WO2014000247A1 - 聚丙烯腈-甲基丙烯酸甲酯凝胶电解质膜的制备方法，及其相应电解质和制备方法 - Google Patents

聚丙烯腈-甲基丙烯酸甲酯凝胶电解质膜的制备方法，及其相应电解质和制备方法 Download PDF

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Publication number
WO2014000247A1
WO2014000247A1 PCT/CN2012/077845 CN2012077845W WO2014000247A1 WO 2014000247 A1 WO2014000247 A1 WO 2014000247A1 CN 2012077845 W CN2012077845 W CN 2012077845W WO 2014000247 A1 WO2014000247 A1 WO 2014000247A1
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Prior art keywords
polyacrylonitrile
methyl methacrylate
mcm
gel electrolyte
molecular sieve
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PCT/CN2012/077845
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English (en)
French (fr)
Inventor
周明杰
刘大喜
王要兵
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Application filed by Oceans King Lighting Science and Technology Co Ltd, Shenzhen Oceans King Lighting Engineering Co Ltd filed Critical Oceans King Lighting Science and Technology Co Ltd
Priority to JP2015518763A priority Critical patent/JP2015525283A/ja
Priority to US14/400,790 priority patent/US20150140440A1/en
Priority to EP12879939.2A priority patent/EP2868689A4/en
Priority to PCT/CN2012/077845 priority patent/WO2014000247A1/zh
Priority to CN201280072978.8A priority patent/CN104271648A/zh
Publication of WO2014000247A1 publication Critical patent/WO2014000247A1/zh
Anticipated expiration legal-status Critical
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    • 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
    • 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
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • 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
    • C08J7/04—Coating
    • C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions 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; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions 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; Compositions of derivatives of such polymers
    • C08L33/18—Homopolymers or copolymers of nitriles
    • C08L33/20—Homopolymers or copolymers of acrylonitrile
    • 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
    • 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
    • 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
    • C08J2333/06—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 of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
    • C08J2333/12—Homopolymers or copolymers of methyl methacrylate
    • 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 relates to the field of electrochemistry, in particular to a method for preparing a polyacrylonitrile-methyl methacrylate gel electrolyte membrane, And its corresponding electrolyte and preparation method.
  • the current conventional liquid electrolyte has the advantage of high electrical conductivity, but because it contains a flammable, volatile organic solvent, it releases flammable gas during charging and discharging, especially under certain unconventional working conditions (such as high power charging). Discharge, overcharge and over discharge, etc.) A large amount of heat will accelerate the generation of gas, resulting in increased internal pressure of the battery, gas leakage, and even fire and explosion, thus posing a serious safety hazard.
  • Polymer electrolyte lithium-ion batteries have attracted the attention of researchers because of their safety, leak-free, and low leakage current. Since the solid polymer electrolyte has a low electrical conductivity at room temperature (10 -5 ⁇ 10 -4 s/cm) and its application is limited, gel polymer electrolytes have become the focus of research.
  • the present invention is directed to a method for preparing a polyacrylonitrile-methyl methacrylate gel electrolyte membrane, And its corresponding electrolyte and preparation method.
  • the polyacrylonitrile-methyl methacrylate gel electrolyte provided by the invention has higher modification by MCM-48 mesoporous molecular sieve. It has good conductivity and safety and can be used as a solid polymer electrolyte for lithium ion batteries.
  • the preparation method provided by the invention has simple process flow and environmental friendliness.
  • the present invention provides a method for preparing a polyacrylonitrile-methyl methacrylate gel electrolyte membrane, comprising the steps of:
  • the step (1) of the present invention is to use polyacrylonitrile-methyl methacrylate (P(AN-MMA)) Dissolved in an organic solvent to obtain a slurry containing MCM-48 mesoporous molecular sieve.
  • P(AN-MMA) polyacrylonitrile-methyl methacrylate
  • the polyacrylonitrile-methyl methacrylate has a mass average molecular weight of 100,000 to 500,000.
  • the organic solvent in the step (1) is N-methylpyrrolidone, N, N- Dimethylformamide, acetonitrile or ethanol.
  • the MCM-48 The mesoporous molecular sieve is prepared as follows: taking cetyltrimethylammonium bromide, dissolving in deionized water, adding sodium hydroxide, heating to 20 ⁇ 50 ° C, stirring at a constant temperature to dissolve the sodium hydroxide, slowly Add 1.0g Ethyl orthosilicate, continue to stir for 4 ⁇ 5h to obtain the reaction stock solution; transfer the reaction liquid into the reactor of polytetrafluoroethylene liner, statically crystallize in 100 °C oven, filter, wash with water and then The MCM-48 precursor is obtained by drying at 70-90 ° C for 12-48 h; the MCM-48 precursor is placed in a muffle furnace and calcined at 500-600 ° C for 4 ⁇ 10 h.
  • the templating agent is removed, and MCM-48 mesoporous molecular sieve is obtained after calcination; wherein the mass ratio of deionized water, sodium hydroxide and tetraethyl orthosilicate is 60-80: 0.3-0.6: 1
  • the mass ratio of cetyltrimethylammonium bromide to deionized water is 0.8% to 1.2%.
  • the MCM-48 mesoporous molecular sieve has a pore diameter of 2 to 5 nm.
  • the addition of MCM-48 mesoporous molecular sieve can make the prepared polyacrylonitrile -
  • the methyl methacrylate gel electrolyte membrane has a good pore structure, and not only has a large number of micropores on the surface, but also has a plurality of interconnected micropores below the surface, and these pore structures will contribute to the improvement of the electrical conductivity of the electrolyte.
  • Step (2) is to transfer the obtained slurry to prepare MCM-48 mesoporous molecular sieve modified polyacrylonitrile - The process of methyl methacrylate gel electrolyte membrane.
  • the slurry is applied onto a substrate and dried under vacuum at 60 to 100 ° C for 24 to 48 hours to obtain a dry film.
  • MCM-48 Mesoporous Molecular Sieve Modified Polyacrylonitrile-Methyl Methacrylate Gel Electrolyte Membrane. The presence of a large number of micropores in the membrane structure contributes to an increase in the conductivity of the electrolyte.
  • the polyacrylonitrile-methyl methacrylate gel film has a thickness of 30 to 50 ⁇ m.
  • the substrate is a glass plate or a polytetrafluoroethylene plate.
  • the present invention provides a method for preparing a polyacrylonitrile-methyl methacrylate gel electrolyte, comprising the steps of:
  • Step (1) is to use polyacrylonitrile-methyl methacrylate (P(AN-MMA)) Dissolved in an organic solvent to obtain a slurry containing MCM-48 mesoporous molecular sieve.
  • P(AN-MMA) polyacrylonitrile-methyl methacrylate
  • the polyacrylonitrile-methyl methacrylate has a mass average molecular weight of from 100,000 to 500,000.
  • the organic solvent in the step (1) is N-methylpyrrolidone, N, N- Dimethylformamide, acetonitrile or ethanol.
  • MCM-48 The mesoporous molecular sieve is prepared as follows: taking cetyltrimethylammonium bromide, dissolving in deionized water, adding sodium hydroxide, heating to 20 ⁇ 50 ° C, stirring at a constant temperature to dissolve the sodium hydroxide, slowly Add 1.0g Ethyl orthosilicate, continue to stir for 4 ⁇ 5h to obtain the reaction stock solution; transfer the reaction liquid into the reactor of polytetrafluoroethylene liner, statically crystallize in 100 °C oven, filter, wash with water and then The MCM-48 precursor is obtained by drying at 70 ⁇ 90 °C for 12 ⁇ 48h; the MCM-48 precursor is placed in a muffle furnace and calcined at 500 ⁇ 600 °C for 4 ⁇ 10 h.
  • the templating agent is removed, and MCM-48 mesoporous molecular sieve is obtained after calcination; wherein the mass ratio of deionized water, sodium hydroxide and tetraethyl orthosilicate is 60-80: 0.3-0.6: 1
  • the mass ratio of cetyltrimethylammonium bromide to deionized water is 0.8% to 1.2%.
  • the MCM-48 mesoporous molecular sieve has a pore diameter of 2 to 5 nm.
  • the addition of MCM-48 mesoporous molecular sieve can make the prepared polyacrylonitrile -
  • the methyl methacrylate gel electrolyte membrane has a good pore structure, and not only has a large number of micropores on the surface, but also has a plurality of interconnected micropores below the surface, and these pore structures will contribute to the improvement of the electrical conductivity of the electrolyte.
  • Step (2) is to transfer the obtained slurry to prepare MCM-48 mesoporous molecular sieve modified polyacrylonitrile - The process of methyl methacrylate gel electrolyte membrane.
  • the slurry is applied onto a substrate and dried under vacuum at 60 to 100 ° C for 24 to 48 hours to obtain a dry film.
  • MCM-48 Mesoporous Molecular Sieve Modified Polyacrylonitrile-Methyl Methacrylate Gel Electrolyte Membrane. The presence of a large number of micropores in the membrane structure contributes to an increase in the conductivity of the electrolyte.
  • the polyacrylonitrile-methyl methacrylate gel film has a thickness of 30 to 50 ⁇ m.
  • the substrate is a glass plate or a polytetrafluoroethylene plate.
  • Step (3) is to prepare a polyacrylonitrile by immersing the obtained polyacrylonitrile-methyl methacrylate gel electrolyte membrane in an electrolyte solution. The process of methyl methacrylate gel electrolyte.
  • the electrolyte consists of LiPF 6 , EC and DMC.
  • the mass ratio of EC : DMC is 1:3 to 2:1.
  • the molar concentration of LiPF 6 is from 0.5 to 1.5 mol/L.
  • the electrolyte is contained in a glove box filled with an inert gas.
  • the electrolyte is contained in a glove box filled with inert gas.
  • the inert gas is nitrogen or argon.
  • the present invention also provides a polyacrylonitrile-methyl methacrylate gel electrolyte
  • a polyacrylonitrile-methyl methacrylate gel electrolyte was prepared according to the aforementioned preparation method.
  • the invention provides a preparation method of polyacrylonitrile-methyl methacrylate gel electrolyte membrane, and corresponding electrolyte and preparation method thereof Has the following beneficial effects:
  • a polyacrylonitrile-methyl methacrylate gel electrolyte provided by the present invention which is subjected to MCM-48 mesoporous molecular sieve After modification, it has high conductivity, high safety performance, good power density and longevity, and high capacity;
  • the preparation method of the polyacrylonitrile-methyl methacrylate gel electrolyte is simple and rapid, has low cost, and is environmentally friendly;
  • the polyacrylonitrile-methyl methacrylate gel electrolyte can be used as a solid polymer electrolyte for lithium ion batteries.
  • a method for preparing a polyacrylonitrile-methyl methacrylate gel electrolyte comprising the steps of:
  • MCM-48 mesoporous molecular sieves were prepared as follows: 0.6 g CTAB (weighed) Cetyltrimethylammonium bromide), dissolved in 65 mL of deionized water, then added 0.47 g of sodium hydroxide, heated to 20 °C, stirred at constant temperature to dissolve sodium hydroxide, slowly added 1.0 g Ethyl orthosilicate, stirring was continued for 4 h to obtain a reaction stock solution; the reaction liquid was transferred into a reaction vessel of a polytetrafluoroethylene liner, statically crystallized in an oven at 100 ° C, filtered, washed with water and dried at 70 ° C. The MCM-48 precursor was obtained for 48 h.
  • the MCM-48 precursor was placed in a muffle furnace at a heating rate of 5 °C / min and calcined at 500 °C for 10 h.
  • the templating agent is removed, and the MCM-48 mesoporous molecular sieve is obtained after calcination.
  • the prepared polyacrylonitrile-methyl methacrylate gel electrolyte membrane has a thickness of 45 ⁇ m. .
  • MCM-48 mesoporous molecular sieve modified polyacrylonitrile in an argon-filled glove box -
  • the methyl methacrylate gel electrolyte membrane was immersed in the electrolyte for 5 min, and the polyacrylonitrile-methyl methacrylate gel electrolyte modified by MCM-48 mesoporous molecular sieve was obtained.
  • the electrolytic solution is composed of LiPF 6 , EC and DMC, wherein the mass ratio of EC : DMC is 1:1, and the molar concentration of LiPF 6 is 1 mol/L.
  • the electrolyte is contained in a glove box filled with argon.
  • Conductivity test method Add the prepared electrolyte between two stainless steel blocking electrodes to form a polymer electrolyte blocking electrode system, perform AC impedance test, obtain the complex impedance plan of GPE, and the intersection of the curve in the high frequency region and the horizontal axis The value is the body impedance. Based on the relationship between the bulk impedance ( R b ) and the ionic conductivity ( ⁇ ):
  • the ionic conductivity can be calculated, where d is the thickness of the polymer electrolyte membrane, S It is the contact area of the polymer electrolyte electrolyte membrane with the electrode.
  • the prepared polyacrylonitrile-methyl methacrylate gel electrolyte was assembled into a lithium ion battery: 9.0 g of LiMn 2 O 4 , 0.45 g of acetylene black and 0.45 g of PVDF were weighed, and 20 g of NMP was added, and the mixture was thoroughly stirred. Become a homogeneously mixed slurry. Then, it was blade-coated on an aluminum foil cleaned with ethanol, dried to a constant weight at 80 ° C under a vacuum of 0.01 MPa, and rolled to a LiMn 2 O 4 electrode under a pressure of 10 to 15 MPa, and cut into a positive electrode wafer. . A lithium sheet is used as a negative electrode.
  • the polyacrylonitrile-methyl methacrylate gel electrolyte gel electrolyte prepared above was placed as a separator between the positive and negative electrodes, and sealed on a press machine to form a button cell.
  • 0.1C charge and discharge test was performed on the assembled lithium ion battery in this example by using the charge and discharge tester.
  • the third discharge specific capacity was 105 mAh/g, and the discharge efficiency was 96%. .
  • the polyacrylonitrile-methyl methacrylate gel electrolyte obtained in the comparative example was found to have a conductivity of only 1.3 ms/cm. . It can be seen that the modification of MCM-48 mesoporous molecular sieves has significantly improved the conductivity of the gel electrolyte.
  • a method for preparing a polyacrylonitrile-methyl methacrylate gel electrolyte comprising the steps of:
  • MCM-48 mesoporous molecular sieves were prepared as follows: 0.48 g CTAB (weighed) Cetyltrimethylammonium bromide), dissolved in 60 mL of deionized water, then added 0.3 g of sodium hydroxide, heated to 30 °C, stirred at constant temperature to dissolve sodium hydroxide, slowly added 1.0 g Ethyl orthosilicate, stirring was continued for 4 h to obtain a reaction stock solution; the reaction liquid was transferred into a reaction vessel of a polytetrafluoroethylene liner, statically crystallized in an oven at 100 ° C, filtered, washed with water and dried at 80 ° C. The MCM-48 precursor was obtained for 36 h.
  • the MCM-48 precursor was placed in a muffle furnace at a heating rate of 5 °C / min and calcined at 500 °C for 8 h.
  • the templating agent is removed, and the MCM-48 mesoporous molecular sieve is obtained after calcination.
  • the prepared polyacrylonitrile-methyl methacrylate gel electrolyte membrane has a thickness of 35 ⁇ m. .
  • MCM-48 mesoporous molecular sieve modified polyacrylonitrile in an argon-filled glove box -
  • the methyl methacrylate gel film was immersed in the electrolyte for 20 min, and the polyacrylonitrile-methyl methacrylate gel electrolyte modified by MCM-48 mesoporous molecular sieve was obtained.
  • the electrolytic solution is composed of LiPF 6 , EC and DMC, wherein the mass ratio of EC : DMC is 1:3 and the molar concentration of LiPF 6 is 0.5 mol/L.
  • the electrolyte is contained in a glove box filled with argon.
  • the obtained polyacrylonitrile-methyl methacrylate gel electrolyte is assembled into a lithium ion battery (method is the same as in the first embodiment), In the voltage range of 2.5 ⁇ 4.2V, the assembled lithium ion battery was tested for 0.1C charge and discharge using the charge and discharge tester. The third discharge specific capacity was 103 mAh/g. The discharge efficiency is 95%.
  • a method for preparing a polyacrylonitrile-methyl methacrylate gel electrolyte comprising the steps of:
  • MCM-48 mesoporous molecular sieves were prepared as follows: 0.96 g CTAB (weighed) Cetyltrimethylammonium bromide), dissolved in 80 mL of deionized water, then added 0.60 g of sodium hydroxide, heated to 40 ° C, stirred at constant temperature to dissolve sodium hydroxide, slowly added 1.0 g Ethyl orthosilicate, stirring for 5 h, to obtain the reaction liquid; the reaction liquid was transferred into a reactor of polytetrafluoroethylene liner, statically crystallized in an oven at 100 ° C, filtered, washed with water and dried at 90 ° C The MCM-48 precursor was obtained in 24h.
  • the MCM-48 precursor was placed in a muffle furnace at a heating rate of 5 °C / min and calcined at 600 °C for 6 h.
  • the templating agent is removed, and the MCM-48 mesoporous molecular sieve is obtained after calcination.
  • the prepared polyacrylonitrile-methyl methacrylate gel film had a thickness of 50 ⁇ m.
  • MCM-48 mesoporous molecular sieve modified polyacrylonitrile in a glove box filled with nitrogen -
  • the methyl methacrylate gel film was immersed in the electrolyte for 40 min, and the polyacrylonitrile-methyl methacrylate gel electrolyte modified by MCM-48 mesoporous molecular sieve was obtained.
  • the electrolytic solution is composed of LiPF 6 , EC and DMC, wherein the mass ratio of EC : DMC is 2:1 and the molar concentration of LiPF 6 is 1.5 mol/L.
  • the electrolyte is contained in a glove box filled with nitrogen.
  • the obtained polyacrylonitrile-methyl methacrylate gel electrolyte is assembled into a lithium ion battery (method is the same as in the first embodiment), In the voltage range of 2.5 ⁇ 4.2V, the assembled lithium ion battery in this example is subjected to 0.1C charge and discharge test using the charge and discharge tester.
  • the third discharge specific capacity is 100 mAh/g.
  • the discharge efficiency is 93%.
  • a method for preparing a polyacrylonitrile-methyl methacrylate gel electrolyte comprising the steps of:
  • MCM-48 mesoporous molecular sieves were prepared as follows: 0.85 g CTAB (weighed) Cetyltrimethylammonium bromide), dissolved in 80 g of deionized water, then added with 0.5 g of sodium hydroxide, heated to 50 ° C, stirred at constant temperature to dissolve sodium hydroxide, slowly added 1.0 g Ethyl orthosilicate, stirring for 5 h, to obtain the reaction liquid; the reaction liquid was transferred into a reactor of polytetrafluoroethylene liner, statically crystallized in an oven at 100 ° C, filtered, washed with water and dried at 90 ° C The MCM-48 precursor was obtained in 12h.
  • the MCM-48 precursor was placed in a muffle furnace at a heating rate of 5 °C / min and calcined at 600 °C for 4 h.
  • the templating agent is removed, and the MCM-48 mesoporous molecular sieve is obtained after calcination.
  • the prepared polyacrylonitrile-methyl methacrylate gel film had a thickness of 30 ⁇ m.
  • MCM-48 mesoporous molecular sieve modified polyacrylonitrile in an argon-filled glove box -
  • the methyl methacrylate gel film was immersed in the electrolyte for 60 min, and the polyacrylonitrile-methyl methacrylate gel electrolyte modified by MCM-48 mesoporous molecular sieve was obtained.
  • the electrolytic solution is composed of LiPF 6 , EC and DMC, wherein the mass ratio of EC : DMC is 1:2 and the molar concentration of LiPF 6 is 0.8 mol/L.
  • the electrolyte is contained in a glove box filled with argon.
  • the obtained polyacrylonitrile-methyl methacrylate gel electrolyte is assembled into a lithium ion battery (method is the same as in the first embodiment), In the voltage range of 2.5V ⁇ 4.2V, the assembled lithium ion battery in this example was tested by 0.1C charge and discharge using the charge and discharge tester. The third discharge specific capacity was 98 mAh/g. The discharge efficiency is 92%.

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Description

聚丙烯腈 - 甲基丙烯酸甲酯凝胶电解质膜的制备方法 ， 及其相应电解质和制备方法 技术领域
本发明涉及电化学领域 ，尤其涉及 聚丙烯腈-甲基丙烯酸甲酯凝胶电解质膜的制备方法， 及其相应电解质和制备方法。
背景技术
随着各种新能源的发展，便携式电子设备的小型化发展及电动汽车对大容量高功率化学电源的广泛需求。一种新型的具有高倍率充放电性能的电池材料的研发变得极其重要。然而，安全问题一直是制约大容量、高功率锂离子电池应用的瓶颈。其中，目前广泛使用的液态电解质产生的漏液、电解质氧化分解及热失控等引起的燃烧、爆炸等问题是电池的主要安全隐患。
当前常规的液体电解质的优点是电导率高，但是由于含有易燃、易挥发的有机溶剂，其在充放电过程中释放出可燃气体，特别是在某些非常规工作条件下（如大功率充放电、过充过放等）产生大量热会加速气体的产生，导致电池内压增高，气体泄漏，甚至起火爆炸，因而存在严重的安全隐患。聚合物电解质锂离子电池因具有安全、无泄漏、漏电流小等优点而被研究者们所重视。由于固态聚合物电解质室温下电导率较低 (10-5~10-4 s/cm) ，使用应用受到限制 , 因而凝胶聚合物电解质成为研究重点。
 发明内容
鉴于此，本发明旨在提供 聚丙烯腈-甲基丙烯酸甲酯凝胶电解质膜的制备方法， 及其相应电解质和制备方法。本发明提供 的 聚丙烯腈-甲基丙烯酸甲酯凝胶电解质 ，经 MCM-48 介孔分子筛 改性后，具备较高 的电导率，安全性好，可用作锂离子电池固态聚合物电解质。 本发明提供的制备方法 工艺流程简单 ，环境友好 。
第一方面，本发明提供了 聚丙烯腈-甲基丙烯酸甲酯凝胶电解质膜 的制备方法 ，包括以下步骤：
（ 1 ）取聚丙烯腈 - 甲基丙烯酸甲酯，溶于 1~3 倍质量的有机溶剂中，加入 MCM-48 介孔分子筛，加热至 30 ℃ ~50℃ ，搅拌均匀，得到含有 MCM-48 介孔分子筛的浆料；其中， MCM-48 介孔分子筛与聚丙烯腈 - 甲基丙烯酸甲酯的质量比为 0.05~0.3 ： 1 ；
（ 2 ）将所述浆料涂布于基板上，在 60~100℃下真空干燥24 h ~48h, 得到 MCM-48 介孔分子筛改性的聚丙烯腈 - 甲基丙烯酸甲酯凝胶电解质膜。
本发明步骤（ 1 ）为 将聚丙烯腈 - 甲基丙烯酸甲酯（ P(AN-MMA) ） 溶于有机溶剂中，从而得到含有 MCM-48 介孔分子筛的浆料的过程。
优选地， 所述聚丙烯腈 - 甲基丙烯酸甲酯的质均分子量为 10~50 万 。
优选地， 步骤（ 1 ）中有机溶剂为 N- 甲基吡咯烷酮、 N,N- 二甲基甲酰胺、乙腈或乙醇。
优选地，所述 MCM-48 介孔分子筛按如下方法制备得到：取十六烷基三甲基溴化胺，溶于去离子水中，加入氢氧化钠，加热至 20~50℃ ，恒温搅拌使所述氢氧化钠溶解，缓慢加入 1.0g 正硅酸乙酯 , 继续搅拌 4~5h ，得到反应原液；将所述反应原液移入聚四氟乙烯衬垫的反应釜中， 100 ℃ 烘箱中静止晶化，过滤，用水洗涤后在 70~90℃下干燥12-48h 得到 MCM-48 前驱体；将所述 MCM-48 前驱体置于马弗炉中，在 500~600℃下焙烧4~10 h ，去除模板剂，锻烧后得 MCM-48 介孔分子筛；其中，去离子水、氢氧化钠和正硅酸乙酯的质量比为 60~80 ： 0.3~0.6 ： 1 ，十六烷基三甲基溴化胺和去离子水的质量比为 0.8%~1.2% 。
优选地， MCM-48 介孔分子筛的孔径为 2~5 nm 。
MCM-48 介孔分子筛的加入，可以使得制备得到的聚丙烯腈 - 甲基丙烯酸甲酯凝胶电解质膜具有良好的孔洞结构，不仅在表面有大量微孔，而且在表面下方也有许多相互连接的微孔，这些孔洞结构将有利于提高电解质的电导率。
步骤（ 2 ）为将得到的浆料进行转移，制备 MCM-48 介孔分子筛改性的聚丙烯腈 - 甲基丙烯酸甲酯凝胶电解质膜的过程。
具体地，将浆料涂布于基板上，在 60~100℃下真空干燥24~48 h, 得到干燥好的 MCM-48 介孔分子筛改性的聚丙烯腈 - 甲基丙烯酸甲酯凝胶电解质膜。膜结构中大量微孔的存在有利于提高电解质的电导率。
优选地， 聚丙烯腈 - 甲基丙烯酸甲酯凝胶薄膜的厚度为 30~ 50μm 。
优选地， 基板为玻璃板或聚四氟乙烯板。
第二方面，本发明提供了 聚丙烯腈 - 甲基丙烯酸甲酯凝胶电解质的制备方法，包括以下步骤：
（ 1 ）取聚丙烯腈 - 甲基丙烯酸甲酯，溶于 1~3 倍质量的有机溶剂中，加入 MCM-48 介孔分子筛，加热至 30~50℃ ，搅拌均匀，得到含有 MCM-48 介孔分子筛的浆料；其中， MCM-48 介孔分子筛与聚丙烯腈 - 甲基丙烯酸甲酯的质量比为 0.05~0.3 ： 1 ；
（ 2 ）将所述浆料涂布于基板上，在 60~100℃下真空干燥24~48h, 得到 MCM-48 介孔分子筛改性的聚丙烯腈 - 甲基丙烯酸甲酯凝胶电解质膜；
（ 3 ）在充满惰性气体的手套箱中，将所述聚丙烯腈 - 甲基丙烯酸甲酯凝胶电解质膜浸于电解液中 5~60 min ，取出即得到 MCM-48 介孔分子筛改性的聚丙烯腈 - 甲基丙烯酸甲酯凝胶电解质。
步骤（ 1 ）为 将聚丙烯腈 - 甲基丙烯酸甲酯（ P(AN-MMA) ） 溶于有机溶剂中，从而得到含有 MCM-48 介孔分子筛的浆料的过程。
优选地， 聚丙烯腈 - 甲基丙烯酸甲酯的质均分子量为 10~50 万 。
优选地， 步骤（ 1 ）中有机溶剂为 N- 甲基吡咯烷酮、 N,N- 二甲基甲酰胺、乙腈或乙醇。
优选地， MCM-48 介孔分子筛按如下方法制备得到：取十六烷基三甲基溴化胺，溶于去离子水中，加入氢氧化钠，加热至 20~50℃ ，恒温搅拌使所述氢氧化钠溶解，缓慢加入 1.0g 正硅酸乙酯 , 继续搅拌 4~5h ，得到反应原液；将所述反应原液移入聚四氟乙烯衬垫的反应釜中， 100 ℃ 烘箱中静止晶化，过滤，用水洗涤后在 70~90℃下干燥12~48h 得到 MCM-48 前驱体；将所述 MCM-48 前驱体置于马弗炉中，在 500~600℃下焙烧4~10 h ，去除模板剂，锻烧后得 MCM-48 介孔分子筛；其中，去离子水、氢氧化钠和正硅酸乙酯的质量比为 60~80 ： 0.3~0.6 ： 1 ，十六烷基三甲基溴化胺和去离子水的质量比为 0.8%~1.2% 。
优选地， MCM-48 介孔分子筛的孔径为 2~5 nm 。
MCM-48 介孔分子筛的加入，可以使得制备得到的聚丙烯腈 - 甲基丙烯酸甲酯凝胶电解质膜具有良好的孔洞结构，不仅在表面有大量微孔，而且在表面下方也有许多相互连接的微孔，这些孔洞结构将有利于提高电解质的电导率。
步骤（ 2 ）为将得到的浆料进行转移，制备 MCM-48 介孔分子筛改性的聚丙烯腈 - 甲基丙烯酸甲酯凝胶电解质膜的过程。
具体地，将浆料涂布于基板上，在 60~100℃下真空干燥24~48 h, 得到干燥好的 MCM-48 介孔分子筛改性的聚丙烯腈 - 甲基丙烯酸甲酯凝胶电解质膜。膜结构中大量微孔的存在有利于提高电解质的电导率。
优选地， 所述聚丙烯腈 - 甲基丙烯酸甲酯凝胶薄膜的厚度为 30~ 50μm 。
优选地， 基板为玻璃板或聚四氟乙烯板。
步骤（ 3 ）为将得到的 聚丙烯腈 - 甲基丙烯酸甲酯凝胶电解质膜浸于电解液中，制备聚丙烯腈 - 甲基丙烯酸甲酯凝胶电解质的过程。
优选地， 电解液由 LiPF6 、 EC 和 DMC 组成。
优选地， EC ： DMC 的质量比为 1:3~2:1 。
优选地， LiPF6 的摩尔浓度为 0.5~1.5 mol/L 。
优选地， 电解液盛装在充满惰性气体的手套箱中。
电解液盛装在充满惰性气体的手套箱中。
优选地，惰性气体为氮气或氩气。
第三方面，本发明还提供了 聚丙烯腈-甲基丙烯酸甲酯凝胶电解质 ，该 聚丙烯腈-甲基丙烯酸甲酯凝胶电解质 按照前述制备方法制备得到。
本发明提供了 聚丙烯腈-甲基丙烯酸甲酯凝胶电解质膜的制备方法， 及其相应电解质和制备方法 ，具有如下有益效果：
（ 1 ）本发明提供的 聚丙烯腈-甲基丙烯酸甲酯凝胶电解质，经 MCM-48 介孔分子筛 改性后，具备较高的电导率，安全性能高，有较好的功率密度以及寿命，有较高的容量；
（ 2 ）本发明提供的 聚丙烯腈-甲基丙烯酸甲酯凝胶电解质的制备方法简单快速，具备低成本性，并且环境友好等特点；
（ 3 ）本发明提供的 聚丙烯腈-甲基丙烯酸甲酯凝胶电解质可作为锂离子电池固态聚合物电解质。
 具体实施方式
以下所述是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也视为本发明的保护范围。
实施例一
聚丙烯腈-甲基丙烯酸甲酯凝胶电解质 的制备方法 ，包括以下步骤：
（ 1 ）取 10 g 质均分子量为 30 万的聚丙烯腈 - 甲基丙烯酸甲酯，溶于 20 g N- 甲基吡咯烷酮（ NMP ）中，加入 1.0g MCM-48 介孔分子筛，加热至 30 ℃ ，搅拌均匀，得到含有 MCM-48 介孔分子筛的浆料；
在本实施例中， MCM-48 介孔分子筛按如下方法制备得到：称取 0.6 g CTAB ( 十六烷基三甲基溴化胺 ) ，溶于 65 mL 去离子水中，然后加入 0.47 g 氢氧化钠 ，加热至 20 ℃ ，恒温搅拌使氢氧化钠溶解，缓慢加入 1.0 g 正硅酸乙酯 , 继续搅拌 4 h ，得到反应原液；将反应原液移入聚四氟乙烯衬垫的反应釜中， 100 ℃ 烘箱中静止晶化，过滤，用水洗涤后在 70 ℃ 下干燥 48 h 得到 MCM-48 前驱体；最后，将 MCM-48 前驱体置于马弗炉中，升温速度 5 ℃ /min, 在 500 ℃ 下焙烧 10 h ，去除模板剂，锻烧后得 MCM-48 介孔分子筛。
（ 2 ）将浆料涂布于玻璃板上，在 60 ℃ 下真空干燥 48 h, 得到 MCM-48 介孔分子筛改性的聚丙烯腈 - 甲基丙烯酸甲酯凝胶电解质膜；
具体地，在本实施例中，制备得到的聚丙烯腈 - 甲基丙烯酸甲酯凝胶电解质膜的厚度为 45μm 。
（ 3 ）在充满氩气的手套箱中，将 MCM-48 介孔分子筛改性的聚丙烯腈 - 甲基丙烯酸甲酯凝胶电解质膜浸于电解液中 5 min ，取出即得到 MCM-48 介孔分子筛改性的聚丙烯腈 - 甲基丙烯酸甲酯凝胶电解质。
具体地，在本实施例中，电解液由 LiPF6 、 EC 和 DMC 组成，其中， EC ： DMC 的质量比为 1:1 ， LiPF6 的摩尔浓度为 1mol/L 。电解液盛装在充满氩气的手套箱中。
本实施例所制得的 MCM-48 介孔分子筛改性的聚丙烯腈 - 甲基丙烯酸甲酯凝胶电解质的电导率为 5.5 ms/cm 。
电导率的测试方法：在两个不锈钢阻塞电极之间加入制备好的电解质，构成聚合物电解质阻塞电极体系，做交流阻抗测试，得到 GPE 的复阻抗平面图，曲线在高频区与横轴的交点值即为本体阻抗。根据本体阻抗 ( Rb ) 与离子电导率 ( σ ) 之间的关系 :
σ = d/ ( S* Rb )
可以计算出离子电导率，其中 d 为聚合物电解质膜的厚度、 S 为聚合物电解质电解质膜与电极的接触面积。
将制得的聚丙烯腈 - 甲基丙烯酸甲酯凝胶电解质组装成锂离子电池：称取 9.0 g LiMn2O4 、 0.45 g 乙炔黑和 0.45 g PVDF ，并加入 20 g NMP ，充分搅拌使之成为混合均匀的浆料。然后将其刮涂于经乙醇清洗过的铝箔上，在 0.01 MPa 的真空下 80 ℃ 干燥至恒重，并于 10~15 MPa 压力下辊压制成 LiMn2O4 电极，并切成正极圆片。锂片作为负极。将上述制备好了的聚丙烯腈 - 甲基丙烯酸甲酯凝胶电解质凝胶电解质作为隔膜置于正负极之间，在冲压机上封口制成扣式电池。在 2.5~4.2V 的电压范围内，利用充放电测试仪对本实施例中组装好的锂离子电池进行 0.1C 充放电测试，第 3 次的放电比容量为 105 mAh/g ，放电效率为 96 % 。
为进一步说明本发明有益效果，特设置如下对比实施例：
将 10 g 聚丙烯腈 - 甲基丙烯酸甲酯（质均分子量 30 万）溶于约 20 g NMP (N- 甲基吡咯烷酮 ) ，并给体系升温到 30 ℃ 搅拌混合均匀，得到均匀的浆料。将得到的浆料均匀地涂在洁净的玻璃板上，再在 60 ℃ 、 0.01 MPa 真空下干燥后，得到厚度约 45 μm 的聚丙烯腈 - 甲基丙烯酸甲酯凝胶膜。将干燥好的聚丙烯腈 - 甲基丙烯酸甲酯凝胶膜放入充满氩气的手套箱中，并将其浸入 1mol/L LiPF6/EC+DMC ( 质量比 1:1) 的电解液中 5 min 。将其取出即得到聚丙烯腈 - 甲基丙烯酸甲酯基凝胶聚合物电解质。
经检测，该对比实施例所得聚丙烯腈 - 甲基丙烯酸甲酯凝胶电解质的电导率仅为 1.3 ms/cm 。由此可见， MCM-48 介孔分子筛改性后，使得凝胶电解质的电导率得到了明显的提高。
实施例二
聚丙烯腈-甲基丙烯酸甲酯凝胶电解质 的制备方法 ，包括以下步骤：
（ 1 ）取 10 g 质均分子量为 10 万的聚丙烯腈 - 甲基丙烯酸甲酯，溶于 10 g N,N- 二甲基甲酰胺中，加入 0.5g MCM-48 介孔分子筛，加热至 40 ℃ ，搅拌均匀，得到含有 MCM-48 介孔分子筛的浆料；
在本实施例中， MCM-48 介孔分子筛按如下方法制备得到：称取 0.48 g CTAB ( 十六烷基三甲基溴化胺 ) ，溶于 60 mL 去离子水中，然后加入 0.3 g 氢氧化钠，加热至 30 ℃ ，恒温搅拌使氢氧化钠溶解，缓慢加入 1.0 g 正硅酸乙酯 , 继续搅拌 4 h ，得到反应原液；将反应原液移入聚四氟乙烯衬垫的反应釜中， 100 ℃ 烘箱中静止晶化，过滤，用水洗涤后在 80 ℃ 下干燥 36 h 得到 MCM-48 前驱体；最后，将 MCM-48 前驱体置于马弗炉中，升温速度 5 ℃ /min, 在 500 ℃ 下焙烧 8 h ，去除模板剂，锻烧后得 MCM-48 介孔分子筛。
（ 2 ）将浆料涂布于玻璃板上，在 80 ℃ 下真空干燥 36 h, 得到 MCM-48 介孔分子筛改性的聚丙烯腈 - 甲基丙烯酸甲酯凝胶电解质膜；
具体地，在本实施例中，制备得到的聚丙烯腈 - 甲基丙烯酸甲酯凝胶电解质膜的厚度为 35μm 。
（ 3 ）在充满氩气的手套箱中，将 MCM-48 介孔分子筛改性的聚丙烯腈 - 甲基丙烯酸甲酯凝胶薄膜浸于电解液中 20 min ，取出即得到 MCM-48 介孔分子筛改性的聚丙烯腈 - 甲基丙烯酸甲酯凝胶电解质。
具体地，在本实施例中，电解液由 LiPF6 、 EC 和 DMC 组成，其中， EC ： DMC 的质量比为 1:3 ， LiPF6 的摩尔浓度为 0.5 mol/L 。电解液盛装在充满氩气的手套箱中。
本实施例所制得的 MCM-48 介孔分子筛改性的聚丙烯腈 - 甲基丙烯酸甲酯凝胶电解质的电导率为 4.2ms/cm 。
将制得的聚丙烯腈 - 甲基丙烯酸甲酯凝胶电解质组装成锂离子电池（方法同实施例一），在 2.5~4.2V 的电压范围内，利用充放电测试仪对本实施例中组装好的锂离子电池进行 0.1C 充放电测试，第 3 次的放电比容量为 103 mAh/g ，放电效率为 95% 。
实施例三
聚丙烯腈-甲基丙烯酸甲酯凝胶电解质 的制备方法 ，包括以下步骤：
（ 1 ）取 10 g 质均分子量为 50 万的聚丙烯腈 - 甲基丙烯酸甲酯，溶于 30 g 乙腈中，加入 2.0g MCM-48 介孔分子筛，加热至 45 ℃ ，搅拌均匀，得到含有 MCM-48 介孔分子筛的浆料；
在本实施例中， MCM-48 介孔分子筛按如下方法制备得到：称取 0.96 g CTAB ( 十六烷基三甲基溴化胺 ) ，溶于 80 mL 去离子水中，然后加入 0.60 g 氢氧化钠，加热至 40 ℃ ，恒温搅拌使氢氧化钠溶解，缓慢加入 1.0 g 正硅酸乙酯 , 继续搅拌 5 h ，得到反应原液；将反应原液移入聚四氟乙烯衬垫的反应釜中， 100 ℃ 烘箱中静止晶化，过滤，用水洗涤后在 90 ℃ 下干燥 24h 得到 MCM-48 前驱体；最后，将 MCM-48 前驱体置于马弗炉中，升温速度 5 ℃ /min, 在 600 ℃ 下焙烧 6 h ，去除模板剂，锻烧后得 MCM-48 介孔分子筛。
（ 2 ）将浆料涂布于玻璃板上 , 在 90 ℃ 下真空干燥 30 h, 得到 MCM-48 介孔分子筛改性的聚丙烯腈 - 甲基丙烯酸甲酯凝胶薄膜；
具体地，在本实施例中，制备得到的聚丙烯腈 - 甲基丙烯酸甲酯凝胶薄膜的厚度为 50μm 。
（ 3 ）在充满氮气的手套箱中，将 MCM-48 介孔分子筛改性的聚丙烯腈 - 甲基丙烯酸甲酯凝胶薄膜浸于电解液中 40 min ，取出即得到 MCM-48 介孔分子筛改性的聚丙烯腈 - 甲基丙烯酸甲酯凝胶电解质。
具体地，在本实施例中，电解液由 LiPF6 、 EC 和 DMC 组成，其中， EC ： DMC 的质量比为 2:1 ， LiPF6 的摩尔浓度为 1.5 mol/L 。电解液盛装在充满氮气的手套箱中。
本实施例所制得的 MCM-48 介孔分子筛改性的聚丙烯腈 - 甲基丙烯酸甲酯凝胶电解质的电导率为 4.7ms/cm 。
将制得的聚丙烯腈 - 甲基丙烯酸甲酯凝胶电解质组装成锂离子电池（方法同实施例一），在 2.5~4.2V 的电压范围内，利用充放电测试仪对本实施例中组装好的锂离子电池进行 0.1C 充放电测试，第 3 次的放电比容量为 100 mAh/g ，放电效率为 93% 。
实施例四
聚丙烯腈 - 甲基丙烯酸甲酯凝胶电解质的制备方法，包括以下步骤：
（ 1 ）取 10 g 质均分子量为 30 万的聚丙烯腈 - 甲基丙烯酸甲酯，溶于 30g 乙醇中，加入 3.0g MCM-48 介孔分子筛，加热至 50 ℃ ，搅拌均匀，得到含有 MCM-48 介孔分子筛的浆料；
在本实施例中， MCM-48 介孔分子筛按如下方法制备得到：称取 0.85 g CTAB ( 十六烷基三甲基溴化胺 ) ，溶于 80 g 去离子水中，然后加入 0.5 g 氢氧化钠，加热至 50 ℃ ，恒温搅拌使氢氧化钠溶解，缓慢加入 1.0 g 正硅酸乙酯 , 继续搅拌 5 h ，得到反应原液；将反应原液移入聚四氟乙烯衬垫的反应釜中， 100 ℃ 烘箱中静止晶化，过滤，用水洗涤后在 90 ℃ 下干燥 12h 得到 MCM-48 前驱体；最后，将 MCM-48 前驱体置于马弗炉中，升温速度 5 ℃ /min, 在 600 ℃ 下焙烧 4 h ，去除模板剂，锻烧后得 MCM-48 介孔分子筛。
（ 2 ）将浆料涂布于玻璃板上，在 100 ℃ 下真空干燥 24h, 得到 MCM-48 介孔分子筛改性的聚丙烯腈 - 甲基丙烯酸甲酯凝胶薄膜；
具体地，在本实施例中，制备得到的聚丙烯腈 - 甲基丙烯酸甲酯凝胶薄膜的厚度为 30μm 。
（ 3 ）在充满氩气的手套箱中，将 MCM-48 介孔分子筛改性的聚丙烯腈 - 甲基丙烯酸甲酯凝胶薄膜浸于电解液中 60 min ，取出即得到 MCM-48 介孔分子筛改性的聚丙烯腈 - 甲基丙烯酸甲酯凝胶电解质。
具体地，在本实施例中，电解液由 LiPF6 、 EC 和 DMC 组成，其中， EC ： DMC 的质量比为 1:2 ， LiPF6 的摩尔浓度为 0.8 mol/L 。电解液盛装在充满氩气的手套箱中。
本实施例所制得的 MCM-48 介孔分子筛改性的聚丙烯腈 - 甲基丙烯酸甲酯凝胶电解质的电导率为 5.1ms/cm 。
将制得的聚丙烯腈 - 甲基丙烯酸甲酯凝胶电解质组装成锂离子电池（方法同实施例一），在 2.5V~4.2V 的电压范围内，利用充放电测试仪对本实施例中组装好的锂离子电池进行 0.1C 充放电测试，第 3 次的放电比容量为 98 mAh/g ，放电效率为 92% 。
以上所述是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也视为本发明的保护范围。

Claims (10)

1 、 聚丙烯腈-甲基丙烯酸甲酯凝胶电解质膜 的制备方法， 其特征在于，包括以下步骤：
（ 1 ）取聚丙烯腈 - 甲基丙烯酸甲酯，溶于 1~3 倍质量的有机溶剂中，加入 MCM-48 介孔分子筛，加热至 30 ℃ ~50℃ ，搅拌均匀，得到含有 MCM-48 介孔分子筛的浆料；其中，所述 MCM-48 介孔分子筛与所述聚丙烯腈 - 甲基丙烯酸甲酯的质量比为 0.05~0.3 ： 1 ；
（ 2 ）将所述浆料涂布于基板上，在 60 ℃ ~100℃下真空干燥24 h ~48h, 得到 MCM-48 介孔分子筛改性的聚丙烯腈 - 甲基丙烯酸甲酯凝胶电解质膜。
2、如权利要求1所述的聚丙烯腈-甲基丙烯酸甲酯凝胶电解质膜的制备方法，其特征在于，所述聚丙烯腈-甲基丙烯酸甲酯的质均分子量为10 ~50万。
3、如权利要求1所述的聚丙烯腈-甲基丙烯酸甲酯凝胶电解质膜的制备方法，其特征在于，步骤（1）中所述有机溶剂为N-甲基吡咯烷酮、N,N-二甲基甲酰胺、乙腈或乙醇。
4、如权利要求1所述的聚丙烯腈-甲基丙烯酸甲酯凝胶电解质膜的制备方法，其特征在于，所述MCM-48介孔分子筛按如下方法制备得到：取十六烷基三甲基溴化胺，溶于去离子水中，加入氢氧化钠，加热至20~50℃，恒温搅拌使所述氢氧化钠溶解，缓慢加入正硅酸乙酯, 继续搅拌4~5h，得到反应原液；将所述反应原液移入聚四氟乙烯衬垫的反应釜中，100℃烘箱中静止晶化，过滤，用水洗涤后在70~90℃下干燥12~48h，得到MCM-48前驱体；将所述MCM-48前驱体置于马弗炉中，在500~600℃下焙烧4~10 h，去除模板剂，锻烧后得MCM-48介孔分子筛；其中，去离子水、氢氧化钠和正硅酸乙酯的质量比为60~80：0.3~0.6：1，十六烷基三甲基溴化胺和去离子水的质量比为0.8%~1.2%。
5、如权利要求1所述的聚丙烯腈-甲基丙烯酸甲酯凝胶电解质膜的制备方法，其特征在于，步骤（2）中所述聚丙烯腈-甲基丙烯酸甲酯凝胶电解质膜的厚度为30μm ~ 50μm。
6、聚丙烯腈-甲基丙烯酸甲酯凝胶电解质的制备方法，其特征在于，包括以下步骤：
（1）取聚丙烯腈-甲基丙烯酸甲酯，溶于 1~3倍质量的有机溶剂中，加入MCM-48介孔分子筛，加热至30~50℃，搅拌均匀，得到含有MCM-48介孔分子筛的浆料；其中，所述MCM-48介孔分子筛与所述聚丙烯腈-甲基丙烯酸甲酯的质量比为0.05~0.3：1；
（2）将所述浆料涂布于基板上，在60~100℃下真空干燥24~48h, 得到MCM-48介孔分子筛改性的聚丙烯腈-甲基丙烯酸甲酯凝胶电解质膜；
（3）在充满惰性气体的手套箱中，将所述聚丙烯腈-甲基丙烯酸甲酯凝胶电解质膜浸于电解液中5~60 min，取出即得到MCM-48介孔分子筛改性的聚丙烯腈-甲基丙烯酸甲酯凝胶电解质。
7、如权利要求1所述的聚丙烯腈-甲基丙烯酸甲酯凝胶电解质的制备方法，其特征在于，步骤（3）中所述电解液由LiPF6、EC和DMC组成，所述EC：DMC的质量比为1:3~2:1，所述LiPF6的摩尔浓度为0.5 mol/L ~1.5 mol/L。
8、如权利要求1所述的聚丙烯腈-甲基丙烯酸甲酯凝胶电解质的制备方法，其特征在于，步骤（1）中所述有机溶剂为N-甲基吡咯烷酮、N,N-二甲基甲酰胺、乙腈或乙醇。
9、如权利要求1所述的聚丙烯腈-甲基丙烯酸甲酯凝胶电解质的制备方法，其特征在于，所述MCM-48介孔分子筛按如下方法制备得到：取十六烷基三甲基溴化胺，溶于去离子水中，加入氢氧化钠，加热至20~50℃，恒温搅拌使所述氢氧化钠溶解，缓慢加入正硅酸乙酯, 继续搅拌4~5h，得到反应原液；将所述反应原液移入聚四氟乙烯衬垫的反应釜中，100℃烘箱中静止晶化，过滤，用水洗涤后在70~90℃下干燥12~48h，得到MCM-48前驱体；将所述MCM-48前驱体置于马弗炉中，在500~600℃下焙烧4~10 h，去除模板剂，锻烧后得MCM-48介孔分子筛；其中，去离子水、氢氧化钠和正硅酸乙酯的质量比为60~80：0.3~0.6：1，十六烷基三甲基溴化胺和去离子水的质量比为0.8%~1.2%。
10. 聚丙烯腈-甲基丙烯酸甲酯凝胶电解质，其特征在于，根据权利要求6至9择一所述方法制备得到的聚丙烯腈-甲基丙烯酸甲酯凝胶电解质。
PCT/CN2012/077845 2012-06-29 2012-06-29 聚丙烯腈-甲基丙烯酸甲酯凝胶电解质膜的制备方法，及其相应电解质和制备方法 Ceased WO2014000247A1 (zh)

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