CN113363567A - Halide solid electrolyte and preparation method and application thereof - Google Patents

Halide solid electrolyte and preparation method and application thereof Download PDF

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Publication number
CN113363567A
CN113363567A CN202110729896.7A CN202110729896A CN113363567A CN 113363567 A CN113363567 A CN 113363567A CN 202110729896 A CN202110729896 A CN 202110729896A CN 113363567 A CN113363567 A CN 113363567A
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halide solid
solid electrolyte
electrolyte
halide
structural
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孙学良
王长虹
徐国峰
梁剑文
王建涛
李晓娜
赵尚骞
黄欢
杨容
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University of Western Ontario
China Automotive Battery Research Institute Co Ltd
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University of Western Ontario
China Automotive Battery Research Institute Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/008—Halides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention provides a halide solid electrolyte and a preparation method and application thereof, wherein the chemical formula of the halide solid electrolyte is Li3MX6M is at least one of rare earth elements, and X is at least one of F, Cl, Br and I; the halide solid electrolyte has a structural microstress of 0.001 to 0.01. According to the halide solid electrolyte provided by the invention, the internal stress of the material is induced, so that the obvious structural micro stress reaches 0.001-0.01, the ionic conductivity is obviously improved and is 6-10 times higher than that of the electrolyte prepared by the traditional high-temperature solid phase method; furthermore, the electrochemical window and other properties are not affected, so that the solid-state secondary battery can be widely applied to the solid-state secondary battery.

Description

Halide solid electrolyte and preparation method and application thereof
Technical Field
The invention relates to the technical field of secondary batteries, in particular to a halide solid electrolyte and a preparation method and application thereof.
Background
The all-solid secondary battery has higher safety than the lithium ion secondary battery currently in commercial use. This is because the all-solid-state secondary battery employs a nonflammable inorganic fast-ion material as an electrolyte. With the development of recent years, several ion conductance higher than 1mS cm have been developed-1The solid electrolyte material of (1). These materials are based on sulfide and oxide electrolytes, including Li10Ge2P2S12，Li6PS5Cl，Li7P3S11And Li3PS4Etc.; the oxide electrolyte mainly contains Li1.3Al0.3Ti1.7(PO4)3，Li7La3Zr2O12And the like. However, sulfide electrolytes are unstable in air and water, and are liable to generate toxic gases such as hydrogen sulfide, and therefore, the operation needs to be performed in an environment in which inert gas is a protective atmosphere; the oxide electrolyte can form a phase under the high-temperature condition, the phase forming temperature is over 1000 ℃, and the mass preparation and production are difficult.
In recent years, halide solid electrolytes have been used for their good mechanical properties and stability to high voltage positive electrode materials, and there is no sulfide electrolysisThe electrolyte generates hydrogen sulfide gas, oxide electrolyte is difficult to prepare in large quantity, and the like, and the electrolyte is gradually favored by people. However, the prior art halide solid state electrolytes, particularly halide electrolytes of hcp structure, have low room temperature ionic conductivity (10 to 10)-5S/cm), poor dynamic conditions of the electrode process, and low lithium ion transmission efficiency, which may affect the rate characteristics of the solid-state secondary battery, and the battery may not maintain normal operation at high power.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a halide solid electrolyte, a preparation method and application thereof, and the halide solid electrolyte with high ionic conductivity is obtained, so that the electrochemical performance of a solid secondary battery is improved.
The invention provides a halide solid electrolyte with a chemical formula of Li3MX6M is at least one of rare earth elements, and X is at least one of F, Cl, Br and I; the halide solid electrolyte has a structural microstress of 0.001 to 0.01.
Further, the structural microstress of the halide solid electrolyte is expressed as compressive force in the a, b direction and tensile force in the c direction of the unit cell structure, and the unit cell structure is distorted under the structural microstress.
Further, the particle size D50 of the halide solid electrolyte is 10-500 nm.
Further, the anion arrangement of the halide solid state electrolyte is hexagonal close-packed or tetragonal close-packed.
Further, the halide solid electrolyte is Li3YCl6、Li3ErCl6、Li3YbCl6、Li3DyCl6、Li3TmCl6。
The invention also provides a preparation method of the halide solid electrolyte, which adopts a liquid phase synthesis method to prepare and comprises the following steps:
MX is dissolved in polar solvent containing hydrolysis inhibitor3Mixing with LiX for reaction, and pyrolyzing the obtained reaction product at 450-600 ℃ to obtain the halideA solid electrolyte.
Further, after the mixing reaction, the reaction system is dehydrated and dried under vacuum at 80 +/-5 ℃ to obtain the reaction product.
Further, the hydrolysis inhibitor is NH4X and X are halogen.
Preferably, NH4X、MX3And the molar ratio of LiX is 3:1: 3.
Further, the polar solvent is water and/or ethanol.
The invention also provides application of the halide solid electrolyte, in particular to an electrolyte or electrode additive in a solid secondary battery.
According to the halide solid electrolyte provided by the invention, the internal stress of the material is induced, so that the obvious structural micro stress reaches 0.001-0.01, the ionic conductivity is obviously improved and is 6-10 times higher than that of the electrolyte prepared by the traditional high-temperature solid phase method; and does not affect the performances such as electrochemical window, etc., thereby being widely applied to solid secondary batteries.
Drawings
FIG. 1 shows nano-Li in an embodiment of the present invention3YCl6The structural microstress calculation schematic diagram of (1);
FIG. 2 shows Li in an example of the present invention3YCl6Schematic of the crystal structure of (a).
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention are described clearly and completely below, and it is obvious that the described embodiments are some, not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment of the invention provides a halide solid electrolyte with a chemical formula of Li3MX6M is at least one of rare earth elements, and X is at least one of F, Cl, Br and I; the halide solidThe structural microstress of the state electrolyte is 0.001-0.01.
Wherein the calculation formula of the structural micro stress is
Figure BDA0003139651380000031
In the formula: ε is the structural microstress, βTIs the half-value width (unit rad) of the X-ray diffraction peak, and K is the shape factor
Figure BDA0003139651380000032
λ is the wavelength of the incident light (λ ═ 0.15405nm), θ is the diffraction angle (rad), D is the crystallite size (nm), a Williamson-Hall line can be fitted by correlation parameters of at least 5 diffraction peaks, with the abscissa 4sin θ and the ordinate βTThe slope of the cos theta line is the micro stress magnitude epsilon, and the crystallite size D can be determined according to the intercept
Figure BDA0003139651380000041
And was obtained as shown in fig. 1.
According to the research of the invention, the internal stress of the halide solid electrolyte material obtained by the traditional high-temperature solid phase sintering is not obvious, and when a certain means is adopted to induce the internal stress of the material, the material has obvious structural micro stress which is 0.001-0.01, the ionic conductivity of the obtained halide solid electrolyte is obviously improved and is 6-10 times higher than that of the electrolyte prepared by the traditional high-temperature solid phase method.
Specifically, the structural microstress of the halide solid electrolyte is expressed as a compressive force in the a, b direction and an tensile force in the c direction of the unit cell structure, and the unit cell structure is lattice-distorted by the structural microstress. After the lattice distortion occurs, the a axis and the b axis are shortened, the c axis is prolonged, the transmission of ions in the ab plane is accelerated, and therefore the ion conductivity is improved.
With Li3YCl6For example, the schematic crystal structure is shown in fig. 2, which is a hexagonal close-packed (hcp) arrangement, and the transport of lithium ions in the ab direction is octahedral-tetrahedral-octahedral (O-T-O), which is significantly slower than the transport of O-O in the c direction. The material lattice is distorted by the structural micro-stress, the a axis and the b axis are shortened, and the c axisProlonging and accelerating the diffusion of lithium ions on an ab plane, which is equivalent to improving the lithium ion speed-dependent step of Li-Y-Cl. Example of the invention nanosized Li3YCl6With standard Li3YCl6The bond length comparison between them is shown in table 1 below.
TABLE 1 nanosized Li3YCl6With standard Li3YCl6Bond length comparison between
Figure BDA0003139651380000042
Figure BDA0003139651380000051
Further, the particle size D50 of the halide solid electrolyte is 10-500 nm. The nanocrystallization of the halide solid electrolyte is a prerequisite for inducing structural microstress.
Further, the halide solid electrolyte is nano-sized Li3YCl6、Li3ErCl6、Li3YbCl6、Li3DyCl6、Li3TmCl6. In a specific embodiment of the invention, nanosized Li3YCl6The ionic conductivity of the material can reach as high as 0.35mScm-1Nano-sized Li3ErCl6The ionic conductivity of the material can reach as high as 0.47mScm-1。
The embodiment of the invention also provides a preparation method of the halide solid electrolyte, which is prepared by adopting a liquid phase synthesis method and comprises the following steps:
MX is dissolved in polar solvent containing hydrolysis inhibitor3And mixing and reacting with LiX, and pyrolyzing the obtained reaction product at 450-600 ℃ to obtain the halide solid electrolyte.
Due to the easy hydrolysis characteristic of halide precursors, the synthesis of halide materials is mainly based on high-energy ball milling and solid-phase high-temperature sintering at present. However, the solid electrolyte particles prepared by the traditional preparation method are micron-sized, and cannot induce structural micro-stress. The liquid phase synthesis method provided by the invention can synthesize the nano-scale halide solid electrolyte in a liquid phase. In addition, the nano-scale solid electrolyte material can improve the solid-solid interface contact between the nano-scale solid electrolyte material and the anode and cathode materials, and is beneficial to the energy exertion of the solid battery.
Wherein the hydrolysis inhibitor is NH4X and X are halogen. May be in particular NH4F、NH4Cl、NH4Br、NH4And (I) one or more of. The polar solvent is water or ethanol, or a mixture of water and ethanol.
MX3May be YX3、ErX3、ScX3And one or more of rare earth metal halides.
The LiX can be one or more of LiCl, LiBr, LiI and LiF.
Preferably, NH4X、MX3And the molar ratio of LiX is 3:1: 3.
Further, after the mixing reaction, the reaction system is dried in vacuum at 80 +/-5 ℃ to remove water, so as to obtain the reaction product. The reaction product is in powder form and contains (NH) as the component4)3MX3+aComplexes of (1 ≦ a ≦ 3) with LiX (e.g., (NH)4)3YCl6And LiCl). Transferring the electrolyte to an inert atmosphere for pyrolysis/sintering, thereby cracking the hydrolysis inhibitor to obtain the halide solid electrolyte.
The pyrolysis temperature is more critical, influences the ionic conductivity of the final product, and is preferably 450-600 ℃, and more preferably 500 ℃.
The halide solid electrolyte prepared by the embodiment of the invention has the particle size D50 of 100-500 nm, more preferably 100-200 nm, the ionic conductivity is greatly improved, and the performances such as activation energy, an electrochemical window and the like are not influenced, so that the halide solid electrolyte can be widely applied to solid secondary batteries. Specifically, it can be applied to an electrolyte or electrode additive in a solid secondary battery.
Example 1
This example provides a halide solid electrolyte having the formula Li3YCl6The preparation method comprises the following steps:
3mol of NH4Cl and 1mol YCl3Dissolving in water, adding 3mol LiCl, mixing uniformly, removing water and drying at 80 ℃ in vacuum to obtain white powder, calcining the white powder in argon atmosphere (5 hours) at 450 ℃ to obtain nano Li3YCl6。
Example 2
This example provides a halide solid electrolyte having the formula Li3YCl6The preparation method comprises the following steps:
3mol of NH4Cl and 1mol YCl3Dissolving in water, adding 3mol LiCl, mixing uniformly, removing water and drying at 80 ℃ in vacuum to obtain white powder, calcining the white powder in argon atmosphere (5 hours) at 500 ℃ to obtain nano Li3YCl6。
Example 3
This example provides a halide solid electrolyte having the formula Li3YCl6The preparation method comprises the following steps:
3mol of NH4Cl and 1mol YCl3Dissolving in water, adding 3mol LiCl, mixing uniformly, removing water and drying at 80 ℃ in vacuum to obtain white powder, calcining the white powder in argon atmosphere (5 hours) at 550 ℃ to obtain nano Li3YCl6。
Example 4
This example provides a halide solid electrolyte having the formula Li3ErCl6The preparation method comprises the following steps:
3mol of NH4Cl and 1mol of ErCl3Dissolving in water, adding 3mol LiCl, mixing uniformly, removing water and drying at 80 ℃ in vacuum to obtain white powder, calcining the white powder in argon atmosphere (5 hours) at 500 ℃ to obtain nano Li3ErCl6。
Example 5
This example provides a halide solid electrolyte having the formula Li3LaI6The preparation method comprises the following steps:
3mol of NH4I and 1mol of LaI3Dissolving in water, adding 3mol of LiI, uniformly mixing, removing water and drying at the temperature of 80 ℃ in vacuum to obtain white powder, calcining the white powder in the atmosphere of argon (5 hours) at the calcining temperature of 500 ℃ to obtain nano Li3LaI6。
Comparative example 1
This comparative example provides a Li prepared by a conventional solid-phase sintering process3YCl6The preparation method comprises the following steps:
1mol of YCl3And 3mol LiCl are directly sealed in a quartz tube in vacuum, and then are calcined in vacuum at 650 ℃ for 24 hours to obtain high-temperature solid-phase synthesized Li3YCl6And after fully grinding, the particle size is micron-sized.
Comparative example 2
This comparative example provides a Li prepared by a conventional solid-phase sintering process3ErCl6The preparation method comprises the following steps:
1mol of ErCl3And 3mol LiCl are directly sealed in a quartz tube in vacuum, and then are calcined in vacuum at 650 ℃ for 24 hours to obtain high-temperature solid-phase synthesized Li3ErCl6The particle size is micron-sized.
Comparative example 3
This comparative example provides a halide solid electrolyte of the formula Li3YCl6The preparation method comprises the following steps:
3mol of NH4Cl and 1mol YCl3Dissolving in water, adding 3mol LiCl, mixing uniformly, removing water and drying at 80 ℃ in vacuum to obtain white powder, calcining the white powder in argon atmosphere (5 hours) at 350 ℃ to obtain nano Li3YCl6。
Comparative example 4
This comparative example provides a halide solid electrolyte of the formula Li3YCl6The preparation method comprises the following steps:
3mol of NH4Cl and 1mol YCl3Dissolving in water, adding 3mol LiCl, mixing uniformly, removing water and drying at 80 ℃ in vacuum to obtain white powder, calcining the white powder in argon atmosphere (5 hours) at 400 ℃ to obtain nano Li3YCl6。
Performance testing
The solid electrolytes of the respective examples and comparative examples were subjected to performance tests, and the results are shown in table 2.
Table 2 results of performance test of each solid electrolyte
Figure BDA0003139651380000081
Figure BDA0003139651380000091
Note: n/a indicates that there is no XRD peak, so the stress level and grain size cannot be calculated.
As can be seen from table 2, the halide solid electrolyte provided in the embodiments of the present invention has excellent room temperature ion conductivity, activation energy, and electrochemical window, and can be applied to a solid secondary battery.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (10)

1. A halide solid electrolyte characterized by having the formulaLi3MX6M is at least one of rare earth elements, and X is at least one of F, Cl, Br and I; the halide solid electrolyte has a structural microstress of 0.001 to 0.01.
2. The halide solid state electrolyte of claim 1, wherein the structural microstress of the halide solid state electrolyte is manifested by compressive forces in the a, b and tensile forces in the c direction of the unit cell structure, the unit cell structure being lattice distorted by the structural microstress.
3. A halide solid electrolyte according to claim 1 or 2, wherein the anion arrangement of the halide solid electrolyte is hexagonal close-packed or tetragonal close-packed.
4. The halide solid electrolyte according to claim 1 or 2, wherein the particle size D50 of the halide solid electrolyte is 10 to 500 nm.
5. The halide solid state electrolyte of claim 4, wherein the halide solid state electrolyte is Li3YCl6、Li3ErCl6、Li3YbCl6、Li3DyCl6、Li3TmCl6。
6. The method for producing a halide solid electrolyte according to any one of claims 1 to 5, which comprises a liquid phase synthesis method comprising:
MX is dissolved in polar solvent containing hydrolysis inhibitor3And mixing and reacting with LiX, and pyrolyzing the obtained reaction product at 450-600 ℃ to obtain the halide solid electrolyte.
7. The preparation method according to claim 6, wherein after the mixing reaction, the reaction system is dried under vacuum at 80 ± 5 ℃ to remove water, thereby obtaining the reaction product.
8. The method of claim 6 or 7, wherein the hydrolysis inhibitor is NH4X and X are halogen;
preferably, NH4X、MX3And the molar ratio of LiX is 3:1: 3.
9. The method of claim 6 or 7, wherein the polar solvent is water and/or ethanol.
10. Use of the halide solid electrolyte according to any one of claims 1 to 5 as an electrolyte or electrode additive in a solid secondary battery.
CN202110729896.7A 2021-06-29 2021-06-29 Halide solid electrolyte and preparation method and application thereof Pending CN113363567A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113991167A (en) * 2021-10-26 2022-01-28 西安交通大学 Halide solid electrolyte material and preparation method and application thereof
CN114335681A (en) * 2021-11-29 2022-04-12 蜂巢能源科技(无锡)有限公司 Inorganic halide solid electrolyte, preparation method thereof, lithium ion battery and application
CN115528298A (en) * 2022-08-12 2022-12-27 中山大学 Sodium ion halide solid electrolyte material and preparation method and application thereof
WO2023117698A1 (en) * 2021-12-23 2023-06-29 Rhodia Operations Process for the preparation of lithium rare-earth halides
CN116443914A (en) * 2023-03-26 2023-07-18 长江大学 Preparation method and application of halide solid electrolyte

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5578475A (en) * 1978-12-07 1980-06-13 Matsushita Electric Ind Co Ltd Solid electrolyte battery
KR20200021731A (en) * 2018-08-21 2020-03-02 전자부품연구원 Positive electrode nanocomposite for all-solid secondary battery and method for manufacturing the same
CN111566757A (en) * 2018-01-26 2020-08-21 松下知识产权经营株式会社 Solid electrolyte material and battery
CN111916820A (en) * 2019-05-08 2020-11-10 国联汽车动力电池研究院有限责任公司 Solid electrolyte material of secondary battery and preparation method and application thereof
CN112789692A (en) * 2018-12-26 2021-05-11 松下知识产权经营株式会社 Solid electrolyte material and battery using the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5578475A (en) * 1978-12-07 1980-06-13 Matsushita Electric Ind Co Ltd Solid electrolyte battery
CN111566757A (en) * 2018-01-26 2020-08-21 松下知识产权经营株式会社 Solid electrolyte material and battery
KR20200021731A (en) * 2018-08-21 2020-03-02 전자부품연구원 Positive electrode nanocomposite for all-solid secondary battery and method for manufacturing the same
CN112789692A (en) * 2018-12-26 2021-05-11 松下知识产权经营株式会社 Solid electrolyte material and battery using the same
CN111916820A (en) * 2019-05-08 2020-11-10 国联汽车动力电池研究院有限责任公司 Solid electrolyte material of secondary battery and preparation method and application thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113991167A (en) * 2021-10-26 2022-01-28 西安交通大学 Halide solid electrolyte material and preparation method and application thereof
CN114335681A (en) * 2021-11-29 2022-04-12 蜂巢能源科技(无锡)有限公司 Inorganic halide solid electrolyte, preparation method thereof, lithium ion battery and application
CN114335681B (en) * 2021-11-29 2023-11-28 蜂巢能源科技(无锡)有限公司 Inorganic halide solid electrolyte, preparation method thereof, lithium ion battery and application
WO2023117698A1 (en) * 2021-12-23 2023-06-29 Rhodia Operations Process for the preparation of lithium rare-earth halides
CN115528298A (en) * 2022-08-12 2022-12-27 中山大学 Sodium ion halide solid electrolyte material and preparation method and application thereof
CN116443914A (en) * 2023-03-26 2023-07-18 长江大学 Preparation method and application of halide solid electrolyte

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Application publication date: 20210907