positive electrode current collector 22.
  • the positive electrode active material layer 24 preferably contains a binder.
  • the binder preferably has oxidation resistance and good adhesiveness.
  • Binders used in the positive electrode active material layer 24 include polyvinylidene fluoride (PVDF) or copolymers thereof, polytetrafluoroethylene (PTFE), polyamide (PA), polyimide (PI), polyamideimide (PAI), polybenzimidazole (PBI), polyethersulfone (PES), polyacrylic acid (PA) and copolymers thereof, metal ion crosslinked products of polyacrylic acid (PA) and copolymers thereof, polypropylene (PP) grafted with maleic anhydride, polyethylene (PE) grafted with maleic anhydride, or mixtures thereof.
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • PA polyamide
  • PI polyimide
  • PAI polyamideimide
  • PBI polybenzimidazole
  • PES polyethersulfone
  • PA polyacrylic acid
  • PA metal ion crosslinked products of polyacrylic acid (PA) and copolymers
  • the binder content in the positive electrode active material layer 24 is not particularly limited, but is preferably 0.3% to 10% by mass, and more preferably 0.3% to 5% by mass, based on the total mass of the positive electrode active material, solid electrolyte, conductive additive, and binder. If the amount of binder is too small, it tends not to be possible to form a positive electrode 20 with sufficient adhesive strength. Conversely, if the amount of binder is too large, it tends to be difficult to obtain sufficient volume or mass energy density, as typical binders are electrochemically inactive and do not contribute to the discharge capacity.
  • the conductive additive improves the electronic conductivity of the positive electrode active material layer 24.
  • Known conductive additives can be used.
  • the conductive additive include carbon materials such as carbon black, graphite, carbon nanotubes, and graphene; metals such as aluminum, copper, nickel, stainless steel, iron, and amorphous metals; conductive oxides such as ITO; and mixtures of these.
  • the conductive additive may be in the form of a powder or fiber.
  • the content of the conductive additive in the positive electrode active material layer 24 is not particularly limited.
  • the mass ratio of the conductive additive is preferably 0.5% by mass to 20% by mass, and more preferably 1% by mass to 5% by mass, based on the total mass of the positive electrode active material, solid electrolyte, conductive additive, and binder.
  • the negative electrode 30 has a negative electrode current collector 32 and a negative electrode active material layer 34.
  • the negative electrode active material layer 34 is in contact with the negative electrode current collector 32.
  • the negative electrode active material layer 34 is between the negative electrode current collector 32 and the solid electrolyte layer 10.
  • the negative electrode current collector 32 may have electronic conductivity.
  • the negative electrode current collector 32 may be, for example, a metal such as copper, aluminum, nickel, stainless steel, or iron, or a conductive resin.
  • the negative electrode current collector 32 may be in the form of a powder, foil, punching, or expanded.
  • the negative electrode active material layer 34 contains a negative electrode active material, and optionally a solid electrolyte, a binder, and a conductive additive.
  • the negative electrode active material is not particularly limited as long as it can reversibly absorb and release lithium ions, and insert and detach lithium ions.
  • the negative electrode active material can be any negative electrode active material used in known solid electrolyte batteries.
  • the negative electrode active material layer 34 may contain, for example, lithium metal as the negative electrode active material, or may contain one or more selected from graphite, silicon, tin, and silver. In addition, graphite, silicon, tin, and silver may be pre-alloyed.
  • the content of one or more selected from graphite, silicon, tin, and silver in the negative electrode active material layer 34 may be 20 mass% or more and 100 mass% or less, 30 mass% or more and 100 mass% or less, or 50 mass% or more and 85 mass% or less, based on the total mass of the negative electrode active material layer 34.
  • the negative electrode 30 may also have only the negative electrode current collector 32, with lithium metal being precipitated between the negative electrode current collector 32 and the solid electrolyte layer 10 during charging, and the lithium metal dissolving during discharging.
  • the solid electrolyte contained in the negative electrode 30 is, for example, the solid electrolyte described above.
  • the solid electrolyte contained in the positive electrode 20 may be, for example, different from the solid electrolyte contained in the solid electrolyte layer 10.
  • the negative electrode 30 may contain, for example, Li, Zr, SO x , one or more halogens, and P.
  • the negative electrode 30 may contain, for example, a solid electrolyte containing Li, Zr, SO x , one or more halogens, and P.
  • P may be contained as one of the constituent elements constituting the solid electrolyte, or may be contained as another phosphorus compound different from the solid electrolyte.
  • the phosphorus compound is, for example, a phosphorus oxide.
  • the phosphorus oxide is, for example, P 2 O 5.
  • the negative electrode 30 may contain, for example, lithium oxide powder.
  • the content of the lithium oxide powder in the negative electrode 30 may be 0.2 mass% or more and 10 mass% or less, 0.5 mass% or more and 8.0 mass% or less, or 1.0 mass% or more and 5.0 mass% or less, relative to the total mass of the negative electrode 30.
  • the molar ratio of SO x to Zr is, for example, 0.25 to 3.0, preferably 1.0 to 3.0.
  • the molar ratio of P to Zr is, for example, 0.02 to 0.6, preferably 0.05 to 0.3.
  • the molar ratio of halogen to Zr is, for example, 3.0 to 6.1, preferably 4.0 to 5.0.
  • the molar ratio of Li to Zr is, for example, 0.6 to 6.0, preferably 1.5 to 5.0.
  • the binder and conductive additive contained in the negative electrode 30 are the same as the binder and conductive additive contained in the positive electrode 20.
  • the exterior body 50 houses the power generating element 40 therein.
  • the exterior body 50 prevents moisture and the like from entering from the outside to the inside.
  • the exterior body 50 has a metal foil 52 and a resin layer 54 laminated on each side of the metal foil 52.
  • the exterior body 50 is a metal laminate film in which the metal foil 52 is coated with the resin layer 54 from both sides.
  • the metal foil 52 is, for example, an aluminum foil or a stainless steel foil.
  • the resin layer 54 can be, for example, a resin film such as polypropylene.
  • the materials constituting the resin layer 54 may be different on the inside and outside.
  • the outside material can be a polymer with a high melting point, such as polyethylene terephthalate (PET) or polyamide (PA), and the inside material can be polyethylene (PE) or polypropylene (PP).
  • the terminals 60 and 62 are connected to the negative electrode 30 and the positive electrode 20, respectively.
  • the terminal 62 connected to the positive electrode 20 is a positive electrode terminal
  • the terminal 60 connected to the negative electrode 30 is a negative electrode terminal.
  • the terminals 60 and 62 are responsible for electrical connection to the outside.
  • the terminals 60 and 62 are made of a conductive material such as aluminum, nickel, or copper.
  • the connection method may be welding or screwing.
  • the terminals 60 and 62 are preferably protected with insulating tape to prevent short circuits.
  • the solid electrolyte of this embodiment is prepared by the first method or the second method.
  • the first method is a method in which Li2SO4 and ZrCl4 are reacted to synthesize the solid electrolyte , and then a phosphorus compound is added to synthesize the solid electrolyte.
  • the second method is a method in which Li2SO4 , ZrCl4, and a phosphorus compound are simultaneously synthesized.
  • the first method will be specifically described. First, the raw materials Li2SO4 and ZrCl4 are mixed in a predetermined molar ratio and charged into a synthesis pot.
  • the first synthesis product and a phosphorus compound are mixed in a predetermined molar ratio and charged into a synthesis pot.
  • the phosphorus compound is, for example, P 2 O 5 or PCl 5.
  • the mixture mixed in the predetermined molar ratio is synthesized using a mechanochemical method.
  • the mechanochemical reaction at this time is carried out, for example, for 30 minutes under conditions of a rotation speed of 300 rpm.
  • the second synthesis product after the reaction is taken out from the synthesis pot. This second synthesis product becomes a solid electrolyte.
  • the second method will be specifically described.
  • the raw materials Li2SO4 , ZrCl4, and a phosphorus compound are mixed in a predetermined molar ratio and charged into a synthesis pot .
  • the phosphorus compound is, for example, P2O5 or PCl5 .
  • the mixture mixed in a specified molar ratio is synthesized using a mechanochemical method.
  • the mechanochemical reaction is carried out for 7 hours, for example, at a rotation speed of 300 rpm.
  • the compound after the reaction is then removed from the synthesis pot. This compound becomes the solid electrolyte.
  • Solid electrolytes can be produced by either the first or second method.
  • the phosphorus compound added as a raw material is more likely to remain intact in the solid electrolyte layer 10 than when produced by the second method.
  • the positive electrode is manufactured by applying a paste containing a positive electrode active material onto a positive electrode current collector 22 and drying it to form a positive electrode active material layer 24.
  • the above-mentioned solid electrolyte may be added to the paste containing the positive electrode active material.
  • the negative electrode 30 is prepared.
  • the negative electrode is manufactured by applying a paste containing a negative electrode active material onto the negative electrode current collector 32 and drying it to form a negative electrode active material layer 34.
  • the above-mentioned solid electrolyte may be added to the paste containing the negative electrode active material.
  • the power generating element 40 can be produced, for example, by using a powder molding method.
  • a guide with a hole is placed on top of the positive electrode 20, and the guide is filled with a solid electrolyte.
  • the surface of the solid electrolyte is then smoothed, and the negative electrode 30 is placed on top of the solid electrolyte. This results in the solid electrolyte being sandwiched between the positive electrode 20 and the negative electrode 30.
  • Pressure is then applied to the positive electrode 20 and the negative electrode 30 to pressure mold the solid electrolyte.
  • pressure molding a laminate is obtained in which the positive electrode 20, solid electrolyte layer 10, and negative electrode 30 are stacked in this order.
  • the solid electrolyte battery 100 contains a predetermined amount of P in the first region where the solid electrolyte layer 10 contacts the negative electrode 30.
  • the solid electrolyte layer 10 becomes difficult to reduce, and the stability of the solid electrolyte layer 10 itself with respect to the negative electrode 30 increases. Therefore, the solid electrolyte layer 10 becomes stable even without inserting a buffer layer containing a compound stable with respect to Li between the solid electrolyte layer 10 and the negative electrode 30.
  • Example 1 A solid electrolyte was produced using the first method. First, in a glove box with a dew point of about -75°C, lithium sulfate (Li 2 SO 4 ) and zirconium chloride (ZrCl 4 ) were weighed out as raw material powders so that the molar ratio was 1:1. Next, the raw material powder was charged into a zirconia sealed container for a planetary ball mill, which had zirconia balls of 5 mm ⁇ in advance. Next, the sealed container was covered with a lid, the lid was screwed onto the container body, and the gap between the lid and the container was sealed with polyimide tape. The polyimide tape has the effect of blocking moisture.
  • Li 2 SO 4 lithium sulfate
  • ZrCl 4 zirconium chloride
  • the zirconia sealed container was set in a planetary ball mill.
  • the rotation speed was set to 300 rpm
  • the revolution speed was set to 300 rpm
  • the rotation direction and the revolution direction were set in the opposite directions, and a mechanochemical reaction was carried out for 7 hours to produce a first synthesis product.
  • P2O5 was added to the first synthesis product.
  • the molar ratio of P2O5 to lithium sulfate was 0.07.
  • the rotation speed was 300 rpm
  • the revolution speed was 300 rpm
  • the rotation direction and the revolution direction were reversed to each other, and a mechanochemical reaction was carried out for 30 minutes to produce a solid electrolyte.
  • the solid electrolyte thus prepared was subjected to a composition analysis by surface analysis using an electron probe microanalyzer (EPMA).
  • EPMA electron probe microanalyzer
  • the molar ratio of Li to Zr in the solid electrolyte was 2.0, the molar ratio of SO4 to Zr was 1.0, the molar ratio of P to Zr was 0.14, and the molar ratio of Cl to Zr was 4.0.
  • P2O5 was also confirmed in the solid electrolyte.
  • the pressure molding die consists of a 10 mm diameter cylinder made of PEEK (polyether ether ketone), and upper and lower punches made of SKD11 material with a diameter of 9.99 mm.
  • PEEK polyether ether ketone
  • a stainless steel disk and a Teflon (registered trademark) disk both 50 mm in diameter and 5 mm thick and with four screw holes, were prepared, and the pressure molding die was set up as follows: Stainless steel disk / Teflon (registered trademark) disk / pressure molding die / Teflon (registered trademark) disk / stainless steel disk.
  • the four screws were tightened with a torque of approximately 3 N ⁇ m. Screws were also inserted into the screw holes on the sides of the upper and lower punches to serve as external connection terminals.
  • the external connection terminal was connected to a potentiostat (VersaSTAT3 manufactured by Princeton Applied Research) equipped with a frequency response analyzer, and the ionic conductivity was measured using the impedance measurement method. Measurements were performed at a measurement frequency range of 1 MHz to 0.1 Hz, an amplitude of 10 mV, and a temperature of 25°C.
  • the ionic conductivity of the solid electrolyte of Example 1 was 0.50 mS/cm.
  • the Li symmetric cell was charged and discharged in a temperature environment of 25°C.
  • the charge and discharge rates were 0.1C (the current value at which charging or discharging ends in 10 hours when charging or discharging at a constant current of 1 mA is performed at 25°C), and a charge and discharge test was performed at 100 cycles per hour.
  • the maximum voltage of the Li symmetric cell after 100 hours was then measured.
  • the voltage of the Li symmetric cell of Example 1 after 100 hours was 17.7mV.
  • Example 2 differs from Example 1 in that the phosphorus compound was changed from P 2 O 5 to PCl 5.
  • Example 2 was similar to Example 1 in that the ionic conductivity and the voltage after 100 hours were measured.
  • the composition of the prepared solid electrolyte was analyzed by surface analysis using an electron probe microanalyzer (EPMA).
  • EPMA electron probe microanalyzer
  • the molar ratio of Li to Zr in the solid electrolyte was 2.0, the molar ratio of SO4 to Zr was 1.0, the molar ratio of P to Zr was 0.07, and the molar ratio of Cl to Zr was 4.35.
  • PCl5 was also confirmed in the solid electrolyte.
  • Example 3 differs from Example 1 in that the solid electrolyte was prepared by the second method.
  • Example 3 was similar to Example 1 in that the ionic conductivity and the voltage after 100 hours were measured.
  • raw material powders of zirconium chloride (ZrCl 4 ), lithium sulfate (Li 2 SO 4 ), and diphosphorus pentoxide (P 2 O 5 ) were weighed out so that the molar ratio was 1:1:0.07.
  • the raw material powder was put into a zirconia sealed container for a planetary ball mill, which had zirconia balls of 5 mm diameter in advance.
  • the sealed container was covered with a lid, the lid was screwed onto the container body, and the gap between the lid and the container was sealed with polyimide tape.
  • the polyimide tape has the effect of blocking moisture.
  • the zirconia sealed container was set in the planetary ball mill.
  • the rotation speed was set to 300 rpm
  • the revolution speed was set to 300 rpm
  • the rotation direction and the revolution direction were set in the opposite directions, and a mechanochemical reaction was carried out for 7 hours to produce a solid electrolyte.
  • Example 4 to 7 differ from Example 3 in that the molar ratio of diphosphorus pentoxide (P 2 O 5 ) was changed when preparing the solid electrolyte. In Examples 4 to 7, the ionic conductivity and the voltage after 100 hours were measured in the same manner as in Example 1.
  • Example 8 to 11 Examples 8 to 11 differ from Example 3 in that the molar ratio of lithium sulfate (Li 2 SO 4 ) was changed when preparing the solid electrolyte. In Examples 8 to 11, the ionic conductivity and the voltage after 100 hours were measured in the same manner as in Example 1.
  • Example 12 and 13 are different from Example 3 in that LiCl was further added when preparing the solid electrolyte.
  • Example 12 raw material powders of zirconium chloride (ZrCl 4 ), lithium sulfate (Li 2 SO 4 ), diphosphorus pentoxide (P 2 O 5 ), and lithium chloride (LiCl) were weighed out so that the molar ratio was 1:0.6:0.07:1.0.
  • Example 13 raw material powders of zirconium chloride (ZrCl 4 ), lithium sulfate (Li 2 SO 4 ), diphosphorus pentoxide (P 2 O 5 ), and lithium chloride (LiCl) were weighed out so that the molar ratio was 1:0.25:0.07:1.0.
  • the ion conductivity and the voltage after 100 hours were measured in the same manner as in Example 1.
  • Example 14 differs from Example 1 in that lithium oxide powder was added after the solid electrolyte was synthesized. Specifically, zirconium chloride ( ZrCl4 ), lithium sulfate ( Li2SO4 ), and diphosphorus pentoxide ( P2O5 ) were mechanochemically reacted for 7 hours based on the second method, and then lithium oxide powder was added and mixed for about 10 minutes using a planetary ball mill. Hereinafter, this method is referred to as the third method. Then, in Example 14 , the ionic conductivity and the voltage after 100 hours were measured in the same manner as in Example 1.
  • ZrCl4 zirconium chloride
  • Li2SO4 lithium sulfate
  • P2O5 diphosphorus pentoxide
  • Comparative Example 1 differs from Example 3 in that diphosphorus pentoxide was not added to the raw material. In Comparative Example 1, the ionic conductivity and the voltage after 100 hours were measured in the same manner as in Example 1.
  • Comparative Examples 2 to 4" Comparative Examples 2 to 4 differ from Example 3 in that the molar ratio of diphosphorus pentoxide (P 2 O 5 ) was changed when preparing the solid electrolyte. In Comparative Examples 2 to 4, the ionic conductivity and the voltage after 100 hours were measured in the same manner as in Example 1.
  • Comparative Examples 5 and 6 are different from Example 3 in that lithium sulfate (Li 2 SO 4 ) was replaced with lithium oxide (Li 2 O) when preparing the solid electrolyte, and the molar ratio of the raw materials was changed.
  • Comparative Example 5 raw material powders were weighed so that zirconium chloride (ZrCl 4 ), lithium oxide (Li 2 O), and diphosphorus pentoxide (P 2 O 5 ) were in a molar ratio of 1:1:0.1, respectively.
  • Comparative Example 6 raw material powders were weighed so that zirconium chloride (ZrCl 4 ), lithium oxide (Li 2 O), and diphosphorus pentoxide (P 2 O 5 ) were in a molar ratio of 1:1:0.3, respectively.
  • ZrCl 4 zirconium chloride
  • Li 2 O lithium oxide
  • P 2 O 5 diphosphorus pentoxide
  • Comparative Examples 7 and 8 are different from Example 3 in that the raw materials and the molar ratio of the raw materials when preparing the solid electrolyte were changed.
  • Comparative Example 7 raw material powders of zirconium chloride (ZrCl 4 ) and lithium oxide (Li 2 O) were weighed out so that the molar ratio was 1:1.
  • Comparative Example 8 raw material powders of zirconium chloride (ZrCl 4 ) and lithium phosphate (Li 3 PO 4 ) were weighed out so that the molar ratio was 1:1.
  • the ionic conductivity and the voltage after 100 hours were measured in the same manner as in Example 1.
  • Example 15 In Example 15, a full cell was prepared in a glove box with a dew point of about -70°C. The full cell was prepared using a pellet preparation jig.
  • the pellet preparation jig had a PEEK (polyether ether ketone) holder with an inner diameter of 10 mm, and an upper punch and a lower punch with a diameter of 9.99 mm.
  • the material of the upper and lower punches was die steel (SKD11 material).
  • a lower punch was inserted into the PEEK holder of the pellet making jig, and 50 mg of solid electrolyte was placed on top of the lower punch.
  • the solid electrolyte used was the solid electrolyte from Example 1.
  • an upper punch was inserted on top of the solid electrolyte, and pressed for 1 minute with a press machine under a load of 0.6 tons.
  • the negative electrode mixture contained graphite, the solid electrolyte of Example 1, and a conductive additive.
  • the graphite was the negative electrode active material.
  • the positive electrode mixture contains LiCoO2 , a halide -based solid electrolyte consisting of Li2ZrCl6 (LZC), and a conductive assistant.
  • a solid electrolyte battery was produced in which the negative electrode mixture layer, solid electrolyte layer, and positive electrode mixture layer were laminated in this order using the above procedure.
  • the initial efficiency of the produced solid electrolyte battery was then measured.
  • the initial efficiency was measured using a charge/discharge tester (manufactured by Hokuto Denko Corporation) in a thermostatic chamber (manufactured by Espec Corporation) at 25°C, where the battery was charged at a constant current of 0.1 C rate until it reached 4.2 V, and then discharged at a constant current of 0.1 C rate.
  • Examples 16 to 27 differ from Example 15 in that the solid electrolyte contained in the negative electrode mixture was changed. The other conditions were the same as in Example 15, and the initial efficiency of the solid electrolyte battery was measured.
  • Example 28 differs from Example 15 in that the solid electrolyte contained in the positive electrode mixture was the solid electrolyte of Example 1. The other conditions were the same as in Example 15, and the initial efficiency of the solid electrolyte battery was measured.
  • Example 29 and 30 Examples 29 and 30 differ from Example 17 in that the negative electrode active material contained in the negative electrode mixture was changed. The other conditions were the same as in Example 17, and the initial efficiency of the solid electrolyte battery was measured.
  • Example 31 differs from Example 15 in that the negative electrode mixture contained only metallic Li. The other conditions were the same as in Example 15, and the initial efficiency of the solid electrolyte battery was measured.
  • Example 32 differs from Example 15 in that no negative electrode mixture was provided. The initial efficiency of the solid electrolyte battery was measured under the same conditions as Example 15. In Example 32, metallic lithium was precipitated between the Cu foil and the solid electrolyte layer during charging, and the metallic lithium was dissolved during discharging.
  • Comparative Examples 9 to 15 differ from Example 15 in that the solid electrolyte of the solid electrolyte layer and the solid electrolyte contained in the negative electrode mixture were changed. The other conditions were the same as in Example 15, and the initial efficiency of the solid electrolyte battery was measured.
  • Comparative Examples 16 to 18 Comparative Examples 16 to 18 differ from Comparative Example 9 in that the negative electrode active material was changed. The other conditions were the same as in Comparative Example 9, and the initial efficiency of the solid electrolyte battery was measured.
  • Comparative Examples 19 and 20 differ from Comparative Example 18 in that the solid electrolyte of the solid electrolyte layer was changed. The other conditions were the same as in Comparative Example 18, and the initial efficiency of the solid electrolyte battery was measured.
  • Comparative Example 21 differs from Comparative Example 9 in that no negative electrode mixture was provided. The initial efficiency of the solid electrolyte battery was measured under the same conditions as Comparative Example 9. In Comparative Example 21, metallic lithium was precipitated between the Cu foil and the solid electrolyte layer during charging, and the metallic lithium was dissolved during discharging.
  • Table 3 summarizes the manufacturing conditions of the solid electrolyte contained in the negative electrode active material
  • Table 5 summarizes the evaluation results of the solid electrolyte contained in the negative electrode active material.
  • Examples 35 to 55 solid electrolytes were prepared under the production conditions summarized in the following Table 6.
  • the ionic conductivity and voltage after 100 hours of the solid electrolytes of Examples 35 to 55 were measured in the same manner as in Example 1, and the results are summarized in Table 7.
  • Examples 56 to 81 solid electrolyte batteries were produced under the production conditions summarized in the following Tables 8 to 10. Furthermore, the initial efficiency of the solid electrolyte batteries of Examples 56 to 81 was measured in the same manner as in Example 15, and the results are summarized in Table 8. In addition, Table 9 summarizes the production conditions of the solid electrolyte contained in the negative electrode active material, and Table 10 summarizes the evaluation results of the solid electrolyte contained in the negative electrode active material.

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WO2020184718A1 (ja) * 2019-03-13 2020-09-17 Tdk株式会社 全固体二次電池
WO2022186211A1 (ja) * 2021-03-01 2022-09-09 Tdk株式会社 電池及び電池の製造方法
WO2023171825A1 (ja) * 2022-03-11 2023-09-14 Tdk株式会社 固体電解質、固体電解質層及び固体電解質電池

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* Cited by examiner, † Cited by third party
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WO2020184718A1 (ja) * 2019-03-13 2020-09-17 Tdk株式会社 全固体二次電池
WO2022186211A1 (ja) * 2021-03-01 2022-09-09 Tdk株式会社 電池及び電池の製造方法
WO2023171825A1 (ja) * 2022-03-11 2023-09-14 Tdk株式会社 固体電解質、固体電解質層及び固体電解質電池

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