WO2022205669A1 - Self-repairing polymer solid-state electrolyte based on double-sulfur bonds and preparation method therefor - Google Patents

Self-repairing polymer solid-state electrolyte based on double-sulfur bonds and preparation method therefor Download PDF

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WO2022205669A1
WO2022205669A1 PCT/CN2021/105917 CN2021105917W WO2022205669A1 WO 2022205669 A1 WO2022205669 A1 WO 2022205669A1 CN 2021105917 W CN2021105917 W CN 2021105917W WO 2022205669 A1 WO2022205669 A1 WO 2022205669A1
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disulfide bond
polyethylene oxide
solid electrolyte
modified polyurethane
preparation
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PCT/CN2021/105917
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French (fr)
Chinese (zh)
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田军
陈彬
苏敏
韩笑
李凡群
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万向一二三股份公司
万向集团公司
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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
    • H01M10/0564—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
    • 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
    • H01M10/058—Construction or manufacture
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the invention relates to the field of polymer solid-state batteries, in particular to a self-repairing polymer solid-state electrolyte based on disulfide bonds and a preparation method thereof.
  • lithium-ion batteries Due to the advantages of high specific energy, low self-discharge, wide chemical window, and green environmental protection, lithium-ion batteries have been widely used in portable electronic devices, electric vehicles, smart grids and other fields.
  • the energy density of commercial lithium-ion batteries is still difficult to meet the increasing demand, and the safety performance and other issues limit their further development.
  • all-solid-state lithium batteries Different from traditional liquid lithium-ion batteries, all-solid-state lithium batteries have the advantages of high specific energy, high safety performance, and long cycle life. In recent years, they have become a research and development focus in the field of new chemical batteries.
  • solid electrolytes can be divided into inorganic solid electrolytes and polymer solid electrolytes according to chemical components.
  • Inorganic solid electrolytes include oxides, sulfides, etc., with high room temperature ionic conductivity and wide chemical window, but their large solid/solid interface impedance limits their further applications.
  • the polymer solid electrolyte (such as the patent with publication number CN108281704A) includes polyethylene oxide, polyvinylidene fluoride-hexafluoropropylene copolymer, polyacrylonitrile, etc., especially polyethylene oxide, which is a relatively mature polymer solid electrolyte material at present.
  • the polymer solid electrolyte with self-healing function can solve the defects of polymer solid electrolyte very well, and it is a kind of polymer electrolyte material with development potential. Therefore, based on the shortcomings of current polymer solid electrolytes, it is necessary to develop a polymer solid electrolyte with self-healing ability.
  • the present invention provides a self-healing polymer solid electrolyte based on disulfide bonds and a preparation method thereof.
  • the solid electrolyte can self-repair when damaged, and has high mechanical strength and room temperature ionic conductivity.
  • a self-healing polymer solid electrolyte based on disulfide bonds comprising a disulfide bond-modified polyurethane/polyethylene oxide composite polymer and a lithium salt; the disulfide bond-modified polyurethane is prepolymerized by a disulfide bond monomer and a polyurethane
  • the polyurethane prepolymer contains at least two isocyanate end groups; the disulfide bond monomer contains at least one disulfide bond and the total number of hydroxyl groups and amino groups is at least two.
  • a disulfide bond modified polyurethane is introduced into the polyethylene oxide solid electrolyte, wherein the polyurethane and the polyethylene oxide are combined by hydrogen bonds, covalent bonds, etc. to form a cross-linked network, and the disulfide bond is introduced into the polyurethane.
  • a reversible dynamic covalent bond in this way, a self-healing function can be achieved when the polymer solid-electrolyte interface is damaged, preventing the battery from short-circuiting.
  • the present invention introduces disulfide bonds by introducing modified polyurethane, which improves the film formation of the polymer solid electrolyte and the solid/solid interface impedance: the introduction of the hard segment can improve the mechanical strength of the solid electrolyte membrane, while the soft segment can improve the mechanical strength of the solid electrolyte membrane. It is beneficial to improve the room temperature ionic conductivity of the solid electrolyte; at the same time, a cross-linked network can be formed between polyurethane and polyethylene oxide, which further improves the mechanical strength of the polymer solid electrolyte membrane, and the cross-linked structure can reduce the crystallinity of the polymer, and then Improve the room temperature ionic conductivity of solid electrolytes.
  • the lithium salt is one or more of lithium bis(trifluoromethylsulfonyl)imide, lithium difluoromethylsulfonimide, and lithium perchlorate.
  • the lithium salt accounts for 1-10% of the total mass of the solid electrolyte.
  • a preparation method of the above-mentioned solid electrolyte comprising the following steps:
  • Lithium salt is added to the disulfide bond-modified polyurethane/polyethylene oxide composite polymer solution, mixed uniformly, poured into a polytetrafluoroethylene plate, and dried to obtain a self-healing polymer solid electrolyte .
  • step (1) the isocyanate end group in the polyurethane prepolymer reacts with the hydroxyl group or amino group in the disulfide bond monomer, so that the disulfide bond is introduced into the polyurethane, and the self-repairing function of the electrolyte is given; in step (2) , the isocyanate end group in the polyurethane prepolymer reacts with the hydroxyl group in the polyethylene oxide, so that the two are cross-linked by covalent bonds, and the bonding strength of the cross-linked network is improved, thereby improving the mechanical strength of the solid electrolyte.
  • step (1) the structural formula of the disulfide bond monomer is as follows:
  • R and R' are one or both of them.
  • the molar ratio between the isocyanate end group and the disulfide bond monomer end group in the polyurethane prepolymer is 1-1.5:1.
  • the mass ratio between the disulfide bond-modified polyurethane and the polyethylene oxide is 1:1-10.
  • the molecular weight of the polyurethane prepolymer is 500-5000.
  • the molecular weight of the polyethylene oxide is 50,000-200,000.
  • the catalyst is dibutyltin dilaurate.
  • the organic solvent is N,N-dimethylacetamide.
  • step (1) the polyurethane prepolymer is dissolved in an organic solvent, after adding the catalyst, polyisocyanate graft modification is first performed on the polyurethane prepolymer, and then disulfide monomers are added; the polyisocyanate
  • the specific method of graft modification is as follows: adding hydroxypropyl acrylate, stirring and reacting at 60-70° C. for 0.5-1 h; then adding N,N'-methylenebisacrylamide and a molar ratio of 5-6:1.
  • Tris(2-aminoethyl)amine continue to stir and react at 60 ⁇ 70°C for 3 ⁇ 4h; then heat up to 130 ⁇ 140°C, replace the gas in the reaction vessel with inert gas, add 3-isocyanatopropene and The initiator is stirred and reacted for 2-3 hours to obtain the modified polyurethane prepolymer solution.
  • a plurality of terminal alkenyl groups can be grafted on the isocyanate end groups of the polyurethane prepolymer, and then a plurality of isocyanates can be grafted through an addition reaction, thereby increasing the isocyanate end group content in the polyurethane prepolymer, introducing More disulfide bonds improve the self-healing ability of polymer solid electrolytes.
  • the molar ratio between the isocyanate end group and hydroxypropyl acrylate in the polyurethane prepolymer is 1:1-2; the molar ratio between the hydroxypropyl acrylate and tris(2-aminoethyl)amine The molar ratio is 1:1-2; the molar ratio between the hydroxypropyl acrylate and 3-isocyanatopropene is 1:15-18.
  • the present invention has the following advantages:
  • the present invention can realize self-repair when the electrolyte membrane is damaged by introducing disulfide bonds into the polymer solid electrolyte, and prevent the battery from short-circuiting;
  • the present invention introduces disulfide bonds by introducing disulfide bond modified polyurethane, and the polyurethane can improve the mechanical strength and room temperature ionic conductivity of the polymer solid electrolyte;
  • the present invention performs polyisocyanate graft modification on the polyurethane prepolymer, which can increase the content of isocyanate end groups therein, thereby improving the self-healing ability of the polymer solid electrolyte.
  • a self-healing polymer solid electrolyte based on disulfide bonds includes disulfide bond-modified polyurethane/polyethylene oxide composite polymer and lithium salt.
  • the lithium salt is one or more of lithium bis(trifluoromethylsulfonyl)imide, lithium difluoromethylsulfonimide, and lithium perchlorate; the lithium salt accounts for 30% of the total mass of the solid electrolyte. 1 to 10%.
  • a preparation method of the solid electrolyte comprising the following steps:
  • the structural formula of the disulfide bond monomer is as follows:
  • R and R' are one or both of them
  • Lithium salt is added to the disulfide bond-modified polyurethane/polyethylene oxide composite polymer solution, mixed uniformly, poured into a polytetrafluoroethylene plate, and dried to obtain a self-healing polymer solid electrolyte .
  • step (1) the polyurethane prepolymer is dissolved in an organic solvent, and after adding a catalyst, polyisocyanate graft modification is first performed on the polyurethane prepolymer, and then disulfide monomers are added;
  • the specific method of isocyanate graft modification is as follows: adding hydroxypropyl acrylate, the molar ratio between the isocyanate end group in the polyurethane prepolymer and the hydroxypropyl acrylate is 1:1 ⁇ 2, at 60 ⁇ 70 °C The reaction is stirred for 0.5 to 1 h; then N,N'-methylenebisacrylamide and tris(2-aminoethyl)amine in a molar ratio of 5 to 6:1 are added, and the hydroxypropyl acrylate and tris(2- The molar ratio between aminoethyl)amines is 1:1 ⁇ 2, continue to stir the reaction at 60 ⁇ 70°C for 3 ⁇ 4h; then heat up to 130 ⁇ 140°C, replace the gas in the reaction
  • a self-healing polymer solid electrolyte based on disulfide bonds includes disulfide bond-modified polyurethane/polyethylene oxide composite polymer and lithium salt.
  • the lithium salt is lithium bis(trifluoromethylsulfonyl)imide; the lithium salt accounts for 10% of the total mass of the solid electrolyte.
  • a preparation method of the solid electrolyte comprising the following steps:
  • Lithium salt is added to the disulfide bond-modified polyurethane/polyethylene oxide composite polymer solution to make the mass between the polyethylene oxide in step (2) and the lithium salt in step (3) The ratio is 4.5:1. After mixing evenly, pour it into a polytetrafluoroethylene plate and dry it to obtain a self-healing polymer solid electrolyte.
  • a self-healing polymer solid electrolyte based on disulfide bonds includes disulfide bond-modified polyurethane/polyethylene oxide composite polymer and lithium salt.
  • the lithium salt is lithium bis(trifluoromethylsulfonyl)imide; the lithium salt accounts for 10% of the total mass of the solid electrolyte.
  • a preparation method of the solid electrolyte comprising the following steps:
  • cystamine dihydrochloride In methylacetamide, cystamine dihydrochloride and dibutyltin dilaurate are added, so that the molar ratio between the isocyanate end group in the polyurethane prepolymer and the amino group in cystamine dihydrochloride is 1.2:1,
  • the mass fraction of dibutyltin dilaurate in the reaction solution was 1 wt%, and the disulfide bond modified polyurethane solution was obtained after stirring and reacting at 60 °C for 3 hours;
  • Lithium salt is added to the disulfide bond-modified polyurethane/polyethylene oxide composite polymer solution to make the mass between the polyethylene oxide in step (2) and the lithium salt in step (3) The ratio is 6.75:1. After mixing evenly, pour it into a polytetrafluoroethylene plate and dry it to obtain a self-healing polymer solid electrolyte.
  • a self-healing polymer solid electrolyte based on disulfide bonds includes disulfide bond-modified polyurethane/polyethylene oxide composite polymer and lithium salt.
  • the lithium salt is lithium difluoromethanesulfonimide; the lithium salt accounts for 10% of the total mass of the solid electrolyte.
  • a preparation method of the solid electrolyte comprising the following steps:
  • Lithium salt is added to the disulfide bond-modified polyurethane/polyethylene oxide composite polymer solution to make the mass between the polyethylene oxide in step (2) and the lithium salt in step (3) The ratio is 7.5:1. After mixing evenly, pour it into a polytetrafluoroethylene plate and dry it to obtain a self-healing polymer solid electrolyte.
  • a self-healing polymer solid electrolyte based on disulfide bonds includes disulfide bond-modified polyurethane/polyethylene oxide composite polymer and lithium salt.
  • the lithium salt is lithium bis(trifluoromethylsulfonyl)imide; the lithium salt accounts for 10% of the total mass of the solid electrolyte.
  • a preparation method of the solid electrolyte comprising the following steps:
  • Lithium salt is added to the disulfide bond-modified polyurethane/polyethylene oxide composite polymer solution to make the mass between the polyethylene oxide in step (2) and the lithium salt in step (3) The ratio is 8:1. After mixing evenly, pour it into a polytetrafluoroethylene plate and dry it to obtain a self-healing polymer solid electrolyte.
  • a self-healing polymer solid electrolyte based on disulfide bonds includes disulfide bond-modified polyurethane/polyethylene oxide composite polymer and lithium salt.
  • the lithium salt is lithium bis(trifluoromethylsulfonyl)imide; the lithium salt accounts for 10% of the total mass of the solid electrolyte.
  • a preparation method of the solid electrolyte comprising the following steps:
  • Lithium salt is added to the disulfide bond-modified polyurethane/polyethylene oxide composite polymer solution to make the mass between the polyethylene oxide in step (2) and the lithium salt in step (3) The ratio is 6.75:1. After mixing evenly, pour it into a polytetrafluoroethylene plate and dry it to obtain a self-healing polymer solid electrolyte.
  • a self-healing polymer solid electrolyte based on disulfide bonds includes disulfide bond-modified polyurethane/polyethylene oxide composite polymer and lithium salt.
  • the lithium salt is lithium perchlorate; the lithium salt accounts for 10% of the total mass of the solid electrolyte.
  • a preparation method of the solid electrolyte comprising the following steps:
  • cystamine dihydrochloride In methylacetamide, cystamine dihydrochloride and dibutyltin dilaurate are added, so that the molar ratio between the isocyanate end group in the polyurethane prepolymer and the amino group in cystamine dihydrochloride is 1.5:1,
  • the mass fraction of dibutyltin dilaurate in the reaction solution was 1 wt%, and the disulfide bond modified polyurethane solution was obtained after stirring and reacting at 60 °C for 3 hours;
  • Lithium salt is added to the disulfide bond-modified polyurethane/polyethylene oxide composite polymer solution to make the mass between the polyethylene oxide in step (2) and the lithium salt in step (3) The ratio is 6.75:1. After mixing evenly, pour it into a polytetrafluoroethylene plate and dry it to obtain a self-healing polymer solid electrolyte.
  • a self-healing polymer solid electrolyte based on disulfide bonds includes disulfide bond-modified polyurethane/polyethylene oxide composite polymer and lithium salt.
  • the lithium salt is lithium difluoromethanesulfonimide; the lithium salt accounts for 10% of the total mass of the solid electrolyte.
  • a preparation method of the solid electrolyte comprising the following steps:
  • Polyisocyanate graft modification in a nitrogen atmosphere, a polyurethane prepolymer with a weight average molecular weight of 3500 and containing at least two isocyanate end groups was dissolved in N,N-dimethyl methacrylate at a mass volume ratio of 1g:2mL.
  • Lithium salt is added to the disulfide bond-modified polyurethane/polyethylene oxide composite polymer solution to make the mass between the polyethylene oxide in step (2) and the lithium salt in step (3) The ratio is 7.5:1. After mixing evenly, pour it into a polytetrafluoroethylene plate and dry it to obtain a self-healing polymer solid electrolyte.
  • a self-healing polymer solid electrolyte based on disulfide bonds includes disulfide bond-modified polyurethane/polyethylene oxide composite polymer and lithium salt.
  • the lithium salt is lithium difluoromethanesulfonimide; the lithium salt accounts for 10% of the total mass of the solid electrolyte.
  • a preparation method of the solid electrolyte comprising the following steps:
  • Polyisocyanate graft modification in a nitrogen atmosphere, a polyurethane prepolymer with a weight average molecular weight of 3500 and containing at least two isocyanate end groups was dissolved in N,N-dimethyl methacrylate at a mass volume ratio of 1g:2mL.
  • Lithium salt is added to the disulfide bond-modified polyurethane/polyethylene oxide composite polymer solution to make the mass between the polyethylene oxide in step (2) and the lithium salt in step (3) The ratio is 7.5:1. After mixing evenly, pour it into a polytetrafluoroethylene plate and dry it to obtain a self-healing polymer solid electrolyte.
  • a polymer solid electrolyte includes polyethylene oxide composite polymer and lithium salt.
  • the lithium salt is lithium bis(trifluoromethylsulfonyl)imide; the lithium salt accounts for 10% of the total mass of the solid electrolyte.
  • a preparation method of the solid electrolyte comprising the following steps:
  • the polyoxyethylene with a weight-average molecular weight of 116400 is dissolved in N,N-dimethylacetamide with a mass volume ratio of 1g:2mL, and a lithium salt is added, so that the mass ratio between the polyoxyethylene and the lithium salt is 9: 1. After mixing evenly, pour it into a polytetrafluoroethylene plate and dry it to obtain a polymer solid electrolyte.
  • a polymer solid electrolyte includes a polyurethane/polyethylene oxide composite polymer and a lithium salt.
  • the lithium salt is lithium bis(trifluoromethylsulfonyl)imide; the lithium salt accounts for 10% of the total mass of the solid electrolyte.
  • a preparation method of the solid electrolyte comprising the following steps:
  • Lithium salt is added to the polyurethane/polyethylene oxide composite polymer solution, so that the mass ratio between the polyethylene oxide in step (2) and the lithium salt in step (3) is 4.5:1 , after mixing evenly, poured into a polytetrafluoroethylene plate and dried to obtain a polymer solid electrolyte.
  • the solid electrolyte membrane is prepared into a sample with a width of 15mm, placed on the fixture of the universal testing machine at room temperature, and stretched at a speed of 100mm/s to obtain the tensile strength;
  • Example 1 Compared with Comparative Example 2 (polyurethane is not modified with disulfide bonds), the electrolyte of Example 1 has better self-healing ability, which shows that the introduction of disulfide bonds in polyurethane can give the polymer solid electrolyte a better performance. Good self-healing ability. The reason is that the disulfide bond is a reversible dynamic covalent bond that can self-repair after being broken.
  • the electrolyte of Example 1 has higher tensile strength, room temperature ionic conductivity and self-healing ability, indicating that the method of the present invention can While endowing the polymer solid electrolyte with self-healing ability, it can also effectively improve its mechanical strength and ionic conductivity.
  • polyurethane can form a cross-linked network with polyethylene oxide through covalent bonds and hydrogen bonds, and at the same time, there are soft segments and hard segments in polyurethane, which help to improve the mechanical strength and ionic conductivity of the electrolyte.
  • Example 3 Compared with Example 3, the electrolyte self-repairing time of Examples 7 and 8 is shorter, indicating that the polyisocyanate graft modification of the polyurethane prepolymer can effectively improve the polymerization The self-healing ability of solid-state electrolytes. The reason is that by increasing the isocyanate end group content in the polyurethane prepolymer, more disulfide bonds can be introduced.
  • the raw materials and equipment used in the present invention are the common raw materials and equipment in the art; the methods used in the present invention, unless otherwise specified, are the conventional methods in the art.

Abstract

The present invention relates to the field of polymer solid-state batteries, and discloses a self-repairing polymer solid-state electrolyte based on double-sulfur bonds and a preparation method therefor. The polymer solid-state electrolyte comprises a double-sulfur bond-modified polyurethane/polyethylene oxide composite polymer and a lithium salt, and the preparation method is as follows: in an inert gas atmosphere, dissolving a polyurethane prepolymer in an organic solvent, adding a double-sulfur bond monomer and a catalyst, and stirring and reacting at 50-90°C for 2-5 h; after the reaction is completed, adding polyethylene oxide, and stirring and reacting at 50-90°C for 2-5 h; and after the reaction is completed, adding a lithium salt, uniformly mixing, pouring the mixture into a polytetrafluoroethylene plate, and drying to obtain a self-repairing polymer solid-state electrolyte. According to the present invention, double-sulfur bond-modified polyurethane is introduced into a polyethylene oxide solid-state electrolyte, so that self-repairing can be carried out when the electrolyte is damaged; meanwhile, high mechanical strength and room temperature ionic conductivity are achieved.

Description

一种基于双硫键的自修复聚合物固态电解质及其制备方法A kind of self-healing polymer solid electrolyte based on disulfide bond and preparation method thereof 技术领域technical field
本发明涉及聚合物固态电池领域，尤其涉及一种基于双硫键的自修复聚合物固态电解质及其制备方法。The invention relates to the field of polymer solid-state batteries, in particular to a self-repairing polymer solid-state electrolyte based on disulfide bonds and a preparation method thereof.
背景技术Background technique
锂离子电池由于高比能、低自放电、宽化学窗口、绿色环保等优点，已广泛应用于便携式电子器件、电动汽车、智能电网等领域。然而，目前商业化离锂离子电池能量密度仍然难以满足日益增长的需求，加之其安全性能等问题限制了其进一步发展。与传统液态锂离子电池不同，全固态锂电池具有高比能量、高安全性能、长循环寿命等优点，近年来已成为新型化学电池领域的研究开发热点。Due to the advantages of high specific energy, low self-discharge, wide chemical window, and green environmental protection, lithium-ion batteries have been widely used in portable electronic devices, electric vehicles, smart grids and other fields. However, the energy density of commercial lithium-ion batteries is still difficult to meet the increasing demand, and the safety performance and other issues limit their further development. Different from traditional liquid lithium-ion batteries, all-solid-state lithium batteries have the advantages of high specific energy, high safety performance, and long cycle life. In recent years, they have become a research and development focus in the field of new chemical batteries.
通常，固态电解质按化学组分可分为无机固态电解质和聚合物固态电解质。无机固态电解质包括氧化物、硫化物等，具有高室温离子导电率及宽化学窗口，但其固/固界面阻抗偏大限制了其进一步应用。聚合物固态电解质(如公开号为CN108281704A的专利)包括聚氧化乙烯、聚偏氟乙烯-六氟丙烯共聚物、聚丙烯腈等，尤其是聚氧化乙烯，是目前较为成熟的聚合物固态电解质材料，其溶剂化锂盐能力强，成膜性好，对金属锂稳定，但其室温离子导电率及机械强度偏低，容易被锂枝晶刺穿，导致电池短路。而具有自修复功能的聚合物固态电解质可以很好解决聚合物固态电解质的缺陷，是一种具有发展潜力的聚合物电解质材料。因此，基于当前聚合物固态电解质的不足，开发一种具有自修复能力的聚合物固态电解质是有必要的。Generally, solid electrolytes can be divided into inorganic solid electrolytes and polymer solid electrolytes according to chemical components. Inorganic solid electrolytes include oxides, sulfides, etc., with high room temperature ionic conductivity and wide chemical window, but their large solid/solid interface impedance limits their further applications. The polymer solid electrolyte (such as the patent with publication number CN108281704A) includes polyethylene oxide, polyvinylidene fluoride-hexafluoropropylene copolymer, polyacrylonitrile, etc., especially polyethylene oxide, which is a relatively mature polymer solid electrolyte material at present. , It has strong ability to solvate lithium salts, good film-forming properties, and is stable to metal lithium, but its room temperature ionic conductivity and mechanical strength are low, and it is easy to be pierced by lithium dendrites, resulting in a short circuit of the battery. The polymer solid electrolyte with self-healing function can solve the defects of polymer solid electrolyte very well, and it is a kind of polymer electrolyte material with development potential. Therefore, based on the shortcomings of current polymer solid electrolytes, it is necessary to develop a polymer solid electrolyte with self-healing ability.
发明内容SUMMARY OF THE INVENTION
为了解决上述技术问题，本发明提供了一种基于双硫键的自修复聚合物固态电解质及其制备方法。该固态电解质能在受损时进行自修复，且具有较高的机械强度和室温离子导电率。In order to solve the above technical problems, the present invention provides a self-healing polymer solid electrolyte based on disulfide bonds and a preparation method thereof. The solid electrolyte can self-repair when damaged, and has high mechanical strength and room temperature ionic conductivity.
本发明的具体技术方案为：The specific technical scheme of the present invention is:
一种基于双硫键的自修复聚合物固态电解质，包括双硫键改性聚氨酯/聚氧化乙烯复合聚合物和锂盐；所述双硫键改性聚氨酯由双硫键单体与聚氨酯预聚体聚合而得；所述聚氨酯预聚体中含有至少两个异氰酸酯端基；所述双硫键单体中含有至少一个双硫键且羟基和氨基的总数量至少为两个。A self-healing polymer solid electrolyte based on disulfide bonds, comprising a disulfide bond-modified polyurethane/polyethylene oxide composite polymer and a lithium salt; the disulfide bond-modified polyurethane is prepolymerized by a disulfide bond monomer and a polyurethane The polyurethane prepolymer contains at least two isocyanate end groups; the disulfide bond monomer contains at least one disulfide bond and the total number of hydroxyl groups and amino groups is at least two.
本发明在聚氧化乙烯固态电解质中引入双硫键改性聚氨酯，其中，聚氨酯与聚氧化乙烯之间通过氢键、共价键等方式结合而形成交联网络，并在聚氨酯中引入双硫键作为可逆动 态共价键，通过这种方式，可在聚合物固态电解质界面受损时实现自修复功能，防止电池短路。In the present invention, a disulfide bond modified polyurethane is introduced into the polyethylene oxide solid electrolyte, wherein the polyurethane and the polyethylene oxide are combined by hydrogen bonds, covalent bonds, etc. to form a cross-linked network, and the disulfide bond is introduced into the polyurethane. As a reversible dynamic covalent bond, in this way, a self-healing function can be achieved when the polymer solid-electrolyte interface is damaged, preventing the battery from short-circuiting.
此外，本发明通过引入改性聚氨酯的方式引入双硫键，对于聚合物固态电解质成膜及固/固界面阻抗均有改善作用：硬段的引入可提高固态电解质膜的机械强度，软段则有利于提高固态电解质的室温离子导电率；同时，聚氨酯与聚氧化乙烯之间能够形成交联网络，进一步提高聚合物固态电解质膜的机械强度，且交联结构可降低聚合物的结晶度，进而提高固态电解质室温离子导电率。In addition, the present invention introduces disulfide bonds by introducing modified polyurethane, which improves the film formation of the polymer solid electrolyte and the solid/solid interface impedance: the introduction of the hard segment can improve the mechanical strength of the solid electrolyte membrane, while the soft segment can improve the mechanical strength of the solid electrolyte membrane. It is beneficial to improve the room temperature ionic conductivity of the solid electrolyte; at the same time, a cross-linked network can be formed between polyurethane and polyethylene oxide, which further improves the mechanical strength of the polymer solid electrolyte membrane, and the cross-linked structure can reduce the crystallinity of the polymer, and then Improve the room temperature ionic conductivity of solid electrolytes.
作为优选，所述锂盐为双(三氟甲基磺酰)亚胺锂、二氟甲基磺酰亚胺锂、高氯酸锂中的一种或多种。Preferably, the lithium salt is one or more of lithium bis(trifluoromethylsulfonyl)imide, lithium difluoromethylsulfonimide, and lithium perchlorate.
作为优选，所述锂盐占固态电解质总质量的1～10％。Preferably, the lithium salt accounts for 1-10% of the total mass of the solid electrolyte.
一种上述固态电解质的制备方法，包括以下步骤：A preparation method of the above-mentioned solid electrolyte, comprising the following steps:
(1)制备双硫键改性聚氨酯：在惰性气体氛围中，将聚氨酯预聚体溶解于有机溶剂中，加入双硫键单体和催化剂，在50～90℃下搅拌反应2～5h，获得双硫键改性聚氨酯溶液；所述聚氨酯预聚体中含有至少两个异氰酸酯端基；所述双硫键单体中，双硫键两端各含有至少一个羟基和/或氨基；(1) Preparation of disulfide bond-modified polyurethane: in an inert gas atmosphere, dissolve the polyurethane prepolymer in an organic solvent, add a disulfide bond monomer and a catalyst, and stir and react at 50 to 90 ° C for 2 to 5 hours to obtain Disulfide bond-modified polyurethane solution; the polyurethane prepolymer contains at least two isocyanate end groups; in the disulfide bond monomer, each end of the disulfide bond contains at least one hydroxyl group and/or amino group;
(2)制备双硫键改性聚氨酯/聚氧化乙烯复合聚合物：将聚氧化乙烯加入双硫键改性聚氨酯溶液中，在50～90℃下搅拌反应2～5h，获得双硫键改性聚氨酯/聚氧化乙烯复合聚合物溶液；(2) Preparation of disulfide bond-modified polyurethane/polyethylene oxide composite polymer: adding polyethylene oxide to the disulfide bond-modified polyurethane solution, stirring and reacting at 50-90 °C for 2-5 h to obtain disulfide-modified polyurethane Polyurethane/polyethylene oxide composite polymer solution;
(3)制备固态电解质：在双硫键改性聚氨酯/聚氧化乙烯复合聚合物溶液中加入锂盐，混合均匀后，倒入聚四氟乙烯板中，烘干，获得自修复聚合物固态电解质。(3) Preparation of solid electrolyte: Lithium salt is added to the disulfide bond-modified polyurethane/polyethylene oxide composite polymer solution, mixed uniformly, poured into a polytetrafluoroethylene plate, and dried to obtain a self-healing polymer solid electrolyte .
步骤(1)中，聚氨酯预聚体中的异氰酸酯端基与双硫键单体中的羟基或氨基发生反应，从而将双硫键引入聚氨酯中，赋予电解质自修复的功能；步骤(2)中，聚氨酯预聚体中的异氰酸酯端基与聚氧化乙烯中的羟基发生反应，从而使两者之间通过共价键交联，提高交联网络的结合强度，从而提高固态电解质的机械强度。In step (1), the isocyanate end group in the polyurethane prepolymer reacts with the hydroxyl group or amino group in the disulfide bond monomer, so that the disulfide bond is introduced into the polyurethane, and the self-repairing function of the electrolyte is given; in step (2) , the isocyanate end group in the polyurethane prepolymer reacts with the hydroxyl group in the polyethylene oxide, so that the two are cross-linked by covalent bonds, and the bonding strength of the cross-linked network is improved, thereby improving the mechanical strength of the solid electrolyte.
作为优选，步骤(1)中，所述双硫键单体的结构式如下：Preferably, in step (1), the structural formula of the disulfide bond monomer is as follows:
Figure PCTCN2021105917-appb-000001
Figure PCTCN2021105917-appb-000001
其中，R和R′为
Figure PCTCN2021105917-appb-000002
中的一种或两种。 where R and R' are
Figure PCTCN2021105917-appb-000002
one or both of them.
作为优选，步骤(1)中，聚氨酯预聚体中的异氰酸酯端基与双硫键单体端基之间的 摩尔比为1～1.5:1。Preferably, in step (1), the molar ratio between the isocyanate end group and the disulfide bond monomer end group in the polyurethane prepolymer is 1-1.5:1.
作为优选，步骤(2)中，双硫键改性聚氨酯与聚氧化乙烯之间的质量比为1:1～10。Preferably, in step (2), the mass ratio between the disulfide bond-modified polyurethane and the polyethylene oxide is 1:1-10.
作为优选，步骤(1)中，所述聚氨酯预聚体的分子量为500～5000。Preferably, in step (1), the molecular weight of the polyurethane prepolymer is 500-5000.
作为优选，步骤(2)中，所述聚氧化乙烯分子量为50000～200000。Preferably, in step (2), the molecular weight of the polyethylene oxide is 50,000-200,000.
作为优选，步骤(1)中，所述催化剂为二月桂酸二丁基锡。Preferably, in step (1), the catalyst is dibutyltin dilaurate.
作为优选，步骤(1)中，所述有机溶剂为N,N-二甲基乙酰胺。Preferably, in step (1), the organic solvent is N,N-dimethylacetamide.
作为优选，步骤(1)中，将聚氨酯预聚体溶解于有机溶剂中，加入催化剂后，先对聚氨酯预聚体进行多异氰酸酯接枝改性，再加入双硫键单体；所述多异氰酸酯接枝改性的具体方法如下：加入丙烯酸羟丙酯，在60～70℃下搅拌反应0.5～1h；再加入摩尔比为5～6:1的N,N'-亚甲基双丙烯酰胺和三(2-氨基乙基)胺，继续在60～70℃下搅拌反应3～4h；而后升温至130～140℃，用惰性气体置换反应容器内的气体后，加入3-异氰酸丙烯和引发剂，搅拌反应2～3h，制得改性聚氨酯预聚体溶液。Preferably, in step (1), the polyurethane prepolymer is dissolved in an organic solvent, after adding the catalyst, polyisocyanate graft modification is first performed on the polyurethane prepolymer, and then disulfide monomers are added; the polyisocyanate The specific method of graft modification is as follows: adding hydroxypropyl acrylate, stirring and reacting at 60-70° C. for 0.5-1 h; then adding N,N'-methylenebisacrylamide and a molar ratio of 5-6:1. Tris(2-aminoethyl)amine, continue to stir and react at 60～70℃ for 3～4h; then heat up to 130～140℃, replace the gas in the reaction vessel with inert gas, add 3-isocyanatopropene and The initiator is stirred and reacted for 2-3 hours to obtain the modified polyurethane prepolymer solution.
通过以上过程，可在聚氨酯预聚体的异氰酸酯端基上接枝上多个端烯基，进而通过加成反应接枝上多个异氰酸酯，从而增加聚氨酯预聚体中的异氰酸酯端基含量，引入更多的双硫键，提高聚合物固态电解质的自修复能力。Through the above process, a plurality of terminal alkenyl groups can be grafted on the isocyanate end groups of the polyurethane prepolymer, and then a plurality of isocyanates can be grafted through an addition reaction, thereby increasing the isocyanate end group content in the polyurethane prepolymer, introducing More disulfide bonds improve the self-healing ability of polymer solid electrolytes.
作为优选，所述聚氨酯预聚体中的异氰酸酯端基与丙烯酸羟丙酯之间的摩尔比为1:1～2；所述丙烯酸羟丙酯与三(2-氨基乙基)胺之间的摩尔比为1:1～2；所述丙烯酸羟丙酯与3-异氰酸丙烯之间的摩尔比为1:15～18。Preferably, the molar ratio between the isocyanate end group and hydroxypropyl acrylate in the polyurethane prepolymer is 1:1-2; the molar ratio between the hydroxypropyl acrylate and tris(2-aminoethyl)amine The molar ratio is 1:1-2; the molar ratio between the hydroxypropyl acrylate and 3-isocyanatopropene is 1:15-18.
与现有技术相比，本发明具有以下优点：Compared with the prior art, the present invention has the following advantages:
(1)本发明通过在聚合物固态电解质中引入双硫键，能在电解质膜受损时实现自修复，防止电池短路；(1) The present invention can realize self-repair when the electrolyte membrane is damaged by introducing disulfide bonds into the polymer solid electrolyte, and prevent the battery from short-circuiting;
(2)本发明通过引入双硫键改性聚氨酯的方式引入双硫键，聚氨酯能提高聚合物固态电解质的机械强度和室温离子导电率；(2) The present invention introduces disulfide bonds by introducing disulfide bond modified polyurethane, and the polyurethane can improve the mechanical strength and room temperature ionic conductivity of the polymer solid electrolyte;
(3)本发明对聚氨酯预聚体进行多异氰酸酯接枝改性，能提高其中的异氰酸酯端基含量，进而提高聚合物固态电解质的自修复能力。(3) The present invention performs polyisocyanate graft modification on the polyurethane prepolymer, which can increase the content of isocyanate end groups therein, thereby improving the self-healing ability of the polymer solid electrolyte.
具体实施方式Detailed ways
下面结合实施例对本发明作进一步的描述。The present invention will be further described below in conjunction with the examples.
总实施例General Example
一种基于双硫键的自修复聚合物固态电解质，包括双硫键改性聚氨酯/聚氧化乙烯复合聚合物和锂盐。所述锂盐为双(三氟甲基磺酰)亚胺锂、二氟甲基磺酰亚胺锂、高氯酸锂中的一种或 多种；所述锂盐占固态电解质总质量的1～10％。A self-healing polymer solid electrolyte based on disulfide bonds includes disulfide bond-modified polyurethane/polyethylene oxide composite polymer and lithium salt. The lithium salt is one or more of lithium bis(trifluoromethylsulfonyl)imide, lithium difluoromethylsulfonimide, and lithium perchlorate; the lithium salt accounts for 30% of the total mass of the solid electrolyte. 1 to 10%.
一种所述固态电解质的制备方法，包括以下步骤：A preparation method of the solid electrolyte, comprising the following steps:
(1)制备双硫键改性聚氨酯：在惰性气体氛围中，将分子量为500～5000的聚氨酯预聚体溶解于有机溶剂中，加入双硫键单体和催化剂，使聚氨酯预聚体中的异氰酸酯端基与双硫键单体端基之间的摩尔比为1～1.5:1，在50～90℃下搅拌反应2～5h后，获得双硫键改性聚氨酯溶液；所述聚氨酯预聚体中含有至少两个异氰酸酯端基；(1) Preparation of disulfide bond-modified polyurethane: in an inert gas atmosphere, a polyurethane prepolymer with a molecular weight of 500 to 5000 is dissolved in an organic solvent, and disulfide bond monomers and catalysts are added to make the polyurethane prepolymer. The molar ratio between the isocyanate end group and the disulfide bond monomer end group is 1 to 1.5:1, and after stirring and reacting at 50 to 90° C. for 2 to 5 hours, a disulfide bond modified polyurethane solution is obtained; the polyurethane prepolymerization The body contains at least two isocyanate end groups;
所述双硫键单体的结构式如下：The structural formula of the disulfide bond monomer is as follows:
Figure PCTCN2021105917-appb-000003
Figure PCTCN2021105917-appb-000003
其中，R和R′为
Figure PCTCN2021105917-appb-000004
中的一种或两种； where R and R' are
Figure PCTCN2021105917-appb-000004
one or both of them;
(2)制备双硫键改性聚氨酯/聚氧化乙烯复合聚合物：将分子量为50000～200000的聚氧化乙烯加入双硫键改性聚氨酯溶液中，使双硫键改性聚氨酯与聚氧化乙烯之间的质量比为1:1～10，在50～90℃下搅拌反应2～5h后，获得双硫键改性聚氨酯/聚氧化乙烯复合聚合物溶液；(2) Preparation of disulfide bond-modified polyurethane/polyethylene oxide composite polymer: Polyethylene oxide with a molecular weight of 50,000 to 200,000 is added to the disulfide bond-modified polyurethane solution to make the disulfide bond-modified polyurethane and polyethylene oxide. The mass ratio between them is 1:1～10, and after stirring and reacting at 50～90 ℃ for 2～5h, the disulfide bond-modified polyurethane/polyethylene oxide composite polymer solution is obtained;
(3)制备固态电解质：在双硫键改性聚氨酯/聚氧化乙烯复合聚合物溶液中加入锂盐，混合均匀后，倒入聚四氟乙烯板中，烘干，获得自修复聚合物固态电解质。(3) Preparation of solid electrolyte: Lithium salt is added to the disulfide bond-modified polyurethane/polyethylene oxide composite polymer solution, mixed uniformly, poured into a polytetrafluoroethylene plate, and dried to obtain a self-healing polymer solid electrolyte .
可选地，步骤(1)中，将聚氨酯预聚体溶解于有机溶剂中，加入催化剂后，先对聚氨酯预聚体进行多异氰酸酯接枝改性，再加入双硫键单体；所述多异氰酸酯接枝改性的具体方法如下：加入丙烯酸羟丙酯，所述聚氨酯预聚体中的异氰酸酯端基与丙烯酸羟丙酯之间的摩尔比为1:1～2，在60～70℃下搅拌反应0.5～1h；再加入摩尔比为5～6:1的N,N'-亚甲基双丙烯酰胺和三(2-氨基乙基)胺，所述丙烯酸羟丙酯与三(2-氨基乙基)胺之间的摩尔比为1:1～2，继续在60～70℃下搅拌反应3～4h；而后升温至130～140℃，用惰性气体置换反应容器内的气体后，加入3-异氰酸丙烯和引发剂，所述丙烯酸羟丙酯与3-异氰酸丙烯之间的摩尔比为1:15～18，搅拌反应2～3h，制得改性聚氨酯预聚体溶液。Optionally, in step (1), the polyurethane prepolymer is dissolved in an organic solvent, and after adding a catalyst, polyisocyanate graft modification is first performed on the polyurethane prepolymer, and then disulfide monomers are added; The specific method of isocyanate graft modification is as follows: adding hydroxypropyl acrylate, the molar ratio between the isocyanate end group in the polyurethane prepolymer and the hydroxypropyl acrylate is 1:1～2, at 60～70 ℃ The reaction is stirred for 0.5 to 1 h; then N,N'-methylenebisacrylamide and tris(2-aminoethyl)amine in a molar ratio of 5 to 6:1 are added, and the hydroxypropyl acrylate and tris(2- The molar ratio between aminoethyl)amines is 1:1～2, continue to stir the reaction at 60～70℃ for 3～4h; then heat up to 130～140℃, replace the gas in the reaction vessel with inert gas, add 3-isocyanatopropylene and an initiator, the molar ratio between the hydroxypropyl acrylate and 3-isocyanatopropylene is 1:15-18, and the reaction is stirred for 2-3 hours to obtain a modified polyurethane prepolymer solution .
实施例1Example 1
一种基于双硫键的自修复聚合物固态电解质，包括双硫键改性聚氨酯/聚氧化乙烯复合聚合物和锂盐。所述锂盐为双(三氟甲基磺酰)亚胺锂；所述锂盐占固态电解质总质量的10％。A self-healing polymer solid electrolyte based on disulfide bonds includes disulfide bond-modified polyurethane/polyethylene oxide composite polymer and lithium salt. The lithium salt is lithium bis(trifluoromethylsulfonyl)imide; the lithium salt accounts for 10% of the total mass of the solid electrolyte.
一种所述固态电解质的制备方法，包括以下步骤：A preparation method of the solid electrolyte, comprising the following steps:
(1)制备双硫键改性聚氨酯：在氮气氛围中，将重均分子量为3500、含有至少两个异氰酸 酯端基的聚氨酯预聚体以1g:2mL的质量体积比溶解于N,N-二甲基乙酰胺中，加入2-羟乙基二硫化物和二月桂酸二丁基锡，使聚氨酯预聚体中的异氰酸酯端基与2-羟乙基二硫化物端基之间的摩尔比为1.2:1，二月桂酸二丁基锡在反应液中的质量分数为1wt％，在60℃下搅拌反应3h后，获得双硫键改性聚氨酯溶液；(1) Preparation of disulfide bond-modified polyurethane: in a nitrogen atmosphere, a polyurethane prepolymer with a weight average molecular weight of 3500 and containing at least two isocyanate end groups was dissolved in N,N-disulfide at a mass volume ratio of 1g:2mL. In methylacetamide, 2-hydroxyethyl disulfide and dibutyltin dilaurate were added, so that the molar ratio between the isocyanate end group and the 2-hydroxyethyl disulfide end group in the polyurethane prepolymer was 1.2 : 1, the mass fraction of dibutyltin dilaurate in the reaction solution is 1wt%, after stirring and reacting at 60°C for 3h, a disulfide bond-modified polyurethane solution is obtained;
(2)制备双硫键改性聚氨酯/聚氧化乙烯复合聚合物：将重均分子量为116400的聚氧化乙烯加入双硫键改性聚氨酯溶液中，使双硫键改性聚氨酯与聚氧化乙烯之间的质量比为1:1，在60℃下搅拌反应3h后，获得双硫键改性聚氨酯/聚氧化乙烯复合聚合物溶液；(2) Preparation of disulfide bond-modified polyurethane/polyethylene oxide composite polymer: Polyethylene oxide with a weight average molecular weight of 116400 was added to the disulfide bond-modified polyurethane solution, so that the disulfide bond-modified polyurethane and polyethylene oxide were mixed. The mass ratio between the two is 1:1, and after stirring and reacting at 60 °C for 3 h, the disulfide bond-modified polyurethane/polyethylene oxide composite polymer solution is obtained;
(3)制备固态电解质：在双硫键改性聚氨酯/聚氧化乙烯复合聚合物溶液中加入锂盐，使步骤(2)中的聚氧化乙烯与步骤(3)中的锂盐之间的质量比为4.5:1，混合均匀后，倒入聚四氟乙烯板中，烘干，获得自修复聚合物固态电解质。(3) Preparation of solid electrolyte: Lithium salt is added to the disulfide bond-modified polyurethane/polyethylene oxide composite polymer solution to make the mass between the polyethylene oxide in step (2) and the lithium salt in step (3) The ratio is 4.5:1. After mixing evenly, pour it into a polytetrafluoroethylene plate and dry it to obtain a self-healing polymer solid electrolyte.
实施例2Example 2
一种基于双硫键的自修复聚合物固态电解质，包括双硫键改性聚氨酯/聚氧化乙烯复合聚合物和锂盐。所述锂盐为双(三氟甲基磺酰)亚胺锂；所述锂盐占固态电解质总质量的10％。A self-healing polymer solid electrolyte based on disulfide bonds includes disulfide bond-modified polyurethane/polyethylene oxide composite polymer and lithium salt. The lithium salt is lithium bis(trifluoromethylsulfonyl)imide; the lithium salt accounts for 10% of the total mass of the solid electrolyte.
一种所述固态电解质的制备方法，包括以下步骤：A preparation method of the solid electrolyte, comprising the following steps:
(1)制备双硫键改性聚氨酯：在氮气氛围中，将重均分子量为3500、含有至少两个异氰酸酯端基的聚氨酯预聚体以1g:2mL的质量体积比溶解于N,N-二甲基乙酰胺中，加入胱胺二盐酸盐和二月桂酸二丁基锡，使聚氨酯预聚体中的异氰酸酯端基与胱胺二盐酸盐中的氨基之间的摩尔比为1.2:1，二月桂酸二丁基锡在反应液中的质量分数为1wt％，在60℃下搅拌反应3h后，获得双硫键改性聚氨酯溶液；(1) Preparation of disulfide bond-modified polyurethane: in a nitrogen atmosphere, a polyurethane prepolymer with a weight average molecular weight of 3500 and containing at least two isocyanate end groups was dissolved in N,N-disulfide at a mass volume ratio of 1g:2mL. In methylacetamide, cystamine dihydrochloride and dibutyltin dilaurate are added, so that the molar ratio between the isocyanate end group in the polyurethane prepolymer and the amino group in cystamine dihydrochloride is 1.2:1, The mass fraction of dibutyltin dilaurate in the reaction solution was 1 wt%, and the disulfide bond modified polyurethane solution was obtained after stirring and reacting at 60 °C for 3 hours;
(2)制备双硫键改性聚氨酯/聚氧化乙烯复合聚合物：将重均分子量为116400的聚氧化乙烯加入双硫键改性聚氨酯溶液中，使双硫键改性聚氨酯与聚氧化乙烯之间的质量比为1:3，在60℃下搅拌反应3h后，获得双硫键改性聚氨酯/聚氧化乙烯复合聚合物溶液；(2) Preparation of disulfide bond-modified polyurethane/polyethylene oxide composite polymer: Polyethylene oxide with a weight average molecular weight of 116400 was added to the disulfide bond-modified polyurethane solution, so that the disulfide bond-modified polyurethane and polyethylene oxide were mixed. The mass ratio between the two was 1:3, and after stirring and reacting at 60 °C for 3 h, the disulfide bond-modified polyurethane/polyethylene oxide composite polymer solution was obtained;
(3)制备固态电解质：在双硫键改性聚氨酯/聚氧化乙烯复合聚合物溶液中加入锂盐，使步骤(2)中的聚氧化乙烯与步骤(3)中的锂盐之间的质量比为6.75:1，混合均匀后，倒入聚四氟乙烯板中，烘干，获得自修复聚合物固态电解质。(3) Preparation of solid electrolyte: Lithium salt is added to the disulfide bond-modified polyurethane/polyethylene oxide composite polymer solution to make the mass between the polyethylene oxide in step (2) and the lithium salt in step (3) The ratio is 6.75:1. After mixing evenly, pour it into a polytetrafluoroethylene plate and dry it to obtain a self-healing polymer solid electrolyte.
实施例3Example 3
一种基于双硫键的自修复聚合物固态电解质，包括双硫键改性聚氨酯/聚氧化乙烯复合聚合物和锂盐。所述锂盐为二氟甲基磺酰亚胺锂；所述锂盐占固态电解质总质量的10％。A self-healing polymer solid electrolyte based on disulfide bonds includes disulfide bond-modified polyurethane/polyethylene oxide composite polymer and lithium salt. The lithium salt is lithium difluoromethanesulfonimide; the lithium salt accounts for 10% of the total mass of the solid electrolyte.
一种所述固态电解质的制备方法，包括以下步骤：A preparation method of the solid electrolyte, comprising the following steps:
(1)制备双硫键改性聚氨酯：在氮气氛围中，将重均分子量为3500、含有至少两个异氰酸 酯端基的聚氨酯预聚体以1g:2mL的质量体积比溶解于N,N-二甲基乙酰胺中，加入2-羟乙基二硫化物和二月桂酸二丁基锡，使聚氨酯预聚体中的异氰酸酯端基与2-羟乙基二硫化物中的羟基之间的摩尔比为1.2:1，二月桂酸二丁基锡在反应液中的质量分数为1wt％，在60℃下搅拌反应3h后，获得双硫键改性聚氨酯溶液；(1) Preparation of disulfide bond-modified polyurethane: in a nitrogen atmosphere, a polyurethane prepolymer with a weight average molecular weight of 3500 and containing at least two isocyanate end groups was dissolved in N,N-disulfide at a mass volume ratio of 1g:2mL. In methylacetamide, add 2-hydroxyethyl disulfide and dibutyltin dilaurate, so that the molar ratio between the isocyanate end group in the polyurethane prepolymer and the hydroxyl group in the 2-hydroxyethyl disulfide is 1.2:1, the mass fraction of dibutyltin dilaurate in the reaction solution is 1wt%, after stirring and reacting at 60 ° C for 3h, a disulfide bond modified polyurethane solution is obtained;
(2)制备双硫键改性聚氨酯/聚氧化乙烯复合聚合物：将重均分子量为116400的聚氧化乙烯加入双硫键改性聚氨酯溶液中，使双硫键改性聚氨酯与聚氧化乙烯之间的质量比为1:5，在60℃下搅拌反应3h后，获得双硫键改性聚氨酯/聚氧化乙烯复合聚合物溶液；(2) Preparation of disulfide bond-modified polyurethane/polyethylene oxide composite polymer: Polyethylene oxide with a weight average molecular weight of 116400 was added to the disulfide bond-modified polyurethane solution, so that the disulfide bond-modified polyurethane and polyethylene oxide were mixed. The mass ratio between the two was 1:5, and after stirring and reacting at 60 °C for 3 h, the disulfide bond-modified polyurethane/polyethylene oxide composite polymer solution was obtained;
(3)制备固态电解质：在双硫键改性聚氨酯/聚氧化乙烯复合聚合物溶液中加入锂盐，使步骤(2)中的聚氧化乙烯与步骤(3)中的锂盐之间的质量比为7.5:1，混合均匀后，倒入聚四氟乙烯板中，烘干，获得自修复聚合物固态电解质。(3) Preparation of solid electrolyte: Lithium salt is added to the disulfide bond-modified polyurethane/polyethylene oxide composite polymer solution to make the mass between the polyethylene oxide in step (2) and the lithium salt in step (3) The ratio is 7.5:1. After mixing evenly, pour it into a polytetrafluoroethylene plate and dry it to obtain a self-healing polymer solid electrolyte.
实施例4Example 4
一种基于双硫键的自修复聚合物固态电解质，包括双硫键改性聚氨酯/聚氧化乙烯复合聚合物和锂盐。所述锂盐为双(三氟甲基磺酰)亚胺锂；所述锂盐占固态电解质总质量的10％。A self-healing polymer solid electrolyte based on disulfide bonds includes disulfide bond-modified polyurethane/polyethylene oxide composite polymer and lithium salt. The lithium salt is lithium bis(trifluoromethylsulfonyl)imide; the lithium salt accounts for 10% of the total mass of the solid electrolyte.
一种所述固态电解质的制备方法，包括以下步骤：A preparation method of the solid electrolyte, comprising the following steps:
(1)制备双硫键改性聚氨酯：在氮气氛围中，将重均分子量为3500、含有至少两个异氰酸酯端基的聚氨酯预聚体以1g:2mL的质量体积比溶解于N,N-二甲基乙酰胺中，加入4,4'-二硫代二苯胺和二月桂酸二丁基锡，使聚氨酯预聚体中的异氰酸酯端基与4,4'-二硫代二苯胺中的氨基之间的摩尔比为1.2:1，二月桂酸二丁基锡在反应液中的质量分数为1wt％，在60℃下搅拌反应3h后，获得双硫键改性聚氨酯溶液；(1) Preparation of disulfide bond-modified polyurethane: in a nitrogen atmosphere, a polyurethane prepolymer with a weight average molecular weight of 3500 and containing at least two isocyanate end groups was dissolved in N,N-disulfide at a mass volume ratio of 1g:2mL. In methylacetamide, 4,4'-dithiodiphenylamine and dibutyltin dilaurate were added to make the gap between the isocyanate end group in the polyurethane prepolymer and the amino group in 4,4'-dithiodiphenylamine The molar ratio of dibutyltin dilaurate in the reaction solution was 1.2:1, and the mass fraction of dibutyltin dilaurate in the reaction solution was 1 wt%. After stirring and reacting at 60 °C for 3 h, a disulfide bond-modified polyurethane solution was obtained;
(2)制备双硫键改性聚氨酯/聚氧化乙烯复合聚合物：将重均分子量为116400的聚氧化乙烯加入双硫键改性聚氨酯溶液中，使双硫键改性聚氨酯与聚氧化乙烯之间的质量比为1:8，在60℃下搅拌反应3h后，获得双硫键改性聚氨酯/聚氧化乙烯复合聚合物溶液；(2) Preparation of disulfide bond-modified polyurethane/polyethylene oxide composite polymer: Polyethylene oxide with a weight average molecular weight of 116400 was added to the disulfide bond-modified polyurethane solution, so that the disulfide bond-modified polyurethane and polyethylene oxide were mixed. The mass ratio between the two was 1:8, and the disulfide bond-modified polyurethane/polyethylene oxide composite polymer solution was obtained after stirring and reacting at 60 °C for 3 h;
(3)制备固态电解质：在双硫键改性聚氨酯/聚氧化乙烯复合聚合物溶液中加入锂盐，使步骤(2)中的聚氧化乙烯与步骤(3)中的锂盐之间的质量比为8:1，混合均匀后，倒入聚四氟乙烯板中，烘干，获得自修复聚合物固态电解质。(3) Preparation of solid electrolyte: Lithium salt is added to the disulfide bond-modified polyurethane/polyethylene oxide composite polymer solution to make the mass between the polyethylene oxide in step (2) and the lithium salt in step (3) The ratio is 8:1. After mixing evenly, pour it into a polytetrafluoroethylene plate and dry it to obtain a self-healing polymer solid electrolyte.
实施例5Example 5
一种基于双硫键的自修复聚合物固态电解质，包括双硫键改性聚氨酯/聚氧化乙烯复合聚合物和锂盐。所述锂盐为双(三氟甲基磺酰)亚胺锂；所述锂盐占固态电解质总质量的10％。A self-healing polymer solid electrolyte based on disulfide bonds includes disulfide bond-modified polyurethane/polyethylene oxide composite polymer and lithium salt. The lithium salt is lithium bis(trifluoromethylsulfonyl)imide; the lithium salt accounts for 10% of the total mass of the solid electrolyte.
一种所述固态电解质的制备方法，包括以下步骤：A preparation method of the solid electrolyte, comprising the following steps:
(1)制备双硫键改性聚氨酯：在氮气氛围中，将重均分子量为3500、含有至少两个异氰酸 酯端基的聚氨酯预聚体以1g:2mL的质量体积比溶解于N,N-二甲基乙酰胺中，加入4,4'-二硫二基双(4,1-亚苯)二甲醇和二月桂酸二丁基锡，使聚氨酯预聚体中的异氰酸酯端基与4,4'-二硫二基双(4,1-亚苯)二甲醇中的羟基之间的摩尔比为1.3:1，二月桂酸二丁基锡在反应液中的质量分数为1wt％，在60℃下搅拌反应3h后，获得双硫键改性聚氨酯溶液；(1) Preparation of disulfide bond-modified polyurethane: in a nitrogen atmosphere, a polyurethane prepolymer with a weight average molecular weight of 3500 and containing at least two isocyanate end groups was dissolved in N,N-disulfide at a mass volume ratio of 1g:2mL. In methylacetamide, 4,4'-dithiodiylbis(4,1-phenylene)dimethanol and dibutyltin dilaurate were added to make the isocyanate end group in the polyurethane prepolymer and 4,4'- The molar ratio between the hydroxyl groups in dithiodiylbis(4,1-phenylene)dimethanol is 1.3:1, the mass fraction of dibutyltin dilaurate in the reaction solution is 1wt%, and the reaction is stirred at 60°C After 3h, a disulfide bond-modified polyurethane solution was obtained;
(2)制备双硫键改性聚氨酯/聚氧化乙烯复合聚合物：将重均分子量为116400的聚氧化乙烯加入双硫键改性聚氨酯溶液中，使双硫键改性聚氨酯与聚氧化乙烯之间的质量比为1:3，在60℃下搅拌反应3h后，获得双硫键改性聚氨酯/聚氧化乙烯复合聚合物溶液；(2) Preparation of disulfide bond-modified polyurethane/polyethylene oxide composite polymer: Polyethylene oxide with a weight average molecular weight of 116400 was added to the disulfide bond-modified polyurethane solution, so that the disulfide bond-modified polyurethane and polyethylene oxide were mixed. The mass ratio between the two was 1:3, and after stirring and reacting at 60 °C for 3 h, the disulfide bond-modified polyurethane/polyethylene oxide composite polymer solution was obtained;
(3)制备固态电解质：在双硫键改性聚氨酯/聚氧化乙烯复合聚合物溶液中加入锂盐，使步骤(2)中的聚氧化乙烯与步骤(3)中的锂盐之间的质量比为6.75:1，混合均匀后，倒入聚四氟乙烯板中，烘干，获得自修复聚合物固态电解质。(3) Preparation of solid electrolyte: Lithium salt is added to the disulfide bond-modified polyurethane/polyethylene oxide composite polymer solution to make the mass between the polyethylene oxide in step (2) and the lithium salt in step (3) The ratio is 6.75:1. After mixing evenly, pour it into a polytetrafluoroethylene plate and dry it to obtain a self-healing polymer solid electrolyte.
实施例6Example 6
一种基于双硫键的自修复聚合物固态电解质，包括双硫键改性聚氨酯/聚氧化乙烯复合聚合物和锂盐。所述锂盐为高氯酸锂；所述锂盐占固态电解质总质量的10％。A self-healing polymer solid electrolyte based on disulfide bonds includes disulfide bond-modified polyurethane/polyethylene oxide composite polymer and lithium salt. The lithium salt is lithium perchlorate; the lithium salt accounts for 10% of the total mass of the solid electrolyte.
一种所述固态电解质的制备方法，包括以下步骤：A preparation method of the solid electrolyte, comprising the following steps:
(1)制备双硫键改性聚氨酯：在氮气氛围中，将重均分子量为3500、含有至少两个异氰酸酯端基的聚氨酯预聚体以1g:2mL的质量体积比溶解于N,N-二甲基乙酰胺中，加入胱胺二盐酸盐和二月桂酸二丁基锡，使聚氨酯预聚体中的异氰酸酯端基与胱胺二盐酸盐中的氨基之间的摩尔比为1.5:1，二月桂酸二丁基锡在反应液中的质量分数为1wt％，在60℃下搅拌反应3h后，获得双硫键改性聚氨酯溶液；(1) Preparation of disulfide bond-modified polyurethane: in a nitrogen atmosphere, a polyurethane prepolymer with a weight average molecular weight of 3500 and containing at least two isocyanate end groups was dissolved in N,N-disulfide at a mass volume ratio of 1g:2mL. In methylacetamide, cystamine dihydrochloride and dibutyltin dilaurate are added, so that the molar ratio between the isocyanate end group in the polyurethane prepolymer and the amino group in cystamine dihydrochloride is 1.5:1, The mass fraction of dibutyltin dilaurate in the reaction solution was 1 wt%, and the disulfide bond modified polyurethane solution was obtained after stirring and reacting at 60 °C for 3 hours;
(2)制备双硫键改性聚氨酯/聚氧化乙烯复合聚合物：将重均分子量为116400的聚氧化乙烯加入双硫键改性聚氨酯溶液中，使双硫键改性聚氨酯与聚氧化乙烯之间的质量比为1:3，在60℃下搅拌反应3h后，获得双硫键改性聚氨酯/聚氧化乙烯复合聚合物溶液；(2) Preparation of disulfide bond-modified polyurethane/polyethylene oxide composite polymer: Polyethylene oxide with a weight average molecular weight of 116400 was added to the disulfide bond-modified polyurethane solution, so that the disulfide bond-modified polyurethane and polyethylene oxide were mixed. The mass ratio between the two was 1:3, and after stirring and reacting at 60 °C for 3 h, the disulfide bond-modified polyurethane/polyethylene oxide composite polymer solution was obtained;
(3)制备固态电解质：在双硫键改性聚氨酯/聚氧化乙烯复合聚合物溶液中加入锂盐，使步骤(2)中的聚氧化乙烯与步骤(3)中的锂盐之间的质量比为6.75:1，混合均匀后，倒入聚四氟乙烯板中，烘干，获得自修复聚合物固态电解质。(3) Preparation of solid electrolyte: Lithium salt is added to the disulfide bond-modified polyurethane/polyethylene oxide composite polymer solution to make the mass between the polyethylene oxide in step (2) and the lithium salt in step (3) The ratio is 6.75:1. After mixing evenly, pour it into a polytetrafluoroethylene plate and dry it to obtain a self-healing polymer solid electrolyte.
实施例7Example 7
一种基于双硫键的自修复聚合物固态电解质，包括双硫键改性聚氨酯/聚氧化乙烯复合聚合物和锂盐。所述锂盐为二氟甲基磺酰亚胺锂；所述锂盐占固态电解质总质量的10％。A self-healing polymer solid electrolyte based on disulfide bonds includes disulfide bond-modified polyurethane/polyethylene oxide composite polymer and lithium salt. The lithium salt is lithium difluoromethanesulfonimide; the lithium salt accounts for 10% of the total mass of the solid electrolyte.
一种所述固态电解质的制备方法，包括以下步骤：A preparation method of the solid electrolyte, comprising the following steps:
(1)多异氰酸酯接枝改性：在氮气氛围中，将重均分子量为3500、含有至少两个异氰酸酯 端基的聚氨酯预聚体以1g:2mL的质量体积比溶解于N,N-二甲基乙酰胺中，加入二月桂酸二丁基锡和丙烯酸羟丙酯，所述聚氨酯预聚体中的异氰酸酯端基与丙烯酸羟丙酯之间的摩尔比为1:1，二月桂酸二丁基锡在反应液中的质量分数为1wt％，在70℃下搅拌反应0.5h；再加入N,N'-亚甲基双丙烯酰胺和三(2-氨基乙基)胺，所述丙烯酸羟丙酯、N,N'-亚甲基双丙烯酰胺、三(2-氨基乙基)胺之间的摩尔比为1:5:1，继续在60℃下搅拌反应3h；而后升温至130℃，用惰性气体置换反应容器内的气体后，加入3-异氰酸丙烯和引发剂，所述丙烯酸羟丙酯、3-异氰酸丙烯、过氧化二异丙苯之间的摩尔比为1:15:1，搅拌反应2h，制得改性聚氨酯预聚体溶液；(1) Polyisocyanate graft modification: in a nitrogen atmosphere, a polyurethane prepolymer with a weight average molecular weight of 3500 and containing at least two isocyanate end groups was dissolved in N,N-dimethyl methacrylate at a mass volume ratio of 1g:2mL. In the base acetamide, dibutyltin dilaurate and hydroxypropyl acrylate are added, and the molar ratio between the isocyanate end group in the polyurethane prepolymer and the hydroxypropyl acrylate is 1:1, and the dibutyltin dilaurate is in the reaction The mass fraction in the liquid was 1wt%, and the reaction was stirred at 70°C for 0.5h; then N,N'-methylenebisacrylamide and tris(2-aminoethyl)amine were added, and the hydroxypropyl acrylate, N , The molar ratio between N'-methylenebisacrylamide and tris(2-aminoethyl)amine was 1:5:1, and the reaction was continued to stir at 60 °C for 3 h; then the temperature was raised to 130 °C, and an inert gas After replacing the gas in the reaction vessel, add 3-isocyanatopropene and an initiator, and the molar ratio between the described hydroxypropyl acrylate, 3-isocyanatopropene, and dicumyl peroxide is 1:15:1 , and the reaction was stirred for 2h to obtain the modified polyurethane prepolymer solution;
(2)制备双硫键改性聚氨酯：向改性聚氨酯预聚体溶液中加入2-羟乙基二硫化物，使改性聚氨酯预聚体中的异氰酸酯端基与2-羟乙基二硫化物中的羟基之间的摩尔比为1.2:1，在60℃下搅拌反应3h后，获得双硫键改性聚氨酯溶液；(2) Preparation of disulfide bond-modified polyurethane: adding 2-hydroxyethyl disulfide to the modified polyurethane prepolymer solution, so that the isocyanate end group in the modified polyurethane prepolymer and 2-hydroxyethyl disulfide The molar ratio between the hydroxyl groups in the product was 1.2:1, and after stirring and reacting at 60 °C for 3 h, a disulfide bond-modified polyurethane solution was obtained;
(3)制备双硫键改性聚氨酯/聚氧化乙烯复合聚合物：将重均分子量为116400的聚氧化乙烯加入双硫键改性聚氨酯溶液中，使双硫键改性聚氨酯与聚氧化乙烯之间的质量比为1:5，在60℃下搅拌反应3h后，获得双硫键改性聚氨酯/聚氧化乙烯复合聚合物溶液；(3) Preparation of disulfide bond-modified polyurethane/polyethylene oxide composite polymer: Polyethylene oxide with a weight average molecular weight of 116400 was added to the disulfide bond-modified polyurethane solution, so that the disulfide bond-modified polyurethane and polyethylene oxide were mixed. The mass ratio between the two was 1:5, and after stirring and reacting at 60 °C for 3 h, the disulfide bond-modified polyurethane/polyethylene oxide composite polymer solution was obtained;
(4)制备固态电解质：在双硫键改性聚氨酯/聚氧化乙烯复合聚合物溶液中加入锂盐，使步骤(2)中的聚氧化乙烯与步骤(3)中的锂盐之间的质量比为7.5:1，混合均匀后，倒入聚四氟乙烯板中，烘干，获得自修复聚合物固态电解质。(4) Preparation of solid electrolyte: Lithium salt is added to the disulfide bond-modified polyurethane/polyethylene oxide composite polymer solution to make the mass between the polyethylene oxide in step (2) and the lithium salt in step (3) The ratio is 7.5:1. After mixing evenly, pour it into a polytetrafluoroethylene plate and dry it to obtain a self-healing polymer solid electrolyte.
实施例8Example 8
一种基于双硫键的自修复聚合物固态电解质，包括双硫键改性聚氨酯/聚氧化乙烯复合聚合物和锂盐。所述锂盐为二氟甲基磺酰亚胺锂；所述锂盐占固态电解质总质量的10％。A self-healing polymer solid electrolyte based on disulfide bonds includes disulfide bond-modified polyurethane/polyethylene oxide composite polymer and lithium salt. The lithium salt is lithium difluoromethanesulfonimide; the lithium salt accounts for 10% of the total mass of the solid electrolyte.
一种所述固态电解质的制备方法，包括以下步骤：A preparation method of the solid electrolyte, comprising the following steps:
(1)多异氰酸酯接枝改性：在氮气氛围中，将重均分子量为3500、含有至少两个异氰酸酯端基的聚氨酯预聚体以1g:2mL的质量体积比溶解于N,N-二甲基乙酰胺中，加入二月桂酸二丁基锡和丙烯酸羟丙酯，所述聚氨酯预聚体中的异氰酸酯端基与丙烯酸羟丙酯之间的摩尔比为1:2，二月桂酸二丁基锡在反应液中的质量分数为1wt％，在60℃下搅拌反应1h；再加入N,N'-亚甲基双丙烯酰胺和三(2-氨基乙基)胺，所述丙烯酸羟丙酯、N,N'-亚甲基双丙烯酰胺、三(2-氨基乙基)胺之间的摩尔比为1:12:2，继续在70℃下搅拌反应4h；而后升温至140℃，用惰性气体置换反应容器内的气体后，加入3-异氰酸丙烯和过氧化二异丙苯，所述丙烯酸羟丙酯、3-异氰酸丙烯、过氧化二异丙苯之间的摩尔比为1:18:1.5，搅拌反应3h，制得改性聚氨酯预聚体溶液；(1) Polyisocyanate graft modification: in a nitrogen atmosphere, a polyurethane prepolymer with a weight average molecular weight of 3500 and containing at least two isocyanate end groups was dissolved in N,N-dimethyl methacrylate at a mass volume ratio of 1g:2mL. In the base acetamide, add dibutyltin dilaurate and hydroxypropyl acrylate, the molar ratio between the isocyanate end group and hydroxypropyl acrylate in the polyurethane prepolymer is 1:2, and dibutyltin dilaurate is in the reaction The mass fraction in the solution was 1 wt%, and the reaction was stirred at 60 ° C for 1 h; then N,N'-methylenebisacrylamide and tris(2-aminoethyl)amine were added, and the hydroxypropyl acrylate, N, The molar ratio between N'-methylenebisacrylamide and tris(2-aminoethyl)amine was 1:12:2, and the reaction was continued to stir at 70 °C for 4 h; then the temperature was raised to 140 °C and replaced with an inert gas After the gas in the reaction vessel, add 3-isocyanatopropene and dicumyl peroxide, and the mol ratio between described hydroxypropyl acrylate, 3-isocyanatopropene, dicumyl peroxide is 1: 18:1.5, stirring and reacting for 3h to obtain a modified polyurethane prepolymer solution;
(2)制备双硫键改性聚氨酯：向改性聚氨酯预聚体溶液中加入2-羟乙基二硫化物，使改性聚氨酯预聚体中的异氰酸酯端基与2-羟乙基二硫化物中的羟基之间的摩尔比为1.2:1，在60℃下搅拌反应3h后，获得双硫键改性聚氨酯溶液；(2) Preparation of disulfide bond-modified polyurethane: adding 2-hydroxyethyl disulfide to the modified polyurethane prepolymer solution, so that the isocyanate end group in the modified polyurethane prepolymer and 2-hydroxyethyl disulfide The molar ratio between the hydroxyl groups in the product was 1.2:1, and after stirring and reacting at 60 °C for 3 h, a disulfide bond-modified polyurethane solution was obtained;
(3)制备双硫键改性聚氨酯/聚氧化乙烯复合聚合物：将重均分子量为116400的聚氧化乙烯加入双硫键改性聚氨酯溶液中，使双硫键改性聚氨酯与聚氧化乙烯之间的质量比为1:5，在60℃下搅拌反应3h后，获得双硫键改性聚氨酯/聚氧化乙烯复合聚合物溶液；(3) Preparation of disulfide bond-modified polyurethane/polyethylene oxide composite polymer: Polyethylene oxide with a weight average molecular weight of 116400 was added to the disulfide bond-modified polyurethane solution, so that the disulfide bond-modified polyurethane and polyethylene oxide were mixed. The mass ratio between the two was 1:5, and after stirring and reacting at 60 °C for 3 h, the disulfide bond-modified polyurethane/polyethylene oxide composite polymer solution was obtained;
(4)制备固态电解质：在双硫键改性聚氨酯/聚氧化乙烯复合聚合物溶液中加入锂盐，使步骤(2)中的聚氧化乙烯与步骤(3)中的锂盐之间的质量比为7.5:1，混合均匀后，倒入聚四氟乙烯板中，烘干，获得自修复聚合物固态电解质。(4) Preparation of solid electrolyte: Lithium salt is added to the disulfide bond-modified polyurethane/polyethylene oxide composite polymer solution to make the mass between the polyethylene oxide in step (2) and the lithium salt in step (3) The ratio is 7.5:1. After mixing evenly, pour it into a polytetrafluoroethylene plate and dry it to obtain a self-healing polymer solid electrolyte.
对比例1Comparative Example 1
一种聚合物固态电解质，包括聚氧化乙烯复合聚合物和锂盐。所述锂盐为双(三氟甲基磺酰)亚胺锂；所述锂盐占固态电解质总质量的10％。A polymer solid electrolyte includes polyethylene oxide composite polymer and lithium salt. The lithium salt is lithium bis(trifluoromethylsulfonyl)imide; the lithium salt accounts for 10% of the total mass of the solid electrolyte.
一种所述固态电解质的制备方法，包括以下步骤：A preparation method of the solid electrolyte, comprising the following steps:
将重均分子量为116400的聚氧化乙烯以1g:2mL的质量体积比溶解于N,N-二甲基乙酰胺中，加入锂盐，使聚氧化乙烯与锂盐之间的质量比为9:1，混合均匀后，倒入聚四氟乙烯板中，烘干，获得聚合物固态电解质。The polyoxyethylene with a weight-average molecular weight of 116400 is dissolved in N,N-dimethylacetamide with a mass volume ratio of 1g:2mL, and a lithium salt is added, so that the mass ratio between the polyoxyethylene and the lithium salt is 9: 1. After mixing evenly, pour it into a polytetrafluoroethylene plate and dry it to obtain a polymer solid electrolyte.
对比例2Comparative Example 2
一种聚合物固态电解质，包括聚氨酯/聚氧化乙烯复合聚合物和锂盐。所述锂盐为双(三氟甲基磺酰)亚胺锂；所述锂盐占固态电解质总质量的10％。A polymer solid electrolyte includes a polyurethane/polyethylene oxide composite polymer and a lithium salt. The lithium salt is lithium bis(trifluoromethylsulfonyl)imide; the lithium salt accounts for 10% of the total mass of the solid electrolyte.
一种所述固态电解质的制备方法，包括以下步骤：A preparation method of the solid electrolyte, comprising the following steps:
(1)制备聚氨酯：在氮气氛围中，将重均分子量为3500、含有至少两个异氰酸酯端基的聚氨酯预聚体以1g:2mL的质量体积比溶解于N,N-二甲基乙酰胺中，加入二月桂酸二丁基锡，使二月桂酸二丁基锡在反应液中的质量分数为1wt％，在60℃下搅拌反应3h后，获得聚氨酯溶液；(1) Preparation of polyurethane: in a nitrogen atmosphere, a polyurethane prepolymer with a weight average molecular weight of 3500 and containing at least two isocyanate end groups was dissolved in N,N-dimethylacetamide at a mass volume ratio of 1g:2mL , adding dibutyltin dilaurate so that the mass fraction of dibutyltin dilaurate in the reaction solution is 1wt%, and after stirring and reacting at 60°C for 3h, a polyurethane solution is obtained;
(2)制备聚氨酯/聚氧化乙烯复合聚合物：将重均分子量为116400的聚氧化乙烯加入聚氨酯溶液中，使聚氨酯与聚氧化乙烯之间的质量比为1:1，在60℃下搅拌反应3h后，获得聚氨酯/聚氧化乙烯复合聚合物溶液；(2) Preparation of polyurethane/polyethylene oxide composite polymer: Polyethylene oxide with a weight average molecular weight of 116400 was added to the polyurethane solution, so that the mass ratio between polyurethane and polyethylene oxide was 1:1, and the reaction was stirred at 60 °C After 3h, a polyurethane/polyethylene oxide composite polymer solution was obtained;
(3)制备固态电解质：在聚氨酯/聚氧化乙烯复合聚合物溶液中加入锂盐，使步骤(2)中的聚氧化乙烯与步骤(3)中的锂盐之间的质量比为4.5:1，混合均匀后，倒入聚四氟乙烯板中，烘干，获得聚合物固态电解质。(3) Preparation of solid electrolyte: Lithium salt is added to the polyurethane/polyethylene oxide composite polymer solution, so that the mass ratio between the polyethylene oxide in step (2) and the lithium salt in step (3) is 4.5:1 , after mixing evenly, poured into a polytetrafluoroethylene plate and dried to obtain a polymer solid electrolyte.
测试例test case
对实施例1～8和对比例1～2制得的聚合物固态电解质进行性能测试，测试方法如下：The performance of the polymer solid electrolytes prepared in Examples 1-8 and Comparative Examples 1-2 was tested, and the test method was as follows:
(1)机械强度：将固态电解质膜制备成宽度为15mm的试样，在室温下，置于万能测试机夹具上，以100mm/s速度进行拉伸，即可得到拉伸强度；(1) Mechanical strength: The solid electrolyte membrane is prepared into a sample with a width of 15mm, placed on the fixture of the universal testing machine at room temperature, and stretched at a speed of 100mm/s to obtain the tensile strength;
(2)室温离子导电率：将固态电解质膜冲成圆片，与不锈钢组装成对电极，频率范围为10 6～1Hz，振幅为10Mv，测试样品离子导电率； (2) Room temperature ionic conductivity: The solid electrolyte membrane is punched into a disc, and assembled with stainless steel to form a counter electrode, the frequency range is 10 6 ～ 1 Hz, the amplitude is 10 Mv, and the ionic conductivity of the sample is tested;
(3)自修复能力：在室温下将固态电解质膜裁切成长为50cm、宽为5cm的长方形状试样，用洁净的剪刀从试样中间剪成两部分，将两块长方形试样反向且错位拼接，人工拼压1min，然后放入70℃烘箱进行自修复，观测自修复所需要的时间。(3) Self-healing ability: Cut the solid electrolyte membrane into a rectangular sample with a length of 50 cm and a width of 5 cm at room temperature, cut it into two parts from the middle of the sample with clean scissors, and reverse the two rectangular samples And dislocation splicing, manual splicing and pressing for 1 min, and then put into a 70 ° C oven for self-repair, and observe the time required for self-repair.
测试结果见表1。The test results are shown in Table 1.
表1Table 1
Figure PCTCN2021105917-appb-000005
Figure PCTCN2021105917-appb-000005
根据表1可获得以下结论：According to Table 1, the following conclusions can be obtained:
(1)相较于对比例2(聚氨酯未采用双硫键改性)而言，实施例1的电解质自修复能力较好，说明在聚氨酯中引入双硫键后，能赋予聚合物固态电解质较好的自修复能力。原因在于：双硫键是一种可逆动态共价键，其断裂后可进行自修复。(1) Compared with Comparative Example 2 (polyurethane is not modified with disulfide bonds), the electrolyte of Example 1 has better self-healing ability, which shows that the introduction of disulfide bonds in polyurethane can give the polymer solid electrolyte a better performance. Good self-healing ability. The reason is that the disulfide bond is a reversible dynamic covalent bond that can self-repair after being broken.
(2)相较于对比例1(未使用双硫键改性聚氨酯)而言，实施例1的电解质具有较高的拉伸强度、室温离子导电率和自修复能力，说明本发明的方法能在赋予聚合物固态电解质自修复能力的同时，还能有效提高其机械强度和离子导电性。原因在于：聚氨酯能通过共价键和氢键与聚氧化乙烯形成交联网络，同时，聚氨酯中存在软段和硬段，这些都有助于提高电解质的机械强度和离子导电性。(2) Compared with Comparative Example 1 (without using disulfide bond-modified polyurethane), the electrolyte of Example 1 has higher tensile strength, room temperature ionic conductivity and self-healing ability, indicating that the method of the present invention can While endowing the polymer solid electrolyte with self-healing ability, it can also effectively improve its mechanical strength and ionic conductivity. The reason is that polyurethane can form a cross-linked network with polyethylene oxide through covalent bonds and hydrogen bonds, and at the same time, there are soft segments and hard segments in polyurethane, which help to improve the mechanical strength and ionic conductivity of the electrolyte.
(3)相较于实施例3而言，实施例7和8的电解质自修复所需的时间较短，说明对聚氨酯预聚体进行多异腈酸酯接枝改性后，能有效提高聚合物固态电解质的自修复能力。原 因在于：通过增加聚氨酯预聚体中的异腈酸酯端基含量，能引入更多的双硫键。(3) Compared with Example 3, the electrolyte self-repairing time of Examples 7 and 8 is shorter, indicating that the polyisocyanate graft modification of the polyurethane prepolymer can effectively improve the polymerization The self-healing ability of solid-state electrolytes. The reason is that by increasing the isocyanate end group content in the polyurethane prepolymer, more disulfide bonds can be introduced.
本发明中所用原料、设备，若无特别说明，均为本领域的常用原料、设备；本发明中所用方法，若无特别说明，均为本领域的常规方法。The raw materials and equipment used in the present invention, unless otherwise specified, are the common raw materials and equipment in the art; the methods used in the present invention, unless otherwise specified, are the conventional methods in the art.
以上所述，仅是本发明的较佳实施例，并非对本发明作任何限制，凡是根据本发明技术实质对以上实施例所作的任何简单修改、变更以及等效变换，均仍属于本发明技术方案的保护范围。The above are only preferred embodiments of the present invention and do not limit the present invention. Any simple modifications, changes and equivalent transformations made to the above embodiments according to the technical essence of the present invention still belong to the technical solutions of the present invention. scope of protection.

Claims (10)

  1. 一种基于双硫键的自修复聚合物固态电解质，其特征在于，包括双硫键改性聚氨酯/聚氧化乙烯复合聚合物和锂盐；所述双硫键改性聚氨酯由双硫键单体与聚氨酯预聚体聚合而得；所述聚氨酯预聚体中含有至少两个异氰酸酯端基；所述双硫键单体中含有至少一个双硫键且羟基和氨基的总数量至少为两个。A self-healing polymer solid electrolyte based on disulfide bonds, characterized in that it comprises a disulfide bond-modified polyurethane/polyethylene oxide composite polymer and a lithium salt; the disulfide bond-modified polyurethane is composed of disulfide bond monomers It is obtained by polymerizing with a polyurethane prepolymer; the polyurethane prepolymer contains at least two isocyanate end groups; the disulfide bond monomer contains at least one disulfide bond and the total number of hydroxyl and amino groups is at least two.
  2. 如权利要求1所述的固态电解质，其特征在于，所述双硫键单体的结构式如下：The solid electrolyte of claim 1, wherein the structural formula of the disulfide monomer is as follows:
    Figure PCTCN2021105917-appb-100001
    Figure PCTCN2021105917-appb-100001
    其中，R和R′独立地选自
    Figure PCTCN2021105917-appb-100002
    wherein R and R' are independently selected from
    Figure PCTCN2021105917-appb-100002
  3. 如权利要求1所述的固态电解质，，其特征在于，所述双硫键改性聚氨酯与聚氧化乙烯的质量比为1:1～10。The solid electrolyte according to claim 1, wherein the mass ratio of the disulfide bond-modified polyurethane to polyethylene oxide is 1:1-10.
  4. 如权利要求1或3所述的制备方法，其特征在于：preparation method as claimed in claim 1 or 3, is characterized in that:
    所述聚氨酯预聚体的分子量为500～5000；和/或The molecular weight of the polyurethane prepolymer is 500-5000; and/or
    所述聚氧化乙烯的分子量为50000～200000。The molecular weight of the polyethylene oxide is 50,000-200,000.
  5. 如权利要求1所述的固态电解质，其特征在于，所述锂盐为双(三氟甲基磺酰)亚胺锂、二氟甲基磺酰亚胺锂和高氯酸锂中的一种或多种。The solid-state electrolyte according to claim 1, wherein the lithium salt is one of lithium bis(trifluoromethylsulfonyl)imide, lithium difluoromethylsulfonimide and lithium perchlorate or more.
  6. 如权利要求1或5所述的固态电解质，其特征在于，所述锂盐占固态电解质总质量的1～10％。The solid electrolyte according to claim 1 or 5, wherein the lithium salt accounts for 1-10% of the total mass of the solid electrolyte.
  7. 一种如权利要求1-6之一所述固态电解质的制备方法，其特征在于，包括以下步骤：A method for preparing a solid electrolyte as claimed in one of claims 1-6, characterized in that, comprising the following steps:
    (1)制备双硫键改性聚氨酯：在惰性气体氛围中，将聚氨酯预聚体溶解于有机溶剂中，加入双硫键单体和催化剂，在50～90℃下搅拌反应2～5h，获得双硫键改性聚氨酯溶液；(1) Preparation of disulfide bond-modified polyurethane: in an inert gas atmosphere, dissolve the polyurethane prepolymer in an organic solvent, add a disulfide bond monomer and a catalyst, and stir and react at 50 to 90 ° C for 2 to 5 hours to obtain Disulfide bond modified polyurethane solution;
    (2)制备双硫键改性聚氨酯/聚氧化乙烯复合聚合物：将聚氧化乙烯加入双硫键改性聚氨酯溶液中，在50～90℃下搅拌反应2～5h，获得双硫键改性聚氨酯/聚氧化乙烯复合聚合物溶液；(2) Preparation of disulfide bond-modified polyurethane/polyethylene oxide composite polymer: adding polyethylene oxide to the disulfide bond-modified polyurethane solution, stirring and reacting at 50-90 °C for 2-5 h to obtain disulfide-modified polyurethane Polyurethane/polyethylene oxide composite polymer solution;
    (3)制备固态电解质：在双硫键改性聚氨酯/聚氧化乙烯复合聚合物溶液中加入锂盐，混合均匀并干燥处理后，获得自修复聚合物固态电解质。(3) Preparation of solid electrolyte: Lithium salt is added to the disulfide bond-modified polyurethane/polyethylene oxide composite polymer solution, mixed uniformly and dried to obtain a self-healing polymer solid electrolyte.
  8. 如权利要求7所述的制备方法，其特征在于，步骤(1)中，将聚氨酯预聚体溶解于有机溶剂中，加入催化剂后，先对聚氨酯预聚体进行多异氰酸酯接枝改性，再加入双硫键单体；所述多异氰酸酯接枝改性的具体方法如下：加入丙烯酸羟丙酯，在60～70℃下搅拌反应0.5～1h；再加入摩尔比为5～6:1的N,N'-亚甲基双丙烯酰胺和三(2-氨基乙基)胺，继续在60～70℃下搅拌反应3～4h；而后升温至130～140℃，用惰性气体置换反应容器内的气体后，加入3-异氰酸丙 烯和引发剂，搅拌反应2～3h，制得改性聚氨酯预聚体溶液。The preparation method according to claim 7, wherein in step (1), the polyurethane prepolymer is dissolved in an organic solvent, and after adding the catalyst, the polyurethane prepolymer is first subjected to polyisocyanate graft modification, and then Add disulfide bond monomer; the specific method for graft modification of polyisocyanate is as follows: add hydroxypropyl acrylate, stir and react at 60～70°C for 0.5～1h; then add N with a molar ratio of 5～6:1 , N'-methylenebisacrylamide and tris(2-aminoethyl)amine, continue to stir and react at 60～70℃ for 3～4h; then heat up to 130～140℃, replace the inert gas in the reaction vessel After the gas, 3-isocyanatopropene and an initiator are added, and the reaction is stirred for 2-3 hours to obtain a modified polyurethane prepolymer solution.
  9. 如权利要求8所述的制备方法，其特征在于，所述聚氨酯预聚体中的异氰酸酯端基与丙烯酸羟丙酯之间的摩尔比为1:1～2；所述丙烯酸羟丙酯与三(2-氨基乙基)胺之间的摩尔比为1:1～2；所述丙烯酸羟丙酯与3-异氰酸丙烯之间的摩尔比为1:15～18。The preparation method according to claim 8, wherein the molar ratio between the isocyanate end group and the hydroxypropyl acrylate in the polyurethane prepolymer is 1:1 to 2; The molar ratio between the (2-aminoethyl)amines is 1:1-2; the molar ratio between the hydroxypropyl acrylate and 3-isocyanatopropene is 1:15-18.
  10. 如权利要求7-9之一所述的制备方法，其特征在于，步骤(1)中，聚氨酯预聚体或多异氰酸酯接枝改性所得的聚氨酯预聚体中的异氰酸酯端基与双硫键单体中氨基和羧基总数量的摩尔比为1～1.5:1。The preparation method according to any one of claims 7-9, wherein in step (1), the isocyanate end group and the disulfide bond in the polyurethane prepolymer or the polyurethane prepolymer obtained by polyisocyanate graft modification The molar ratio of the total number of amino groups and carboxyl groups in the monomer is 1-1.5:1.
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