WO2024058053A1 - Alkali metal element-containing halide, electrolyte, battery, and method for producing halide solid electrolyte - Google Patents

Alkali metal element-containing halide, electrolyte, battery, and method for producing halide solid electrolyte Download PDF

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WO2024058053A1
WO2024058053A1 PCT/JP2023/032725 JP2023032725W WO2024058053A1 WO 2024058053 A1 WO2024058053 A1 WO 2024058053A1 JP 2023032725 W JP2023032725 W JP 2023032725W WO 2024058053 A1 WO2024058053 A1 WO 2024058053A1
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alkali metal
mol
halide
metal element
containing halide
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French (fr)
Japanese (ja)
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篤典 土居
貴裕 平井
洋 陰山
セドリック タッセル
風華 丁
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住友化学株式会社
国立大学法人京都大学
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Publication of WO2024058053A1 publication Critical patent/WO2024058053A1/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/30—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6
    • C01F17/36—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6 halogen being the only anion, e.g. NaYF4
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G15/00—Compounds of gallium, indium or thallium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G17/00—Compounds of germanium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G19/00—Compounds of tin
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G25/00—Compounds of zirconium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G29/00—Compounds of bismuth
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G30/00—Compounds of antimony
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G33/00—Compounds of niobium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G35/00—Compounds of tantalum
    • 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
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/56—Solid electrolytes, e.g. gels; Additives therein
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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

Definitions

  • the present disclosure relates to an alkali metal-containing halide, an electrolyte, a battery, and a method for producing a halide solid electrolyte.
  • Solid electrolytes have attracted attention as electrolytes used in electrochemical devices such as lithium ion batteries (Patent Documents 1 to 3). Solid electrolytes have superior high-temperature durability and high-voltage resistance compared to conventional electrolytes, so they are useful for improving battery performance such as safety, high capacity, rapid charging and discharging, and pack energy density. It is believed that.
  • solid electrolytes of lithium and halides containing metal elements other than lithium are known as materials used for solid electrolytes of lithium ion batteries.
  • Halide solid electrolytes are highly flexible, so they do not require sintering, and they do not emit harmful substances such as H 2 S, so they are highly safe. It has no advantages.
  • halide solid electrolytes have room for improvement in ionic conductivity.
  • the present disclosure has been made in view of the above circumstances, and aims to provide an alkali metal-containing halide with excellent ionic conductivity, a method for producing a halide solid electrolyte, and an electrolyte and battery comprising the same. do.
  • a compound containing an alkali metal element at least one metal element M selected from the group consisting of Mg, Ca, Sr, Ba, Zn, Sc, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu, Y, Al, Ga, In, Bi, Sb, Ge, Ti, Zr, Hf, Sn, Nb, Ta, and W, and a halogen element, and having a crystal structure belonging to the space group P63mc .
  • the halogen element comprises Cl.
  • [3] The compound of [1] or [2], wherein the metal element includes a trivalent metal element.
  • [5] The compound according to any one of [1] to [4], wherein the metal element M contains at least one element selected from the group consisting of Al, Ga, In, Sc, La, and Y.
  • [6] The compound according to any one of [1] to [5], wherein the metal element M contains two or more kinds of metal elements.
  • an alkali metal-containing halide with excellent ionic conductivity a method for producing a halide solid electrolyte, and an electrolyte and a battery including the same.
  • FIG. 1 is a diagram showing the results of single crystal X-ray diffraction measurement corresponding to the c-axis direction (001 direction) for the sample of Example 1.
  • FIG. 2 shows powder X-ray diffraction patterns of samples of Examples 1 to 4.
  • FIG. 3 is a powder X-ray diffraction chart for three crystal polymorphs of Li 3 ScCl 6 .
  • FIG. 4 is a ball-and-stick and polyhedral representation of the structure of ⁇ -Li 3 ScCl 6 .
  • FIG. 5 is a Cole-Cole diagram of ionic conductivity in Example 3.
  • FIG. 6 is a diagram showing the results of a charge/discharge test conducted at 0.1 C for Example 1.
  • FIG. 7 is a diagram showing the results of a charge/discharge test conducted at 0.2C for Example 1.
  • FIG. 8 is a diagram showing the cycle number and discharge capacity for Example 1 and ⁇ -Li 3 ScCl 6 .
  • the compound of this embodiment includes an alkali metal element, Mg, Ca, Sr, Ba, Zn, Sc, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Contains at least one metal element M selected from the group consisting of Lu, Y, Al, Ga, In, Bi, Sb, Ge, Ti, Zr, Hf, Sn, Nb, Ta, and W, and a halogen element It has a crystal structure belonging to the space group P6 3 mc.
  • the compound of this embodiment is also called an alkali metal containing halide.
  • Such compounds have excellent ionic conductivity. Therefore, it can be used as an ion conductive material containing the alkali metal-containing halide of this embodiment.
  • the crystal structure can be identified by X-ray diffraction measurements. In particular, it can be identified by Rietveld analysis.
  • the alkali metal element contained in the alkali metal-containing halide of this embodiment may be any of Li, Na, K, Rb, and Cs, but may also contain at least one of Li, Na, and K; and Na, and may contain Li.
  • the proportion of one type of alkali metal element may be 80 mol% or more, 90 mol% or more, or 95 mol% or more.
  • the one kind of alkali metal element may be at least one of Li, Na, and K, it may be at least one of Li and Na, and it may be Li.
  • the content of the alkali metal element in the alkali metal-containing halide may be 10 to 40 mol%, 15 to 35 mol%, 20 to 40 mol%, based on the total amount of atoms contained in the alkali metal-containing halide. It may be up to 30 mol%.
  • the metal element M may contain at least one element selected from the group consisting of La, Y, Ga, In, Sc, Bi, Sb, Ge, Zr, Sn, Nb, and Ta, and may include Ga, In, It may contain at least one element selected from the group consisting of Sc, La, Y, Sb and Bi, and may contain at least one element selected from the group consisting of Ga, In, Sc and La. It may contain Sc.
  • the alkali metal-containing halide may contain only one type of metal element M, or may contain two or more types of metal elements M. Further, the alkali metal-containing halide may contain a trivalent metal element M. When two or more types of metal elements M are included, two or more types of trivalent metal elements M may be included, but a trivalent metal element M and a valence other than trivalent (for example, divalent or tetravalent) or above or tetravalent) metal element M may be included. Examples of the divalent metal element M include Mg, Ca, Sr, Ba, and Zn.
  • Trivalent metal elements M include Sc, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu, Y, Al, Ga, In, Bi, and Sb. Can be mentioned.
  • Examples of the tetravalent metal element M include Ge, Ti, Zr, Hf, and Sn.
  • Examples of the pentavalent metal element M include Nb, Ta, Sb, and Bi.
  • the metal elements M are selected from the group consisting of Sc, La, Y, Ga, In, Bi, Sb, Ge, Zr, Sn, Nb, and Ta. Sc and at least one element selected from the group consisting of Ga, Bi, Sb, Ge, Zr, Sn, Nb, and Ta. .
  • the content of trivalent metal elements may be 30 mol% or more, 40 mol% or more, 50 mol% or more, 80 mol% or more. Often, it may be 90 mol% or more, and it may be 95 mol% or more.
  • the content of Sc may be 30 mol% or more, 40 mol% or more, 50 mol% or more, 80 mol% or more, and 90 mol%. % or more, and may be 95 mol% or more.
  • the metal element M may include a trivalent metal element and a metal element other than trivalent.
  • the metal element other than trivalent may be a tetravalent metal element or a pentavalent metal element, and is at least one element selected from the group consisting of Ga, Ge, Sn, Zr, Bi, Nb, and Ta. It's good to be there.
  • the content of metal elements other than trivalent metal elements may be 50 mol% or less, may be 30 mol% or less, may be 20 mol% or less, and may be 15 mol% or less. The content may be 10 mol% or less.
  • the content of the metal element M in the alkali metal-containing halide may be 5 to 20 mol%, 8 to 15 mol%, 10 to 20 mol%, based on the total amount of atoms contained in the alkali metal-containing halide. It may be up to 15 mol%.
  • the halogen element contained in the alkali metal-containing halide of this embodiment may be any of F, Cl, Br, and I, and may contain at least one of Cl, Br, and I; , Cl, and Br, may contain at least one of F and Cl, and may contain Cl.
  • the alkali metal-containing halide may contain only one type of halogen element, or may contain two or more types of halogen elements. When the alkali metal-containing halide contains two or more types of halogen elements, the alkali metal-containing halide may contain Cl and at least one halogen element other than Cl, and may contain Cl and F. .
  • the content of the halogen element in the alkali metal-containing halide may be 40 to 80 mol%, 50 to 70 mol%, 55 to 80 mol%, based on the total amount of atoms contained in the alkali metal-containing halide. It may be 65 mol%.
  • the content of Cl in the alkali metal-containing halide may be 50 mol% or more, 60 mol% or more, 70 mol% or more based on the total amount of halogen elements contained in the alkali metal-containing halide. It may be 80 mol% or more.
  • the content of halogen elements other than Cl in the alkali metal-containing halide may be 50 mol% or less, 40 mol% or less, and 30 mol% or less based on the total amount of halogen elements contained in the alkali metal-containing halide. It may be mol% or less, and may be 20 mol% or less.
  • the content of halogen elements other than Cl in the alkali metal-containing halide may be 0.5 mol% or more, and 1 to 30 mol%, based on the total amount of halogen elements contained in the alkali metal-containing halide. It may well be between 3 and 20%.
  • the content of F in the alkali metal-containing halide may be 50 mol% or less, 40 mol% or less, and 30 mol% or less based on the total amount of halogen elements contained in the alkali metal-containing halide.
  • the amount may be 20 mol% or less.
  • the content of F in the alkali metal-containing halide may be 0.5 mol% or more, 1 to 30 mol%, 3 to 3 mol%, based on the total amount of halogen elements contained in the alkali metal-containing halide. It may be 20%.
  • the alkali metal-containing halide may be represented by the following compositional formula (1).
  • A is an alkali metal element
  • X is a halogen element
  • Z is an element other than A, M, and X, and 1 ⁇ 4, 0.5 ⁇ 2, 4 ⁇ 8, 0 ⁇ 0.5.
  • ⁇ may be between 1.5 and 3.5, and between 2 and 3.2. ⁇ may be between 0.8 and 1.5, and between 1 and 1.5. ⁇ may be between 5 and 7, and between 5.5 and 6.5. ⁇ may be 2.1 to 3.1, or 2.3 to 3.05. ⁇ may be between 0.9 and 1.4, and between 0.95 and 1.3. ⁇ may be between 5.7 and 6.3, and between 5.9 and 6.1. ⁇ may be from 0 to 0.1, may be from 0 to 0.01, may be from 0 to 0.001, and ⁇ may be 0.
  • the element that can be introduced as Z is not particularly limited, but may be, for example, at least one selected from the group consisting of C, N, P, O and S; There may be at least one of the following.
  • the method for producing the alkali metal-containing halide of the present embodiment may include, for example, a method including a step of heating a raw material under a pressure of 1 GPa or more.
  • the heating temperature may be 200° C. or more.
  • the pressure to be applied is preferably 2 GPa or more, more preferably 4 GPa or more. Also, it is preferably 15 GPa or less, more preferably 10 GPa or less.
  • the upper and lower limits can be arbitrarily combined. By controlling the pressure within this range, it becomes easy to stabilize the structure of the alkali metal-containing halide.
  • the heating temperature is more preferably 250° C. or higher.
  • the heating temperature is also preferably 1500° C. or lower, and more preferably 1300° C. or lower.
  • the temperature rise rate may be 5° C./min to 200° C./min, 10° C./min to 150° C./min, 20° C./min to 100° C./min, or 30° C./min to 80° C./min.
  • the time required to reach the target heating temperature from the ambient temperature may be 0.1 to 45 minutes, 1 to 30 minutes, 5 to 25 minutes, or 10 to 20 minutes.
  • the temperature drop rate may be 50° C./min to 500° C./min, 80° C./min to 400° C./min, 100° C./min to 300° C./min, or 150° C./min to 250° C./min.
  • the time required to reach the ambient temperature (e.g., 25° C.) from the heating temperature may be 0.1 to 20 minutes, 0.5 to 15 minutes, 1 to 10 minutes, or 2 to 8 minutes.
  • the retention time at the heating temperature may be 0.1 to 10 hours, may be 0.5 to 7 hours, or may be 1 to 5 hours.
  • the pressure may be applied until a predetermined pressure is reached, and then the material may be heated. Alternatively, the temperature may be lowered until the predetermined temperature is reached, and then the pressure may be lowered.
  • raw materials include halides of alkali metals and halides of metal element M.
  • the alkali metal-containing halide of this embodiment can be used, for example, as a material for electrochemical devices such as capacitors and batteries.
  • electrolyte (solid electrolyte) materials examples include electrolyte (solid electrolyte) materials.
  • the battery examples include batteries such as lithium ion batteries and sodium ion batteries that charge and discharge by moving alkali metal ions between a positive electrode and a negative electrode.
  • the alkali metal-containing halide of this embodiment can be used as an electrode material, and may be included in at least one of the positive electrode and the negative electrode.
  • a lithium ion battery includes a positive electrode, a negative electrode, and an electrolyte (solid electrolyte) disposed between the positive electrode and the negative electrode.
  • the alkali metal-containing halide of this embodiment (in this case, a lithium-containing halide) may be included in the electrolyte of a lithium ion battery.
  • the positive electrode of a lithium ion battery is not particularly limited, and may contain a positive electrode active material and, if necessary, a conductive additive, a binder, and the like.
  • the positive electrode may be one in which a layer containing these materials is formed on a current collector.
  • a lithium-containing composite metal oxide containing lithium (Li) and at least one transition metal selected from the group consisting of V, Cr, Mn, Fe, Co, Ni, and Cu is used.
  • Examples of such lithium composite metal oxides include LiCoO 2 , LiNiO 2 , LiMn 2 O 4 , Li 2 MnO 3 , LiNix Mny Co 1-x-y O 2 (0 ⁇ x+y ⁇ 1]), LiNix Co y Al 1-x-y O 2 [0 ⁇ x+y ⁇ 1]), LiCr 0.5 Mn 0.5 O 2 , LiFePO 4 , Li 2 FeP 2 O 7 , LiMnPO 4 , LiFeBO 3 , Li 3
  • Examples include V 2 (PO 4 ) 3 , Li 2 CuO 2 , Li 2 FeSiO 4 , Li 2 MnSiO 4 and the like.
  • the negative electrode of a lithium ion battery is not particularly limited, and may contain a negative electrode active material and, if necessary, a conductive aid, a binder, etc.
  • a negative electrode active material such as Li, Si, P, Sn, Si-Mn, Si-Co, Si-Ni, In, and Au, alloys containing these metals, carbon materials such as graphite, and lithium ions between the layers of the carbon materials. Examples include substances into which .
  • the material of the current collector is not particularly limited, and may be a single metal or an alloy of metals such as Cu, Mg, Ti, Fe, Co, Ni, Zn, Al, Ge, In, Au, Pt, Ag, and Pd.
  • the solid electrolyte layer may have multiple layers.
  • the structure may include a sulfide solid electrolyte layer.
  • a structure having a sulfide solid electrolyte layer between the solid electrolyte containing the lithium-containing halide of this embodiment and the negative electrode may be used.
  • the solid electrolyte layer containing a lithium-containing halide of this embodiment has high electrochemical stability, a short circuit will not occur within the battery even if it does not include a sulfide solid electrolyte layer and is in direct contact with the negative electrode. Hateful.
  • the sulfide solid electrolyte is not particularly limited, but includes, for example, Li 6 PS 5 Cl, Li 2 S-PS 5 , Li 10 GeP 2 S 12 , Li 9.6 P 3 S 12 , Li 9.54 Si 1. 74 P 1.44 S 11.7 Cl 0.3 , Li 3 PS 4 and the like.
  • Example 1 Synthesis of hexagonal Li 3 ScCl 6 ( ⁇ -Li 3 ScCl 6 )
  • stoichiometric amounts of LiCl and ScCl 3 were first mixed in a glove box with a nitrogen atmosphere. The mixture was then pressed into pellets with gold foil as a protective material. Typically, the pellets were inserted into a homemade gold crucible sleeve tube with a boron nitride (BN) lid. The sample-to-sleeve interface was then inserted into a graphite tube and encapsulated within a pyrophyllite cube for high-pressure reactions.
  • BN boron nitride
  • the sample cell was pressed to reach 5 GPa in 1 hour and then heated to 1000° C. for 3 hours. After being held at this temperature for 3 hours, the sample was quenched to room temperature within 5 minutes and then the pressure was released to atmospheric pressure for 2 hours. This yielded a lithium-containing chloride ( ⁇ -Li 3 ScCl 6 ).
  • Example 1' A lithium-containing chloride was produced in the same manner as in Example 1, except that the sample cell was pressed to a pressure of 8 GPa in 2 hours, and when the pressure was released, it was brought to atmospheric pressure in 12 hours.
  • FIG. 1 shows an X-ray diffraction measurement of the sample of Example 1 corresponding to the c-axis direction (001 direction).
  • Example 2 A lithium-containing chloride was produced in the same manner as in Example 1, except that LiCl and ScCl 3 were used in amounts having the composition shown in Table 2.
  • Example 5 A lithium-containing chloride was produced in the same manner as in Example 1, except that LiCl, ZrCl 4 and ScCl 3 were used in amounts having the composition shown in Table 2.
  • Example 20 A lithium-containing chloride was produced in the same manner as in Example 1, except that LiCl, LiF, and ScCl 3 were used in amounts having the composition shown in Table 2.
  • Comparative example 1 Ball mill Raw materials were prepared by weighing 0.3201 g of LiCl and 0.8799 g of ZrCl 4 in an argon atmosphere having a dew point of -70° C. or lower (hereinafter referred to as dry argon atmosphere). The above raw materials were put into a 50 ml zirconia pot for a planetary ball mill described below, and 65 g of 4 mm diameter zirconia balls were added thereto. A crude composition of Comparative Example 1 was obtained by mechanochemically treating at 380 rpm for 48 hours. The ball mill was operated in a mode in which the ball mill was stopped for 1 minute after every 10 minutes of rotation, and the direction of rotation was alternately switched between clockwise and counterclockwise.
  • the charged composition of the lithium-containing chloride is Li 2 ZrCl 6 .
  • Planetary ball mill device PM 400 manufactured by Verder Scientific Co., Ltd. - Annealing
  • the crude composition of Comparative Example 1 obtained above was heated at 230° C. for 5 hours in an argon atmosphere to obtain a lithium-containing chloride of Comparative Example 1 with a charging composition of Li 2 ZrCl 6 .
  • Measuring device SmartLab (manufactured by Rigaku Co., Ltd.)
  • X-ray generator CuK ⁇ source, voltage 40kV, current 50mA
  • ⁇ -Li 3 ScCl 6 (Synthesis of ⁇ -Li 3 ScCl 6 ) ⁇ -Li 3 ScCl 6 was obtained by heating a stoichiometric mixture of LiCl and ScCl 3 at 650° C. for 12 hours in a sealed silica tube. In addition, the temperature increase rate during heating was 2° C./min, and the temperature decreasing rate was also 2° C./min.
  • FIG. 3 shows the three crystal polymorphs of Li 3 ScCl 6 obtained by performing powder X-ray diffraction measurements on a sample ground in an agate mortar under the same conditions as the powder X-ray diffraction measurements described above. It is an X-ray diffraction chart.
  • Li 3 ScCl 6 has an ⁇ phase ( ⁇ -Li 3 ScCl 6 ) having a monoclinic (space group: C2/m) crystal structure and a cubic (space group: Fd-3m) crystal structure. It is known that two types of crystal polymorphs of the ⁇ phase ( ⁇ -Li 3 ScCl 6 ) exist. As shown in FIG.
  • Li 3 ScCl 6 synthesized as described above has a hexagonal crystal structure (space group: P6 3 mc), and is a novel crystal structure different from both ⁇ and ⁇ phases. It has a structure. Li 3 ScCl 6 with this new crystal structure is also called ⁇ -Li 3 ScCl 6 .
  • the wavelength of the CuK ⁇ ray (1.54059 ⁇ ) was input into crystal structure analysis software VESTA (Visualization for Electronic and Structural Analysis). By performing a simulation (theoretical calculation), a diffraction chart of ⁇ phase-Li 3 ScCl 6 was obtained. It also agrees well with the diffraction chart of ⁇ phase-Li 3 ScCl 6 (lowermost graph) obtained by theoretical calculation.
  • Table 1 shows ⁇ -Li 3 ScCl 6 crystal data obtained from single-crystal X-ray diffraction at 123K and structure optimization data.
  • Li 3 ScCl 6 -5 GPa and Li 3 ScCl 6 -8 GPa refer to samples obtained under pressures of 5 GPa and 8 GPa (ie Example 1 and Example 1'), respectively.
  • FIG. 4 is a ball-and-stick and polyhedral representation of the structure of ⁇ -Li 3 ScCl 6 .
  • a pressure molding die including a frame, a punch lower part, and a punch upper part was prepared.
  • the frame mold was made of insulating polycarbonate.
  • both the punch upper part and the punch lower part were made of electronically conductive stainless steel, and were electrically connected to terminals of an impedance analyzer (Solatron Analytical, Sl1260).
  • the ionic conductivity of the lithium-containing halide was measured by the following method. First, in a dry argon atmosphere, lithium-containing halide powder was filled onto the lower part of a punch inserted into the hollow part of the frame from vertically below. Then, by pushing the upper part of the punch into the hollow part of the frame from above, a pressure of 370 MPa was applied to the lithium-containing halide powder inside the pressure molding die. After pressure is applied, the punch is tightened and fixed from above and below with a jig, and while a constant pressure is maintained, the lithium-containing halide is measured by electrochemical impedance measurement using the impedance analyzer described above. Impedance was measured.
  • a Cole-Cole diagram was created from the impedance measurement results.
  • 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 value of the halide solid electrolyte material to ionic conduction.
  • the ionic conductivity was calculated based on the following mathematical formula (III). Table 2 shows the ionic conductivity ( ⁇ 25°C ) of each sample at 25°C.
  • ⁇ (R SE ⁇ S/t) -1 ...(III) here, ⁇ is the ionic conductivity, S is the contact area of the lithium-containing halide with the upper part of the punch (equal to the cross-sectional area of the hollow part of the frame), R SE is the resistance value of the solid electrolyte material in impedance measurement, t is the thickness of the lithium-containing halide when pressure is applied.
  • FIG. 5 is a Cole-Cole diagram of ionic conductivity in Example 3.
  • FIG. 5 shows the measurement results at 25°C, 40°C, 60°C, 80°C and 100°C, respectively.
  • the charge/discharge test was carried out using the following product.
  • Charge/discharge tester Toyo System Co., Ltd. TOSCAT-3100
  • a charge/discharge test was conducted at 60° C. at three C rates: 0.1C, 1C, and 3C.
  • Charging was performed to 3.7 V using constant current and constant voltage (CCCV charging) at a current density corresponding to each C rate.
  • the discharge was carried out to 1.9V at a current density corresponding to each C rate.
  • a secondary battery was determined to be chargeable and dischargeable if an open circuit voltage was obtained without short circuiting after fabrication, and the charge capacity and discharge capacity were confirmed in the charge and discharge test described above.
  • Example 1 a charge/discharge test was conducted five times at a C rate of 0.1C and 0.2.
  • FIG. 6 is a diagram showing the results of a charge/discharge test conducted at 0.1 C for Example 1.
  • FIG. 7 is a diagram showing the results of a charge/discharge test conducted at 0.2C for Example 1.
  • FIG. 8 is a diagram showing the cycle number and discharge capacity for Example 1 and ⁇ -Li 3 ScCl 6 .
  • FIG. 8 shows the discharge capacity of ⁇ -Li 3 ScCl 6 measured for 5 cycles each at C rates of 0.1C, 0.2C, and 0.5C, and the discharge capacity measured for 10 cycles at 1C thereafter. Also shown is the discharge capacity of ⁇ -Li 3 ScCl 6 measured for 5 cycles each at a C rate of 0.1C and 0.2C.
  • the lithium-containing chlorides of Examples 1 to 5 and 20 had better ionic conductivity than the comparative example.
  • Li ion diffusion behavior was determined by calculating the Li mean square displacement of a compound belonging to the space group P6 3 mc based on a molecular dynamics simulation.
  • the density functional PBE was used, the nPT ensemble was used, the time step width was 1 fs, the simulation time was 300 ps, and the simulation temperature was 700K. Occupancy/occupancy of non-integer occupied number sites of trivalent atoms was selected according to the occupancy rate so as to be thermodynamically most stable.
  • Li ion mean square displacement ( ⁇ n (r(n, t) - r(n, 0)) 2 )/N...(nn)
  • r(n, t) is the coordinate of the n-th Li atom at time t
  • N is the total number of Li included in the calculation cell.
  • Example 1 Regarding ⁇ -Li 3 ScCl 6 of Example 1, the mean square displacement of Li in the compound was calculated based on molecular dynamics simulation. The results are listed in Table 3 below.
  • Example 12 For a compound having a crystal structure similar to ⁇ -Li 3 ScCl 6 and in which the Sc element site is occupied by two types of trivalent elements, the Li mean square displacement of the compound was calculated based on molecular dynamics simulation. I asked. For reference, an example in which Ga and Sc occupy 50 mol % of each site is shown, but this does not exclude other compositions. The results are listed in Table 3 below.
  • each of the compounds of Examples 1 and 6 to 19 exhibits a mean square displacement of Li ions of several ⁇ 2 or more.
  • the fact that the mean square displacement greatly exceeds several angstroms 2 means that Li is diffused in the solid, and the solid electrolyte is capable of conducting Li.

Abstract

Provided is a compound containing: an alkali metal element; at least one metal element M selected from the group consisting of Mg, Ca, Sr, Ba, Zn, Sc, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu, Y, Al, Ga, In, Bi, Sb, Ge, Ti, Zr, Hf, Sn, Nb, Ta, and W; and a halogen element, wherein the compound has a crystal structure belonging to a space group P63mc.

Description

アルカリ金属含有ハロゲン化物、電解質、電池及びハロゲン化物固体電解質の製造方法Alkali metal-containing halide, electrolyte, battery, and method for producing halide solid electrolyte
　本開示は、アルカリ金属含有ハロゲン化物、電解質、電池及びハロゲン化物固体電解質の製造方法に関する。 The present disclosure relates to an alkali metal-containing halide, an electrolyte, a battery, and a method for producing a halide solid electrolyte.
　近年、リチウムイオン電池等の電気化学デバイスに使用される電解質として、固体電解質が注目されている（特許文献１～３）。固体電解質は、従来の電解液と比較して、高温耐久性、高電圧耐性等に優れるため、安全性、高容量化、急速充放電、パックエネルギー密度などの電池の性能の向上に有用であると考えられている。 In recent years, solid electrolytes have attracted attention as electrolytes used in electrochemical devices such as lithium ion batteries (Patent Documents 1 to 3). Solid electrolytes have superior high-temperature durability and high-voltage resistance compared to conventional electrolytes, so they are useful for improving battery performance such as safety, high capacity, rapid charging and discharging, and pack energy density. It is believed that.
　特許文献１～３に記載されるように、リチウムイオン電池の固体電解質に使用される材料としてリチウム及びリチウム以外の金属元素を含むハロゲン化物の固体電解質が知られている。ハロゲン化物固体電解質は、柔軟性が高いため焼結を必要としないこと、Ｈ２Ｓ等の有害な物質を放出しないため安全性が高いことなど、酸化物系又は硫化物系の固体電解質にはない利点を備えている。 As described in Patent Documents 1 to 3, solid electrolytes of lithium and halides containing metal elements other than lithium are known as materials used for solid electrolytes of lithium ion batteries. Halide solid electrolytes are highly flexible, so they do not require sintering, and they do not emit harmful substances such as H 2 S, so they are highly safe. It has no advantages.
国際公開第２０２０１３７０２６号International Publication No. 2020137026 国際公開第２０２２０３２３１１号International Publication No. 2022032311 国際公開第２０２１２３４４１６号International Publication No. 2021234416
　しかしながら、ハロゲン化物固体電解質は、イオン伝導度に改善の余地がある。 However, halide solid electrolytes have room for improvement in ionic conductivity.
　本開示は上述の事情に鑑みてなされたものであり、イオン伝導度に優れるアルカリ金属含有ハロゲン化物、及びハロゲン化物固体電解質の製造方法、並びにそれらを備える電解質、及び電池を提供することを目的とする。 The present disclosure has been made in view of the above circumstances, and aims to provide an alkali metal-containing halide with excellent ionic conductivity, a method for producing a halide solid electrolyte, and an electrolyte and battery comprising the same. do.
　本開示は、以下の実施形態［１］～［１０］を含む。
［１］アルカリ金属元素と、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｚｎ、Ｓｃ、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｐｍ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｙｂ、Ｌｕ、Ｙ、Ａｌ、Ｇａ、Ｉｎ、Ｂｉ、Ｓｂ、Ｇｅ、Ｔｉ、Ｚｒ、Ｈｆ、Ｓｎ、Ｎｂ、Ｔａ、及びＷからなる群から選択される少なくとも一種の金属元素Ｍと、ハロゲン元素とを含有し、空間群Ｐ６３ｍｃに帰属される結晶構造を有する、化合物。
［２］前記ハロゲン元素がＣｌを含む、［２］の化合物。
［３］前記金属元素が３価の金属元素を含む、［１］又は［２］の化合物。
［４］下記組成式（１）で表される、［１］～［３］のいずれか一つの化合物。
ＡαＭβＸγ・・・（１）
（式中、Ａはアルカリ金属元素であり、Ｘは、ハロゲン元素であり、１≦α≦４、０．５≦β≦２、４≦γ≦８である。）
［５］金属元素ＭがＡｌ、Ｇａ、Ｉｎ、Ｓｃ、Ｌａ、及びＹからなる群から選択される少なくとも一種の元素を含む、［１］～［４］のいずれか一つの化合物。
［６］前記金属元素Ｍが２種以上の金属元素を含む、［１］～［５］のいずれか一つの化合物。
［７］前記ハロゲン元素が２種以上のハロゲン元素を含む、［１］～［６］のいずれか一つの化合物。
［８］［１］～［７］のいずれか一つの化合物を含む、電解質。
［９］［８］の電解質を含む、電池。
［１０］原料を１ＧＰａ以上の圧力下で加熱する工程を含む、ハロゲン化物固体電解質の製造方法。 The present disclosure includes the following embodiments [1] to [10].
[1] A compound containing an alkali metal element, at least one metal element M selected from the group consisting of Mg, Ca, Sr, Ba, Zn, Sc, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu, Y, Al, Ga, In, Bi, Sb, Ge, Ti, Zr, Hf, Sn, Nb, Ta, and W, and a halogen element, and having a crystal structure belonging to the space group P63mc .
[2] The compound according to [2], wherein the halogen element comprises Cl.
[3] The compound of [1] or [2], wherein the metal element includes a trivalent metal element.
[4] Any one of the compounds [1] to [3] represented by the following composition formula (1):
A α M β X γ ... (1)
(In the formula, A is an alkali metal element, X is a halogen element, and 1≦α≦4, 0.5≦β≦2, and 4≦γ≦8.)
[5] The compound according to any one of [1] to [4], wherein the metal element M contains at least one element selected from the group consisting of Al, Ga, In, Sc, La, and Y.
[6] The compound according to any one of [1] to [5], wherein the metal element M contains two or more kinds of metal elements.
[7] The compound according to any one of [1] to [6], wherein the halogen element comprises two or more kinds of halogen elements.
[8] An electrolyte comprising any one of the compounds according to [1] to [7].
[9] A battery comprising the electrolyte of [8].
[10] A method for producing a halide solid electrolyte, comprising the step of heating a raw material under a pressure of 1 GPa or more.
　本開示によれば、イオン伝導度に優れるアルカリ金属含有ハロゲン化物、及びハロゲン化物固体電解質の製造方法、並びにそれらを備える電解質、及び電池を提供することができる。 According to the present disclosure, it is possible to provide an alkali metal-containing halide with excellent ionic conductivity, a method for producing a halide solid electrolyte, and an electrolyte and a battery including the same.
図１は、実施例１のサンプルについてｃ軸方向（００１方向）に対応した単結晶Ｘ線回折測定の結果を示す図である。FIG. 1 is a diagram showing the results of single crystal X-ray diffraction measurement corresponding to the c-axis direction (001 direction) for the sample of Example 1. 図２は、実施例１～４のサンプルの粉末Ｘ線回折パターンである。FIG. 2 shows powder X-ray diffraction patterns of samples of Examples 1 to 4. 図３は、Ｌｉ３ＳｃＣｌ６の３つの結晶多形についての粉末Ｘ線回折チャートである。FIG. 3 is a powder X-ray diffraction chart for three crystal polymorphs of Li 3 ScCl 6 . 図４は、γ－Ｌｉ３ＳｃＣｌ６の構造のボール－アンド－スティック及び多面体表示である。FIG. 4 is a ball-and-stick and polyhedral representation of the structure of γ-Li 3 ScCl 6 . 図５は、実施例３のイオン伝導度のＣｏｌｅ－Ｃｏｌｅ線図である。FIG. 5 is a Cole-Cole diagram of ionic conductivity in Example 3. 図６は、実施例１について０．１Ｃで充放電試験を行った結果を示す図である。FIG. 6 is a diagram showing the results of a charge/discharge test conducted at 0.1 C for Example 1. 図７は、実施例１について０．２Ｃで充放電試験を行った結果を示す図である。FIG. 7 is a diagram showing the results of a charge/discharge test conducted at 0.2C for Example 1. 図８は、実施例１と、α－Ｌｉ３ＳｃＣｌ６について、サイクル数と放電容量を示す図である。FIG. 8 is a diagram showing the cycle number and discharge capacity for Example 1 and α-Li 3 ScCl 6 .
　本実施形態の化合物は、アルカリ金属元素と、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｚｎ、Ｓｃ、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｐｍ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｙｂ、Ｌｕ、Ｙ、Ａｌ、Ｇａ、Ｉｎ、Ｂｉ、Ｓｂ、Ｇｅ、Ｔｉ、Ｚｒ、Ｈｆ、Ｓｎ、Ｎｂ、Ｔａ、及びＷからなる群から選択される少なくとも一種の金属元素Ｍと、ハロゲン元素とを含有し、空間群Ｐ６３ｍｃに帰属される結晶構造を有する。なお、以下では、本実施形態の化合物をアルカリ金属含有ハロゲン化物とも呼ぶ。このような化合物はイオン伝導度に優れる。そのため、本実施形態のアルカリ金属含有ハロゲン化物を含むイオン伝導性物質として使用できる。
　結晶構造はＸ線回折測定によって同定することが可能である。特に、リートベルト解析によって同定することができる。 The compound of this embodiment includes an alkali metal element, Mg, Ca, Sr, Ba, Zn, Sc, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Contains at least one metal element M selected from the group consisting of Lu, Y, Al, Ga, In, Bi, Sb, Ge, Ti, Zr, Hf, Sn, Nb, Ta, and W, and a halogen element It has a crystal structure belonging to the space group P6 3 mc. In addition, below, the compound of this embodiment is also called an alkali metal containing halide. Such compounds have excellent ionic conductivity. Therefore, it can be used as an ion conductive material containing the alkali metal-containing halide of this embodiment.
The crystal structure can be identified by X-ray diffraction measurements. In particular, it can be identified by Rietveld analysis.
　また、ハロゲン化物固体電解質は、電気化学的な安定性に改善の余地があり、例えば、固体電解質として使用する場合に、負極との間に硫化物の分離膜を配置するなどしなければ、電池内で短絡が発生する場合がある。本実施形態のアルカリ金属含有ハロゲン化物は電気化学的な安定性にも優れる傾向にある。 In addition, there is room for improvement in electrochemical stability of halide solid electrolytes. For example, when used as a solid electrolyte, unless a sulfide separation membrane is placed between the negative electrode and the battery A short circuit may occur within the The alkali metal-containing halide of this embodiment also tends to have excellent electrochemical stability.
　本実施形態のアルカリ金属含有ハロゲン化物に含まれるアルカリ金属元素は、Ｌｉ、Ｎａ、Ｋ、Ｒｂ及びＣｓのいずれであってもよいが、Ｌｉ、Ｎａ及びＫの少なくとも一種を含んでいてよく、Ｌｉ及びＮａの少なくとも一方を含んでいてよく、Ｌｉを含んでいてよい。 The alkali metal element contained in the alkali metal-containing halide of this embodiment may be any of Li, Na, K, Rb, and Cs, but may also contain at least one of Li, Na, and K; and Na, and may contain Li.
　アルカリ金属含有ハロゲン化物に含まれるアルカリ金属元素のうち、１種のアルカリ金属元素の割合が８０モル％以上であってよく、９０モル％以上であってよく、９５モル％以上であってよい。当該１種のアルカリ金属元素はＬｉ、Ｎａ及びＫの少なくとも一種であってよく、Ｌｉ及びＮａの少なくとも一方であってよく、Ｌｉであってよい。 Among the alkali metal elements contained in the alkali metal-containing halide, the proportion of one type of alkali metal element may be 80 mol% or more, 90 mol% or more, or 95 mol% or more. The one kind of alkali metal element may be at least one of Li, Na, and K, it may be at least one of Li and Na, and it may be Li.
　アルカリ金属含有ハロゲン化物におけるアルカリ金属元素の含有量は、アルカリ金属含有ハロゲン化物に含まれる原子の総量に対して、１０～４０モル％であってよく、１５～３５モル％であってよく、２０～３０モル％であってよい。 The content of the alkali metal element in the alkali metal-containing halide may be 10 to 40 mol%, 15 to 35 mol%, 20 to 40 mol%, based on the total amount of atoms contained in the alkali metal-containing halide. It may be up to 30 mol%.
　金属元素Ｍは、Ｌａ、Ｙ、Ｇａ、Ｉｎ、Ｓｃ、Ｂｉ、Ｓｂ、Ｇｅ、Ｚｒ、Ｓｎ、Ｎｂ、及びＴａからなる群から選択される少なくとも一種の元素を含んでいてよく、Ｇａ、Ｉｎ、Ｓｃ、Ｌａ、Ｙ、Ｓｂ及びＢｉからなる群から選択される少なくとも一種の元素を含んでいてよく、Ｇａ、Ｉｎ、Ｓｃ、及びＬａからなる群から選択される少なくとも一種の元素を含んでいても良く、Ｓｃを含んでいてよい。 The metal element M may contain at least one element selected from the group consisting of La, Y, Ga, In, Sc, Bi, Sb, Ge, Zr, Sn, Nb, and Ta, and may include Ga, In, It may contain at least one element selected from the group consisting of Sc, La, Y, Sb and Bi, and may contain at least one element selected from the group consisting of Ga, In, Sc and La. It may contain Sc.
　アルカリ金属含有ハロゲン化物は、１種のみの金属元素Ｍを含んでいてもよいが、２種以上の金属元素Ｍを含んでいてよい。また、アルカリ金属含有ハロゲン化物は、３価の金属元素Ｍを含んでいてよい。２種以上の金属元素Ｍが含まれる場合、３価の金属元素Ｍが２種以上含まれていてもよいが、３価の金属元素Ｍと３価以外の価数（例えば２価若しくは４価以上、又は４価）の金属元素Ｍとが含まれていてもよい。２価の金属元素Ｍとしては、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、及びＺｎが挙げられる。３価の金属元素Ｍとしては、Ｓｃ、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｙｂ、Ｌｕ、Ｙ、Ａｌ、Ｇａ、Ｉｎ、Ｂｉ、及びＳｂが挙げられる。４価の金属元素ＭとしてはＧｅ、Ｔｉ、Ｚｒ、Ｈｆ、及びＳｎが挙げられる。５価の金属元素Ｍとしては、Ｎｂ、Ｔａ、Ｓｂ及びＢｉが挙げられる。アルカリ金属含有ハロゲン化物が金属元素Ｍを２種以上含む場合、金属元素Ｍは、Ｓｃと、Ｌａ、Ｙ、Ｇａ、Ｉｎ、Ｂｉ、Ｓｂ、Ｇｅ、Ｚｒ、Ｓｎ、Ｎｂ、及びＴａからなる群から選択される少なくとも一種の元素とを含んでいてよく、Ｓｃと、Ｇａ、Ｂｉ、Ｓｂ、Ｇｅ、Ｚｒ、Ｓｎ、Ｎｂ、及びＴａからなる群から選択される少なくとも一種の元素とを含んでいてよい。 The alkali metal-containing halide may contain only one type of metal element M, or may contain two or more types of metal elements M. Further, the alkali metal-containing halide may contain a trivalent metal element M. When two or more types of metal elements M are included, two or more types of trivalent metal elements M may be included, but a trivalent metal element M and a valence other than trivalent (for example, divalent or tetravalent) or above or tetravalent) metal element M may be included. Examples of the divalent metal element M include Mg, Ca, Sr, Ba, and Zn. Trivalent metal elements M include Sc, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu, Y, Al, Ga, In, Bi, and Sb. Can be mentioned. Examples of the tetravalent metal element M include Ge, Ti, Zr, Hf, and Sn. Examples of the pentavalent metal element M include Nb, Ta, Sb, and Bi. When the alkali metal-containing halide contains two or more metal elements M, the metal elements M are selected from the group consisting of Sc, La, Y, Ga, In, Bi, Sb, Ge, Zr, Sn, Nb, and Ta. Sc and at least one element selected from the group consisting of Ga, Bi, Sb, Ge, Zr, Sn, Nb, and Ta. .
　金属元素Ｍのうち、３価の金属元素の含有量は、３０モル％以上であってよく、４０モル％以上であってよく、５０モル％以上であってよく、８０モル％以上であってよく、９０モル％以上であってよく、９５モル％以上であってよい。金属元素Ｍのうち、Ｓｃの含有量は、３０モル％以上であってよく、４０モル％以上であってよく、５０モル％以上であってよく、８０モル％以上であってよく、９０モル％以上であってよく、９５モル％以上であってよい。 Of the metal elements M, the content of trivalent metal elements may be 30 mol% or more, 40 mol% or more, 50 mol% or more, 80 mol% or more. Often, it may be 90 mol% or more, and it may be 95 mol% or more. Among the metal elements M, the content of Sc may be 30 mol% or more, 40 mol% or more, 50 mol% or more, 80 mol% or more, and 90 mol%. % or more, and may be 95 mol% or more.
　金属元素Ｍは、３価の金属元素と、３価以外の金属元素とを含んでいてよい。３価以外の金属元素は、４価の金属元素又は５価の金属元素であってよく、Ｇａ、Ｇｅ、Ｓｎ、Ｚｒ、Ｂｉ、Ｎｂ、及びＴａからなる群から選択される少なくとも一種の元素であってよい。金属元素Ｍのうち、３価以外の金属元素の含有量は、５０モル％以下であってよく、３０モル％以下であってよく、２０モル％以下であってよく、１５モル％以下であってよく、１０モル％以下であってよい。 The metal element M may include a trivalent metal element and a metal element other than trivalent. The metal element other than trivalent may be a tetravalent metal element or a pentavalent metal element, and is at least one element selected from the group consisting of Ga, Ge, Sn, Zr, Bi, Nb, and Ta. It's good to be there. Among the metal elements M, the content of metal elements other than trivalent metal elements may be 50 mol% or less, may be 30 mol% or less, may be 20 mol% or less, and may be 15 mol% or less. The content may be 10 mol% or less.
　アルカリ金属含有ハロゲン化物における金属元素Ｍの含有量は、アルカリ金属含有ハロゲン化物に含まれる原子の総量に対して、５～２０モル％であってよく、８～１５モル％であってよく、１０～１５モル％であってよい。 The content of the metal element M in the alkali metal-containing halide may be 5 to 20 mol%, 8 to 15 mol%, 10 to 20 mol%, based on the total amount of atoms contained in the alkali metal-containing halide. It may be up to 15 mol%.
　本実施形態のアルカリ金属含有ハロゲン化物に含まれるハロゲン元素は、Ｆ、Ｃｌ、Ｂｒ、及びＩのうちいずれであってもよいが、Ｃｌ、Ｂｒ、及びＩの少なくとも一種を含んでいてよく、Ｆ、Ｃｌ及びＢｒの少なくとも一方を含んでいてよく、Ｆ及びＣｌの少なくとも一方を含んでいてよく、Ｃｌを含んでいてよい。アルカリ金属含有ハロゲン化物は、１種のみのハロゲン元素を含んでいてもよいが、２種以上のハロゲン元素を含んでいてもよい。アルカリ金属含有ハロゲン化物が２種以上のハロゲン元素を含む場合、アルカリ金属含有ハロゲン化物は、ＣｌとＣｌ以外のハロゲン元素のうち少なくとも一つとを含んでいてよく、ＣｌとＦとを含んでいてよい。 The halogen element contained in the alkali metal-containing halide of this embodiment may be any of F, Cl, Br, and I, and may contain at least one of Cl, Br, and I; , Cl, and Br, may contain at least one of F and Cl, and may contain Cl. The alkali metal-containing halide may contain only one type of halogen element, or may contain two or more types of halogen elements. When the alkali metal-containing halide contains two or more types of halogen elements, the alkali metal-containing halide may contain Cl and at least one halogen element other than Cl, and may contain Cl and F. .
　アルカリ金属含有ハロゲン化物におけるハロゲン元素の含有量は、アルカリ金属含有ハロゲン化物に含まれる原子の総量に対して、４０～８０モル％であってよく、５０～７０モル％であってよく、５５～６５モル％であってよい。アルカリ金属含有ハロゲン化物におけるＣｌの含有量は、アルカリ金属含有ハロゲン化物に含まれるハロゲン元素の総量に対して５０モル％以上であってよく、６０モル％以上であってよく、７０モル％以上であってよく、８０モル％以上であってよい。アルカリ金属含有ハロゲン化物におけるＣｌ以外のハロゲン元素の含有量は、アルカリ金属含有ハロゲン化物に含まれるハロゲン元素の総量に対して５０モル％以下であってよく、４０モル％以下であってよく、３０モル％以下であってよく、２０モル％以下であってよい。アルカリ金属含有ハロゲン化物におけるＣｌ以外のハロゲン元素の含有量は、アルカリ金属含有ハロゲン化物に含まれるハロゲン元素の総量に対して０．５モル％以上であってよく、１～３０モル％であってよく、３～２０％であってよい。アルカリ金属含有ハロゲン化物におけるＦの含有量は、アルカリ金属含有ハロゲン化物に含まれるハロゲン元素の総量に対して５０モル％以下であってよく、４０モル％以下であってよく、３０モル％以下であってよく、２０モル％以下であってよい。アルカリ金属含有ハロゲン化物におけるＦの含有量は、アルカリ金属含有ハロゲン化物に含まれるハロゲン元素の総量に対して０．５モル％以上であってよく、１～３０モル％であってよく、３～２０％であってよい。 The content of the halogen element in the alkali metal-containing halide may be 40 to 80 mol%, 50 to 70 mol%, 55 to 80 mol%, based on the total amount of atoms contained in the alkali metal-containing halide. It may be 65 mol%. The content of Cl in the alkali metal-containing halide may be 50 mol% or more, 60 mol% or more, 70 mol% or more based on the total amount of halogen elements contained in the alkali metal-containing halide. It may be 80 mol% or more. The content of halogen elements other than Cl in the alkali metal-containing halide may be 50 mol% or less, 40 mol% or less, and 30 mol% or less based on the total amount of halogen elements contained in the alkali metal-containing halide. It may be mol% or less, and may be 20 mol% or less. The content of halogen elements other than Cl in the alkali metal-containing halide may be 0.5 mol% or more, and 1 to 30 mol%, based on the total amount of halogen elements contained in the alkali metal-containing halide. It may well be between 3 and 20%. The content of F in the alkali metal-containing halide may be 50 mol% or less, 40 mol% or less, and 30 mol% or less based on the total amount of halogen elements contained in the alkali metal-containing halide. The amount may be 20 mol% or less. The content of F in the alkali metal-containing halide may be 0.5 mol% or more, 1 to 30 mol%, 3 to 3 mol%, based on the total amount of halogen elements contained in the alkali metal-containing halide. It may be 20%.
　アルカリ金属含有ハロゲン化物は、下記組成式（１）で表されるものであってよい。
ＡαＭβＸγＺδ・・・（１）
（式中、Ａはアルカリ金属元素であり、Ｘはハロゲン元素であり、ＺはＡ、Ｍ及びＸ以外の元素であり、１≦α≦４、０．５≦β≦２、４≦γ≦８、０≦δ≦０．５である。） The alkali metal-containing halide may be represented by the following compositional formula (1).
A α M β X γ Z δ ...(1)
(In the formula, A is an alkali metal element, X is a halogen element, Z is an element other than A, M, and X, and 1≦α≦4, 0.5≦β≦2, 4≦γ≦ 8, 0≦δ≦0.5.)
　αは、１．５～３．５であってよく、２～３．２であってよい。βは、０．８～１．５であってよく、１～１．５であってよい。γは５～７であってよく、５．５～６．５であってよい。αとしては２．１～３．1であってよく、２．３～３．０５であってよい。
　βは、０．９～１．４であってよく、０．９５～１．３であってよく。
　γは、５．７～６．３であってよく、５．９～６．１であってよい。
　δは、０～０．１であってよく、０～０．０１であってよく、０～０．００１であってよく、δは０であってもよい。
　Ｚとして導入できる元素は、特に限定はされないが、例えば、Ｃ、Ｎ、Ｐ、Ｏ及びＳからなる群から選択される少なくとも一つであってよく、Ｎ、Ｐ及びＳからなる群から選択される少なくとも一つであってよい。 α may be between 1.5 and 3.5, and between 2 and 3.2. β may be between 0.8 and 1.5, and between 1 and 1.5. γ may be between 5 and 7, and between 5.5 and 6.5. α may be 2.1 to 3.1, or 2.3 to 3.05.
β may be between 0.9 and 1.4, and between 0.95 and 1.3.
γ may be between 5.7 and 6.3, and between 5.9 and 6.1.
δ may be from 0 to 0.1, may be from 0 to 0.01, may be from 0 to 0.001, and δ may be 0.
The element that can be introduced as Z is not particularly limited, but may be, for example, at least one selected from the group consisting of C, N, P, O and S; There may be at least one of the following.
　本実施形態のアルカリ金属含有ハロゲン化物の製造方法としては、例えば、原料を１ＧＰａ以上の圧力下で加熱する工程を含む方法が挙げられる。加熱温度としては、２００℃以上であってよい。
　加圧する圧力としては、２ＧＰａ以上が好ましく、４ＧＰａ以上がより好ましい。また、１５ＧＰａ以下が好ましく、１０ＧＰａ以下が好ましい。上限と下限は任意に組み合わせることが可能である。この圧力範囲に制御することによって、アルカリ金属含有ハロゲン化物の構造を安定化させることが容易になる。
　加熱温度は２５０℃以上がより好ましい。また、加熱温度は１５００℃以下であることが好ましく、１３００℃以下であることが好ましい。この温度範囲に制御することによって、本実施形態のアルカリ金属含有ハロゲン化物の構造を安定化させることが容易になる。
　昇温レートは、５℃／分～２００℃／分であってよく、１０℃／分～１５０℃／分であってよく、２０℃／分～１００℃／分であってよく、３０℃／分～８０℃／分であってよい。雰囲気温度（例えば２５℃）から目的の加熱温度まで達するのに要する時間は、０．１～４５分であってよく、１～３０分であってよく、５～２５分であってよく、１０～２０分であってよい。
　降温レートは、５０℃／分～５００℃／分であってよく、８０℃／分～４００℃／分であってよく、１００℃／分～３００℃／分であってよく、１５０℃／分～２５０℃／分であってよい。加熱温度から雰囲気温度（例えば２５℃）まで達するのに要する時間は、０．１～２０分であってよく、０．５～１５分であってよく、１～１０分であってよく、２～８分であってよい。
　加熱温度での保持時間は、０．１～１０時間であってよく、０．５～７時間であってよく、１～５時間であってよい。
　圧力を所定の圧力となるまで印加した後、加熱しても良い。また、降温し、所定の温度となった後、圧力を降圧しても良い。 The method for producing the alkali metal-containing halide of the present embodiment may include, for example, a method including a step of heating a raw material under a pressure of 1 GPa or more. The heating temperature may be 200° C. or more.
The pressure to be applied is preferably 2 GPa or more, more preferably 4 GPa or more. Also, it is preferably 15 GPa or less, more preferably 10 GPa or less. The upper and lower limits can be arbitrarily combined. By controlling the pressure within this range, it becomes easy to stabilize the structure of the alkali metal-containing halide.
The heating temperature is more preferably 250° C. or higher. The heating temperature is also preferably 1500° C. or lower, and more preferably 1300° C. or lower. By controlling the temperature within this range, it becomes easy to stabilize the structure of the alkali metal-containing halide of this embodiment.
The temperature rise rate may be 5° C./min to 200° C./min, 10° C./min to 150° C./min, 20° C./min to 100° C./min, or 30° C./min to 80° C./min. The time required to reach the target heating temperature from the ambient temperature (e.g., 25° C.) may be 0.1 to 45 minutes, 1 to 30 minutes, 5 to 25 minutes, or 10 to 20 minutes.
The temperature drop rate may be 50° C./min to 500° C./min, 80° C./min to 400° C./min, 100° C./min to 300° C./min, or 150° C./min to 250° C./min. The time required to reach the ambient temperature (e.g., 25° C.) from the heating temperature may be 0.1 to 20 minutes, 0.5 to 15 minutes, 1 to 10 minutes, or 2 to 8 minutes.
The retention time at the heating temperature may be 0.1 to 10 hours, may be 0.5 to 7 hours, or may be 1 to 5 hours.
The pressure may be applied until a predetermined pressure is reached, and then the material may be heated. Alternatively, the temperature may be lowered until the predetermined temperature is reached, and then the pressure may be lowered.
　原料としては、アルカリ金属のハロゲン化物及び金属元素Ｍのハロゲン化物が挙げられる。 Examples of raw materials include halides of alkali metals and halides of metal element M.
　本実施形態のアルカリ金属含有ハロゲン化物は、例えば、キャパシタ、電池等の電気化学デバイスの材料として使用することができる。そのような材料としては、例えば、電解質（固体電解質）の材料が挙げられる。電池としては、リチウムイオン電池、ナトリウムイオン電池等の正極及び負極の間をアルカリ金属イオンが移動することにより充放電を行う電池が挙げられる。また、本実施形態のアルカリ金属含有ハロゲン化物は、電極材料として使用することができ、正極及び負極の少なくとも一方に含まれていてよい。 The alkali metal-containing halide of this embodiment can be used, for example, as a material for electrochemical devices such as capacitors and batteries. Examples of such materials include electrolyte (solid electrolyte) materials. Examples of the battery include batteries such as lithium ion batteries and sodium ion batteries that charge and discharge by moving alkali metal ions between a positive electrode and a negative electrode. Further, the alkali metal-containing halide of this embodiment can be used as an electrode material, and may be included in at least one of the positive electrode and the negative electrode.
　以下、本実施形態の電池について、リチウムイオン電池を例にとって説明する。リチウムイオン電池は、正極及び負極と、当該正極及び負極の間に配置された電解質（固体電解質）とを含む。本実施形態のアルカリ金属含有ハロゲン化物（この場合、リチウム含有ハロゲン化物である）は、リチウムイオン電池の電解質に含まれていてよい。
　リチウムイオン電池の正極としては、特に限定されず、正極活物質を含み、且つ必要に応じて導電助剤、結合剤等を含むものであってよい。
　正極は、これらの材料を含む層が集電体上に形成されたものであってよい。正極活物質としては、例えば、リチウム（Ｌｉ）と、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕからなる群から選択される少なくとも１種の遷移金属とを含むリチウム含有複合金属酸化物が挙げられる。このようなリチウム複合金属酸化物としては、例えば、ＬｉＣｏＯ２、ＬｉＮｉＯ２、ＬｉＭｎ２Ｏ４、Ｌｉ２ＭｎＯ３、ＬｉＮｉｘＭｎｙＣｏ１－ｘ－ｙＯ２［０＜ｘ＋ｙ＜１］）、ＬｉＮｉｘＣｏｙＡｌ１－ｘ－ｙＯ２［０＜ｘ＋ｙ＜１］）、ＬｉＣｒ０．５Ｍｎ０．５Ｏ２、ＬｉＦｅＰＯ４、Ｌｉ２ＦｅＰ２Ｏ７、ＬｉＭｎＰＯ４、ＬｉＦｅＢＯ３、Ｌｉ３Ｖ２（ＰＯ４）３、Ｌｉ２ＣｕＯ２、Ｌｉ２ＦｅＳｉＯ４、Ｌｉ２ＭｎＳｉＯ４などが挙げられる。 The battery of this embodiment will be described below, taking a lithium ion battery as an example. A lithium ion battery includes a positive electrode, a negative electrode, and an electrolyte (solid electrolyte) disposed between the positive electrode and the negative electrode. The alkali metal-containing halide of this embodiment (in this case, a lithium-containing halide) may be included in the electrolyte of a lithium ion battery.
The positive electrode of a lithium ion battery is not particularly limited, and may contain a positive electrode active material and, if necessary, a conductive additive, a binder, and the like.
The positive electrode may be one in which a layer containing these materials is formed on a current collector. As the positive electrode active material, for example, a lithium-containing composite metal oxide containing lithium (Li) and at least one transition metal selected from the group consisting of V, Cr, Mn, Fe, Co, Ni, and Cu is used. Can be mentioned. Examples of such lithium composite metal oxides include LiCoO 2 , LiNiO 2 , LiMn 2 O 4 , Li 2 MnO 3 , LiNix Mny Co 1-x-y O 2 (0<x+y<1]), LiNix Co y Al 1-x-y O 2 [0<x+y<1]), LiCr 0.5 Mn 0.5 O 2 , LiFePO 4 , Li 2 FeP 2 O 7 , LiMnPO 4 , LiFeBO 3 , Li 3 Examples include V 2 (PO 4 ) 3 , Li 2 CuO 2 , Li 2 FeSiO 4 , Li 2 MnSiO 4 and the like.
　リチウムイオン電池の負極としては特に限定されず、負極活物質を含み、且つ必要に応じて導電助剤、結合剤等を含むものであってよい。例えば、Ｌｉ、Ｓｉ、Ｐ、Ｓｎ、Ｓｉ－Ｍｎ、Ｓｉ－Ｃｏ、Ｓｉ－Ｎｉ、Ｉｎ、Ａｕなどの金属及びこれらの金属を含む合金、グラファイト等の炭素材料、当該炭素材料の層間にリチウムイオンが挿入された物質などを挙げることができる。 The negative electrode of a lithium ion battery is not particularly limited, and may contain a negative electrode active material and, if necessary, a conductive aid, a binder, etc. For example, metals such as Li, Si, P, Sn, Si-Mn, Si-Co, Si-Ni, In, and Au, alloys containing these metals, carbon materials such as graphite, and lithium ions between the layers of the carbon materials. Examples include substances into which .
　集電体の材質は特に限定されず、Ｃｕ、Ｍｇ、Ｔｉ、Ｆｅ、Ｃｏ、Ｎｉ、Ｚｎ、Ａｌ、Ｇｅ、Ｉｎ、Ａｕ、Ｐｔ、Ａｇ、Ｐｄ等の金属の単体又は合金であってよい。 The material of the current collector is not particularly limited, and may be a single metal or an alloy of metals such as Cu, Mg, Ti, Fe, Co, Ni, Zn, Al, Ge, In, Au, Pt, Ag, and Pd.
　固体電解質層としては、複数の層を有していて良い。例えば、本実施形態のリチウム含有ハロゲン化物を含む固体電解質層に加え、硫化物固体電解質層を有する構成であっても良い。本実施形態のリチウム含有ハロゲン化物を含む固体電解質と負極の間に硫化物固体電解質層を有する構成であっても良い。ただし、本実施形態のリチウム含有ハロゲン化物を含む固体電解質層は電気化学的な安定性が高いため、硫化物固体電解質層を含まず、直接負極と接していても電池内での短絡が発生しにくい。硫化物固体電解質としては特に限定はされないが、例えば、Ｌｉ６ＰＳ５Ｃｌ、Ｌｉ２Ｓ－ＰＳ５、Ｌｉ１０ＧｅＰ２Ｓ１２、Ｌｉ９．６Ｐ３Ｓ１２、Ｌｉ９．５４Ｓｉ１．７４Ｐ１．４４Ｓ１１．７Ｃｌ０．３、Ｌｉ３ＰＳ４などが挙げられる。 The solid electrolyte layer may have multiple layers. For example, in addition to the lithium-containing halide-containing solid electrolyte layer of this embodiment, the structure may include a sulfide solid electrolyte layer. A structure having a sulfide solid electrolyte layer between the solid electrolyte containing the lithium-containing halide of this embodiment and the negative electrode may be used. However, since the solid electrolyte layer containing a lithium-containing halide of this embodiment has high electrochemical stability, a short circuit will not occur within the battery even if it does not include a sulfide solid electrolyte layer and is in direct contact with the negative electrode. Hateful. The sulfide solid electrolyte is not particularly limited, but includes, for example, Li 6 PS 5 Cl, Li 2 S-PS 5 , Li 10 GeP 2 S 12 , Li 9.6 P 3 S 12 , Li 9.54 Si 1. 74 P 1.44 S 11.7 Cl 0.3 , Li 3 PS 4 and the like.
（実施例１：六方晶Ｌｉ３ＳｃＣｌ６（γ－Ｌｉ３ＳｃＣｌ６）の合成）
　γ－Ｌｉ３ＳｃＣｌ６を合成するために、まず、化学量論量のＬｉＣｌ及びＳｃＣｌ３を窒素雰囲気のグローブボックス内で混合した。そして、混合物を保護材としての金箔と共にプレスしてペレットにした。典型的には、ペレットは、手製の金のるつぼ窒化ホウ素（ＢＮ）の蓋が付いたスリーブ管内に挿入された。次に、サンプルとスリーブ間は黒鉛管内に挿入され、高圧反応のためにパイロフィライトのキューブ内に封入された。サンプルセルはプレスされて１時間で５ＧＰａに達し、その後、３時間で１０００℃まで加熱された。この温度で３時間保持した後、サンプルは５分以内に室温までクエンチされ、その後圧力を開放し、２時間で大気圧とした。これにより、リチウム含有塩化物（γ－Ｌｉ３ＳｃＣｌ６）が得られた。 (Example 1: Synthesis of hexagonal Li 3 ScCl 6 (γ-Li 3 ScCl 6 ))
To synthesize γ-Li 3 ScCl 6 , stoichiometric amounts of LiCl and ScCl 3 were first mixed in a glove box with a nitrogen atmosphere. The mixture was then pressed into pellets with gold foil as a protective material. Typically, the pellets were inserted into a homemade gold crucible sleeve tube with a boron nitride (BN) lid. The sample-to-sleeve interface was then inserted into a graphite tube and encapsulated within a pyrophyllite cube for high-pressure reactions. The sample cell was pressed to reach 5 GPa in 1 hour and then heated to 1000° C. for 3 hours. After being held at this temperature for 3 hours, the sample was quenched to room temperature within 5 minutes and then the pressure was released to atmospheric pressure for 2 hours. This yielded a lithium-containing chloride (γ-Li 3 ScCl 6 ).
（実施例１’）
　サンプルセルを２時間で８ＧＰａとなるようにプレスし、圧力を開放した際に１２時間で大気圧としたこと以外は、実施例１と同様にリチウム含有塩化物を製造した。 (Example 1')
A lithium-containing chloride was produced in the same manner as in Example 1, except that the sample cell was pressed to a pressure of 8 GPa in 2 hours, and when the pressure was released, it was brought to atmospheric pressure in 12 hours.
＜結晶構造の評価＞
　無色透明な板状の結晶が構造決定のために選択された。単結晶Ｘ線構造決定（ＸＲＤ）データは、Ｂｒｕｋｅｒ　Ｋａｐｐａ　ＡＰＥＸ　２　ＣＣＤ　ｄｉｆｆｒａｃｔｏｍｅｔｅｒを用い、１２３Ｋで単色化されたＭｏＫα放射（λ＝０．７１０７Å）により得られた。結晶と検出器の距離は５０ｍｍに調節された。データの縮小と統合にＳＡＩＮＴプログラムが使用された。構造は、直接法により確立され、ＯＬＥＸ２を使用してＦ２に基づくフルマトリクスの最小二乗フィッティングにより最適化された。すべての原子はフルマトリクスの最小二乗法により最適化され、最終的な最小二乗最適化はＦ０ ２≧２σ（Ｆ０ ２）を有するＦ０ ２に基づいた。数値的な吸収補正は、面検出器のためのＳＡＤＡＢＳプログラムを使用して実行した。構造は、金属カチオンの原子座標を決定するためにＳＨＥＬ－ＸＳを使用して解析された。
　代表的な単結晶のＸ線回折図形として、図１に、実施例１のサンプルについてｃ軸方向（００１方向）に対応したＸ線回折測定を示す。 <Evaluation of crystal structure>
Colorless and transparent plate-like crystals were selected for structure determination. Single crystal X-ray structure determination (XRD) data were obtained using a Bruker Kappa APEX 2 CCD diffractometer with monochromated MoK α radiation (λ=0.7107 Å) at 123 K. The distance between the crystal and the detector was adjusted to 50 mm. The SAINT program was used for data reduction and consolidation. The structure was established by direct methods and optimized by full matrix least squares fitting based on F2 using OLEX2. All atoms were optimized by full matrix least squares, and the final least squares optimization was based on F 0 2 with F 0 2 ≧2σ (F 0 2 ). Numerical absorption corrections were performed using the SADABS program for area detectors. The structure was solved using SHEL-XS to determine the atomic coordinates of the metal cations.
As a typical single crystal X-ray diffraction pattern, FIG. 1 shows an X-ray diffraction measurement of the sample of Example 1 corresponding to the c-axis direction (001 direction).
（実施例２～４）
　表２の組成となる量でＬｉＣｌ及びＳｃＣｌ３を使用したこと以外は、実施例１と同様にリチウム含有塩化物を製造した。 (Examples 2 to 4)
A lithium-containing chloride was produced in the same manner as in Example 1, except that LiCl and ScCl 3 were used in amounts having the composition shown in Table 2.
（実施例５）
　表２の組成となる量でＬｉＣｌ、ＺｒＣｌ４及びＳｃＣｌ３を使用したこと以外は、実施例１と同様にリチウム含有塩化物を製造した。 (Example 5)
A lithium-containing chloride was produced in the same manner as in Example 1, except that LiCl, ZrCl 4 and ScCl 3 were used in amounts having the composition shown in Table 2.
（実施例２０）
　表２の組成となる量でＬｉＣｌ、ＬｉＦ及びＳｃＣｌ３を使用したこと以外は、実施例１と同様にリチウム含有塩化物を製造した。 (Example 20)
A lithium-containing chloride was produced in the same manner as in Example 1, except that LiCl, LiF, and ScCl 3 were used in amounts having the composition shown in Table 2.
（比較例１）
・ボールミル
　－７０℃以下の露点を有するアルゴン雰囲気中（以下、乾燥アルゴン雰囲気と記載する）で、ＬｉＣｌを０．３２０１ｇ、ＺｒＣｌ４を０．８７９９ｇ秤量し、原料を用意した。
　下記の遊星ボールミル用の５０ｍｌの容積のジルコニアポットに上記原料を入れ、直径４ｍｍのジルコニアボールを６５ｇ投入した。４８時間、３８０ｒｐｍの条件でメカノケミカル的に反応するように処理することで比較例１の粗組成物を得た。ボールミルは、１０分間回転させる毎に、インターバルとして１分間停止させ、回転方向を時計回りと反時計回り交互に切り替えるモードで実施した。当該リチウム含有塩化物の仕込み組成は、Ｌｉ２ＺｒＣｌ6である。
遊星ボールミル装置：ヴァーダー・サイエンティフィック株式会社製　ＰＭ　４００
・アニーリング
　上記で得られた比較例１の粗組成物について、アルゴン雰囲気中で２３０℃で５時間加熱することにより、仕込み組成がＬｉ２ＺｒＣｌ6の比較例１のリチウム含有塩化物を得た。 (Comparative example 1)
- Ball mill Raw materials were prepared by weighing 0.3201 g of LiCl and 0.8799 g of ZrCl 4 in an argon atmosphere having a dew point of -70° C. or lower (hereinafter referred to as dry argon atmosphere).
The above raw materials were put into a 50 ml zirconia pot for a planetary ball mill described below, and 65 g of 4 mm diameter zirconia balls were added thereto. A crude composition of Comparative Example 1 was obtained by mechanochemically treating at 380 rpm for 48 hours. The ball mill was operated in a mode in which the ball mill was stopped for 1 minute after every 10 minutes of rotation, and the direction of rotation was alternately switched between clockwise and counterclockwise. The charged composition of the lithium-containing chloride is Li 2 ZrCl 6 .
Planetary ball mill device: PM 400 manufactured by Verder Scientific Co., Ltd.
- Annealing The crude composition of Comparative Example 1 obtained above was heated at 230° C. for 5 hours in an argon atmosphere to obtain a lithium-containing chloride of Comparative Example 1 with a charging composition of Li 2 ZrCl 6 .
＜粉末Ｘ線回折測定＞
　得られたリチウム含有ハロゲン化物について、２５℃での粉末Ｘ線回折測定により、結晶構造の評価を行った。結果を表２に示す。また、実施例１～４の回折パターンを、図２に示す。いずれの実施例においても、空間群Ｐ６３ｍｃの結晶構造に帰属される回折ピークを有していることを確認した。粉末Ｘ線回折測定の測定条件について、下記の条件にて実施した。また、試料が直接大気に触れないように、グローブボックス中でサンプルスペースをポリイミドテープで保護してから測定を実施した。
　測定装置：　　ＳｍａｒｔＬａｂ　（株式会社　リガク　製）
　Ｘ線発生器：　ＣｕＫα線源　電圧４０ｋＶ、電流５０ｍＡ
　Ｘ線検出器：　半導体検出器
　測定範囲：　　回折角２θ＝５°～８０°
　スキャンスピード：２．５°／分 <Powder X-ray diffraction measurement>
The crystal structure of the obtained lithium-containing halide was evaluated by powder X-ray diffraction measurement at 25°C. The results are shown in Table 2. Further, the diffraction patterns of Examples 1 to 4 are shown in FIG. It was confirmed that each of the examples had a diffraction peak attributed to the crystal structure of space group P6 3 mc. The powder X-ray diffraction measurement was carried out under the following conditions. In addition, measurements were performed after protecting the sample space with polyimide tape in a glove box so that the sample did not come into direct contact with the atmosphere.
Measuring device: SmartLab (manufactured by Rigaku Co., Ltd.)
X-ray generator: CuKα source, voltage 40kV, current 50mA
X-ray detector: Semiconductor detector Measurement range: Diffraction angle 2θ = 5° to 80°
Scan speed: 2.5°/min
（α－Ｌｉ３ＳｃＣｌ６の合成）
　α－Ｌｉ３ＳｃＣｌ６は、ＬｉＣｌ及びＳｃＣｌ３の化学量論的な混合物を封じたシリカ管内で６５０℃で１２時間加熱することにより得られた。なお、加熱の際の昇温速度は２℃／分、降温速度も２℃／分で実施した。 (Synthesis of α-Li 3 ScCl 6 )
α-Li 3 ScCl 6 was obtained by heating a stoichiometric mixture of LiCl and ScCl 3 at 650° C. for 12 hours in a sealed silica tube. In addition, the temperature increase rate during heating was 2° C./min, and the temperature decreasing rate was also 2° C./min.
（β－Ｌｉ３ＳｃＣｌ６の合成）
　化学量論量のＬｉＣｌ及びＳｃＣｌ３を混合した。混合物をペレット化し、真空下で封じた石英管中に配置した。サンプルは、６５０℃で４８時間加熱することにより得られた。なお、加熱の際の昇温速度、降温速度は５℃／分で実施した。 (Synthesis of β-Li 3 ScCl 6 )
Stoichiometric amounts of LiCl and ScCl3 were mixed. The mixture was pelleted and placed in a sealed quartz tube under vacuum. Samples were obtained by heating at 650°C for 48 hours. Note that the heating rate and cooling rate during heating were 5° C./min.
　図３は上述の粉末Ｘ線回折測定と同じ条件で、試料をメノウ乳鉢で粉砕したものについて、粉末Ｘ線回折測定を実施することで得られたＬｉ３ＳｃＣｌ６の３つの結晶多形についてのＸ線回折チャートである。Ｌｉ３ＳｃＣｌ６には、単斜晶（空間群：Ｃ２／ｍ）の結晶構造を有するα相（α－Ｌｉ３ＳｃＣｌ６）と、立方晶（空間群：Ｆｄ－３ｍ）の結晶構造を有するβ相（β－Ｌｉ３ＳｃＣｌ６）の２種類の結晶多形が存在することが知られている。図３に示されるように、上記のとおり合成されたＬｉ３ＳｃＣｌ６は、六方晶（空間群：Ｐ６３ｍｃ）の結晶構造をしており、α相及びβ相のいずれとも異なる新規な結晶構造を有している。この新規な結晶構造のＬｉ３ＳｃＣｌ６をγ－Ｌｉ３ＳｃＣｌ６とも呼ぶ。また、上述の単結晶Ｘ線構造解析で得られた結晶構造データを用いて、結晶構造解析ソフトウェアＶＥＳＴＡ（Ｖｉｓｕａｌｉｚａｔｉｏｎ　ｆｏｒ　Ｅｌｅｃｔｒｏｎｉｃ　ａｎｄ　Ｓｔｒｕｃｔｕｒａｌ　Ａｎａｌｙｓｉｓ）によって、ＣｕＫα線の波長（１．５４０５９Å）を入力して、シミュレーション（理論計算）を行うことによりγ相－Ｌｉ３ＳｃＣｌ６の回折チャートが得られた。理論計算により求められたγ相－Ｌｉ３ＳｃＣｌ６の回折チャート（最も下のグラフ）ともよく一致している。 Figure 3 shows the three crystal polymorphs of Li 3 ScCl 6 obtained by performing powder X-ray diffraction measurements on a sample ground in an agate mortar under the same conditions as the powder X-ray diffraction measurements described above. It is an X-ray diffraction chart. Li 3 ScCl 6 has an α phase (α-Li 3 ScCl 6 ) having a monoclinic (space group: C2/m) crystal structure and a cubic (space group: Fd-3m) crystal structure. It is known that two types of crystal polymorphs of the β phase (β-Li 3 ScCl 6 ) exist. As shown in FIG. 3, Li 3 ScCl 6 synthesized as described above has a hexagonal crystal structure (space group: P6 3 mc), and is a novel crystal structure different from both α and β phases. It has a structure. Li 3 ScCl 6 with this new crystal structure is also called γ-Li 3 ScCl 6 . Furthermore, using the crystal structure data obtained by the single crystal X-ray structure analysis described above, the wavelength of the CuKα ray (1.54059 Å) was input into crystal structure analysis software VESTA (Visualization for Electronic and Structural Analysis). By performing a simulation (theoretical calculation), a diffraction chart of γ phase-Li 3 ScCl 6 was obtained. It also agrees well with the diffraction chart of γ phase-Li 3 ScCl 6 (lowermost graph) obtained by theoretical calculation.
　表１に１２３Ｋにおける単結晶Ｘ線回折から得られたγ－Ｌｉ３ＳｃＣｌ６結晶データと構造最適化のデータを示す。Ｌｉ３ＳｃＣｌ６－５ＧＰａ及びＬｉ３ＳｃＣｌ６－８ＧＰａはそれぞれ５ＧＰａ及び８ＧＰａの圧力下で得られたサンプル（つまり、実施例１及び実施例１’）を意味する。図４は、γ－Ｌｉ３ＳｃＣｌ６の構造のボール－アンド－スティック及び多面体表示である。 Table 1 shows γ-Li 3 ScCl 6 crystal data obtained from single-crystal X-ray diffraction at 123K and structure optimization data. Li 3 ScCl 6 -5 GPa and Li 3 ScCl 6 -8 GPa refer to samples obtained under pressures of 5 GPa and 8 GPa (ie Example 1 and Example 1'), respectively. FIG. 4 is a ball-and-stick and polyhedral representation of the structure of γ-Li 3 ScCl 6 .
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
＜イオン伝導度の評価＞
　枠型、パンチ下部及びパンチ上部を備える加圧成形ダイスを用意した。なお、枠型は、絶縁性ポリカーボネートから形成されていた。また、パンチ上部及びパンチ下部は、いずれも、電子伝導性のステンレスから形成されており、インピーダンスアナライザー（Ｓｏｌａｔｒｏｎ　Ａｎａｌｙｔｉｃａｌ社製　Ｓｌ１２６０）の端子にそれぞれ電気的に接続されていた。 <Evaluation of ionic conductivity>
A pressure molding die including a frame, a punch lower part, and a punch upper part was prepared. Note that the frame mold was made of insulating polycarbonate. Moreover, both the punch upper part and the punch lower part were made of electronically conductive stainless steel, and were electrically connected to terminals of an impedance analyzer (Solatron Analytical, Sl1260).
　上記加圧成形ダイスを用いて、下記の方法により、リチウム含有ハロゲン化物のイオン伝導度が測定された。まず、乾燥アルゴン雰囲気中で、リチウム含有ハロゲン化物の粉末を、枠型の中空部に鉛直下方から挿入されたパンチ下部上に充填した。そして、パンチ上部を枠型の中空部に上から押し込むことにより、加圧成形ダイスの内部で、リチウム含有ハロゲン化物の粉末に３７０ＭＰａの圧力が印加された。圧力が印加された後、治具でパンチを上下から締め付けて固定し、一定圧力が保持されたままの状態で、上記インピーダンスアナライザーを用いて、電気化学的インピーダンス測定法により、リチウム含有ハロゲン化物のインピーダンスが測定された。 Using the pressure molding die described above, the ionic conductivity of the lithium-containing halide was measured by the following method. First, in a dry argon atmosphere, lithium-containing halide powder was filled onto the lower part of a punch inserted into the hollow part of the frame from vertically below. Then, by pushing the upper part of the punch into the hollow part of the frame from above, a pressure of 370 MPa was applied to the lithium-containing halide powder inside the pressure molding die. After pressure is applied, the punch is tightened and fixed from above and below with a jig, and while a constant pressure is maintained, the lithium-containing halide is measured by electrochemical impedance measurement using the impedance analyzer described above. Impedance was measured.
　インピーダンス測定結果から、Ｃｏｌｅ－Ｃｏｌｅ線図のグラフを作成した。Ｃｏｌｅ－Ｃｏｌｅ線図において、複素インピーダンスの位相の絶対値が最も小さい測定点でのインピーダンスの実数値を、ハロゲン化物固体電解質材料のイオン伝導に対する抵抗値と見なした。当該抵抗値を用いて、以下の数式（ＩＩＩ）に基づいてイオン伝導度が算出された。各試料の２５℃でのイオン伝導度（σ２５℃）を表２に示す。
σ＝（ＲＳＥ×Ｓ／ｔ）－１・・・（ＩＩＩ）
ここで、
σはイオン伝導度であり、
Ｓは、リチウム含有ハロゲン化物のパンチ上部との接触面積（枠型の中空部の断面積に等しい）であり、
ＲＳＥは、インピーダンス測定における固体電解質材料の抵抗値であり、
ｔは、圧力が印加された際のリチウム含有ハロゲン化物の厚みである。 A Cole-Cole diagram was created from the impedance measurement results. In the Cole-Cole diagram, 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 value of the halide solid electrolyte material to ionic conduction. Using the resistance value, the ionic conductivity was calculated based on the following mathematical formula (III). Table 2 shows the ionic conductivity (σ 25°C ) of each sample at 25°C.
σ=(R SE ×S/t) -1 ...(III)
here,
σ is the ionic conductivity,
S is the contact area of the lithium-containing halide with the upper part of the punch (equal to the cross-sectional area of the hollow part of the frame),
R SE is the resistance value of the solid electrolyte material in impedance measurement,
t is the thickness of the lithium-containing halide when pressure is applied.
　図５は実施例３のイオン伝導度のＣｏｌｅ－Ｃｏｌｅ線図である。図５には、それぞれ、２５℃、４０℃、６０℃、８０℃及び１００℃での測定結果が示されている。 FIG. 5 is a Cole-Cole diagram of ionic conductivity in Example 3. FIG. 5 shows the measurement results at 25°C, 40°C, 60°C, 80°C and 100°C, respectively.
＜二次電池の作製＞
　乾燥アルゴン雰囲気中で、リチウム含有ハロゲン化物、及びＬｉＮｉ１／３Ｍｎ１／３Ｃｏ１／３Ｏ２、及びアセチレンブラックをそれぞれ２９質量部、６７質量部、及び４質量部秤量し、乳鉢で混合することで、混合物を得た。
　内径１０ｍｍの絶縁性の筒の中でリチウム含有ハロゲン化物を１００ｍｇ、上記の混合物を１５ｍｇを順に積層して、積層体を得た。積層体に３７０ＭＰａの圧力を印加し、第１電極（上記混合物の層）及び固体電解質層（上記リチウム含有ハロゲン化物の層）が形成された。
　次に、Ｉｎ箔６０ｍｇを固体電解質層に接触させるようにして入れ、さらにＬｉ箔２ｍｇをＩｎ箔と接触させるように入れ、積層体を得た。積層体に３７０ＭＰａの圧力を印加し、第２電極が形成された。
　ステンレス鋼で形成された集電体が第１電極及び第２電極に取り付けられ、次いで、当該集電体にリード線が取り付けられた。全ての部材はデシケータ中に配置され、密閉されており、このようにして二次電池が得られた。 <Preparation of secondary battery>
In a dry argon atmosphere, 29 parts by mass, 67 parts by mass, and 4 parts by mass of a lithium-containing halide, LiNi 1/3 Mn 1/3 Co 1/3 O 2 , and acetylene black were weighed, respectively, and mixed in a mortar. A mixture was thus obtained.
In an insulating cylinder having an inner diameter of 10 mm, 100 mg of a lithium-containing halide and 15 mg of the above mixture were stacked in order to obtain a laminate. A pressure of 370 MPa was applied to the laminate to form a first electrode (layer of the above mixture) and a solid electrolyte layer (layer of the lithium-containing halide).
Next, 60 mg of In foil was placed in contact with the solid electrolyte layer, and 2 mg of Li foil was placed in contact with the In foil to obtain a laminate. A pressure of 370 MPa was applied to the laminate to form a second electrode.
A current collector made of stainless steel was attached to the first and second electrodes, and then a lead wire was attached to the current collector. All the members were placed in a desiccator and sealed, and thus a secondary battery was obtained.
＜充放電試験＞
　充放電試験機としては、下記の製品を用いて実施した。
　充放電試験機：東洋システム株式会社　ＴＯＳＣＡＴ－３１００
　６０℃において、０．１Ｃ、１Ｃ及び３Ｃの３通りのＣレートで充放電試験を実施した。
　定電流定電圧（ＣＣＣＶ充電）で、それぞれのＣレートに対応した電流密度で３．７Ｖまで充電を行った。
放電は、それぞれのＣレートに対応した電流密度で、１．９Ｖまで放電した。
　二次電池作製後に短絡することなく、開回路電圧が得られ、上記の充放電試験において充電容量、及び放電容量が確認されたものを、充放電可能と判断した。
　また、実施例１について、０．１Ｃ及び０．２のＣレートで５回の充放電試験を行った。図６は、実施例１について０．１Ｃで充放電試験を行った結果を示す図である。図７は、実施例１について０．２Ｃで充放電試験を行った結果を示す図である。図８は、実施例１と、α－Ｌｉ３ＳｃＣｌ６について、サイクル数と放電容量を示す図である。図８において、γ－Ｌｉ３ＳｃＣｌ６について、０．１Ｃ、０．２Ｃ及び０．５ＣのＣレートでそれぞれ５サイクルずつ測定した放電容量と、その後１Ｃで１０サイクル測定した放電容量を示す。また、α－Ｌｉ３ＳｃＣｌ６について、０．１Ｃ及び０．２ＣのＣレートでそれぞれ５サイクルずつ測定した放電容量を示す。 <Charge/discharge test>
The charge/discharge test was carried out using the following product.
Charge/discharge tester: Toyo System Co., Ltd. TOSCAT-3100
A charge/discharge test was conducted at 60° C. at three C rates: 0.1C, 1C, and 3C.
Charging was performed to 3.7 V using constant current and constant voltage (CCCV charging) at a current density corresponding to each C rate.
The discharge was carried out to 1.9V at a current density corresponding to each C rate.
A secondary battery was determined to be chargeable and dischargeable if an open circuit voltage was obtained without short circuiting after fabrication, and the charge capacity and discharge capacity were confirmed in the charge and discharge test described above.
Further, for Example 1, a charge/discharge test was conducted five times at a C rate of 0.1C and 0.2. FIG. 6 is a diagram showing the results of a charge/discharge test conducted at 0.1 C for Example 1. FIG. 7 is a diagram showing the results of a charge/discharge test conducted at 0.2C for Example 1. FIG. 8 is a diagram showing the cycle number and discharge capacity for Example 1 and α-Li 3 ScCl 6 . FIG. 8 shows the discharge capacity of γ-Li 3 ScCl 6 measured for 5 cycles each at C rates of 0.1C, 0.2C, and 0.5C, and the discharge capacity measured for 10 cycles at 1C thereafter. Also shown is the discharge capacity of α-Li 3 ScCl 6 measured for 5 cycles each at a C rate of 0.1C and 0.2C.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　実施例１～５及び２０のリチウム含有塩化物は、比較例と比較して、良好なイオン伝導度が得られた。 The lithium-containing chlorides of Examples 1 to 5 and 20 had better ionic conductivity than the comparative example.
＜Ｌｉイオン拡散挙動の計算及び計算結果の評価＞
　Ｌｉイオン拡散挙動について分子動力学シミュレーションに基づいて、空間群Ｐ６３ｍｃに属する化合物のＬｉ平均二乗変位を計算して求めた。 <Calculation of Li ion diffusion behavior and evaluation of calculation results>
Li ion diffusion behavior was determined by calculating the Li mean square displacement of a compound belonging to the space group P6 3 mc based on a molecular dynamics simulation.
　目下、本願特許請求の範囲を制限することを望むものではないが、本願で示される全てのＬｉイオンの拡散挙動およびその結果として得られる平均二乗変位は、当業者に広く使用されかつ知られているオーストリア共和国・ウイーン大学が提供する計算化学ソフトウェア「Ｖｉｅｎｎａ　ａｂ　ｉｎｉｔｉｏ　ｓｉｍｕｌａｔｉｏｎ　ｐａｃｋａｇｅ　（ＶＡＳＰ）」を使用することで計算した。
　具体的には、Ｌｉが３６個、３価原子が１２個、Ｃｌが７２個のスーパーセルを用いて分子動力学計算を実施し、Ｌｉの平均二乗変位を求めた。元素置換構造についてはこの構造をもとに上記方法にて元素置換を行った。計算条件としては、密度汎関数ＰＢＥを使用して、ｎＰＴアンサンブルを使用し、時間刻み幅は１ｆｓ、シミュレーション時間は３００ｐｓ、シミュレーション温度７００ＫでＭＤ計算をすることによって求めた。３価原子の非整数占有数サイトは熱力学的に最も安定となるように占有率に従って占有／被占有を選択した。 At present, without wishing to limit the scope of the claims herein, all Li ion diffusion behaviors and resulting mean square displacements presented herein are widely used and known to those skilled in the art. The calculations were performed using the computational chemistry software "Vienna ab initio simulation package (VASP)" provided by the University of Vienna in the Republic of Austria.
Specifically, a molecular dynamics calculation was performed using a supercell with 36 Li atoms, 12 trivalent atoms, and 72 Cl atoms, and the mean square displacement of Li was determined. Regarding the element substitution structure, element substitution was performed using the above method based on this structure. As calculation conditions, the density functional PBE was used, the nPT ensemble was used, the time step width was 1 fs, the simulation time was 300 ps, and the simulation temperature was 700K. Occupancy/occupancy of non-integer occupied number sites of trivalent atoms was selected according to the occupancy rate so as to be thermodynamically most stable.
　Ｌｉイオンの平均二乗変位に関しては、下記の式（ｎｎ）により求めた。
 
Ｌｉイオン平均二乗変位＝（Σｎ（ｒ（ｎ，ｔ）－ｒ（ｎ，０））２）／Ｎ…（ｎｎ）
　ここで、ｒ（ｎ，ｔ）は時刻ｔにおけるｎ番目のＬｉ原子の座標であり、Ｎは計算セルに含まれるＬｉの総数である。 The mean square displacement of Li ions was determined using the following formula (nn).

Li ion mean square displacement = (Σ n (r(n, t) - r(n, 0)) 2 )/N...(nn)
Here, r(n, t) is the coordinate of the n-th Li atom at time t, and N is the total number of Li included in the calculation cell.
〔実施例１〕
　実施例１のγ－Ｌｉ３ＳｃＣｌ６について、分子動力学シミュレーションに基づいて、当該化合物のＬｉの平均二乗変位を計算して求めた。結果を以下の表３に記載する。 [Example 1]
Regarding γ-Li 3 ScCl 6 of Example 1, the mean square displacement of Li in the compound was calculated based on molecular dynamics simulation. The results are listed in Table 3 below.
〔実施例６～１１〕
　γ－Ｌｉ３ＳｃＣｌ６と同様の結晶構造を持ち、Ｓｃ元素が、３価元素で置換された化合物について、分子動力学シミュレーションに基づいて、当該化合物のＬｉ平均二乗変位を計算して求めた。結果を以下の表３に記載する。 [Examples 6 to 11]
For a compound having a crystal structure similar to γ-Li 3 ScCl 6 and in which the Sc element was replaced with a trivalent element, the Li mean square displacement of the compound was calculated based on molecular dynamics simulation. The results are listed in Table 3 below.
〔実施例１２〕
　γ－Ｌｉ３ＳｃＣｌ６と同様の結晶構造を持ち、Ｓｃ元素のサイトが２種の３価元素で占められた化合物について、分子動力学シミュレーションに基づいて、当該化合物のＬｉ平均二乗変位を計算して求めた。なお参考としてＧａとＳｃが５０モル％ずつサイトを占有した際の例を示すが、これは他の組成を排除するものではない。結果を以下の表３に記載する。 [Example 12]
For a compound having a crystal structure similar to γ-Li 3 ScCl 6 and in which the Sc element site is occupied by two types of trivalent elements, the Li mean square displacement of the compound was calculated based on molecular dynamics simulation. I asked. For reference, an example in which Ga and Sc occupy 50 mol % of each site is shown, but this does not exclude other compositions. The results are listed in Table 3 below.
〔実施例１３～１９〕
　γ－Ｌｉ３ＳｃＣｌ６のうちスーパーセル中の１個のＳｃが、４価あるいは５価の元素に置換された化合物について、分子動力学シミュレーションに基づいて、当該化合物のＬｉ平均二乗変位を計算して求めた。本モデルにおいては、Ｓｃ原子を４価元素で置換した場合には電荷補償として、置換した原子数と等量のＬｉを最近接サイトから削除した。また、５価元素で置換した場合には電荷補償として、置換した原子数の倍量のＬｉを最近接サイトから削除した。なお計算モデルの制約としてＳｃが約８モル％置換された組成を示すが、これは他の組成を排除するものではない。得られた結果を以下の表３に記載する。 [Examples 13 to 19]
For a compound in which one Sc in the supercell of γ-Li 3 ScCl 6 is replaced with a tetravalent or pentavalent element, the Li mean square displacement of the compound is calculated based on molecular dynamics simulation. I asked. In this model, when a Sc atom is replaced with a tetravalent element, Li in an amount equal to the number of replaced atoms is removed from the nearest site as charge compensation. Furthermore, when substitution was made with a pentavalent element, Li in an amount twice the number of substituted atoms was removed from the nearest site as charge compensation. Note that as a limitation of the calculation model, a composition in which approximately 8 mol% of Sc is substituted is shown, but this does not exclude other compositions. The results obtained are listed in Table 3 below.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　上記、表３に示すように、実施例１及び６～１９の各化合物は、数Å２以上のＬｉイオンの平均二乗変位を示す。平均二乗変位が数Å２を大きく上回るということは、固体中でＬｉが拡散していることを意味し、Ｌｉを伝導可能な固体電解質である。 As shown in Table 3 above, each of the compounds of Examples 1 and 6 to 19 exhibits a mean square displacement of Li ions of several Å 2 or more. The fact that the mean square displacement greatly exceeds several angstroms 2 means that Li is diffused in the solid, and the solid electrolyte is capable of conducting Li.

Claims (10)

  1. 　アルカリ金属元素と、
    　Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｚｎ、Ｓｃ、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｐｍ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｙｂ、Ｌｕ、Ｙ、Ａｌ、Ｇａ、Ｉｎ、Ｂｉ、Ｓｂ、Ｇｅ、Ｔｉ、Ｚｒ、Ｈｆ、Ｓｎ、Ｎｂ、Ｔａ、及びＷからなる群から選択される少なくとも一種の金属元素Ｍと、
    　ハロゲン元素とを含有し、
    　空間群Ｐ６３ｍｃに帰属される結晶構造を有する、化合物。     an alkali metal element,
    Mg, Ca, Sr, Ba, Zn, Sc, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu, Y, Al, Ga, In, Bi, At least one metal element M selected from the group consisting of Sb, Ge, Ti, Zr, Hf, Sn, Nb, Ta, and W;
    Contains a halogen element,
    A compound having a crystal structure belonging to space group P6 3 mc.
  2. 　前記ハロゲン元素がＣｌを含む、請求項１に記載の化合物。 The compound according to claim 1, wherein the halogen element contains Cl.
  3. 　前記金属元素が３価の金属元素を含む、請求項１又は２に記載の化合物。 The compound according to claim 1 or 2, wherein the metal element includes a trivalent metal element.
  4. 　下記組成式（１）で表される、請求項１又は２に記載の化合物。
    ＡαＭβＸγ・・・（１）
    （式中、Ａはアルカリ金属元素であり、Ｘは、ハロゲン元素であり、１≦α≦４、０．５≦β≦２、４≦γ≦８である。）     The compound according to claim 1 or 2, which is represented by the following compositional formula (1).
    A α M β X γ ...(1)
    (In the formula, A is an alkali metal element, X is a halogen element, and 1≦α≦4, 0.5≦β≦2, 4≦γ≦8.)
  5. 　金属元素ＭがＧａ、Ｉｎ、Ｓｃ、Ｌａ、Ｙ、Ｓｂ及びＢｉからなる群から選択される少なくとも一種の元素を含む、請求項１又は２に記載の化合物。 The compound according to claim 1 or 2, wherein the metal element M contains at least one element selected from the group consisting of Ga, In, Sc, La, Y, Sb, and Bi.
  6. 　前記金属元素Ｍが２種以上の金属元素を含む、請求項１又は２に記載の化合物。 The compound according to claim 1 or 2, wherein the metal element M contains two or more types of metal elements.
  7. 　前記ハロゲン元素が２種以上のハロゲン元素を含む、請求項１又は２に記載の化合物。 The compound according to claim 1 or 2, wherein the halogen element contains two or more types of halogen elements.
  8. 　請求項１又は２に記載の化合物を含む、電解質。 An electrolyte comprising the compound according to claim 1 or 2.
  9. 　請求項８に記載の電解質を含む、電池。 A battery comprising the electrolyte according to claim 8.
  10. 　原料を１ＧＰａ以上の圧力下で加熱する工程を含む、ハロゲン化物固体電解質の製造方法。 A method for producing a halide solid electrolyte, which includes a step of heating raw materials under a pressure of 1 GPa or more.
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