EP3994756A1 - The preparation method of gel polymer electrolyte for lithium-sulphur battery - Google Patents

The preparation method of gel polymer electrolyte for lithium-sulphur battery

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Publication number
EP3994756A1
EP3994756A1 EP20727909.2A EP20727909A EP3994756A1 EP 3994756 A1 EP3994756 A1 EP 3994756A1 EP 20727909 A EP20727909 A EP 20727909A EP 3994756 A1 EP3994756 A1 EP 3994756A1
Authority
EP
European Patent Office
Prior art keywords
bma
pegdma
photo
gel polymer
lithium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP20727909.2A
Other languages
German (de)
French (fr)
Inventor
Elif Vargün
Petr Saha
Qilin Cheng
Haojie Fei
Natalia Kazantseva
Tomas Saha
Gengchao WANG
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tomas Bata University in Zlín
Original Assignee
Tomas Bata University in Zlín
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tomas Bata University in Zlín filed Critical Tomas Bata University in Zlín
Publication of EP3994756A1 publication Critical patent/EP3994756A1/en
Pending legal-status Critical Current

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Classifications

    • 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
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/28—Treatment by wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2218—Synthetic macromolecular compounds
    • C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • 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
    • H01M2300/0082—Organic polymers
    • 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

Definitions

  • the invention is related to the simple preparation of gel polymer electrolyte for lithium- sulphur (Li-S) battery based on the polyethylene glycol dimethacrylate (PEGDMA) and butyl methacrylate (BMA).
  • PEGDMA polyethylene glycol dimethacrylate
  • BMA butyl methacrylate
  • the gel polymer electrolyte for Li-S battery is described in USA patent application US2004029016.
  • the electrolyte production is based on monomer with a methacrylate group, initiator, organic solvent and lithium salt.
  • the monomer has been chosen from the group of multifunctional acrylates, which includes polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol divinyl ether, ethylene glycol dimethacrylate, ethylene glycol diacrylate, ethylene glycol divinyl ether, hexanediol diacrylate, tripropylene glycol diacrylate, tetraethylene glycol monoacrylate, caprolactone acrylate and their mixtures, whereby multifunctional acrylate is polyester methacrylate, which includes hydroxide groups in polyester polyol, partly or completely substituted by methacrylic ester, and unsubstituted hydroxide groups are substituted by a group which does not have radical reactivity.
  • European patent EP1368849 deals with gel polymer electrolyte which contains (A) copolymer of ethylene and unsaturated carboxylic acid or its derivative and (B) poly alky lene oxide with a hydroxyl group on one end or its derivative, which are connected by ester bonding.
  • Copolymer of ethylene and unsaturated carboxylic acid or its derivative (A) contains ethylene in the amount ranging from 50 to 98 wt.%, unsaturated carboxylic acid or its anhydride in the amount of 2 to 50 wt.%, and alternatively other monomers in the amount ranging from 0% to 30%.
  • Polyalkylene oxide with a hydroxyl group on one end or its derivative (B) has the number average molecular weight of 200 to 100 000 and contains ethylene oxide in the amount of 30 to 100 mol %.
  • the gel polymer is impregnated by non-aqueous solution which contains electrolytic salt.
  • Gel polymer electrolyte has a high ion conductivity and enables to create cells with excellent charge/discharge characteristics at both low and high temperatures. It can be prepared in the form of film and utilised for polymer lithium cells which suppress lithium dendrite formation, a feature that can be found on the negative electrode surface during charge process.
  • South Korean patent application KR20010086972 deals with gel polymer electrolytes or complex electrodes using gel electrolytes for secondary lithium batteries with high energy density, longer life cycle, better low and high temperature characteristics, improved charge/discharge efficiency and stability of the battery.
  • Gel polymer electrolytes contain 5 to 90 wt.% of type I polymer selected from materials based on polyacrylonitrile and on polymethyl methacrylate (PMMA); 5 to 80 wt.% type II polymer selected from materials based on polyvinylidene fluoride (PVDF) and on PMMA; and 5 to 80 wt.% type III polymer selected from materials based on PVC and on PVDF.
  • the gel polymer electrolyte contains also plasticizer or organic solvent and/or fillers.
  • the complex electrode contains gel polymer electrolyte in the anode or cathode pores and a layer of the gel polymer electrolyte with the thickness of 2 to 20 pm on the surface of electrodes.
  • the method of preparation of the gel polymer electrolyte for lithium- sulphur (Li-S) battery based on PEGDMA and BMA contributes to the elimination of deficiencies of the current state of the art.
  • the invention consists in film preparation via photo-initiated crosslinking reaction of PEGDMA with BMA.
  • silicon dioxide nanoparticles (S1O2) of the size below 12 nm are dispersed in BMA.
  • electrolyte which is bis(trifluoromethane)sulfonimide lithium salt (LiTFSI) dissolved in a mixture of solvents, preferably ethylene / diethylene carbonate.
  • the applied PEGDMA has the molecular weight of 550 to 750 Da.
  • 2-hydroxy-2-methylpropiophenone is effectively used as a photo -initiator of the crosslinking reaction.
  • Photo-initiated crosslinking is a useful method for preparing polymer electrolytes due to the one-step, rapid reaction and crosslinking at the low temperatures. Absence of any solvents during photo-crosslinking enables to prepare environmentally friendly gel polymer electrolytes. Moreover, using simple instruments and manufacturing conditions results in low production cost.
  • the photo-initiated crosslinking reaction of PEGDMA with BMA takes 15 to 20 minutes, is run under the UV-radiation of 245-280 nm wavelength and the film thus prepared has a convenient thickness of 15-30 pm.
  • the main contribution of gel polymer electrolyte according to the invention is the use of ceramic filler, which suppresses dendrite growth at the electrolyte/electrode interface during cycling.
  • Ideal polymer electrolytes require a wide potential window and a high ionic conductivity.
  • the ionic conductivity of gel polymer electrolyte is directly related to the optimized composition, PEGDMA/BMA chain length ratio and crosslinking density. Ionic conductivity is increased by adjusting these parameters through enhanced ions mobility.
  • Conventional polyethylene oxide -based polymer electrolytes show the conductivities ranging from 10 5 to 10 4 S.cm 1 at room temperature.
  • the ionic conductivity with added SiCE nanoparticles to PEGDMA/BMA gel electrolyte reaches ⁇ lxlO 3 S.cm 1 at 25°C.
  • a cross- linked polymeric material based on the photo -initiated crosslinking reaction of PEGDMA with BMA is prepared.
  • photo-initiator 2-hydroxy-2-methylpropiophenone (Darocure 1173) in the amount of 5 mg is added to 0.5 g PEGDMA with the molecular weight of 550 to 750 Da at room temperature and the mixture is vortexed mixed for 2 minutes.
  • Si0 2 nanoparticles of a maximum size of 12 nm are dispersed in BMA; they act as ceramic filler.
  • the nanoparticles in the amount of 50 mg (5 wt.% of the total monomer weight) are dispersed in 0.5 g of BMA by magnetic stirring for 12 hours, and then by ultrasound for another 3 minutes.
  • Si0 2 -BMA dispersion is slowly added to the mixture of PEGDMA and photo-initiator and the content is stirred at continuous purging with nitrogen gas for 15 minutes.
  • the mixture is then injected in between 2 mould plates with a Teflon spacer 15 -30 pm thick, which is consequently the thickness of the film.
  • Photo-polymerization is performed under a 245-280 nm wavelength UV-lamp for 15-20 minutes in a chamber continuously purged with nitrogen gas.
  • the prepared film is taken out of the mould and post-cured in an oven at 70°C for 2 hours to ensure complete polymerization.
  • the film is soaked in 1.0 M organic electrolyte solution of LiTFSI in ethylene carbonate/diethylene carbonate (volume ratio 1/1) mixture with 1 wt.% of LiN0 3 , for 12 h in an argon-filled glovebox.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Nanotechnology (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Composite Materials (AREA)
  • Dispersion Chemistry (AREA)
  • Secondary Cells (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

The method of preparation of gel polymer electrolyte for lithium-sulphur (Li-S) battery based on polyethylene glycol dimethacrylate (PEGDMA) and butyl methacrylate (BMA) consists in film preparation via the photo-initiated crosslinking reaction of PEGDMA BMA and subsequent soaking the film in bis(trifluoromethane)sulfonimide lithium salt (LiTFSI) electrolyte solution, whereby before mixing PEGDMA with photo -initiator and BMA, silicon dioxide (SiO2) nanoparticles are dispersed in BMA.

Description

THE PREPARATION METHOD OF GEL POLYMER ELECTROLYTE FOR LITHIUM-SULPHUR BATTERY
Technical area
The invention is related to the simple preparation of gel polymer electrolyte for lithium- sulphur (Li-S) battery based on the polyethylene glycol dimethacrylate (PEGDMA) and butyl methacrylate (BMA).
Current state of the art
The gel polymer electrolyte for Li-S battery is described in USA patent application US2004029016. The electrolyte production is based on monomer with a methacrylate group, initiator, organic solvent and lithium salt. The monomer has been chosen from the group of multifunctional acrylates, which includes polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol divinyl ether, ethylene glycol dimethacrylate, ethylene glycol diacrylate, ethylene glycol divinyl ether, hexanediol diacrylate, tripropylene glycol diacrylate, tetraethylene glycol monoacrylate, caprolactone acrylate and their mixtures, whereby multifunctional acrylate is polyester methacrylate, which includes hydroxide groups in polyester polyol, partly or completely substituted by methacrylic ester, and unsubstituted hydroxide groups are substituted by a group which does not have radical reactivity.
European patent EP1368849 deals with gel polymer electrolyte which contains (A) copolymer of ethylene and unsaturated carboxylic acid or its derivative and (B) poly alky lene oxide with a hydroxyl group on one end or its derivative, which are connected by ester bonding. Copolymer of ethylene and unsaturated carboxylic acid or its derivative (A) contains ethylene in the amount ranging from 50 to 98 wt.%, unsaturated carboxylic acid or its anhydride in the amount of 2 to 50 wt.%, and alternatively other monomers in the amount ranging from 0% to 30%. Polyalkylene oxide with a hydroxyl group on one end or its derivative (B) has the number average molecular weight of 200 to 100 000 and contains ethylene oxide in the amount of 30 to 100 mol %. The gel polymer is impregnated by non-aqueous solution which contains electrolytic salt.
Gel polymer electrolyte has a high ion conductivity and enables to create cells with excellent charge/discharge characteristics at both low and high temperatures. It can be prepared in the form of film and utilised for polymer lithium cells which suppress lithium dendrite formation, a feature that can be found on the negative electrode surface during charge process. South Korean patent application KR20010086972 deals with gel polymer electrolytes or complex electrodes using gel electrolytes for secondary lithium batteries with high energy density, longer life cycle, better low and high temperature characteristics, improved charge/discharge efficiency and stability of the battery. Gel polymer electrolytes contain 5 to 90 wt.% of type I polymer selected from materials based on polyacrylonitrile and on polymethyl methacrylate (PMMA); 5 to 80 wt.% type II polymer selected from materials based on polyvinylidene fluoride (PVDF) and on PMMA; and 5 to 80 wt.% type III polymer selected from materials based on PVC and on PVDF. The gel polymer electrolyte contains also plasticizer or organic solvent and/or fillers. The complex electrode contains gel polymer electrolyte in the anode or cathode pores and a layer of the gel polymer electrolyte with the thickness of 2 to 20 pm on the surface of electrodes.
Subject of invention
According to the invention, the method of preparation of the gel polymer electrolyte for lithium- sulphur (Li-S) battery based on PEGDMA and BMA contributes to the elimination of deficiencies of the current state of the art.
The invention consists in film preparation via photo-initiated crosslinking reaction of PEGDMA with BMA. Before blending PEGDMA, photo -initiator and BMA, silicon dioxide nanoparticles (S1O2) of the size below 12 nm are dispersed in BMA. Subsequently, the prepared film is soaked in electrolyte, which is bis(trifluoromethane)sulfonimide lithium salt (LiTFSI) dissolved in a mixture of solvents, preferably ethylene / diethylene carbonate.
The applied PEGDMA has the molecular weight of 550 to 750 Da. As a photo -initiator of the crosslinking reaction, 2-hydroxy-2-methylpropiophenone is effectively used.
Photo-initiated crosslinking is a useful method for preparing polymer electrolytes due to the one-step, rapid reaction and crosslinking at the low temperatures. Absence of any solvents during photo-crosslinking enables to prepare environmentally friendly gel polymer electrolytes. Moreover, using simple instruments and manufacturing conditions results in low production cost.
The photo-initiated crosslinking reaction of PEGDMA with BMA takes 15 to 20 minutes, is run under the UV-radiation of 245-280 nm wavelength and the film thus prepared has a convenient thickness of 15-30 pm.
The main contribution of gel polymer electrolyte according to the invention is the use of ceramic filler, which suppresses dendrite growth at the electrolyte/electrode interface during cycling. Ideal polymer electrolytes require a wide potential window and a high ionic conductivity. The ionic conductivity of gel polymer electrolyte is directly related to the optimized composition, PEGDMA/BMA chain length ratio and crosslinking density. Ionic conductivity is increased by adjusting these parameters through enhanced ions mobility. Conventional polyethylene oxide -based polymer electrolytes show the conductivities ranging from 10 5 to 104 S.cm 1 at room temperature. The ionic conductivity with added SiCE nanoparticles to PEGDMA/BMA gel electrolyte reaches ~ lxlO 3 S.cm 1 at 25°C.
Example of technical application
In the preparation of gel polymer electrolyte for lithium- sulphur (Li-S) battery, a cross- linked polymeric material based on the photo -initiated crosslinking reaction of PEGDMA with BMA is prepared. First, photo-initiator 2-hydroxy-2-methylpropiophenone (Darocure 1173) in the amount of 5 mg is added to 0.5 g PEGDMA with the molecular weight of 550 to 750 Da at room temperature and the mixture is vortexed mixed for 2 minutes.
Then, Si02 nanoparticles of a maximum size of 12 nm are dispersed in BMA; they act as ceramic filler. The nanoparticles in the amount of 50 mg (5 wt.% of the total monomer weight) are dispersed in 0.5 g of BMA by magnetic stirring for 12 hours, and then by ultrasound for another 3 minutes. After it, Si02-BMA dispersion is slowly added to the mixture of PEGDMA and photo-initiator and the content is stirred at continuous purging with nitrogen gas for 15 minutes.
The mixture is then injected in between 2 mould plates with a Teflon spacer 15 -30 pm thick, which is consequently the thickness of the film. Photo-polymerization is performed under a 245-280 nm wavelength UV-lamp for 15-20 minutes in a chamber continuously purged with nitrogen gas. The prepared film is taken out of the mould and post-cured in an oven at 70°C for 2 hours to ensure complete polymerization.
Afterwards, the film is soaked in 1.0 M organic electrolyte solution of LiTFSI in ethylene carbonate/diethylene carbonate (volume ratio 1/1) mixture with 1 wt.% of LiN03, for 12 h in an argon-filled glovebox.

Claims

PATENT CLAIMS
1. The method of preparation of gel polymer electrolyte for lithium- sulphur (Li-S) battery based on polyethylene glycol dimethacrylate (PEGDMA) and butyl methacrylate (BMA), characterized by film preparation via the photo -initiated crosslinking reaction of PEGDMA BMA, and subsequent soaking the film in bis(trifluoromethane)sulfonimide lithium salt (LiTFSI) electrolyte solution, whereby before mixing PEGDMA with photo-initiator and BMA, silicon dioxide (S1O2) nanoparticles are dispersed in BMA.
2. The method according to claim 1, characterized by the use of PEGDMA with the molecular weight of 550 to 750Da.
3. The method according to claim 1, characterized by the use of photo -initiator 2-hydroxy-2- methy lpropiophenone .
4. The method according to claim 1, characterized by the use of photo-initiated crosslinking reaction of PEGDMA with BMA to prepare film of a thickness of 15-30 pm.
5. The method according to claims 1 to 4, characterized by the fact that the photo-initiated crosslinking reaction of PEGDMA with BMA runs under the UV radiation of 245-280 nm wavelength for 15 to 20 minutes.
6. The method according to claim 1, characterized by the size of S1O2 nanoparticles dispersed in BMA - up to 12 nm.
EP20727909.2A 2019-07-01 2020-04-08 The preparation method of gel polymer electrolyte for lithium-sulphur battery Pending EP3994756A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CZ2019-434A CZ308295B6 (en) 2019-07-01 2019-07-01 A method of preparing a gel type polymer electrolyte for a lithium-sulphur battery
PCT/CZ2020/050022 WO2021000973A1 (en) 2019-07-01 2020-04-08 The preparation method of gel polymer electrolyte for lithium-sulphur battery

Publications (1)

Publication Number Publication Date
EP3994756A1 true EP3994756A1 (en) 2022-05-11

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WO (1) WO2021000973A1 (en)

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CN115716894B (en) * 2022-11-18 2025-05-23 东南大学 Ion conductive elastomer and preparation method thereof

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JP2002280072A (en) * 2001-03-19 2002-09-27 National Institute Of Advanced Industrial & Technology Battery incorporating inorganic / organic composite polymer solid electrolyte
KR100411235B1 (en) * 2001-04-02 2003-12-18 한국과학기술원 Process for Preparing Lithium Polymer Secondary Batteries
JP2004071560A (en) * 2002-08-07 2004-03-04 Samsung Sdi Co Ltd Polymer electrolyte for lithium-sulfur battery and lithium-sulfur battery including the same
CN101150182B (en) * 2006-09-18 2011-12-07 深圳市比克电池有限公司 Lithium ion battery electrode slice, electric core and its making method
CN102779966B (en) * 2012-08-10 2015-03-04 龙能科技（苏州）有限公司 Method for preparing battery diaphragm through in-situ reaction
CN103985899B (en) * 2014-03-13 2016-03-30 江苏科技大学 The Semi-IPN method for preparing gel polymer electrolyte of Doped ions compound
CN104393336B (en) * 2014-11-13 2018-03-09 湘潭大学 A kind of nano-composite fiber enhancing gel polymer electrolyte and preparation method thereof
CN111477952B (en) * 2018-01-03 2022-02-25 清陶（昆山）能源发展有限公司 Polyacrylate solid polymer electrolyte, preparation method and application thereof in solid lithium battery

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CZ308295B6 (en) 2020-04-22
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