WO2024204182A1 - 電極及び全固体電池 - Google Patents

電極及び全固体電池 Download PDF

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Publication number
WO2024204182A1
WO2024204182A1 PCT/JP2024/011923 JP2024011923W WO2024204182A1 WO 2024204182 A1 WO2024204182 A1 WO 2024204182A1 JP 2024011923 W JP2024011923 W JP 2024011923W WO 2024204182 A1 WO2024204182 A1 WO 2024204182A1
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Prior art keywords
solid electrolyte
positive electrode
peak intensity
compound
summarized
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French (fr)
Japanese (ja)
Inventor
太輔 堀川
雅人 栗原
長 鈴木
寛子 坂元
米田　真弓
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TDK Corp
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TDK Corp
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Priority to JP2025510918A priority Critical patent/JPWO2024204182A1/ja
Priority to EP24780294.5A priority patent/EP4693510A1/en
Priority to CN202480021552.2A priority patent/CN121002678A/zh
Publication of WO2024204182A1 publication Critical patent/WO2024204182A1/ja
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • 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 an electrode and an all-solid-state battery. This application claims priority based on Japanese Patent Application No. 2023-058719, filed on March 31, 2023, the contents of which are incorporated herein by reference.
  • all-solid-state batteries have been attracting attention from the perspective of improving safety and increasing output.
  • One of the features of all-solid-state batteries is the use of a solid electrolyte.
  • the properties required of a solid electrolyte include ionic conductivity, redox resistance, and formability.
  • One of the challenges is to improve ionic conductivity compared to conventional organic electrolytes. In general, most solid electrolytes have lower conductivity compared to organic electrolytes.
  • Patent Document 1 discloses a solid electrolyte represented by the following composition formula (1) (wherein 0 ⁇ z ⁇ 2 is satisfied and X is Cl or Br). Li 6-3z Y z X 6 ...Formula (1)
  • Patent Document 2 discloses a solid electrolyte made of a compound represented by the following formula (2): (wherein A is at least one element selected from the group consisting of Li, Cs, and Ca, and X is at least one element selected from the group consisting of F, Cl, Br, and I). AaEbGcXd...(2)
  • Such a solid electrolyte is used in a solid electrolyte layer, and may also be used together with an active material in an electrode. It is desirable that the solid electrolyte contained in the electrode also has high ionic conductivity, similar to the solid electrolyte used in the solid electrolyte layer.
  • the present invention was made in consideration of the problems with the above-mentioned conventional technology, and provides an electrode and an all-solid-state battery that include a solid electrolyte with high ionic conductivity.
  • the present invention provides the following means to solve the above problems.
  • a first aspect of the present invention is an electrode comprising a compound containing Li, one or more elements selected from the group consisting of elements of Groups 3 to 15, and S, in which the peak intensity Ra of SO 3 ⁇ and the peak intensity Rb of SO 4 ⁇ obtained by negative ion analysis by time-of-flight secondary ion mass spectrometry satisfy Ra>Rb.
  • a peak intensity ratio R1 (Ra/Rb) of a peak intensity Ra of SO 3 -- to a peak intensity Rb of SO 4 -- in the compound satisfies 6.0>R1>1.0.
  • a peak intensity ratio R1 (Ra/Rb) of a peak intensity Ra of SO 3 -- to a peak intensity Rb of SO 4 -- in the compound satisfies 1.8>R1>1.2.
  • a fourth aspect of the present invention is such that, in the electrode of the first aspect, a peak intensity ratio R1 (Ra/Rb) of a peak intensity Ra of SO 3 -- to a peak intensity Rb of SO 4 -- in the compound satisfies 1.7>R1>1.4.
  • Aspect 5 of the present invention is an electrode according to any one of Aspects 1 to 4, wherein the compound is detected as having an SO - peak, an SO 2 - peak, an SO 3 - peak, and an SO 4 - peak in negative ion analysis by time-of-flight secondary ion mass spectrometry, and among the four peaks, the SO 3 - peak has the strongest peak intensity.
  • a sixth aspect of the present invention relates to the electrode of any one of the first to fifth aspects, wherein the compound is represented by the following formula (1): LiaEbGcXd...(1)
  • E is at least one element selected from the group consisting of Al, Sc, Y, Zr, Hf , and lanthanoids.
  • G is at least one group selected from the group consisting of SO3 , SO4 , SO5 , S2O3 , S2O4 , S2O5 , S2O6 , S2O7 , and S2O8 .
  • X is at least one element selected from the group consisting of F, Cl, Br, and I. 0.5 ⁇ a ⁇ 6 , 0 ⁇ b ⁇ 2, 0.1 ⁇ c ⁇ 6, and 0 ⁇ d ⁇ 6.1.
  • Aspect 7 of the present invention is an all-solid-state battery in which a positive electrode and a negative electrode face each other via a solid electrolyte layer, and at least one of the solid electrolyte layer, the positive electrode, and the negative electrode includes any one of the electrodes of aspects 1 to 6.
  • the solid electrolyte layer contains a compound represented by the following formula (2): LiaEbGcXd...(2)
  • E is at least one element selected from the group consisting of Al, Sc, Y, Zr, Hf , and lanthanoids.
  • G is at least one group selected from the group consisting of SO3 , SO4 , SO5 , S2O3 , S2O4 , S2O5 , S2O6 , S2O7 , and S2O8 .
  • X is at least one element selected from the group consisting of F, Cl, Br, and I. 0.5 ⁇ a ⁇ 6 , 0 ⁇ b ⁇ 2, 0.1 ⁇ c ⁇ 6, and 0 ⁇ d ⁇ 6.1.
  • the electrode of the present invention can provide an electrode containing a solid electrolyte with high ionic conductivity.
  • FIG. 1 is a schematic cross-sectional view of an all-solid-state battery according to an embodiment of the present invention.
  • FIG. 1 is a schematic cross-sectional view of an all-solid-state battery 100 according to this embodiment.
  • the all-solid-state 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 that are connected to each other.
  • a stacked type battery is shown in FIG. 1, a wound type battery may also be used.
  • the all-solid-state battery 100 is used, for example, in a laminated battery, a square battery, a cylindrical battery, a coin battery, a button battery, and the like.
  • 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.
  • At least one of the positive electrode 20 and the negative electrode 30 contains a compound in an electrode mixture layer that contains Li, one or more elements selected from the group consisting of elements of Groups 3 to 15, and S, and in which the peak intensity Ra of SO 3 ⁇ and the peak intensity Rb of SO 4 ⁇ obtained by negative ion analysis by time-of-flight secondary ion mass spectrometry satisfy Ra>Rb.
  • the compound is contained in both the positive electrode 20 and the negative electrode 30.
  • the positive electrode 20 has a plate-shaped (foil-shaped) positive electrode current collector 22 and a positive electrode mixture layer 24.
  • the positive electrode mixture layer 24 is in contact with at least one surface of the positive electrode current collector 22.
  • the positive electrode current collector 22 may be made of any material as long as it is an electronically conductive material that is resistant to oxidation during charging and is not easily corroded.
  • the positive electrode current collector 22 is, for example, a metal such as aluminum, stainless steel, nickel, or titanium, a conductive resin, etc.
  • the positive electrode current collector 22 may be in the form of a powder, a foil, a punched piece, or an expanded piece.
  • the positive electrode mixture layer 24 includes a positive electrode active material and a solid electrolyte, and may include a binder and a conductive assistant. Known binders and conductive assistants may be used.
  • the conductive assistant is, for example, carbon black.
  • the conductive assistant may be vapor-grown carbon fiber, carbon nanotubes, metals, or the like.
  • the positive electrode active material is not particularly limited as long as it can reversibly absorb and release lithium ions and insert and remove them (intercalation and deintercalation), and any positive electrode active material used in known lithium ion secondary batteries can be used.
  • Examples of the positive electrode active material 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.), non-lithium-containing fluorides (FeF 3 , VF 3 , etc.), and sulfur-modified polyacrylonitrile.
  • the negative electrode is doped with lithium ions in advance, or a negative electrode containing lithium ions is used.
  • the content of the positive electrode active material in the positive electrode mixture layer 24 is not particularly limited, but is preferably 50% to 98% by mass, and more preferably 55% to 95% by mass, based on the total mass of the positive electrode active material, solid electrolyte, conductive additive, and binder.
  • the solid electrolyte contained in the positive electrode mixture layer 24 contains Li, one or more elements selected from Group 3 to Group 15 elements, and S, and contains a compound in which the peak intensity Ra of SO 3 - and the peak intensity Rb of SO 4 - obtained by negative ion analysis by time-of-flight secondary ion mass spectrometry satisfy Ra>Rb.
  • a configuration in which the solid electrolyte contained in the positive electrode mixture layer 24 contains the compound includes a configuration in which the solid electrolyte contained in the positive electrode mixture layer 24 is made of the compound.
  • the compound itself is a solid electrolyte (solid electrolyte material).
  • a solid electrolyte is a material that can move ions when an external electric field is applied. If the ionic conductivity of the solid electrolyte is high, the exchange of ions in the solid-state battery becomes smoother, and the internal resistance becomes smaller.
  • the peak intensity ratio R1 (Ra/Rb) between the SO 3 -- peak intensity Ra and the SO 4 -- peak intensity Rb in the compound satisfies 6.0>R1>1.0.
  • the ionic conductivity of the compound is 0.1 mS/cm or more.
  • the peak intensity ratio R1 (Ra/Rb) of the SO 3 - peak intensity Ra to the SO 4 - peak intensity Rb in the compound satisfies 1.8>R1>1.2.
  • the ionic conductivity of the compound is 0.5 mS/cm or more.
  • the peak intensity ratio R1 (Ra/Rb) between the SO 3 - peak intensity Ra and the SO 4 - peak intensity Rb in the compound satisfies 1.7>R1>1.4.
  • R1 satisfies this inequality, the ionic conductivity of the compound is 1 mS/cm or more.
  • the compound in negative ion analysis by time - of-flight secondary ion mass spectrometry, can satisfy the following conditions: an SO 2 - peak, an SO 3 - peak, and an SO 4 - peak are detected, and of the four peaks, the SO 3 - peak has the strongest peak intensity.
  • Time-of-Flight Secondary Ion Mass Spectrometry is a technique in which an ion beam (primary ions) is irradiated onto the surface of a solid sample, and the ions (secondary ions) emitted from the surface are mass-separated by utilizing the difference in their flight times (the flight time is proportional to the square root of the mass of the ion).
  • the horizontal axis represents time and the vertical axis represents the ion count (intensity).
  • the horizontal axis becomes mass number, and the mass distribution of secondary ions, i.e., the mass spectrum, is obtained.
  • SO 3 - peak intensity refers to the detected count number of SO 3 - (negative ion).
  • SO 4 - peak intensity refers to the detected count number of SO 4 - (negative ion). Therefore, when the SO 3 - peak intensity Ra and the SO 4 - peak intensity Rb satisfy Ra>Rb, this means that the detected count number of SO 3 - (negative ion) is greater than the detected count number of SO 4 - (negative ion).
  • the compound contained in the solid electrolyte contained in the positive electrode mixture layer 24 contains Li, one or more elements selected from the group 3 to group 15 elements, and S, and the peak intensity Ra of SO 3 - is higher than the peak intensity Rb of SO 4 - in TOF-SIMS, thereby improving the ionic conductivity.
  • the O (oxygen) bonds are different, and it is believed that SO3- was detected in addition to SO4- by TOF-SIMS. It is also believed that the difference in the structure of SO4 causes lattice distortion, resulting in high ionic conductivity.
  • the present invention has clarified that in a solid electrolyte containing Li, one or more elements selected from the group 3 to group 15 elements, and S, the peak intensity ratio R1 (Ra/Rb) of the peak intensity Ra of SO 3 - to the peak intensity Rb of SO 4 - in a TOF-SIMS mass spectrum can be used as an index of ionic conductivity.
  • the compound may be represented by the following formula (1): LiaEbGcXd...(1) (In formula (1), E is at least one element selected from the group consisting of Al, Sc, Y, Zr, Hf , and lanthanoids. G is at least one group selected from the group consisting of SO3 , SO4 , SO5 , S2O3 , S2O4 , S2O5 , S2O6 , S2O7 , and S2O8 . X is at least one element selected from the group consisting of F, Cl, Br, and I. 0.5 ⁇ a ⁇ 6 , 0 ⁇ b ⁇ 2, 0.1 ⁇ c ⁇ 6, and 0 ⁇ d ⁇ 6.1.)
  • a satisfies 0.5 ⁇ a ⁇ 6, and when E is Al, Sc, Y, or a lanthanide, it preferably satisfies 2.0 ⁇ a ⁇ 4.0, and more preferably satisfies 2.5 ⁇ a ⁇ 3.5.
  • E is Zr or Hf
  • a preferably satisfies 1.0 ⁇ a ⁇ 3.0, and more preferably satisfies 1.5 ⁇ a ⁇ 2.5.
  • the compound represented by formula (1) if a satisfies 0.5 ⁇ a ⁇ 6, the Li content in the compound becomes appropriate, and the ionic conductivity of the solid electrolyte layer 10 becomes high.
  • E is an essential component and is at least one element selected from the group consisting of Al, Sc, Y, Zr, Hf, and lanthanoids.
  • E improves the ionic conductivity of the solid electrolyte.
  • b is 0 ⁇ b ⁇ 2. Since the effect of including E can be obtained more effectively, it is preferable that b is 0.6 ⁇ b.
  • E is an element that forms the skeleton of the solid electrolyte. When b is b ⁇ 1, it is preferable because the density of the solid electrolyte is low.
  • c is preferably 0.5 ⁇ c because the effect of widening the potential window on the reduction side due to the inclusion of G is more pronounced.
  • c is preferably c ⁇ 3 so that the ionic conductivity of the solid electrolyte does not decrease due to an excessive G content.
  • X is an essential component.
  • X is at least one selected from the group consisting of F, Cl, Br, and I.
  • X has a large ionic radius per valence. Therefore, when the halide-based solid electrolyte represented by formula (1) contains X, it has the effect of making it easier for lithium ions to flow and increasing ionic conductivity.
  • X preferably contains Cl, which results in a solid electrolyte with high ionic conductivity.
  • X preferably contains two or more selected from the group consisting of F and Cl, Br, and I, which results in a solid electrolyte with high ionic conductivity.
  • the resulting solid electrolyte has sufficiently high ionic conductivity and excellent oxidation resistance.
  • X is Cl
  • the resulting solid electrolyte has high ionic conductivity and a good balance of oxidation resistance and reduction resistance.
  • X is Br
  • the resulting solid electrolyte has sufficiently high ionic conductivity and a good balance of oxidation resistance and reduction resistance.
  • X is I
  • the resulting solid electrolyte has high ionic conductivity.
  • d satisfies 0 ⁇ d ⁇ 6.1. It is preferable that d is 1 ⁇ d. If d is 1 ⁇ d, the strength of the pellet increases when the solid electrolyte is pressure-molded into a pellet shape. Furthermore, if d is 1 ⁇ d, the ionic conductivity of the solid electrolyte increases. Furthermore, it is preferable that d is ⁇ 5 so that the potential window of the solid electrolyte does not become narrow due to a shortage of G caused by an excessive content of X.
  • Examples of the halide- based solid electrolyte represented by formula (1) include Li2Zr ( SO4 ) Cl4 , Li2Zr ( SO3 )Cl4, Li2Zr( SO4 ) 0.3 (SO3) 0.7Cl4 , Li2Zr(SO4)0.5(SO3)0.5Cl4, Li2Zr(SO4)0.7 ( SO3 ) 0.3Cl4 , Li2Zr ( S2O3 ) Cl4 , Li2Zr ( SO4 ) 0.3 (S2O3 ) 0.7Cl4 , Li2Zr ( SO4 ) 0.5 ( S2O3 ) 0.5 Cl4 , Li2Zr ( SO4 ) 0.7 ( S2O3 ) 0.3Cl4 .
  • the binder bonds the positive electrode active material, the solid electrolyte, and the conductive assistant to one another in the positive electrode mixture layer 24, and also firmly bonds the positive electrode mixture layer 24 to the positive electrode current collector 22.
  • the positive electrode mixture layer 24 preferably contains a binder.
  • the binder preferably has oxidation resistance and good adhesiveness.
  • Binders used in the positive electrode mixture 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 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 polyacrylic acid
  • PP polypropylene
  • PE polyethylene
  • the content of the solid electrolyte in the positive electrode mixture 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 content in the positive electrode mixture layer 24 is not particularly limited, but is preferably 0.1% to 10% by mass, and more preferably 0.1% to 5% by mass, based on the total mass of the positive electrode active material, solid electrolyte, conductive additive, and binder. If the binder amount is too small, it tends not to be possible to form a positive electrode 20 with sufficient adhesive strength. Conversely, if the binder amount 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 assistant improves the electronic conductivity of the positive electrode mixture layer 24.
  • Known conductive assistants can be used.
  • the conductive assistant 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 thereof.
  • the conductive assistant may be in the form of powder or fiber.
  • the content of the conductive additive in the positive electrode mixture 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 mixture layer 34.
  • the negative electrode mixture layer 34 is in contact with the negative electrode current collector 32.
  • description of components common to the "positive electrode” may be omitted.
  • the negative electrode current collector 32 may have electronic conductivity.
  • the negative electrode current collector 32 is, 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, a foil, a punched piece, or an expanded piece.
  • the negative electrode mixture layer 34 contains a negative electrode active material and a solid electrolyte.
  • the negative electrode mixture layer 34 may contain a binder and a conductive assistant.
  • Known binders and conductive assistants may be used.
  • the conductive assistant is, for example, carbon black.
  • the conductive assistant may be vapor grown carbon fiber, carbon nanotubes, metals, or the like.
  • the binder and conductive assistant may be the same as those described for the positive electrode mixture layer 24 and may be used in the same proportions.
  • the negative electrode active material is not particularly limited as long as it can reversibly absorb and release lithium ions, and insert and remove lithium ions.
  • the negative electrode active material may be any negative electrode active material used in known lithium ion secondary batteries.
  • the negative electrode active material examples include carbon materials such as natural graphite, artificial graphite, mesocarbon microbeads, mesocarbon fiber (MCF), cokes, glassy carbon, and organic compound sintered bodies, metals that can be combined with lithium such as Si, SiOx, Sn, and aluminum, alloys thereof, composite materials of these metals and carbon materials, oxides such as lithium titanate (Li 4 Ti 5 O 12 ) and SnO 2 , sulfur-modified polyacrylonitrile, and metallic lithium.
  • the negative electrode active material is preferably natural graphite or lithium titanate (Li 4 Ti 5 O 12 ).
  • the content of the negative electrode active material in the negative electrode mixture layer 34 is not particularly limited, but is preferably 50% to 98% by mass, and more preferably 55% to 95% by mass, based on the total mass of the negative electrode active material, solid electrolyte, conductive additive, and binder.
  • the solid electrolyte contained in the negative electrode mixture layer 34 contains Li, one or more elements selected from Group 3 to Group 15 elements, and S, and contains a compound in which the peak intensity Ra of SO 3 - and the peak intensity Rb of SO 4 - obtained by negative ion analysis by time-of-flight secondary ion mass spectrometry satisfy Ra>Rb.
  • the configuration in which the solid electrolyte contained in the negative electrode mixture layer 34 contains the compound includes a configuration in which the solid electrolyte contained in the negative electrode mixture layer 34 is made of the compound.
  • the compound may have the same structure as that described for the positive electrode mixture layer 24. The description thereof will be omitted below.
  • the content of the solid electrolyte in the negative electrode mixture layer 34 is not particularly limited, but is preferably 1% by mass to 60% by mass, and more preferably 10% by mass to 55% by mass, based on the total mass of the negative electrode active material, solid electrolyte, conductive additive, and binder.
  • the binder content in the negative electrode mixture layer 34 is not particularly limited, but is preferably 0.1% to 10% by mass, and more preferably 0.1% to 5% by mass, based on the total mass of the negative electrode active material, solid electrolyte, conductive additive, and binder. If the binder amount is too small, it tends not to be possible to form a negative electrode 30 with sufficient adhesive strength. Conversely, if the binder amount 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 content of the conductive additive in the negative electrode mixture layer 34 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 negative electrode active material, solid electrolyte, conductive additive, and binder.
  • Solid electrolyte layer 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 contains, for example, lithium.
  • the solid electrolyte may be, for example, an oxide-based material, a sulfide-based material, or a halide-based material.
  • the compound (solid electrolyte) contained in the electrode according to the present embodiment described above may be used or may be included in part.
  • 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 may be, for example, a halide-based solid electrolyte represented by the following formula (2). LiaEbGcXd...(2)
  • a satisfies 0.5 ⁇ a ⁇ 6, and when E is Al, Sc, Y, or a lanthanide, it preferably satisfies 2.0 ⁇ a ⁇ 4.0, and more preferably satisfies 2.5 ⁇ a ⁇ 3.5.
  • E is Zr or Hf
  • a preferably satisfies 1.0 ⁇ a ⁇ 3.0, and more preferably satisfies 1.5 ⁇ a ⁇ 2.5.
  • the compound represented by formula (2) if a satisfies 0.5 ⁇ a ⁇ 6, the Li content in the compound becomes appropriate, and the ionic conductivity of the solid electrolyte layer 10 becomes high.
  • E is an essential component and is at least one element selected from the group consisting of Al, Sc, Y, Zr, Hf, and lanthanoids.
  • E improves the ionic conductivity of the solid electrolyte.
  • b is 0 ⁇ c ⁇ 2. Since the effect of including E can be obtained more effectively, it is preferable that b is 0.6 ⁇ b.
  • E is an element that forms the skeleton of the solid electrolyte. When b is b ⁇ 1, it is preferable because the resulting solid electrolyte has a low density.
  • c is preferably 0.5 ⁇ c because the effect of widening the potential window on the reduction side due to the inclusion of G is more pronounced.
  • c is preferably c ⁇ 3 so that the ionic conductivity of the solid electrolyte does not decrease due to an excessive G content.
  • X is an essential component.
  • X is at least one selected from the group consisting of F, Cl, Br, and I.
  • X has a large ionic radius per valence. Therefore, when the halide-based solid electrolyte represented by formula (2) contains X, it has the effect of making it easier for lithium ions to flow and increasing ionic conductivity.
  • X preferably contains Cl, which results in a solid electrolyte with high ionic conductivity.
  • X preferably contains two or more selected from the group consisting of F and Cl, Br, and I, which results in a solid electrolyte with high ionic conductivity.
  • the resulting solid electrolyte has sufficiently high ionic conductivity and excellent oxidation resistance.
  • X is Cl
  • the resulting solid electrolyte has high ionic conductivity and a good balance of oxidation resistance and reduction resistance.
  • X is Br
  • the resulting solid electrolyte has sufficiently high ionic conductivity and a good balance of oxidation resistance and reduction resistance.
  • X is I
  • the resulting solid electrolyte has high ionic conductivity.
  • d satisfies 0 ⁇ d ⁇ 6.1. It is preferable that d is 1 ⁇ d. If d is 1 ⁇ d, the strength of the pellets will be high when the solid electrolyte is pressure-molded into pellets. If d is 1 ⁇ d, the ionic conductivity of the solid electrolyte will be high. It is also preferable that d is ⁇ 5 so that the potential window of the solid electrolyte is not narrowed due to a shortage of G caused by an excessively high content of X.
  • Examples of the halide-based solid electrolyte represented by formula (2) include Li2Zr ( SO4 ) Cl4 , Li2Zr ( SO3 )Cl4 , Li2Zr( SO4 ) 0.3 (SO3) 0.7Cl4 , Li2Zr(SO4)0.5(SO3)0.5Cl4, Li2Zr(SO4)0.7 ( SO3 ) 0.3Cl4 , Li2Zr ( S2O3 ) Cl4 , Li2Zr ( SO4 ) 0.3 (S2O3 ) 0.7Cl4 , Li2Zr ( SO4 ) 0.5 ( S2O3 ) 0.5 Cl4 , Li2Zr ( SO4 ) 0.7 ( S2O3 ) 0.3Cl4 .
  • the solid electrolyte may be a sulfide-based solid electrolyte, and the sulfide-based solid electrolyte may be a compound containing Li, S, Si and/or P.
  • the sulfide-based solid electrolyte may further contain Ge, Cl, Br, or I.
  • the sulfide-based solid electrolyte may be amorphous, crystalline, or of the argyrodite type.
  • Examples of sulfide-based solid electrolytes include Li 2 S-P 2 S 5 -based solid electrolytes (Li7P 3 S 11 , Li 3 PS 4 , Li 8 P 2 S 9 , etc.), Li 2 S-SiS 2 , LiI-Li 2 S-SiS 2 , LiI-Li 2 S-P 2 S 5 , LiI-LiBr-Li 2 S-P 2 S 5 , Li 2 S-P 2 S 5 -GeS 2 -based solid electrolytes (Li 13 GeP 3 S 16 , Li 10 GeP 2 S 12 , etc.), LiI-Li 2 S-P 2 O 5 , LiI-Li 3 PO 4 -P 2 S 5 , Li 7-x PS 6-x Cl x (x is 1.0 to 1.9).
  • the sulfide-based solid electrolyte may be a compound represented by the following formula (3).
  • M is preferably Si or Ge.
  • 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 positive electrode 20 and the negative electrode 30, 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 all-solid-state battery according to this embodiment contains the above-mentioned compound (solid electrolyte) in at least one of the positive electrode and the negative electrode. That is, at least one of the positive electrode and the negative electrode contains a compound that contains Li, one or more elements selected from the group 3 to group 15 elements, and S, and in which the peak intensity Ra of SO 3 - and the peak intensity Rb of SO 4 - satisfy Ra>Rb in TOF-SIMS.
  • a solid electrolyte is prepared.
  • This solid electrolyte contains both the solid electrolyte constituting the solid electrolyte layer and the above-mentioned compound (solid electrolyte) contained in the electrode.
  • the solid electrolyte can be manufactured, for example, by mixing raw material powders containing predetermined elements in a predetermined molar ratio and carrying out a mechanochemical reaction.
  • the state of SxOy after synthesis is adjusted to be different. Specifically, the rotation speed, revolution speed, synthesis time, state of the raw material powder at the time of input, and atmosphere inside the pot of the planetary ball mill can be changed to allow unreacted components of the raw material to remain.
  • the raw material powder contains a halide raw material
  • the halide raw material is likely to evaporate when the temperature is raised. For this reason, halogen gas may be present in the atmosphere during sintering to compensate for the halogen.
  • the raw material powder may be sintered by hot pressing using a highly airtight mold. In this case, the highly airtight mold can suppress the evaporation of the halide raw material due to sintering. By sintering in this manner, a solid electrolyte in the form of a sintered body made of a compound having a specified composition is obtained.
  • the positive electrode 20 is prepared.
  • 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 mixture 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 a negative electrode current collector 32 and drying it to form a negative electrode mixture 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 all-solid-state battery 100 contains the above-mentioned solid electrolyte, so Li ions are smoothly conducted and the internal resistance is low.
  • the polyimide tape has the effect of blocking moisture.
  • the zirconia sealed container was set in a planetary ball mill. A mechanochemical reaction was carried out for 24 hours at a rotation speed of 500 rpm and a revolution speed of 500 rpm (the rotation direction and the revolution direction are opposite to each other) to obtain a powder of Li 2 Zr (SO 4 ) Cl 4 of the positive electrode example 1.
  • the planetary ball mill is placed in an Ar gas atmosphere.
  • the zirconia sealed container for the planetary ball mill is screwed and sealed with polyimide tape.
  • the zirconia sealed container is set in the planetary ball mill, it is firmly pressed into place, so it is believed that there is almost no moisture from the air getting into the zirconia sealed container.
  • the TOF-SIMS was measured under the following conditions.
  • Instrument ION-TOF TOF-SIMS5
  • Measurement conditions Measurement mode: Spectrometry Primary ion: Bi3 ++ Acceleration voltage: 25 kV Measurement area: 40,000 ⁇ m 2 (200 ⁇ m x 200 ⁇ m) Measurement ion species: Negative Electron neutralization: Yes
  • the ionic conductivity of the solid electrolyte (Li 2 ZrSO 4 Cl 4 ) of Positive Electrode Example 1 was measured as follows.
  • the obtained solid electrolyte (Li 2 Zr(SO 4 )Cl 4 ) powder was filled into a pressure molding die in a glove box with argon gas circulating at a dew point of about -70°C, and pressure molding was performed under a load of about 30 KN to prepare a measurement cell for ionic conductivity.
  • 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 an impedance measurement method. Measurement was 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 above compound (solid electrolyte) (Li 2 Zr(SO 4 )Cl 4 ) of positive electrode Example 1 was 2.4 ⁇ 10 ⁇ 3 S/cm.
  • lithium cobalt oxide (LiCoO 2 ) and Li 2 Zr(SO 4 )Cl 4 of positive electrode example 1 were prepared as the positive electrode active material.
  • the positive electrode active material and Li 2 Zr(SO 4 )Cl 4 of positive electrode example 1 were weighed out to be 65 wt % and 35 wt %, respectively.
  • the weighed positive electrode active material and Li 2 Zr(SO 4 )Cl 4 of positive electrode example 1 were mixed in an agate mortar for 15 minutes to obtain a positive electrode mixture.
  • the charge/discharge half-cell was prepared in a glove box with a dew point of about -70°C.
  • a pellet making jig was used to prepare the half cell.
  • the pellet making jig had a cylinder made of PEEK (polyether ether ketone) with an outer diameter of 30 mm, an inner diameter of 10 mm, and a height of 20 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 cylinder, and 110 mg of the solid electrolyte Li2Zr ( SO4 ) Cl4 was placed on the lower punch.
  • the PEEK cylinder was vibrated to smooth the surface of the solid electrolyte, and then an upper punch was inserted on the solid electrolyte and pressed with a press machine under a load of 373 MPa to form a solid electrolyte layer.
  • the upper punch was removed, and 15 mg of the above positive electrode mixture was placed on the solid electrolyte layer.
  • the PEEK cylinder was vibrated to level the surface of the positive electrode mixture, and then the upper punch was inserted on the positive electrode mixture and pressed with a press machine under a load of 373 MPa.
  • the lower punch was removed, and a lithium foil with a diameter of 10 mm and a thickness of 100 ⁇ m was placed on the solid electrolyte layer, and the lower punch was inserted.
  • the half cell configuration is (LiCoO 2 + Li 2 Zr (SO 4 ) Cl 4 ) / Li 2 Zr (SO 4 ) Cl 4 / Li.
  • two stainless steel plates with a diameter of 50 mm and a thickness of 5 mm and two Bakelite (registered trademark) plates with a diameter of 50 mm and a thickness of 2 mm were prepared.
  • four holes for passing screws were made in each of the two stainless steel plates and the two Bakelite (registered trademark) plates.
  • the screw holes were made in positions where the two stainless steel plates and the two Bakelite (registered trademark) plates overlap in a planar view when the half-cell and the two stainless steel plates and the two Bakelite (registered trademark) plates are stacked, but do not overlap with the half-cell in a planar view.
  • a stainless steel plate, a Bakelite (registered trademark) plate, a half cell, a Bakelite (registered trademark) plate, and a stainless steel plate were stacked in that order, and screws were inserted into the screw holes and tightened with a torque of 1 N ⁇ m.
  • a half cell was obtained in which the upper and lower punches of the electrochemical cell were insulated by the Bakelite (registered trademark) plate.
  • the half cell was left to stand in a constant temperature bath at 25°C for 48 hours to stabilize the open circuit voltage.
  • Example 1 refers to the solid electrolyte of the positive electrode example 1 and the solid electrolyte of the negative electrode example 1.
  • the solid electrolyte ( Li6PS5Cl ) of positive electrode Example 14 was prepared by weighing out lithium sulfide ( Li2S ), phosphorus sulfide ( P2S5 ), and lithium chloride (LiCl) in a molar ratio of 5:1:2 to prepare raw material powders, and then adding all of these raw material powders at the same time to synthesize the solid electrolyte (Li6PS5Cl ) of positive electrode Example 14 in the same manner as positive electrode Example 1.
  • the solid electrolyte ( Li9.54Si1.74P1.44S11.7Cl0.3 ) of the positive electrode Example 15 was synthesized in the same manner as in the positive electrode Example 1 , except that lithium sulfide ( Li2S ), silicon sulfide ( SiS2 ), phosphorus sulfide ( P2S5 ), and lithium chloride (LiCl) were weighed out to have a molar ratio of 4.62: 1.74 : 0.72 : 0.3 to prepare raw material powders, and all of these raw material powders were added at the same time to synthesize the solid electrolyte ( Li9.54Si1.74P1.44S11.7Cl0.3 ).
  • the solid electrolytes (compounds) of negative electrode Examples 1 to 17 are the same as the solid electrolytes (compounds) of positive electrode Examples 1 to 17, respectively, and correspond to the compounds of Examples 1 to 17 listed in Table 1.
  • the characteristics of negative electrode Examples 1 to 17 correspond to the characteristics of Examples 1 to 17 listed in Table 2.
  • lithium titanate ( Li4Ti5O12 ) and Li2Zr ( SO4 ) Cl4 of negative electrode example 1 were prepared as the negative electrode active material.
  • the negative electrode active material and Li2Zr ( SO4 ) Cl4 of negative electrode example 1 were weighed out to be 60 wt% and 40 wt%, respectively.
  • the weighed negative electrode active material and Li2Zr ( SO4 ) Cl4 of negative electrode example 1 were mixed in an agate mortar for 15 minutes to obtain a negative electrode mixture.
  • the charge/discharge half-cell was prepared in a glove box with a dew point of about -70°C.
  • a pellet making jig was used to prepare the half cell.
  • the pellet making jig had a cylinder made of PEEK (polyether ether ketone) with an outer diameter of 30 mm, an inner diameter of 10 mm, and a height of 20 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 cylinder, and 110 mg of the solid electrolyte Li2Zr ( SO4 ) Cl4 was placed on the lower punch.
  • the PEEK cylinder was vibrated to smooth the surface of the solid electrolyte, and then an upper punch was inserted on the solid electrolyte and pressed with a press machine under a load of 373 MPa to form a solid electrolyte layer.
  • the upper punch was removed, and 15 mg of the above negative electrode mixture was placed on the solid electrolyte layer.
  • the PEEK cylinder was vibrated to level the surface of the negative electrode mixture, and then the upper punch was inserted on the negative electrode mixture and pressed with a press machine under a load of 373 MPa.
  • the lower punch was removed, and a lithium foil with a diameter of 10 mm and a thickness of 100 ⁇ m was placed on the solid electrolyte layer, and the lower punch was inserted.
  • the configuration of the half cell is (Li 4 Ti 5 O 12 + Li 2 Zr (SO 4 ) Cl 4 ) / Li 2 Zr (SO 4 ) Cl 4 / Li.
  • two stainless steel plates with a diameter of 50 mm and a thickness of 5 mm and two Bakelite (registered trademark) plates with a diameter of 50 mm and a thickness of 2 mm were prepared.
  • four holes for passing screws were made in each of the two stainless steel plates and the two Bakelite (registered trademark) plates.
  • the screw holes were made in positions where the two stainless steel plates and the two Bakelite (registered trademark) plates overlap in a planar view when the half-cell and the two stainless steel plates and the two Bakelite (registered trademark) plates are stacked, but do not overlap with the half-cell in a planar view.
  • a stainless steel plate, a Bakelite (registered trademark) plate, a half cell, a Bakelite (registered trademark) plate, and a stainless steel plate were stacked in that order, and screws were inserted into the screw holes and tightened with a torque of 1 N ⁇ m.
  • a half cell was obtained in which the upper and lower punches of the electrochemical cell were insulated by the Bakelite (registered trademark) plate.
  • the half cell was left to stand in a constant temperature bath at 25°C for 48 hours to stabilize the open circuit voltage.
  • the solid electrolytes (compounds) of negative electrode comparative examples 1 to 6 are the same as the solid electrolytes (compounds) of positive electrode comparative examples 1 to 6, respectively, and correspond to the compounds of comparative examples 1 to 6 listed in Table 1.
  • the characteristics of negative electrode comparative examples 1 to 6 correspond to the characteristics of comparative examples 1 to 6 listed in Table 2.
  • half cells of the solid electrolytes (compounds) of Negative Electrode Comparative Examples 1 to 6 were prepared in the same manner as the half cells of the solid electrolytes (compounds) of Negative Electrode Examples 1 to 17, and their rate characteristics were measured. The measurement results are summarized in Table 4 below.
  • the peak intensity ratio R1 (Ra/Rb) satisfies 6.0>R1>1.0, that is, 5.71 (Example 17) ⁇ R1 ⁇ 1.18 (Example 10), for Examples 1 to 17.
  • the ionic conductivity for Examples 1 to 15 is 3.1 ⁇ 10 ⁇ 4 [S/cm] (Example 3) or more and 5.4 ⁇ 10 ⁇ 3 [S/cm] (Example 15) or less.
  • the peak intensity ratio R1 (Ra/Rb) satisfies 1.8>R1>1.2 for Examples 1, 2, 4, 6, 7, 8, 9, 11 to 15.
  • the ionic conductivity for Examples 1, 2, 4, 6, 7, 8, 9, 11 to 15 is 9.4 ⁇ 10 ⁇ 4 (Example 8) or more and 5.4 ⁇ 10 ⁇ 3 [S/cm] (Example 15) or less.
  • the ionic conductivity is 9.4 ⁇ 10 ⁇ 4 [S/cm] or more.
  • the peak intensity ratio R1 (Ra/Rb) can be used as an index relating to the ionic conductivity.
  • Examples 1 to 3 have the same composition, their ionic conductivities are different. This is due to the different atmospheres in which the synthesis was performed (synthesis atmospheres). In this way, the ionic conductivity can be adjusted by adjusting the synthesis atmosphere.
  • the compounds in Examples 4 and 5 have the same composition, but have different ionic conductivities due to the different synthesis atmospheres.
  • Examples 9 and 10 are compounds with the same composition, but have different ionic conductivities due to the different synthesis atmospheres.
  • the compounds have the same constituent elements, but the ratio of SO4 to SO3 is different, and the ionic conductivity is also different. This is due to the different ratios of the raw materials to be synthesized and the different synthesis atmospheres. In this way, by adjusting the synthesis atmosphere, the ratio of SO4 to SO3 can be adjusted, and the ionic conductivity can be adjusted.
  • the compounds have the same constituent elements, but the ratio of SO4 to SO3 is different, and the ionic conductivity is also different. This is due to the different synthesis atmospheres. In this way, by adjusting the synthesis atmosphere, the ratio of SO4 to SO3 can be adjusted, and the ionic conductivity can be adjusted.
  • Example 4 Although the compounds of Examples 4, 16, and 17 have the same composition, their ionic conductivities are different. This is due to the difference in synthesis time. Thus, the ionic conductivities can be adjusted by adjusting the synthesis time.
  • the synthesis times of Examples 4, 16, and 17 were 24 hours, 48 hours, and 72 hours, respectively, and the ionic conductivities were 3.1 ⁇ 10 ⁇ 3 [S/cm], 3.0 ⁇ 10 ⁇ 4 [S/cm], and 2.8 ⁇ 10 ⁇ 4 [S/cm], respectively.
  • Example 4 which had a synthesis time of 24 hours, had the highest ionic conductivity.
  • the ionic conductivity of Example 4 is one order of magnitude higher than that of Examples 16 and 17. In this way, by adjusting the synthesis time, it is possible to improve the ionic conductivity by one order of magnitude or more even for compounds of the same composition.
  • the Ar gas atmosphere had the highest ionic conductivity among the three synthetic atmospheres: an Ar gas atmosphere, a mixed atmosphere of dry air with a dew point of approximately -40°C and argon gas in a volume ratio of 20%:80%, and a mixed atmosphere of dry air with a dew point of approximately -40°C and argon gas in a volume ratio of 40%:60%.

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Publication number Priority date Publication date Assignee Title
WO2018025582A1 (ja) 2016-08-04 2018-02-08 パナソニックＩｐマネジメント株式会社 固体電解質材料、および、電池
WO2021261558A1 (ja) 2020-06-24 2021-12-30 Tdk株式会社 固体電解質および固体電解質電池
WO2022154112A1 (ja) * 2021-01-18 2022-07-21 Tdk株式会社 電池及びその製造方法
WO2022186211A1 (ja) * 2021-03-01 2022-09-09 Tdk株式会社 電池及び電池の製造方法
JP2022176803A (ja) * 2021-05-17 2022-11-30 日亜化学工業株式会社 固体電解質材料、その製造方法及び電池
JP2023058719A (ja) 2017-03-31 2023-04-25 株式会社三洋物産 遊技機
WO2024058052A1 (ja) * 2022-09-12 2024-03-21 住友化学株式会社 イオン伝導性物質、電解質、及び電池

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018025582A1 (ja) 2016-08-04 2018-02-08 パナソニックＩｐマネジメント株式会社 固体電解質材料、および、電池
JP2023058719A (ja) 2017-03-31 2023-04-25 株式会社三洋物産 遊技機
WO2021261558A1 (ja) 2020-06-24 2021-12-30 Tdk株式会社 固体電解質および固体電解質電池
WO2022154112A1 (ja) * 2021-01-18 2022-07-21 Tdk株式会社 電池及びその製造方法
WO2022186211A1 (ja) * 2021-03-01 2022-09-09 Tdk株式会社 電池及び電池の製造方法
JP2022176803A (ja) * 2021-05-17 2022-11-30 日亜化学工業株式会社 固体電解質材料、その製造方法及び電池
WO2024058052A1 (ja) * 2022-09-12 2024-03-21 住友化学株式会社 イオン伝導性物質、電解質、及び電池

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