WO2022254955A1 - 固体電解質材料およびそれを用いた電池 - Google Patents
固体電解質材料およびそれを用いた電池 Download PDFInfo
- Publication number
- WO2022254955A1 WO2022254955A1 PCT/JP2022/016860 JP2022016860W WO2022254955A1 WO 2022254955 A1 WO2022254955 A1 WO 2022254955A1 JP 2022016860 W JP2022016860 W JP 2022016860W WO 2022254955 A1 WO2022254955 A1 WO 2022254955A1
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- WO
- WIPO (PCT)
- Prior art keywords
- solid electrolyte
- electrolyte material
- elements
- negative electrode
- positive electrode
- Prior art date
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 146
- 239000000463 material Substances 0.000 title claims abstract description 131
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 30
- 239000003792 electrolyte Substances 0.000 claims abstract description 28
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000001450 anions Chemical class 0.000 claims abstract description 13
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- 150000003063 pnictogens Chemical class 0.000 claims abstract description 10
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- 239000000203 mixture Substances 0.000 claims description 23
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- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 229910052740 iodine Inorganic materials 0.000 claims description 5
- 229910052711 selenium Inorganic materials 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 3
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- -1 transition metal sulfides Chemical class 0.000 description 14
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 10
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Images
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/22—Alkali metal sulfides or polysulfides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/04—Binary compounds including binary selenium-tellurium compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G30/00—Compounds of antimony
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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
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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
- H01M10/058—Construction or manufacture
- H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
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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
- 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
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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
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
- H01M2300/0071—Oxides
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
- H01M2300/008—Halides
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present disclosure relates to solid electrolyte materials and batteries using the same.
- Non-Patent Document 1 discloses Li 3 SbS 4 as a solid-phase electrolyte containing cationic antimony.
- An object of the present disclosure is to provide a novel solid electrolyte material with lithium ion conductivity.
- the plurality of anion elements provide a solid electrolyte material containing antimony and at least one element selected from the group consisting of pnictogen elements excluding antimony, chalcogen elements, and halogen elements.
- the present disclosure can provide a novel solid electrolyte material with lithium ion conductivity.
- FIG. 1 shows a cross-sectional view of a battery 1000 according to a second embodiment.
- FIG. 2 shows a schematic diagram of a pressure forming die 300 used to evaluate the ionic conductivity of solid electrolyte materials.
- 3 is a graph showing a Cole-Cole plot obtained by impedance measurement of the solid electrolyte material according to Example 4.
- FIG. 4 is a graph showing the initial charge/discharge characteristics of the battery according to Example 2.
- the solid electrolyte material of this embodiment contains lithium and a plurality of anion elements.
- the multiple anion elements include antimony and at least one element selected from the group consisting of pnictogen elements excluding antimony, chalcogen elements, and halogen elements.
- a solid electrolyte material is a solid electrolyte material suitable for improving lithium ion conductivity.
- Solid electrolyte materials for example, have high lithium ion conductivity. Therefore, solid electrolyte materials can be used to obtain batteries with excellent charge-discharge characteristics.
- An example of such a battery is an all-solid secondary battery.
- an example of high lithium ion conductivity is, for example, 6.3 ⁇ 10 ⁇ 5 S/cm or more near room temperature.
- the solid electrolyte material can have, for example, an ionic conductivity of 6.3 ⁇ 10 ⁇ 5 S/cm or higher.
- Room temperature is, for example, 25°C.
- Antimony has a lower electronegativity than chalcogen elements (ie, group 16 elements), halogen elements (ie, group 17 elements), and nitrogen.
- chalcogen elements ie, group 16 elements
- halogen elements ie, group 17 elements
- An anion means a more negatively charged state than a single metal.
- An example of an anionic antimony is -3-charged Sb 3- .
- the solid electrolyte material of this embodiment contains negatively charged antimony.
- One of the methods for determining whether an element is an anion is XPS measurement (X-ray photoelectron spectroscopy).
- XPS measurement X-ray photoelectron spectroscopy
- the binding energy obtained by the XPS measurement is smaller than that of the single metal, the element to be measured is negatively charged and can be determined to be an anion.
- the solid electrolyte material may contain elements that are unavoidably mixed.
- An example of such an element is hydrogen.
- Such elements can be present in the raw powder of the solid electrolyte material or in the atmosphere for manufacturing or storing the solid electrolyte material.
- Elements that are unavoidably mixed in the solid electrolyte material are, for example, 1 mol % or less.
- pnictogen elements mean nitrogen, phosphorus, arsenic, and antimony.
- Chalcogen elements mean oxygen, sulfur, selenium, and tellurium.
- a halogen element means fluorine, chlorine, bromine and iodine.
- the solid electrolyte material may consist of lithium, antimony, and pnictogen elements.
- Composed of lithium, antimony, and pnictogen elements means that no other elements are intentionally added except for inevitable impurities.
- the molar ratio (that is, mole fraction) of the total amount of lithium, antimony, and pnictogen elements to the total amount of all elements constituting the solid electrolyte material is 95% or more. This is also the case when the pnictogen element is replaced by a chalcogen element or a halogen element.
- the solid electrolyte material may be a material represented by the following compositional formula (1).
- Pn is at least one selected from the group consisting of N, P and As.
- the solid electrolyte material represented by compositional formula (1) has high ionic conductivity.
- the composition formula (1) may satisfy 0.01 ⁇ x ⁇ 0.9, and 0.2 ⁇ x ⁇ 0.8.
- the solid electrolyte material may consist of lithium, antimony, and chalcogen elements.
- the solid electrolyte material may be a material represented by the following compositional formula (2).
- Ch is at least one selected from the group consisting of O, S, Se and Te.
- the solid electrolyte material represented by compositional formula (2) has high ionic conductivity.
- Ch may contain Te in order to increase the ionic conductivity of the solid electrolyte material.
- Ch may be Te.
- the composition formula (2) may satisfy 0.01 ⁇ y ⁇ 0.9, and 0.2 ⁇ y ⁇ 0.8.
- the solid electrolyte material may consist of lithium, antimony, and halogen elements.
- the solid electrolyte material may be a material represented by the following compositional formula (3).
- Hal is at least one selected from the group consisting of F, Cl, Br and I;
- the solid electrolyte material represented by compositional formula (3) has high ionic conductivity.
- Hal may contain I in the composition formula (3) in order to increase the ionic conductivity of the solid electrolyte material.
- Hal may be I in the composition formula (3).
- the composition formula (3) may satisfy 0.01 ⁇ z ⁇ 0.9, and 0.2 ⁇ z ⁇ 0.8.
- the solid electrolyte material may be crystalline or amorphous.
- the shape of the solid electrolyte material is not limited. Examples of such shapes are acicular, spherical, or ellipsoidal.
- the solid electrolyte material may be particles.
- the solid electrolyte material may have the shape of pellets or plates.
- the solid electrolyte material When the shape of the solid electrolyte material is particulate (for example, spherical), the solid electrolyte material may have a median diameter of 0.1 ⁇ m or more and 100 ⁇ m or less, or a median diameter of 0.5 ⁇ m or more and 10 ⁇ m or less. diameter. This allows good dispersion of the solid electrolyte material and other materials.
- median particle size is meant the particle size for which the cumulative deposition in the volume-based particle size distribution is equal to 50%.
- the volume-based particle size distribution is measured by, for example, a laser diffraction measurement device or an image analysis device.
- a solid electrolyte material is manufactured, for example, by the following method.
- raw material powder of antimonide is mixed so as to have the desired composition.
- the raw powders may be mixed in pre-adjusted molar ratios to compensate for possible compositional variations in the synthesis process.
- Li metal or Sb metal may be used as the raw material.
- a mixture of raw material powders is mechanochemically reacted with each other in a mixing device such as a planetary ball mill to obtain a reactant. That is, the raw material powders are reacted with each other using the method of mechanochemical milling.
- the reactants may be fired in vacuum or in an inert atmosphere.
- a mixture of raw material powders may be fired in vacuum or in an inert atmosphere to obtain a reactant.
- inert atmospheres include helium atmosphere, argon atmosphere, and nitrogen atmosphere.
- the solid electrolyte material according to the first embodiment is obtained.
- a battery according to the second embodiment includes a positive electrode, an electrolyte layer, and a negative electrode.
- An electrolyte layer is disposed between the positive and negative electrodes.
- At least one selected from the group consisting of the positive electrode, the electrolyte layer, and the negative electrode contains the solid electrolyte material according to the first embodiment.
- the battery according to the second embodiment contains the solid electrolyte material according to the first embodiment, it has excellent charge/discharge characteristics.
- FIG. 1 shows a cross-sectional view of a battery 1000 according to the second embodiment.
- a battery 1000 includes a positive electrode 201 , an electrolyte layer 202 and a negative electrode 203 .
- Electrolyte layer 202 is provided between positive electrode 201 and negative electrode 203 .
- a positive electrode 201 contains a positive electrode active material 204 and a solid electrolyte 100 .
- the negative electrode 203 contains a negative electrode active material 205 and a solid electrolyte 100 .
- the solid electrolyte 100 includes the solid electrolyte material according to the first embodiment.
- the solid electrolyte 100 may be particles containing the solid electrolyte material according to the first embodiment as a main component.
- a particle containing the solid electrolyte material according to the first embodiment as a main component means a particle in which the component contained in the largest molar ratio is the solid electrolyte material according to the first embodiment.
- the solid electrolyte 100 may be particles made of the solid electrolyte material according to the first embodiment.
- the positive electrode 201 contains a material capable of intercalating and deintercalating metal ions such as lithium ions.
- the material is, for example, the positive electrode active material 204 .
- positive electrode active materials are lithium-containing transition metal oxides, transition metal fluorides, polyanion materials, fluorinated polyanion materials, transition metal sulfides, transition metal oxyfluorides, transition metal oxysulfides, or transition metal oxynitrides.
- lithium-containing transition metal oxides are Li(Ni,Co,Mn) O2 , Li(Ni,Co,Al) O2 or LiCoO2 .
- (A, B, C) means "at least one selected from the group consisting of A, B, and C.”
- the shape of the positive electrode active material 204 is not limited to a specific shape.
- the cathode active material 204 may be particles.
- the positive electrode active material 204 may have a median diameter of 0.1 ⁇ m or more and 100 ⁇ m or less.
- positive electrode active material 204 and solid electrolyte 100 can be well dispersed in positive electrode 201 . Thereby, the charge/discharge characteristics of the battery 1000 are improved.
- the positive electrode active material 204 has a median diameter of 100 ⁇ m or less, the diffusion rate of lithium in the positive electrode active material 204 is improved. This allows battery 1000 to operate at high output.
- the positive electrode active material 204 may have a larger median diameter than the solid electrolyte 100 . Thereby, the positive electrode active material 204 and the solid electrolyte 100 can be well dispersed.
- the ratio of the volume of the positive electrode active material 204 to the total volume of the positive electrode active material 204 and the volume of the solid electrolyte 100 is 0.30 or more and 0.95 or less.
- the positive electrode 201 may have a thickness of 10 ⁇ m or more and 500 ⁇ m or less.
- the electrolyte layer 202 contains an electrolyte material.
- the electrolyte material is, for example, a solid electrolyte material.
- the electrolyte layer 202 may be a solid electrolyte layer.
- the electrolyte layer 202 may contain the solid electrolyte material according to the first embodiment.
- the electrolyte layer 202 may contain 50% by mass or more of the solid electrolyte material according to the first embodiment.
- the electrolyte layer 202 may contain 70% by mass or more of the solid electrolyte material according to the first embodiment.
- the electrolyte layer 202 may contain 90% by mass or more of the solid electrolyte material according to the first embodiment.
- the electrolyte layer 202 may consist only of the solid electrolyte material according to the first embodiment.
- the solid electrolyte material according to the first embodiment is hereinafter referred to as the first solid electrolyte material.
- a solid electrolyte material different from the first solid electrolyte material is referred to as a second solid electrolyte material.
- the electrolyte layer 202 may contain not only the first solid electrolyte material but also the second solid electrolyte material. In the electrolyte layer 202, the first solid electrolyte material and the second solid electrolyte material may be uniformly dispersed. A layer made of the first solid electrolyte material and a layer made of the second solid electrolyte material may be stacked along the stacking direction of battery 1000 .
- the electrolyte layer 202 may consist only of the second solid electrolyte material.
- the electrolyte layer 202 may have a thickness of 1 ⁇ m or more and 1000 ⁇ m or less. When the electrolyte layer 202 has a thickness of 1 ⁇ m or more, the short circuit between the positive electrode 201 and the negative electrode 203 is less likely to occur. If the electrolyte layer 202 has a thickness of 1000 ⁇ m or less, the battery 1000 can operate at high power.
- the negative electrode 203 contains a material capable of intercalating and deintercalating metal ions such as lithium ions.
- the material is, for example, the negative electrode active material 205 .
- Examples of the negative electrode active material 205 are metal materials, carbon materials, oxides, nitrides, tin compounds, or silicon compounds.
- the metallic material may be a single metal or an alloy.
- Examples of metallic materials are lithium metal or lithium alloys.
- Examples of carbon materials are natural graphite, coke, ungraphitized carbon, carbon fibers, spherical carbon, artificial graphite, or amorphous carbon.
- suitable examples of negative electrode active material 205 are silicon (ie, Si), tin (ie, Sn), silicon compounds, or tin compounds.
- the shape of the negative electrode active material 205 is not limited to a specific shape.
- the negative electrode active material 205 may be particles.
- the negative electrode active material 205 may have a median diameter of 0.1 ⁇ m or more and 100 ⁇ m or less.
- negative electrode active material 205 and solid electrolyte 100 can be well dispersed in negative electrode 203 . Thereby, the charge/discharge characteristics of the battery 1000 are improved.
- the negative electrode active material 205 has a median diameter of 100 ⁇ m or less, the diffusion rate of lithium in the negative electrode active material 205 is improved. This allows battery 1000 to operate at high output.
- the negative electrode active material 205 may have a larger median diameter than the solid electrolyte 100 . Thereby, the negative electrode active material 205 and the solid electrolyte 100 can be well dispersed.
- the ratio of the volume of the negative electrode active material 205 to the total volume of the negative electrode active material 205 and the volume of the solid electrolyte 100 is 0.30 or more and 0.95 or less.
- the negative electrode 203 may have a thickness of 10 ⁇ m or more and 500 ⁇ m or less.
- At least one selected from the group consisting of positive electrode 201, electrolyte layer 202, and negative electrode 203 contains a second solid electrolyte material for the purpose of enhancing ion conductivity, chemical stability, and electrochemical stability. may be
- the second solid electrolyte material may be a halide solid electrolyte.
- halide solid electrolytes are Li 2 MgX′ 4 , Li 2 FeX′ 4 , Li(Al,Ga,In)X′ 4 or Li 3 (Al,Ga,In)X′ 6 .
- X' is at least one selected from the group consisting of F, Cl, Br and I.
- halide solid electrolyte is the compound represented by Li p Me q Y r Z 6 .
- Me is at least one element selected from the group consisting of metal elements other than Li and Y and metalloid elements.
- the value of m' represents the valence of Me.
- Simetallic elements are B, Si, Ge, As, Sb, and Te.
- Metallic element means all elements contained in groups 1 to 12 of the periodic table (excluding hydrogen) and all elements contained in groups 13 to 16 of the periodic table (however, , B, Si, Ge, As, Sb, Te, C, N, P, O, S, and Se).
- Z is at least one selected from the group consisting of F, Cl, Br and I;
- Me is selected from the group consisting of Mg, Ca, Sr, Ba, Zn, Sc, Al, Ga, Bi, Zr, Hf, Ti, Sn, Ta, and Nb. may be at least one.
- the second solid electrolyte material may be a sulfide solid electrolyte.
- Examples of sulfide solid electrolytes are Li 2 S—P 2 S 5 , Li 2 S—SiS 2 , Li 2 S—B 2 S 3 , Li 2 S—GeS 2 , Li 3.25 Ge 0.25 P 0 .75 S 4 , or Li 10 GeP 2 S 12 .
- the second solid electrolyte material may be an oxide solid electrolyte.
- oxide solid electrolytes are (i) a NASICON-type solid electrolyte such as LiTi2 ( PO4 ) 3 or elemental substitutions thereof; (ii) perovskite-type solid electrolytes such as (LaLi) TiO3 , (iii) LISICON -type solid electrolytes such as Li14ZnGe4O16 , Li4SiO4 , LiGeO4 or elemental substitutions thereof ; (iv) a garnet- type solid electrolyte such as Li7La3Zr2O12 or its elemental substitutions , or (v) Li3PO4 or its N substitutions, is.
- NASICON-type solid electrolyte such as LiTi2 ( PO4 ) 3 or elemental substitutions thereof
- perovskite-type solid electrolytes such as (LaLi) TiO3
- LISICON -type solid electrolytes such as Li14ZnGe4O16 , Li4SiO4 ,
- the second solid electrolyte material may be an organic polymer solid electrolyte.
- organic polymer solid electrolytes are polymeric compounds and lithium salt compounds.
- the polymer compound may have an ethylene oxide structure. Since a polymer compound having an ethylene oxide structure can contain a large amount of lithium salt, the ionic conductivity can be further increased.
- lithium salts are LiPF6 , LiBF4 , LiSbF6, LiAsF6 , LiSO3CF3 , LiN ( SO2CF3 ) 2 , LiN( SO2C2F5 ) 2 , LiN( SO2CF3 ) . ( SO2C4F9 ) , or LiC ( SO2CF3 )3 .
- One lithium salt selected from these may be used alone. Alternatively, a mixture of two or more lithium salts selected from these may be used.
- At least one selected from the group consisting of the positive electrode 201, the electrolyte layer 202, and the negative electrode 203 is composed of a non-aqueous electrolyte liquid, a gel electrolyte, or an ion electrolyte for the purpose of facilitating the transfer of lithium ions and improving the output characteristics of the battery. It may contain liquids.
- the non-aqueous electrolyte contains a non-aqueous solvent and a lithium salt dissolved in the non-aqueous solvent.
- non-aqueous solvents examples include cyclic carbonate solvents, chain carbonate solvents, cyclic ether solvents, chain ether solvents, cyclic ester solvents, chain ester solvents, or fluorine solvents.
- cyclic carbonate solvents are ethylene carbonate, propylene carbonate, or butylene carbonate.
- linear carbonate solvents are dimethyl carbonate, ethyl methyl carbonate, or diethyl carbonate.
- examples of cyclic ether solvents are tetrahydrofuran, 1,4-dioxane, or 1,3-dioxolane.
- linear ether solvents are 1,2-dimethoxyethane or 1,2-diethoxyethane.
- An example of a cyclic ester solvent is ⁇ -butyrolactone.
- An example of a linear ester solvent is methyl acetate.
- fluorosolvents are fluoroethylene carbonate, methyl fluoropropionate, fluorobenzene, fluoroethyl methyl carbonate, or fluorodimethylene carbonate.
- One non-aqueous solvent selected from these may be used alone. Alternatively, a mixture of two or more non-aqueous solvents selected from these may be used.
- lithium salts are LiPF6 , LiBF4 , LiSbF6, LiAsF6 , LiSO3CF3 , LiN ( SO2CF3 ) 2 , LiN( SO2C2F5 ) 2 , LiN( SO2CF3 ) . ( SO2C4F9 ) , or LiC ( SO2CF3 )3 .
- One lithium salt selected from these may be used alone. Alternatively, a mixture of two or more lithium salts selected from these may be used.
- the lithium salt concentration is, for example, 0.5 mol/liter or more and 2 mol/liter or less.
- a polymer material impregnated with a non-aqueous electrolyte can be used as the gel electrolyte.
- examples of polymeric materials are polyethylene oxide, polyacrylonitrile, polyvinylidene fluoride, polymethyl methacrylate, or polymers with ethylene oxide linkages.
- ionic liquids examples include (i) aliphatic chain quaternary salts such as tetraalkylammonium or tetraalkylphosphonium; (ii) aliphatic cyclic ammoniums such as pyrrolidiniums, morpholiniums, imidazoliniums, tetrahydropyrimidiniums, piperaziniums, or piperidiniums; or (iii) nitrogen-containing heterogeneous compounds such as pyridiniums or imidazoliums. ring aromatic cations, is.
- Examples of anions contained in ionic liquids are PF 6 ⁇ , BF 4 ⁇ , SbF 6 ⁇ , AsF 6 ⁇ , SO 3 CF 3 ⁇ , N(SO 2 CF 3 ) 2 ⁇ , N(SO 2 C 2 F 5 ) 2 ⁇ , N(SO 2 CF 3 )(SO 2 C 4 F 9 ) ⁇ , or C(SO 2 CF 3 ) 3 ⁇ .
- the ionic liquid may contain a lithium salt.
- At least one selected from the group consisting of the positive electrode 201, the electrolyte layer 202, and the negative electrode 203 may contain a binder for the purpose of improving adhesion between particles.
- binders include polyvinylidene fluoride, polytetrafluoroethylene, polyethylene, polypropylene, aramid resin, polyamide, polyimide, polyamideimide, polyacrylonitrile, polyacrylic acid, polyacrylic acid methyl ester, polyacrylic acid ethyl ester, Polyacrylic acid hexyl ester, polymethacrylic acid, polymethacrylic acid methyl ester, polymethacrylic acid ethyl ester, polymethacrylic acid hexyl ester, polyvinyl acetate, polyvinylpyrrolidone, polyether, polyether sulfone, hexafluoropolypropylene, styrene-butadiene rubber , or carboxymethyl cellulose.
- Copolymers can also be used as binders.
- binders are tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoroalkyl vinyl ethers, vinylidene fluoride, chlorotrifluoroethylene, ethylene, propylene, pentafluoropropylene, fluoromethyl vinyl ether, acrylic acid , and hexadiene.
- a mixture of two or more selected from the above materials may be used as the binder.
- At least one selected from the positive electrode 201 and the negative electrode 203 may contain a conductive aid for the purpose of increasing electronic conductivity.
- Examples of conductive aids include (i) graphites such as natural or artificial graphite; (ii) carbon blacks such as acetylene black or ketjen black; (iii) conductive fibers such as carbon or metal fibers; (iv) carbon fluoride, (v) metal powders such as aluminum; (vi) conductive whiskers such as zinc oxide or potassium titanate; (vii) a conductive metal oxide such as titanium oxide, or (viii) a conductive polymeric compound such as polyaniline, polypyrrole, or polythiophene; is.
- the conductive aid (i) or (ii) may be used.
- Examples of the shape of the battery according to the second embodiment are coin-shaped, cylindrical, rectangular, sheet-shaped, button-shaped, flat-shaped, and laminated.
- Example 1 Preparation of raw materials
- dry argon atmosphere an argon atmosphere having a dew point of ⁇ 60° C. or less
- These raw powders were ground and mixed in a mortar.
- a mixed powder was obtained.
- the mixed powder was calcined at 650° C. for 1 hour in a dry argon atmosphere.
- the obtained powder was pulverized in a mortar to obtain a Li 3 Sb powder.
- the solid electrolyte material according to Example 1 had a composition represented by Li2.2Sb0.2Te0.8 .
- FIG. 2 is a schematic diagram showing a pressure molding die 300 used to evaluate the ionic conductivity of solid electrolyte materials.
- the pressure forming die 300 had a punch upper part 301 , a frame mold 302 and a punch lower part 303 . Both the punch upper portion 301 and the punch lower portion 303 were made of electronically conductive stainless steel.
- the frame mold 302 was made of insulating polycarbonate.
- the ionic conductivity of the solid electrolyte material according to Example 1 was measured by the following method.
- the solid electrolyte material powder according to Example 1 (that is, the solid electrolyte material powder 101 in FIG. 2) was filled inside the pressure molding die 300 . Inside the pressing die 300, a pressure of 300 MPa was applied to the solid electrolyte material powder 101 according to Example 1 using an upper punch 301 and a lower punch 303. As shown in FIG.
- the upper punch 301 and lower punch 303 were connected to a potentiostat (Princeton Applied Research, VersaSTAT4) equipped with a frequency response analyzer.
- the punch upper part 301 was connected to the working electrode and the terminal for potential measurement.
- the punch bottom 303 was connected to the counter and reference electrodes.
- the impedance of the solid electrolyte material was measured by electrochemical impedance measurement at room temperature.
- FIG. 3 is a graph showing a Cole-Cole plot obtained by impedance measurement of the solid electrolyte material according to Example 4.
- the real value of the impedance at the measurement point where the absolute value of the phase of the complex impedance was the smallest was regarded as the resistance to ion conduction of the solid electrolyte material. See the arrow Rse shown in FIG. 3 for the real value.
- the ionic conductivity was calculated based on the following formula (4) using the resistance value.
- ⁇ represents ionic conductivity.
- S represents the contact area of the solid electrolyte material with the punch upper part 301 .
- S is equal to the cross-sectional area of the hollow portion of the frame mold 302 in FIG.
- Rse represents the resistance value of the solid electrolyte material in impedance measurement.
- t represents the thickness of the solid electrolyte material.
- t represents the thickness of the layer formed from the solid electrolyte material powder 101 in FIG.
- Li 6 PS 5 Cl 80 mg
- the solid electrolyte material according to Example 1 (30 mg)
- the above mixture are placed in this order. laminated.
- the amount of mixture was such that it contained 4 mg of graphite.
- a pressure of 740 MPa was applied to this laminate to form a solid electrolyte layer and a first electrode.
- current collectors made of stainless steel were attached to the first electrode and the second electrode, and current collecting leads were attached to the current collectors.
- Example 1 a battery according to Example 1 was obtained.
- the battery according to Example 1 was placed in a constant temperature bath at 25°C.
- Example 1 The cell according to Example 1 was then discharged at a current density of 74.5 ⁇ A/cm 2 until a voltage of 0.5 V was reached.
- the battery according to Example 1 had an initial discharge capacity of 229 mAh/g.
- Example 2 to 9 Preparation of solid electrolyte material
- the values of y are shown in Table 1.
- Example 6 after the milling treatment, firing was performed at 400 degrees for 0.5 hours in a dry argon atmosphere.
- Batteries according to Examples 2 to 5 were obtained in the same manner as in Example 1 using the solid electrolyte materials according to Examples 2 to 9.
- FIG. 4 is a graph showing the initial discharge characteristics of the battery according to Example 2.
- Li 2 Se As a solid electrolyte material according to Comparative Example 2, Li 2 Se was prepared.
- Li 2 S was prepared.
- LiI was prepared as a solid electrolyte material according to Comparative Example 4.
- the solid electrolyte material according to the present disclosure is a material that can improve lithium ion conductivity, and is suitable for providing batteries that can be charged and discharged satisfactorily.
- the solid electrolyte material of the present disclosure is used, for example, in batteries (eg, all-solid lithium ion secondary batteries).
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Abstract
Description
リチウムおよび複数のアニオン元素を含み、
前記複数のアニオン元素は、アンチモンと、アンチモンを除くプニクトゲン元素、カルコゲン元素、およびハロゲン元素からなる群より選択される少なくとも1種の元素と、を含む、固体電解質材料を提供する。
本実施形態の固体電解質材料は、リチウムおよび複数のアニオン元素を含む。複数のアニオン元素は、アンチモンと、アンチモンを除くプニクトゲン元素、カルコゲン元素、およびハロゲン元素からなる群より選択される少なくとも1種の元素と、を含む。
固体電解質材料は、例えば、下記の方法により、製造される。
以下、第2実施形態が説明される。第1実施形態において説明された事項は、適宜、省略され得る。
(i)LiTi2(PO4)3またはその元素置換体のようなNASICON型固体電解質、
(ii)(LaLi)TiO3のようなペロブスカイト型固体電解質、
(iii)Li14ZnGe4O16、Li4SiO4、LiGeO4またはその元素置換体のようなLISICON型固体電解質、
(iv)Li7La3Zr2O12またはその元素置換体のようなガーネット型固体電解質、または
(v)Li3PO4またはそのN置換体、
である。
(i)テトラアルキルアンモニウムまたはテトラアルキルホスホニウムのような脂肪族鎖状4級塩類、
(ii)ピロリジニウム類、モルホリニウム類、イミダゾリニウム類、テトラヒドロピリミジニウム類、ピペラジニウム類、またはピペリジニウム類のような脂肪族環状アンモニウム、または
(iii)ピリジニウム類またはイミダゾリウム類のような含窒ヘテロ環芳香族カチオン、
である。
イオン液体に含まれるアニオンの例は、PF6 -、BF4 -、SbF6 -、AsF6 -、SO3CF3 -、N(SO2CF3)2 -、N(SO2C2F5)2 -、N(SO2CF3)(SO2C4F9)-、またはC(SO2CF3)3 -である。
(i)天然黒鉛または人造黒鉛のようなグラファイト類、
(ii)アセチレンブラックまたはケッチェンブラックのようなカーボンブラック類、
(iii)炭素繊維または金属繊維のような導電性繊維類、
(iv)フッ化カーボン、
(v)アルミニウムのような金属粉末類、
(vi)酸化亜鉛またはチタン酸カリウムのような導電性ウィスカー類、
(vii)酸化チタンのような導電性金属酸化物、または
(viii)ポリアニリン、ポリピロール、またはポリチオフェンのような導電性高分子化合物、
である。低コスト化のために、上記(i)または(ii)の導電助剤が使用されてもよい。
(原料の作製)
-60℃以下の露点を有するアルゴン雰囲気(以下、「乾燥アルゴン雰囲気」という)中で、原料粉としてLiおよびSbが、3.5:1=Li:Sbのモル比となるように用意された。これらの原料粉が乳鉢中で粉砕され、混合された。このようにして、混合粉が得られた。混合粉は、乾燥アルゴン雰囲気下において650度で1時間焼成された。得られた粉末を乳鉢中で粉砕することで、Li3Sbの粉末が得られた。
乾燥アルゴン雰囲気中で、原料粉としてLi3SbおよびLi2Teが、2:8=Li3Sb:Li2Teのモル比となるように用意された。これらの原料粉が乳鉢中で粉砕され、混合された。このようにして、混合粉が得られた。混合粉は、遊星型ボールミルを用い、12時間、500rpmでミリング処理された。このようにして、実施例1による固体電解質材料の粉末が得られた。実施例1による固体電解質材料は、Li2.2Sb0.2Te0.8により表される組成を有していた。
図2は、固体電解質材料のイオン伝導度を評価するために用いられた加圧成形ダイス300を示す模式図である。
乾燥アルゴン雰囲気中で、実施例1による固体電解質材料およびグラファイトが、1:1の体積比となるように用意された。これらの材料は、乳鉢中で混合された。このようにして、混合物が得られた。
初期充放電特性は、下記の方法により測定された。
(固体電解質材料の作製)
実施例2から6では、原料粉として、Li3SbおよびLi2Teが、y:(1-y)=Li3Sb:Li2Teモル比となるように用意された。yの値は、表1に示される。
実施例2から9による固体電解質材料のイオン伝導度が、実施例1と同様に測定された。測定結果は、表1に示される。
実施例2から9による固体電解質材料を用いて、実施例1と同様にして、実施例2から5による電池が得られた。実施例2から9による電池は、実施例1による電池と同様に、良好に充電および放電された。
(固体電解質材料の作製)
比較例1による固体電解質材料として、Li2Teが用意された。
比較例1による固体電解質材料のイオン伝導度は、実施例1と同様に測定された。測定結果は、表1に示される。
表1において、「yまたはz」の項目は、組成式(2)におけるyの値または組成式(3)におけるzの値を表す。表1から明らかなように、実施例1から9による固体電解質材料は、室温近傍において、6.3×10-5S/cm以上の高いイオン伝導度を有する。したがって、リチウムとアニオンのアンチモンを含有する固体電解質材料は、高いイオン伝導度を有する。
101 固体電解質材料の粉末
201 正極
202 電解質層
203 負極
204 正極活物質
205 負極活物質
300 加圧成形ダイス
301 パンチ上部
302 枠型
303 パンチ下部
1000 電池
Claims (6)
- リチウムおよび複数のアニオン元素を含み、
前記複数のアニオン元素は、アンチモンと、アンチモンを除くプニクトゲン元素、カルコゲン元素、およびハロゲン元素からなる群より選択される少なくとも1種の元素と、を含む、
固体電解質材料。 - 以下の組成式(2)により表され、
Li2+ySbyCh1-y ・・・(2)
ここで、0<y<1、が充足され、
Chは、O、S、Se、およびTeからなる群より選択される少なくとも1つである、
請求項1に記載の固体電解質材料。 - 前記組成式(2)において、Chは、Teを含む、
請求項2に記載の固体電解質材料。 - 以下の組成式(3)により表され、
Li1+2zSbzHal1-z ・・・(3)
ここで、0<z<1、が充足され、
Halは、F、Cl、Br、およびIからなる群より選択される少なくとも1つである、
請求項1に記載の固体電解質材料。 - 前記組成式(3)において、Halは、Iを含む、
請求項4に記載の固体電解質材料。 - 正極、
負極、および
前記正極および前記負極の間に配置されている電解質層、
を備え、
前記正極、前記負極、および前記電解質層からなる群より選択される少なくとも1つは、請求項1から5のいずれか一項に記載の固体電解質材料を含有する、
電池。
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JP2020009595A (ja) * | 2018-07-05 | 2020-01-16 | 国立大学法人豊橋技術科学大学 | リチウムイオン伝導体及びその製造方法、リチウムイオン電池用電極並びにリチウムイオン電池 |
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WO2010084583A1 (ja) * | 2009-01-21 | 2010-07-29 | トヨタ自動車株式会社 | 硫化物固体電解質材料 |
JP2020009595A (ja) * | 2018-07-05 | 2020-01-16 | 国立大学法人豊橋技術科学大学 | リチウムイオン伝導体及びその製造方法、リチウムイオン電池用電極並びにリチウムイオン電池 |
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