WO2022259781A1 - Matériau d'électrolyte solide et batterie l'utilisant - Google Patents

Matériau d'électrolyte solide et batterie l'utilisant Download PDF

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WO2022259781A1
WO2022259781A1 PCT/JP2022/019227 JP2022019227W WO2022259781A1 WO 2022259781 A1 WO2022259781 A1 WO 2022259781A1 JP 2022019227 W JP2022019227 W JP 2022019227W WO 2022259781 A1 WO2022259781 A1 WO 2022259781A1
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solid electrolyte
lii
ybr
libr
cabr
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PCT/JP2022/019227
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English (en)
Japanese (ja)
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知行 小森
健介 若杉
武拓 田中
暁彦 相良
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パナソニックＩｐマネジメント株式会社
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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

Definitions

  • the present disclosure relates to solid electrolyte materials and batteries using the same.
  • Patent Document 1 discloses an all-solid battery using a sulfide solid electrolyte.
  • the purpose of the present disclosure is to provide a new solid electrolyte material suitable for lithium ion conduction.
  • the solid electrolyte material of the present disclosure contains Li, M, Y, Gd, and I, where M is at least two selected from the group consisting of Mg, Ca, Sr, Ba, and Zn.
  • the present disclosure provides a new solid electrolyte material suitable for lithium ion conduction.
  • 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 1.
  • FIG. 4 is a graph showing X-ray diffraction patterns of solid electrolyte materials according to Examples 1 to 25;
  • FIG. 5 is a graph showing the X-ray diffraction patterns of the solid electrolyte materials according to Examples 26-50.
  • FIG. 6 is a graph showing X-ray diffraction patterns of solid electrolyte materials according to Examples 51-75.
  • FIG. 7 is a graph showing the X-ray diffraction patterns of the solid electrolyte materials according to Examples 76-104.
  • 8 is a graph showing the initial discharge characteristics of the battery according to Example 1.
  • FIG. 1 shows a
  • the solid electrolyte material according to the first embodiment contains Li, M, Y, Gd, and I, and M is at least two selected from the group consisting of Mg, Ca, Sr, Ba, and Zn.
  • the solid electrolyte material according to the first embodiment is a solid electrolyte material suitable for ion conduction.
  • the solid electrolyte material according to the first embodiment may for example have a practical lithium ion conductivity, for example a high lithium ion conductivity.
  • the high lithium ion conductivity is, for example, 6.50 ⁇ 10 ⁇ 5 S/cm or more near room temperature.
  • the solid electrolyte material according to the first embodiment can have an ionic conductivity of, for example, 6.50 ⁇ 10 ⁇ 5 S/cm or more.
  • the solid electrolyte material according to the first embodiment can be used to obtain batteries with excellent charge/discharge characteristics.
  • An example of such a battery is an all solid state battery.
  • the all-solid-state battery may be a primary battery or a secondary battery.
  • the solid electrolyte material according to the first embodiment does not substantially contain sulfur.
  • the fact that the solid electrolyte material according to the first embodiment does not substantially contain sulfur means that the solid electrolyte material does not contain sulfur as a constituent element except sulfur that is unavoidably mixed as an impurity.
  • sulfur mixed as an impurity in the solid electrolyte material is, for example, 1 mol % or less.
  • a sulfur-free solid electrolyte material does not generate hydrogen sulfide even when exposed to the atmosphere, and is therefore excellent in safety.
  • the sulfide solid electrolyte disclosed in Patent Document 1 can generate hydrogen sulfide when exposed to the air.
  • the solid electrolyte material according to the first embodiment may contain elements that are unavoidably mixed. Examples of such elements are hydrogen, oxygen or nitrogen. 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.
  • the solid electrolyte material according to the first embodiment may consist essentially of Li, M, Y, Gd, and I.
  • the solid electrolyte material according to the first embodiment consists essentially of Li, M, Y, Gd, and I
  • the substance amount of all elements constituting the solid electrolyte material according to the first embodiment means that the ratio of the total amount of substances of Li, M, Y, Gd, and I (that is, the molar fraction) to the total of is 95% or more.
  • the solid electrolyte material according to the first embodiment may consist only of Li, M, Y, Gd, and I in order to increase the ionic conductivity of the solid electrolyte material.
  • the solid electrolyte material according to the first embodiment may further contain X in order to increase the ionic conductivity of the solid electrolyte material.
  • X is at least one selected from the group consisting of Cl and Br.
  • the solid electrolyte material according to the first embodiment may consist essentially of Li, M, Y, Gd, I, and X in order to increase the ionic conductivity of the solid electrolyte material.
  • the solid electrolyte material according to the first embodiment may consist of Li, M, Y, Gd, I, and X only.
  • M may contain Ca and at least one selected from the group consisting of Mg and Zn.
  • M may be Ca and at least one selected from the group consisting of Mg and Zn.
  • the solid electrolyte material according to the first embodiment may be represented by the following compositional formula (1).
  • M' is at least one selected from the group consisting of Mg and Zn, and the following formula: 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1, 0 ⁇ p ⁇ 1, 0 ⁇ q ⁇ 1, 0 ⁇ p+q ⁇ 1, 0 ⁇ a, 0 ⁇ b, and 0 ⁇ a+b ⁇ 1 is satisfied.
  • compositional formula (1) has high ionic conductivity.
  • the upper and lower limits of the range of x in the composition formula (1) are arbitrary values selected from numbers greater than 0, 0.1, 0.2, 0.5, 0.6, 0.9, and less than 1 It may be defined by a combination.
  • the formula: 0.1 ⁇ x ⁇ 0.9 may be satisfied, and the formula: 0.1 ⁇ x ⁇ 0.2 may be satisfied.
  • the upper and lower limits of the range of y in the composition formula (1) are greater than 0, 0.1, 0.2, 0.4, 0.5, 0.6, 0.8, 0.9, and 1 It may be defined by any combination selected from numerical values below.
  • the formula: 0.1 ⁇ y ⁇ 0.9 may be satisfied, and the formula: 0.4 ⁇ y ⁇ 0.8 may be satisfied.
  • the upper and lower limits of the range of p in the composition formula (1) are selected from 0, 0.2, 0.3, 0.4, 0.6, 0.8, 0.9, and numbers less than 1. may be defined by any combination of
  • the formula: 0 ⁇ p ⁇ 0.9 may be satisfied, and 0 ⁇ p ⁇ 0.9 may be satisfied.
  • the upper and lower limits of the range of q in the composition formula (1) are selected from numerical values greater than 0, 0.1, 0.2, 0.4, 0.6, 0.7, 0.8, and 1. may be defined by any combination of
  • the formula: 0 ⁇ q ⁇ 1 may be satisfied, and 0.1 ⁇ q ⁇ 0.7 may be satisfied.
  • the formula: 0.2 ⁇ q ⁇ 0.4 may be satisfied.
  • the upper and lower limits of the range of a in the composition formula (1) are numerical values greater than 0, 0.05, 0.1, 0.15, 0.2, 0.3, 0.4, and 0.5 may be defined by any combination selected from
  • the formula: 0.05 ⁇ a ⁇ 0.3 may be satisfied, and the formula: 0.05 ⁇ a ⁇ 0.15 is satisfied. may be filled.
  • the upper and lower limits of the range of b in the composition formula (1) are any values selected from 0, 0.05, 0.1, 0.15, 0.2, 0.25, and 0.3 It may be defined by a combination.
  • the formula: 0 ⁇ b ⁇ 0.3 may be satisfied, and the formula: 0 ⁇ b ⁇ 0.1 may be satisfied. good.
  • the formula: 0 ⁇ a+b ⁇ 0.6 may be satisfied, and 0 ⁇ a+b ⁇ 0.5 may be satisfied.
  • 0 ⁇ a+b ⁇ 0.4 may be satisfied, and 0 ⁇ a+b ⁇ 0.4 may be satisfied.
  • the X-ray diffraction pattern of the solid electrolyte material according to the first embodiment was obtained by X It can be obtained by line diffraction measurements.
  • the obtained X-ray diffraction pattern at least one peak exists in the range of the diffraction angle 2 ⁇ of 12.0° or more and 16.0° or less, and the diffraction angle 2 ⁇ is 24.0° or more and less than 29.0°. At least one peak may be present in the range of 2 ⁇ .
  • the crystalline phase with these peaks is called the first crystalline phase.
  • the solid electrolyte material containing the first crystal phase has high ionic conductivity because paths for diffusion of lithium ions are easily formed in the crystal.
  • the first crystal phase may further have at least one peak in the diffraction angle 2 ⁇ range of more than 32.0° and 35.0° or less.
  • the first crystal phase is attributed to monoclinic. That is, the solid electrolyte material according to the first embodiment may contain a crystal phase belonging to monoclinic crystals.
  • the “monoclinic crystal” in the present disclosure has a crystal structure similar to Li3ErBr6 disclosed in ICSD (Inorganic Crystal Structure Database) Collection Code 50182 , and a crystal phase having an X-ray diffraction pattern unique to this structure. means.
  • "having a similar crystal structure” means being classified into the same space group and having a close atomic arrangement structure, and does not limit lattice constants.
  • the solid electrolyte material according to the first embodiment obtained by X-ray diffraction measurement using Cu—K ⁇ rays, at least 1 one peak may be present.
  • a crystalline phase with these peaks is called a secondary crystalline phase.
  • the solid electrolyte material containing the second crystal phase has high ionic conductivity because paths for diffusion of lithium ions are easily formed in the crystal.
  • the second crystal phase is attributed to the trigonal crystal. That is, the solid electrolyte material according to the first embodiment may contain a crystal phase belonging to a trigonal crystal.
  • "Trigonal” in the present disclosure means a crystal phase having a similar crystal structure to Li3ErCl6 disclosed in ICSD (Inorganic Crystal Structure Database) Collection Code 50151 and having an X-ray diffraction pattern unique to this structure. do.
  • the solid electrolyte material according to the first embodiment may further contain a third crystal phase different from the first crystal phase and the second crystal phase. That is, the solid electrolyte material according to the first embodiment may further contain a third crystal phase having a peak outside the diffraction angle 2 ⁇ range described above.
  • the third crystal phase may be interposed between the first crystal phase and the second crystal phase.
  • the third crystal phase may, for example, belong to a cubic crystal.
  • "Orthogonal" in the present disclosure means a crystal phase having a crystal structure similar to Li3YbCl6 disclosed in ICSD (Inorganic Crystal Structure Database) Collection Code 50152 and having an X-ray diffraction pattern unique to this structure. do.
  • the solid electrolyte material according to the first embodiment may be a mixture of crystalline and amorphous.
  • crystalline refers to the presence of sharp peaks (that is, peaks) in the X-ray diffraction pattern.
  • Amorphous refers to the presence of broad peaks (ie halos) in the X-ray diffraction pattern. When amorphous and crystalline are mixed, there are peaks and halos in the X-ray diffraction pattern.
  • the shape of the solid electrolyte material according to the first embodiment is not limited. Examples of such shapes are acicular, spherical, or ellipsoidal.
  • the solid electrolyte material according to the first embodiment may be particles.
  • the solid electrolyte material according to the first embodiment may have the shape of pellets or plates.
  • the solid electrolyte material may have a median diameter of 0.1 ⁇ m or more and 100 ⁇ m or less, It may have a median diameter of 0.5 ⁇ m or more and 10 ⁇ m or less. Thereby, the solid electrolyte material according to the first embodiment and other materials can form a good dispersion state.
  • the median diameter of particles means the particle diameter (d50) corresponding to 50% of the cumulative volume in the volume-based particle size distribution.
  • the volume-based particle size distribution is measured by, for example, a laser diffraction measurement device or an image analysis device.
  • the solid electrolyte material according to the first embodiment is produced, for example, by the following method.
  • One or more halide raw material powders are mixed so as to have the desired composition.
  • the composition of interest is Li2.9Ca0.045Gd0.4Y0.6Mg0.005I2.4Br2.4Cl1.2 .
  • the raw material powders may be mixed in molar ratios adjusted in advance to compensate for possible compositional changes in the synthesis process.
  • a mixture of raw material powders is fired in an inert gas atmosphere to react with each other to obtain a reactant.
  • inert gases are helium, nitrogen, or argon. Firing may be performed in a vacuum.
  • the raw material powder mixture may be placed in a container (eg, a crucible and a vacuum sealed tube) and fired in a heating furnace.
  • the raw material powders may be 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 may be mixed and reacted using a mechanochemical milling method. The reactant thus obtained may be further calcined in an inert gas atmosphere or in vacuum.
  • the solid electrolyte material according to the first embodiment is obtained.
  • the composition of the solid electrolyte material can be determined by, for example, inductively coupled plasma atomic emission spectrometry or ion chromatography.
  • the composition of Li, M, Y and Gd can be determined by inductively coupled plasma atomic emission spectroscopy and the composition of I can be determined by ion chromatography.
  • the second embodiment describes a battery using the solid electrolyte material according to the first embodiment.
  • a battery according to the second embodiment includes a positive electrode, a negative electrode, and an electrolyte layer.
  • the electrolyte layer is provided between the positive electrode and the negative electrode.
  • 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.
  • the battery may be an all solid state battery.
  • FIG. 1 shows a cross-sectional view of a battery 1000 according to the second embodiment.
  • a battery 1000 according to the second embodiment 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 .
  • the positive electrode 201 contains positive electrode active material particles 204 and solid electrolyte particles 100 .
  • the electrolyte layer 202 contains an electrolyte material.
  • the negative electrode 203 contains negative electrode active material particles 205 and solid electrolyte particles 100 .
  • the solid electrolyte particles 100 are particles made of the solid electrolyte material according to the first embodiment, or particles containing the solid electrolyte material according to the first embodiment as a main component.
  • particles containing the solid electrolyte material according to the first embodiment as a main component means particles in which the component contained in the largest molar ratio is the solid electrolyte material according to the first embodiment.
  • the solid electrolyte particles 100 may have a median diameter of 0.1 ⁇ m or more and 100 ⁇ m or less. Solid electrolyte particles 100 having a median diameter of 0.5 ⁇ m or more and 10 ⁇ m or less have higher ionic conductivity.
  • the positive electrode 201 contains a material that can occlude and release metal ions (eg, lithium ions).
  • the material is, for example, a positive electrode active material (eg, positive electrode active material particles 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. be.
  • lithium - containing transition metal oxides are 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 positive electrode active material particles 204 may have a median diameter of 0.1 ⁇ m or more and 100 ⁇ m or less. When the positive electrode active material particles 204 have a median diameter of 0.1 ⁇ m or more, the positive electrode active material particles 204 and the solid electrolyte particles 100 can form a good dispersion state in the positive electrode 201 . This improves the charge/discharge characteristics of the battery. When the positive electrode active material particles 204 have a median diameter of 100 ⁇ m or less, the diffusion rate of lithium in the positive electrode active material particles 204 is improved. This allows the battery to operate at high output.
  • the positive electrode active material particles 204 may have a larger median diameter than the solid electrolyte particles 100 . Thereby, in the positive electrode 201, the positive electrode active material particles 204 and the solid electrolyte particles 100 can form a good dispersion state.
  • the ratio of the positive electrode active material particles 204 to the sum of the volume of the positive electrode active material particles 204 and the volume of the solid electrolyte particles 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 solid electrolyte material according to the first embodiment is called 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.
  • the first solid electrolyte material and the second solid electrolyte material may be uniformly dispersed in the electrolyte layer 202 .
  • 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.
  • the negative electrode 203 contains a material that can occlude and release metal ions.
  • the negative electrode 203 contains, for example, a negative electrode active material.
  • Examples of negative electrode active materials 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. From the viewpoint of capacity density, suitable examples of negative electrode active materials are silicon (ie, Si), tin (ie, Sn), silicon compounds, or tin compounds.
  • the negative electrode active material may be a material containing Li, Ti and O. That is, the negative electrode active material may be lithium titanium oxide. Examples of lithium titanium oxides are Li4Ti5O12 , Li7Ti5O12 or LiTi2O4 .
  • the negative electrode active material particles 205 may have a median diameter of 0.1 ⁇ m or more and 100 ⁇ m or less. When the negative electrode active material particles 205 have a median diameter of 0.1 ⁇ m or more, the negative electrode active material particles 205 and the solid electrolyte particles 100 can form a good dispersion state in the negative electrode 203 . This improves the charge/discharge characteristics of the battery. When the negative electrode active material particles 205 have a median diameter of 100 ⁇ m or less, the diffusion rate of lithium in the negative electrode active material particles 205 is improved. This allows the battery to operate at high output.
  • the negative electrode active material particles 205 may have a larger median diameter than the solid electrolyte particles 100 . Thereby, in the negative electrode 203, the negative electrode active material particles 205 and the solid electrolyte particles 100 can form a good dispersion state.
  • the ratio of the negative electrode active material particles 205 to the sum of the volume of the negative electrode active material particles 205 and the volume of the solid electrolyte particles 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 the positive electrode 201, the electrolyte layer 202, and the negative electrode 203 contains a second solid electrolyte material to enhance ionic conductivity, chemical stability, and electrochemical stability.
  • a second solid electrolyte material may be examples of the second solid electrolyte material are sulfide solid electrolytes, oxide solid electrolytes, halide solid electrolytes, or organic polymer solid electrolytes.
  • halide solid electrolytes are Li 2 MgX' 4 , Li 2 FeX' 4 , Li(Al,Ga,In)X' 4 , Li 3 (Al,Ga,In)X' 6 or LiI.
  • X' is at least one selected from the group consisting of F, Cl, Br and I.
  • a halide solid electrolyte is the compound represented by LiaMebYcZ6 .
  • Me is at least one selected from the group consisting of metal elements other than Li and Y and metalloid elements.
  • Z is at least one selected from the group consisting of F, Cl, Br and I;
  • the value of m represents the valence of Me.
  • “Semimetal elements” are B, Si, Ge, As, Sb, and Te.
  • Metallic elements are 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).
  • Me is selected from the group consisting of Mg, Ca, Sr, Ba, Zn, Sc, Al, Ga, Bi, Zr, Hf, Ti, Sn, Ta, and Nb. At least one may be selected.
  • halide solid electrolytes are Li3YCl6 or Li3YBr6 .
  • sulfide solid electrolytes are Li 2 SP 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 Li10GeP2S12 . _
  • oxide solid electrolytes are (i) NASICON - type solid electrolytes 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) garnet - type solid electrolytes such as Li7La3Zr2O12 or elemental substitutions thereof; or (v) Li3PO4 or its N - substitution.
  • NASICON - type solid electrolytes 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 , LiGeO4 or element
  • 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 a non-aqueous electrolyte, 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 heteroatoms such as pyridiniums or imidazoliums. ring aromatic cations, is.
  • Examples of anions contained in the ionic liquid 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( SO2CF3 ) ( SO2C4F9 ) - , or C ( SO2CF3 ) 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 in order to increase electronic conductivity.
  • Examples of conductive aids are (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.
  • a material for forming a positive electrode, a material for forming an electrolyte layer, and a material for forming a negative electrode are prepared, and the positive electrode, the electrolyte layer, and the negative electrode are arranged in this order by a known method. It may also be manufactured by making laminated laminates.
  • Example 1> (Preparation of solid electrolyte material) LiBr, LiI, MgBr 2 , CaBr 2 , YBr 3 , and GdCl 3 were used as raw material powders in an argon atmosphere having a dew point of ⁇ 60° C. or lower (hereinafter referred to as “dry argon atmosphere”).
  • dry argon atmosphere a dew point of ⁇ 60° C. or lower
  • :CaBr 2 :YBr 3 :GdCl 3 12.7:60.8:0.2:1.2:15.2:10.2.
  • These raw material flours were ground and mixed in an agate mortar. The resulting mixture was placed in an alumina crucible and fired at 500° C. for 1 hour in a dry argon atmosphere. The fired product obtained was ground in an agate mortar.
  • the solid electrolyte material powder according to Example 1 was obtained.
  • composition analysis of solid electrolyte material The contents of Li, Mg, Ca, Y, and Gd in the solid electrolyte material obtained in Example 1 were determined by high-frequency inductively coupled plasma using a high-frequency inductively coupled plasma atomic emission spectrometer (iCAP7400 manufactured by ThermoFisher Scientific). Measured by emission spectroscopy. The contents of Cl, Br, and I were measured by ion chromatography using an ion chromatograph (ICS-2000, manufactured by Dionex). From the measurement results, the composition of the solid electrolyte material was obtained.
  • the solid electrolyte material according to Example 1 had a composition represented by Li2.9Ca0.045Gd0.4Y0.6Mg0.005I2.4Br2.4Cl1.2 .
  • FIG. 2 shows a schematic diagram of a pressure forming 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 evaluated by the following method.
  • the solid electrolyte material powder 101 according to Example 1 was filled inside the pressure molding die 300 . Inside the pressure forming die 300, a pressure of 360 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 punch upper part 301 and the punch lower part 303 were connected to a potentiostat (Toyo Technica Co., Ltd., VSP-300) 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 1.
  • 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 R SE shown in FIG. 3 for the real value.
  • ⁇ represents ionic conductivity.
  • S represents the contact area of the solid electrolyte material with the punch upper part 301 (equal to the cross-sectional area of the hollow part of the frame mold 302 in FIG. 2).
  • R SE represents the resistance value of the solid electrolyte material in impedance measurement.
  • t represents the thickness of the solid electrolyte material (that is, the thickness of the layer formed from the solid electrolyte material powder 101 in FIG. 2).
  • (X-ray diffraction measurement) 4 is a graph showing an X-ray diffraction pattern of the solid electrolyte material according to Example 1.
  • FIG. An X-ray diffraction pattern was measured as follows.
  • the X-ray diffraction pattern of the solid electrolyte material of Example 1 was measured by the ⁇ -2 ⁇ method using an X-ray diffractometer (MiniFlex 600, Rigaku) in a dry environment with a dew point of ⁇ 50° C. or less.
  • Cu-K ⁇ radiation (wavelength 1.5405 ⁇ and 1.5444 ⁇ ) was used as the X-ray source.
  • the solid electrolyte material according to Example 1 In the X-ray diffraction pattern of the solid electrolyte material according to Example 1, at least one peak exists in the diffraction angle 2 ⁇ range of 12.0° or more and 16.0° or less, and 24.0° or more and 29.0°. There was at least one peak in the range of diffraction angles 2-theta less than . Therefore, the solid electrolyte material according to Example 1 had monoclinic crystals. A diffraction peak having the highest intensity (that is, the strongest peak) in the X-ray diffraction pattern was present in the range of 24.0° or more and less than 29.0°. The observed X-ray diffraction peak angles are shown in Table 6.
  • a negative electrode mixture (41.7 mg) and the solid electrolyte material (160 mg) according to Example 1 were layered in this order in an insulating cylinder having an inner diameter of 9.5 mm. A pressure of 360 MPa was applied to this laminate to form a negative electrode and a solid electrolyte layer.
  • metallic In thickness: 200 ⁇ m
  • metallic Li thickness: 300 ⁇ m
  • metallic In thickness: 200 ⁇ m
  • current collectors made of stainless steel were attached to the positive and negative electrodes, and current collecting leads were attached to the current collectors.
  • Example 1 a battery according to Example 1 was obtained.
  • (Charging and discharging test) 8 is a graph showing the initial discharge characteristics of the battery according to Example 1.
  • FIG. The horizontal axis represents discharge capacity.
  • the vertical axis represents voltage.
  • Initial charge/discharge characteristics were measured by the following method.
  • the battery according to Example 1 was placed in a constant temperature bath at 25°C.
  • Example 1 At a current density of 17 ⁇ A/cm 2 the cell according to Example 1 was charged until a potential of 0.4 V versus Li was reached.
  • Example 1 The cell according to Example 1 was then discharged at a current density of 17 ⁇ A/cm 2 until a potential of 1.9 V versus Li was reached.
  • the battery according to Example 1 had an initial discharge capacity of 168.3 mAh/g.
  • Example 2 (Preparation of solid electrolyte material)
  • a molar ratio of .1:62.4:0.3:1.1:16.4:10.4:0.6 was provided.
  • a molar ratio of 3:31.2:0.2:1.2:16.4:10.4:0.6 was provided.
  • a molar ratio of .7:60.8:0.3:1.1:10.2:10.2:5.1 was provided.
  • a molar ratio of .8:62.4:0.8:3.2:5.2:10.4:10.4 was provided.
  • a molar ratio of .8:62.4:0.8:3.2:10.4:10.4:5.2 was provided.
  • a molar ratio of .8:62.4:0.4:3.6:10.4:10.4:5.2 was provided.
  • a molar ratio of 3:31.2:0.2:1.2:4.5:6.5:16.4 was prepared.
  • a molar ratio of .8:62.4:0.4:3.6:5.2:10.4:10.4 was provided.
  • a molar ratio of .2:31.6:0.3:2.4:4.5:6.6:16.6 was provided.
  • a molar ratio of 1:30.8:0.3:2.4:5.2:5.2:15.4 was prepared.
  • a molar ratio of .6:24.2:0.2:1.4:0.3:23:15.6 was provided.
  • a molar ratio of .1:62.4:0.2:1.2:2.8:10.4:14.2 was provided.
  • a molar ratio of .2:31.6:0.3:2.4:5.6:21.1:1.1 was provided.
  • a molar ratio of 3:31.2:0.2:1.2:5.5:20.8:1.1 was prepared.
  • a molar ratio of 3:31.2:0.3:1.1:5.5:20.8:1.1 was prepared.
  • a molar ratio of .6:1.8:0.2:1.4:21.8:11.6:2.9 was provided.
  • a molar ratio of .2:28.3:0.6:5.2:0.3:19.5:13.2 was provided.
  • a molar ratio of .1:62.4:0.2:1.2:2.8:10.4:14.2 was provided.
  • a molar ratio of .1:62.4:0.3:1.1:16.4:10.4:0.6 was provided.
  • a molar ratio of .1:62.4:0.7:0.7:13.7:10.4:3.3 was provided.
  • a molar ratio of .1:62.4:0.2:1.2:7.7:16.9:2.8 was provided.
  • a molar ratio of .6:63.2:0.6:2.2:11.1:10.6:6.1 was provided.
  • a molar ratio of 3:31.2:0.2:1.2:16.4:10.4:0.6 was prepared.
  • a molar ratio of 1:30.4:0.2:1.2:5.1:5.1:15.2 was prepared.
  • a molar ratio of .2:31.6:0.6:2.2:5.6:21.1:1.1 was provided.
  • a molar ratio of 0.5:22.4:3:3:14.2:11.8:9.5 was provided.
  • a molar ratio of .6:5.3:14.2:11.8:9.5 was provided.
  • a molar ratio of .1:62.4:1.2:0.2:2.8:10.4:14.2 was provided.
  • a molar ratio of .1:62.4:0.7:0.7:2.8:10.4:14.2 was provided.
  • Solid electrolyte materials according to Examples 2 to 120 were obtained in the same manner as in Example 1 except for the above matters.
  • composition analysis of solid electrolyte material In the same manner as in Example 1, the compositions of the solid electrolyte materials according to Examples 2 to 120 were analyzed. Tables 1 to 5 show the compositions of the solid electrolyte materials according to Examples 2 to 120, the values of the variables corresponding to the composition formula (1), and the elemental species of M.
  • FIG. 4 is a graph showing X-ray diffraction patterns of solid electrolyte materials according to Examples 1 to 25.
  • FIG. 5 is a graph showing the X-ray diffraction patterns of the solid electrolyte materials according to Examples 26-50.
  • FIG. 6 is a graph showing X-ray diffraction patterns of solid electrolyte materials according to Examples 51-75.
  • FIG. 7 is a graph showing the X-ray diffraction patterns of the solid electrolyte materials according to Examples 76-104. The observed X-ray diffraction peak angles are shown in Tables 6-9. All of the solid electrolyte materials according to Examples 2 to 104 had the first crystal phase.
  • Example 10 contained amorphous portions.
  • Batteries according to Examples 2 to 104 were obtained in the same manner as in Example 1 using the solid electrolyte materials according to Examples 2 to 104. A charge/discharge test was performed in the same manner as in Example 1 using the batteries according to Examples 2 to 104. As a result, the batteries according to Examples 2 to 104 were charged and discharged as well as the battery according to Example 1.
  • Comparative Example 1 (Preparation of solid electrolyte material)
  • a solid electrolyte material according to Comparative Example 1 was obtained in the same manner as in Example 1 except for the above matters.
  • composition analysis of solid electrolyte material In the same manner as in Example 1, the composition of the solid electrolyte material according to Comparative Example 1 was analyzed. Table 5 shows the composition of the solid electrolyte material according to Comparative Example 1, the variable values corresponding to the compositional formula (1), and the element type of M.
  • the solid electrolyte materials according to Examples 1 to 120 have a high lithium ion conductivity of 6.53 ⁇ 10 ⁇ 5 S/cm or more near room temperature.
  • the solid electrolyte material has high ionic conductivity. It is believed that this is because paths for diffusion of lithium ions are likely to be formed. If the value of x is 0.1 or more and 0.9 or less, the solid electrolyte material has higher ionic conductivity. This is believed to be because paths for diffusion of lithium ions are more likely to be formed. If the value of x is 0.1 or more and 0.2 or less, the solid electrolyte material has higher ionic conductivity. It is believed that this is because a path for diffusion of lithium ions is more likely to be formed, resulting in an optimal width for ion conduction.
  • the solid electrolyte material has high ionic conductivity. It is believed that this is because paths for diffusion of lithium ions are likely to be formed. If the value of y is 0.4 or more and 0.8 or less, the solid electrolyte material has higher ionic conductivity. If the value of y is 0.4 or more and 0.6 or less, the solid electrolyte material can have high ionic conductivity. It is considered that this is because the first crystal phase having high lithium ion conductivity is likely to be formed.
  • the solid electrolyte material can have high ionic conductivity. It is believed that this is because paths for diffusion of lithium ions are likely to be formed. If the value of p is 0.4 or the value of q is 0.2 or more and 0.4 or less, the solid electrolyte material can have high ionic conductivity. It is believed that this is because paths for lithium ion diffusion are more likely to be formed and are of optimal width for ionic conduction. If the values of p and q are 0.4, the solid electrolyte material can have high ionic conductivity. It is believed that this is because a path for diffusion of lithium ions is more likely to be formed, resulting in an optimal width for ion conduction.
  • the solid electrolyte material When the value of a is greater than 0, the value of b is 0 or more and less than 0.3, and a+b is less than 0.4, the solid electrolyte material has high ionic conductivity. It is believed that this is because paths for diffusion of lithium ions are likely to be formed. If the value of a is 0.05 or more and 0.15 or less and the value of b is 0 or more and 0.1 or less, the solid electrolyte material can have high ionic conductivity. It is believed that this is because the amount of lithium ions in the crystal is optimized. If the value of a is 0.05 or more and 0.1 or less and the value of b is 0 or more and 0.05 or less, the solid electrolyte material can have even higher ionic conductivity. It is believed that this is because the amount of lithium ions in the crystal is further optimized.
  • the solid electrolyte material according to the present disclosure has practical lithium ion conductivity.
  • Solid electrolyte materials according to the present disclosure are suitable for providing well chargeable and dischargeable batteries.
  • the solid electrolyte material of the present disclosure is used, for example, in batteries (eg, all-solid lithium ion secondary batteries).
  • Solid electrolyte particles 101 Solid electrolyte material powder 201 Positive electrode 202 Electrolyte layer 203 Negative electrode 204 Positive electrode active material particles 205 Negative electrode active material particles 300 Pressure molding die 301 Punch upper part 302 Frame mold 303 Punch lower part 1000 Battery

Abstract

Un matériau d'électrolyte solide selon la présente invention comprend Li, M, Y, Gd et I, M étant au moins deux éléments choisis dans le groupe constitué par Mg, Ca, Sr, Ba, et Zn. Une batterie selon la présente invention comporte une électrode positive 201, une électrode négative 203 et une couche d'électrolyte 202 qui est disposée entre l'électrode positive 201 et l'électrode négative 203, au moins l'un quelconque dans le groupe constitué de l'électrode positive 201, de l'électrode négative 203 et de la couche d'électrolyte 202 contient le matériau d'électrolyte.
PCT/JP2022/019227 2021-06-09 2022-04-28 Matériau d'électrolyte solide et batterie l'utilisant WO2022259781A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020137189A1 (fr) * 2018-12-26 2020-07-02 パナソニックＩｐマネジメント株式会社 Composition d'électrolyte solide et procédé de production d'un élément d'électrolyte solide
WO2021070595A1 (fr) * 2019-10-10 2021-04-15 パナソニックＩｐマネジメント株式会社 Matériau d'électrolyte solide et batterie faisant appel à celui-ci

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020137189A1 (fr) * 2018-12-26 2020-07-02 パナソニックＩｐマネジメント株式会社 Composition d'électrolyte solide et procédé de production d'un élément d'électrolyte solide
WO2021070595A1 (fr) * 2019-10-10 2021-04-15 パナソニックＩｐマネジメント株式会社 Matériau d'électrolyte solide et batterie faisant appel à celui-ci

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