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CN-121975139-A - Anionic coordination polymer electrolyte, preparation method and application thereof, and secondary battery

CN121975139ACN 121975139 ACN121975139 ACN 121975139ACN-121975139-A

Abstract

The invention provides an anionic coordination polymer electrolyte, a preparation method and application thereof, and a secondary battery, belonging to the technical field of secondary batteries. The invention mixes the metal precursor, the organic ligand, the functional molecule and the lithium source into the solvent to carry out solvothermal synthesis reaction, thus obtaining the short-range ordered and long-range disordered anion coordination polymer electrolyte. The method provided by the invention is simple and rapid, has universality, is favorable for modifying different functional molecules, and can be used for grafting the anionic groups of various functional molecules to the metal clusters through covalent bonds by adopting a one-pot method, so that the single-ion conductivity behavior is promoted, the migration number of cations is increased, and the polarization phenomenon of the battery is weakened.

Inventors

  • WU HAOBIN
  • TIAN YUZHU
  • Xiu Mingzhen

Assignees

  • 浙江大学温州研究院
  • 浙江大学

Dates

Publication Date
20260505
Application Date
20260303

Claims (10)

  1. 1. A method for preparing an anionic coordination polymer electrolyte, which is characterized by comprising the following steps: mixing a metal precursor, an organic ligand, a functional molecule, a lithium source and a solvent, and performing solvothermal reaction to obtain an anionic coordination polymer electrolyte; The organic ligand comprises one or more of terephthalic acid, 2, 5-furandicarboxylic acid, 2, 6-naphthalene dicarboxylic acid, trimesic acid, 1,3, 5-tris (4-carboxyphenyl) benzene and 9, 10-anthracene dicarboxylic acid; The structural general formula of the functional molecule is H 2 PO 3 -R 1 、N≡C-S、R 2 -COOH、H 2 PO 3 -R 3 -COOH、SO 3 -R 4 -COOH、S-R 5 -COOH or S-R 6 -SO 3 H, wherein R 1 ~R 6 is independently alkyl, substituted alkyl or fluoro.
  2. 2. The method of claim 1, wherein the metal element in the metal precursor comprises one or more of aluminum, iron, zirconium, zinc, titanium, hafnium, chromium, cobalt, nickel, copper.
  3. 3. The method according to claim 1, wherein the substituted alkyl is independently fluoro substituted alkyl or amino substituted alkyl, and the molar ratio of the metal precursor, the organic ligand and the functional molecule is (1-2): 1 (0.5-2).
  4. 4. The preparation method of claim 1, wherein the lithium source comprises lithium hydroxide or lithium acetate, the molar ratio of the lithium source to the functional molecule is (1-3): 1, the solvent comprises one or more of water, ethanol and N, N-dimethylformamide, and the solvothermal reaction temperature is 80-120 ℃ and the solvothermal reaction time is 30 min-48 h.
  5. 5. The anionic coordination polymer electrolyte prepared by the preparation method according to any one of claims 1 to 4.
  6. 6. The use of the anionic coordination polymer electrolyte according to claim 5 in secondary batteries.
  7. 7. A secondary battery comprising a positive electrode, a negative electrode, and an electrolyte membrane disposed between the positive electrode and the negative electrode, the electrolyte membrane being made of the anionic coordination polymer electrolyte according to claim 5; the type of transport ions of the secondary battery is lithium ions.
  8. 8. The secondary battery according to claim 7, wherein the method of manufacturing the electrolyte membrane comprises: The method for producing an electrolyte membrane comprising mixing the anionic coordination polymer electrolyte according to claim 5 with an organic binder and an organic solvent, coating the resulting slurry, and drying.
  9. 9. The secondary battery according to claim 8, wherein the mass ratio of the anionic coordination polymer electrolyte to the organic binder is (30-90): 10-70; The organic binder comprises one or more of polyvinylidene fluoride, polymethyl methacrylate, polytetrafluoroethylene, polyvinylidene fluoride-hexafluoropropylene, polyacrylonitrile, polyimide, polyethylene glycol, polyethylene oxide, polydopamine, polyvinyl alcohol, polyacrylic acid, lithium polyacrylate, polyvinylpyrrolidone, polylactic acid, sodium alginate, poly (p-styrenesulfonic acid), polybenzimidazole, lithium poly (p-styrenesulfonate) and gelatin.
  10. 10. The secondary battery according to claim 8 or 9, wherein the electrolyte membrane is a self-supporting electrolyte membrane or an electrolyte membrane coated on a base separator; The substrate diaphragm comprises a polyethylene film, a polypropylene film, a glass fiber film, a non-woven fabric or an alumina coating polyolefin film, and the thickness of the electrolyte film is 5-100 mu m.

Description

Anionic coordination polymer electrolyte, preparation method and application thereof, and secondary battery Technical Field The invention relates to the technical field of secondary batteries, in particular to an anionic coordination polymer electrolyte, a preparation method and application thereof, and a secondary battery. Background With the development of scientific technology, battery energy is widely applied to the fields of electronic products, new energy automobiles, intermittent renewable energy sources (such as wind energy and solar energy) and the like. For lithium metal batteries with high energy density and safety, it is very important to develop solid electrolytes with high ionic conductivity, high (electrochemical) stability and good manufacturability. Currently, most of the developed solid electrolytes fall into one of three categories, inorganic electrolytes, polyelectrolyte and polymer-inorganic composite electrolytes. Inorganic electrolytes based on oxides exhibit higher mechanical strength and ionic conductivity but poor interfacial contact and processing difficulties, polymer electrolytes are easier to process and have good interfacial compatibility but their ionic conductivity is often insufficient to accommodate normal temperature battery operation, composite electrolytes appear to inherit the advantages of both components, and challenges remain in mechanism understanding and microstructure optimization. In this regard, the development of solid state electrolytes based on novel design principles will bring new opportunities for achieving high energy and safe batteries. In recent years, metal Organic Frameworks (MOFs) have become an emerging platform for the development of solid and quasi-solid electrolytes as porous crystalline materials. The liquid component may be confined in the nanopores of the framework while retaining its solid-like mechanical properties, forming a so-called "quasi-solid" system. These porous framework materials with open pore channels can accommodate lithium salts and organic solvents and exhibit acceptable ionic conductivity, however, more organic solvents inevitably present a safety risk. Although there have been many studies to improve lithium ion transfer by modification of the framework, the means of modification are limited, essentially limited to modification of the ligand functional groups, and sufficient organic solvents are necessary to maintain a local liquid environment to achieve high ionic conductivity, and safety is not high enough. Disclosure of Invention The invention aims to provide an anionic coordination polymer electrolyte, a preparation method and application thereof, and a secondary battery, wherein the anionic coordination polymer electrolyte belongs to a quasi-solid electrolyte, and has high ionic conductivity and high safety under the condition of less solvent quantity. In order to achieve the above object, the present invention provides the following technical solutions: The invention provides a preparation method of an anionic coordination polymer electrolyte, which comprises the following steps: mixing a metal precursor, an organic ligand, a functional molecule, a lithium source and a solvent, and performing solvothermal reaction to obtain an anionic coordination polymer electrolyte; The organic ligand comprises one or more of terephthalic acid, 2, 5-furandicarboxylic acid, 2, 6-naphthalene dicarboxylic acid, trimesic acid, 1,3, 5-tris (4-carboxyphenyl) benzene and 9, 10-anthracene dicarboxylic acid; The structural general formula of the functional molecule is H2PO3-R1、N≡C-S、R2-COOH、H2PO3-R3-COOH、SO3-R4-COOH、S-R5-COOH or S-R 6-SO3 H, wherein R 1~R6 is independently alkyl, substituted alkyl or fluoro. Preferably, the metal element in the metal precursor comprises one or more of aluminum, iron, zirconium, zinc, titanium, hafnium, chromium, cobalt, nickel and copper. Preferably, the substituted alkyl is independently fluoro substituted alkyl or amino substituted alkyl, and the molar ratio of the metal precursor, the organic ligand and the functional molecule is (1-2): 1 (0.5-2). Preferably, the lithium source comprises lithium hydroxide or lithium acetate, the molar ratio of the lithium source to the functional molecule is (1-3): 1, the solvent comprises one or more of water, ethanol and N, N-dimethylformamide, the temperature of the solvothermal reaction is 80-120 ℃ and the time is 30 min-48 h. The invention provides the anionic coordination polymer electrolyte prepared by the preparation method. The invention provides application of the anionic coordination polymer electrolyte in a secondary battery. The invention provides a secondary battery, which comprises a positive electrode, a negative electrode and an electrolyte membrane arranged between the positive electrode and the negative electrode, wherein the electrolyte membrane is prepared from the anionic coordination polymer electrolyte according to the technical scheme; the type of