WO2024058053A1 - Halogénure contenant un élément métallique alcalin, électrolyte, batterie et méthode de production d'électrolyte solide d'halogénure - Google Patents

Halogénure contenant un élément métallique alcalin, électrolyte, batterie et méthode de production d'électrolyte solide d'halogénure 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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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/fr

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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, LIGHT-SENSITIVE OR TEMPERATURE-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.

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Abstract

L'invention concerne un composé contenant : un élément métallique alcalin ; au moins un élément métallique M choisi dans le groupe constitué par 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, et W ; et un élément halogène, le composé ayant une structure cristalline appartenant à un groupe spatial P63mc.
PCT/JP2023/032725 2022-09-12 2023-09-07 Halogénure contenant un élément métallique alcalin, électrolyte, batterie et méthode de production d'électrolyte solide d'halogénure WO2024058053A1 (fr)

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