WO2020087873A1 - 一种改性固态电解质膜及其制备方法和锂电池 - Google Patents

一种改性固态电解质膜及其制备方法和锂电池 Download PDF

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Publication number
WO2020087873A1
WO2020087873A1 PCT/CN2019/082611 CN2019082611W WO2020087873A1 WO 2020087873 A1 WO2020087873 A1 WO 2020087873A1 CN 2019082611 W CN2019082611 W CN 2019082611W WO 2020087873 A1 WO2020087873 A1 WO 2020087873A1
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Prior art keywords
membrane
solid electrolyte
modified solid
base
composite
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Ceased
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English (en)
French (fr)
Chinese (zh)
Inventor
闫昭
罗飞
陶凌
李泓
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Tianmulake Excellent Anode Materials Co Ltd
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Tianmulake Excellent Anode Materials Co Ltd
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Priority to US17/309,119 priority Critical patent/US20220006118A1/en
Priority to EP19877700.5A priority patent/EP3876323A4/en
Priority to KR1020217012963A priority patent/KR102577441B1/ko
Priority to JP2021523595A priority patent/JP7338897B2/ja
Publication of WO2020087873A1 publication Critical patent/WO2020087873A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • 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
    • H01M10/05—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
    • 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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/497—Ionic conductivity
    • 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
    • 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
    • H01M2300/0088—Composites
    • H01M2300/0094—Composites in the form of layered products, e.g. coatings
    • 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
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the invention relates to the technical field of lithium battery materials, in particular to a modified solid electrolyte membrane, a preparation method thereof and a lithium battery.
  • Lithium-ion battery is a new type of secondary rechargeable battery. Because of its high working voltage, large capacity, long cycle life and no pollution, it is widely used in notebook computers, mobile phones and other equipment and power tools. In recent years, with the continuous development of new energy sources, the demand for secondary batteries is also increasing. Improving the overall safety and electrochemical performance of batteries is the focus of current development of secondary batteries.
  • the separator is an important part of the secondary battery, which affects the interface structure and internal impedance, and plays a vital role in the thermal stability, cycle performance, rate performance and safety performance of the battery. Therefore, the lithium battery separator must have good chemical stability, electrochemical stability, and have a certain tensile strength and puncture resistance.
  • the invention provides a modified solid electrolyte membrane, a preparation method thereof and a lithium battery.
  • the modified solid electrolyte membrane of the invention has the characteristics of good liquid absorption, uniform thickness, high temperature resistance and high ion conductivity, and the preparation method is simple , Suitable for large-scale production.
  • an embodiment of the present invention provides a modified solid electrolyte membrane, including: a base membrane and a solid electrolyte layer; the solid electrolyte layer is coated on or coated on the base membrane
  • the coating slurry formed on the membrane and penetrated into the base membrane the ratio of the thickness of the coating layer coated on the base membrane of the base membrane to the thickness of the base membrane is 10: 1-1: 10.
  • the thickness of the coating layer is 1um-10um, and the density is 50% -100%;
  • the solid electrolyte layer is composed of NASICON solid electrolyte material, the particle size is less than 1um, specifically: Li 1 + x A x B 2-x (PO 4 ) 3 , where x is between 0-0.6; A is Al , Y, Ga, Cr, In, Fe, Se, or La, B is one or more of Ti, Ge, Ta, Zr, Sn, Fe, V, or hafnium element Hf;
  • the X-ray photoelectron spectrum After the cyclic formation of the solid electrolyte membrane, the X-ray photoelectron spectrum has a peak position between 685eV-690eV.
  • the base film includes a polyolefin microporous film, a woven film, a nonwoven fabric film, a composite film, a rolled film, an alumina ceramic separator, a ceramic fiber film, a polyvinylidene fluoride-hexafluoropropylene PVDF-HFP Any one of composite porous polymer membrane, PVDF and its copolymer porous membrane, composite nanofiber membrane, polyethylene oxide PEO-lithium salt composite lithium ion conductive membrane or polymethyl methacrylate PMMA composite membrane.
  • the ratio of the thickness of the coating layer to the base film is 10: 1-1: 5, and the density of the coating layer is 60% -99%.
  • the ratio of the thickness of the coating layer to the base film is 5: 1-1: 5, and the density of the coating layer is 65% -98%.
  • the particle size of the solid electrolyte material is less than 500 nm, the shape is spherical or irregular polygon; the x is between 0.2-0.6.
  • the particle size of the solid electrolyte material is less than 200 nm; the x is between 0.3-0.5.
  • an embodiment of the present invention provides a method for modifying a solid electrolyte membrane, including:
  • the solid electrolyte powder is gradually added to the first mixture according to the required ratio for stirring and dispersion, the stirring speed is 10-50 rpm, the dispersion speed is 1000-5000 rpm, and after being stirred uniformly, it is screened to obtain a coating slurry;
  • the solid electrolyte powder is NASICON type solid electrolyte material, the particle size is less than 1um, specifically: Li 1 + x A x B 2-x (PO 4 ) 3 , where x is between 0-0.6; A is Al, Y , Ga, Cr, In, Fe, Se or La, B is one or more of Ti, Ge, Ta, Zr, Sn, Fe, V or hafnium element Hf;
  • the coating slurry is applied to one or both sides of the base film at a speed of 1m / min-100m / min, and dried at 20 ° C-100 ° C to obtain a modified solid electrolyte membrane;
  • the base membrane includes poly Olefin microporous membrane, woven membrane, non-woven fabric membrane, composite membrane, laminated membrane, alumina ceramic membrane, ceramic fiber membrane, PVDF-HFP composite porous polymer membrane, PVDF and its copolymer porous membrane, composite nanofiber Any one of membrane, PEO-lithium salt composite lithium ion conductive membrane or PMMA composite membrane.
  • the solvent is at least one of water, N-methylpyrrolidone, N, N-dimethylformamide, acetone and acetonitrile;
  • the binder is styrene-butadiene latex, styrene-acrylic latex, polyvinyl alcohol, polyacrylamide, polymethyl methacrylate-butyl acrylate, hydroxyethyl cellulose, methyl hydroxyethyl cellulose , One or more of sodium carboxymethyl cellulose, polyacrylamide; dispersant is sodium polyacrylate, sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, sodium hexametaphosphate, polyacrylic acid, One or more of cetyltrimethylammonium bromide, polyethylene glycol, potassium polyacrylate, octylphenol polyoxyethylene or sulfonate fluoride dispersant;
  • the binder is polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polytetrafluoroethylene One or more of ethylene, polymethyl methacrylate, and polyacrylonitrile;
  • the dispersant is one of stearic acid monoglyceride, tristearic acid glyceride, oleoyl, vinyl bis stearamide One or more.
  • embodiments of the present invention provide a lithium battery including the modified solid electrolyte membrane described in the first aspect above.
  • the modified solid electrolyte membrane of the invention has the characteristics of good liquid absorption, uniform thickness, high temperature resistance, and high ion conductivity.
  • the preparation method is simple and suitable for large-scale production.
  • FIG. 1 is a schematic structural diagram of a modified solid electrolyte membrane provided by an embodiment of the present invention
  • FIG. 2 is a flowchart of a method for preparing a modified solid electrolyte membrane provided by an embodiment of the present invention
  • Example 3 is a scanning electron microscope (SEM) image of the modified solid electrolyte membrane provided in Example 1 of the present invention
  • Example 4 is a comparison of the impedance diagram of the modified solid electrolyte membrane provided in Example 1 of the present invention and the aluminum oxide separator prepared in the comparative example;
  • Example 5 is a comparison of X-ray photoelectron spectroscopy of the electrolyte membranes prepared in Example 1, Example 2, Example 3 and Comparative Example of the present invention.
  • An embodiment of the present invention provides a modified solid electrolyte membrane, including a base membrane and a solid electrolyte layer, the solid electrolyte layer is coated on or coated on the base membrane and penetrated into the base membrane Cover slurry composition.
  • the modified solid electrolyte membrane includes a base membrane and a solid electrolyte layer, the solid electrolyte layer is coated on at least one side of the base membrane or coated on the base membrane Consists of coating slurry that penetrates into the base film.
  • the ratio of the thickness of the coating layer composed of the coating slurry coated on the base film and the base film is 10: 1-1: 5, and the density of the coating layer is 60%- 99%.
  • the ratio of the thickness of the coating layer to the base film is 5: 1-1: 5, and the density of the coating layer is 65% -98%.
  • the base membrane includes polyolefin microporous membrane, woven membrane, non-woven membrane, composite membrane, laminated membrane, alumina ceramic membrane, ceramic fiber membrane, polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) composite Any one of porous polymer membrane, PVDF and its copolymer porous membrane, composite nanofiber membrane, polyethylene oxide (PEO) -lithium salt composite lithium ion conductive membrane or polymethyl methacrylate (PMMA) composite membrane .
  • PVDF-HFP polyvinylidene fluoride-hexafluoropropylene
  • the solid electrolyte layer is composed of NASICON solid electrolyte material, and the particle size is less than 1um.
  • the NASICON solid electrolyte material is: Li 1 + x A x B 2-x (PO 4 ) 3 , where x is between 0-0.6; A is Al, Y, Ga, Cr, In, Fe, Se Or one or more of La, and B is one or more of Ti, Ge, Ta, Zr, Sn, Fe, V or hafnium element Hf.
  • the particle size of the solid electrolyte material is less than 500 nm, and the shape is spherical or irregular polygonal; in Li 1 + x A x B 2-x (PO 4 ) 3 , x is between 0.2-0.6. In a more preferred solution, the particle size of the solid electrolyte material is less than 200 nm; x in Li 1 + x A x B 2-x (PO 4 ) 3 is between 0.3-0.5.
  • the method for preparing the modified solid electrolyte membrane provided in this embodiment has the steps shown in FIG. 2 and includes the following steps:
  • Step 210 Add the dispersant, the binder and the solvent to the pre-stirred tank at the required ratio, and dissolve completely to obtain the first mixture;
  • the solvent is at least one of water, N-methylpyrrolidone, N, N-dimethylformamide, acetone and acetonitrile;
  • the binder is styrene-butadiene latex, styrene-acrylic latex, polyvinyl alcohol, polyacrylamide, polymethyl methacrylate-butyl acrylate, hydroxyethyl cellulose, methyl hydroxyethyl cellulose , One or more of sodium carboxymethyl cellulose, polyacrylamide; dispersant is sodium polyacrylate, sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, sodium hexametaphosphate, polyacrylic acid, One or more of cetyltrimethylammonium bromide, polyethylene glycol, potassium polyacrylate, octylphenol polyoxyethylene or sulfonate fluoride dispersant;
  • the binder is polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polytetrafluoroethylene One or more of ethylene, polymethyl methacrylate, and polyacrylonitrile;
  • the dispersant is one of stearic acid monoglyceride, tristearic acid glyceride, oleoyl, vinyl bis stearamide One or more.
  • Step 220 the solid electrolyte powder is gradually added to the first mixture according to the required ratio for stirring and dispersion, the stirring speed is 10-50 rpm, the dispersion speed is 1000-5000 rpm, and after being stirred evenly, it is passed through a sieve to obtain a coating slurry;
  • the solid electrolyte powder is NASICON solid electrolyte material, the particle size is less than 1um, and the shape is spherical or irregular polygon.
  • the solid electrolyte powder is preferably: Li 1 + x A x B 2-x (PO 4 ) 3 , where x is between 0-0.6; A is in Al, Y, Ga, Cr, In, Fe, Se or La One or more of, B is one or more of Ti, Ge, Ta, Zr, Sn, Fe, V or hafnium element Hf;
  • the particle size of the solid electrolyte material is less than 500 nm, and the shape is spherical or irregular polygonal; in Li 1 + x A x B 2-x (PO 4 ) 3 , x is between 0.2-0.6. In a more preferred solution, the particle size of the solid electrolyte material is less than 200 nm; x in Li 1 + x A x B 2-x (PO 4 ) 3 is between 0.3-0.5.
  • Step 230 apply the coating slurry to one or both sides of the base film at a speed of 1m / min-100m / min, and dry at 20 ° C-100 ° C to obtain a modified solid electrolyte membrane;
  • the base membrane includes polyolefin microporous membrane, woven membrane, nonwoven fabric membrane, composite membrane, laminated membrane, alumina ceramic membrane, ceramic fiber membrane, PVDF-HFP composite porous polymer membrane, PVDF and its copolymer porous Separator, composite nanofiber membrane, PEO-lithium salt composite lithium ion conductive membrane or PMMA composite membrane.
  • the modified solid electrolyte membrane of this method name obtained by the above method has the characteristics of good liquid absorption, uniform thickness, high temperature resistance, and high ion conductivity.
  • the preparation method is simple and suitable for large-scale production.
  • This embodiment provides a modified solid electrolyte membrane, which includes a base membrane and a solid electrolyte layer composed of a coating slurry coated on one side of the base membrane.
  • the base membrane is a polypropylene porous membrane with a thickness of 10um.
  • the coating thickness is 3um
  • the coating slurry used to form the solid electrolyte layer according to the mass ratio is: composition 20%, deionized water 80%; wherein, the composition is prepared according to the mass ratio: nano solid Electrolyte Lithium Titanium Aluminum Phosphate Li 1.5 Al 0.5 Ti 1.5 (PO 4 ) 3 powder 97%, particle size D50 is 200 nm, binder sodium carboxymethyl cellulose 1%, styrene butadiene latex 1%, dispersant: polyacrylic acid Sodium 1%, octylphenol polyoxyethylene 1%.
  • the modified solid electrolyte membrane in this embodiment is prepared by the following method, specifically including steps:
  • the coating slurry is applied to one side of the base film at a coating speed of 5 m / min, dried at 50 ° C, and dried to obtain a modified solid electrolyte membrane.
  • the SEM image of the modified solid electrolyte membrane provided in Example 1 of the present invention is shown in FIG. 3, and it can be seen from FIG. 3 that the solid electrolyte powder is evenly distributed.
  • This embodiment provides a modified solid electrolyte membrane including a base membrane and a solid electrolyte layer composed of a coating slurry coated on one side of the base membrane.
  • the base film is a polypropylene porous film with a thickness of 12um. It is coated on a single side with a thickness of 4um.
  • the coating slurry used to form the solid electrolyte layer according to the mass ratio is: composition 20%, N-methylpyrrolidone 80%; wherein, the preparation of the composition according to the mass ratio is: nano-solid electrolyte lithium titanium aluminum phosphate Li 1.5 Al 0.5 Ti 1.5 (PO 4 ) 3 powder 96%, particle size D50 is 200 nm.
  • Binder polyvinylidene fluoride 2%, dispersant: glyceryl stearate 2%.
  • the method for preparing the modified solid electrolyte membrane is the same as in Example 1.
  • This embodiment provides a modified solid electrolyte membrane including a base membrane and a solid electrolyte coating composed of a coating slurry coated on one side of the base membrane.
  • the base membrane is a polypropylene porous membrane with a thickness of 7um.
  • the coating thickness is 2um
  • the coating slurry used to form the solid electrolyte layer according to the mass ratio is: composition 20%, deionized water 80%; wherein, the composition is prepared according to the mass ratio: nano Solid electrolyte lithium titanium aluminum phosphate Li 1.2 Al 0.2 Ti 1.8 (PO 4 ) 3 powder 97%, particle size D50 is 200nm, binder sodium carboxymethyl cellulose 1%, styrene-butadiene latex 1%, dispersant polyethylene Glycol 0.3%, sodium dodecylbenzenesulfonate 0.7%.
  • the method for preparing the modified solid electrolyte membrane is the same as in Example 1.
  • a porous polypropylene membrane coated with alumina on one side is used, the thickness of the base membrane is 10um, and the alumina coating is 3um.
  • modified solid electrolyte membrane of the present invention also has good stability.
  • Table 1 compares the thermal stability of the alumina membrane prepared in the comparative example and the base membrane-polypropylene porous membrane (PP membrane) in Example 1 and the modified solid electrolyte membrane provided in Example 1.
  • the thermal stability of the modified solid electrolyte membrane of the present invention is better than that of the alumina separator prepared in the comparative example and the polypropylene porous membrane without modification treatment.
  • FIG. 5 is the electrolyte membranes prepared in Example 1, Example 2, Example 3 and Comparative Example of the present invention are assembled into a battery, after being cyclically formed, the electrolyte membrane is disassembled and tested, and the obtained X-ray photoelectron spectrum Figure comparison.
  • Example 1, Example 2, and Example 3 are compared with Comparative Example 1. It can be seen that there is one more peak position between 685 eV and 690 eV, and the corresponding substance can increase the lithium ion conduction.

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PCT/CN2019/082611 2018-10-30 2019-04-15 一种改性固态电解质膜及其制备方法和锂电池 Ceased WO2020087873A1 (zh)

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Application Number Priority Date Filing Date Title
US17/309,119 US20220006118A1 (en) 2018-10-30 2019-04-15 Modified solid electrolyte membrane, preparation method therefor, and lithium battery
EP19877700.5A EP3876323A4 (en) 2018-10-30 2019-04-15 Modified solid electrolyte membrane and preparation method therefor, and lithium battery
KR1020217012963A KR102577441B1 (ko) 2018-10-30 2019-04-15 개질 고체 전해질막 및 그 제조 방법과 리튬전지
JP2021523595A JP7338897B2 (ja) 2018-10-30 2019-04-15 改質固体電解質膜を製造する方法

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CN201811275832.9 2018-10-30
CN201811275832.9A CN109494390A (zh) 2018-10-30 2018-10-30 一种改性固态电解质膜及其制备方法和锂电池

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WO2022177346A1 (ko) * 2021-02-19 2022-08-25 한국전자통신연구원 다공성 프레임 기반의 고체전해질막 및 이의 제조방법 그리고 이를 포함하는 전고체전지
CN119864497A (zh) * 2025-01-14 2025-04-22 天目湖先进储能技术研究院有限公司 一种可连续性生产的柔性复合固态电解质薄膜及其制备方法

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