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CN-122025524-A - Preparation method of zinc negative electrode of in-situ coupled hydrogel electrolyte and application of zinc negative electrode in zinc battery

CN122025524ACN 122025524 ACN122025524 ACN 122025524ACN-122025524-A

Abstract

The invention discloses a preparation method of a zinc negative electrode of an in-situ coupled hydrogel electrolyte and application of the zinc negative electrode to a zinc battery, comprising the following steps of 1) placing the zinc negative electrode in a coupling agent solution, soaking for 0.5-5 h at 30-50 ℃, forming a chelate layer linked with coordination bonds on the surface of the zinc negative electrode, and 2) placing the zinc negative electrode subjected to chelate modification in the step 1) in a hydrogel precursor solution for reaction to obtain the zinc negative electrode of the hydrogel electrolyte which is in-situ coupled on the surface through covalent bonds. The invention adopts the coupling agent with both polar functional groups (chelate with metal zinc through coordination bonds) and active functional groups (coupled with hydrogel electrolyte through covalent bonds), and constructs rich hydrogen bond networks in the hydrogel electrolyte through reasonable formulation design, thereby forming a coordinated structure of coordination bonds, covalent bonds and hydrogen bonds and reducing interface resistance between zinc cathodes and electrolytes.

Inventors

  • HU JI
  • WANG WANHUI
  • YAN HONGCHAO
  • Qi Ruohan
  • MA HAORAN
  • LIU ZIHAN

Assignees

  • 洛阳理工学院

Dates

Publication Date
20260512
Application Date
20260408

Claims (9)

  1. 1. The preparation method of the zinc cathode of the in-situ coupled hydrogel electrolyte is characterized by comprising the following steps of: 1) The preparation method comprises the steps of placing a zinc anode in a coupling agent solution, soaking for 0.5-5 h at 30-50 ℃, taking out, and drying to form a chelate layer linked with coordination bonds on the surface of the zinc anode, wherein the coupling agent solution is prepared from a coupling agent with a polar functional group and an active functional group and a dissolving solvent of the coupling agent, the polar functional group of the coupling agent is amino, hydroxyl or mercaptan, and the active functional group of the coupling agent is alkene, alkyne, mercaptan or epoxy group; 2) And (3) placing the zinc cathode subjected to chelate modification in the step (1) into a hydrogel precursor solution for reaction to obtain the zinc cathode of which the surface is in-situ coupled with the hydrogel electrolyte through a covalent bond.
  2. 2. The preparation method of the zinc cathode of the in-situ coupled hydrogel electrolyte according to claim 1, wherein the coupling agent is 4-ethynylaniline, hydroxyethyl methacrylate, N- (2-hydroxyethyl) acrylamide, 3-butyn-1-ol, glycidol, propylene mercaptan, pentaerythritol tetrakis (3-mercaptopropionic acid), 3, 6-dioxa-1, 8-octanedithiol or ethylene glycol bis (mercaptoacetic acid), the molar ratio of the coupling agent to the coupling agent is 1:1-10, the hydrogel precursor solution is composed of a monomer solution, a zinc salt and an initiator, the monomer solution is prepared from a hydrogel monomer, a main solvent for dissolving the monomer and a cosolvent for dissolving the monomer according to the molar ratio of 1:5-20:0.5-2, and the molar concentration of the zinc salt in the monomer solution is 0.4-4 mol.L –1 .
  3. 3. The preparation method of the zinc cathode of the in-situ coupled hydrogel electrolyte according to claim 2, wherein when the coupling agent is 4-ethynylaniline, hydroxyethyl methacrylate, N- (2-hydroxyethyl) acrylamide, 3-butyn-1-ol, glycidol or propylene mercaptan, the hydrogel monomer is a mixture of a mercaptan monomer and an alkene monomer, the molar ratio of the mercaptan monomer to the alkene monomer is (2-5) to 1, and when the coupling agent is pentaerythritol tetra (3-mercaptopropionate), 3, 6-dioxa-1, 8-octanedithiol or ethylene glycol bis (mercaptoacetate), the hydrogel monomer is an alkene monomer, an alkyne monomer or an epoxy monomer.
  4. 4. The method for preparing the zinc anode of the in-situ coupled hydrogel electrolyte according to claim 3, wherein the mercaptan monomer is trimethylolpropane tri (3-mercaptopropionic acid) ester, 3, 6-dioxa-1, 8-octanedithiol, 4 '-bis (mercaptomethyl) biphenyl or bis (mercaptoacetic acid) glycol ester, the alkene monomer is polyethylene glycol diacrylate, 1, 6-divinyl perfluorohexane, N' -methylenebisacrylamide or pentaerythritol triacrylate, the alkyne monomer is dialkynyl polyethylene glycol or 1, 7-octanedione, and the epoxy monomer is polyethylene glycol diglycidyl ether or bisphenol A diglycidyl ether.
  5. 5. The method for preparing the zinc anode of the in-situ coupled hydrogel electrolyte according to claim 4, wherein the zinc salt is one of ZnSO 4 、ZnCl 2 、Zn（OTf） 2 、Zn（ClO 4 ） 2 、Zn（BF 4 ） 2 , the dissolution solvent of the coupling agent is one of acetonitrile, acetone, ethanol and N, N-dimethylformamide, the dissolution main solvent of the monomer is water, the dissolution cosolvent of the monomer is one of ethanol and acetone, when the hydrogel monomer is a mercaptan monomer, an alkene monomer or an alkyne monomer, the initiator is a thermal initiator or a photoinitiator, the molar ratio of the initiator to the hydrogel monomer is (0.1-2) to 100, when the hydrogel monomer is an epoxy monomer, the initiator is a base catalyst, and the molar ratio of the base catalyst to the epoxy monomer is (0.5-5) to 100.
  6. 6. The method for preparing a zinc anode for in-situ coupling a hydrogel electrolyte according to claim 5, wherein the thermal initiator is azobisisobutyronitrile, benzoyl peroxide or tert-butyl peroxybenzoate, the photoinitiator is propiophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl propiophenone or isooctyl p-dimethylaminobenzoate, and the base catalyst is 1-methylimidazole, trialkylamine or diazabicyclo [4.3.0] non-5-ene.
  7. 7. The method for preparing the zinc anode of the in-situ coupled hydrogel electrolyte according to claim 6, wherein in the step 2), an initiator in a hydrogel precursor solution is a thermal initiator, the reaction condition is that the temperature is 40-70 ℃, the time is 0.5-8 h, the initiator in the hydrogel precursor solution is a photoinitiator, the reaction condition is that the time is 5 min-2 h, and when a hydrogel monomer in the hydrogel precursor solution is an epoxy monomer, the reaction is driven by a base catalyst, and the reaction condition is that the temperature is 40-70 ℃ and the time is 0.5-8 h.
  8. 8. Use of a zinc anode produced by the production method of any one of claims 1 to 7 in a zinc cell.
  9. 9. The use of claim 8, wherein the zinc cell comprises a positive electrode sheet and a zinc negative electrode of an in-situ coupled hydrogel electrolyte, and the zinc negative electrode of the in-situ coupled hydrogel electrolyte is assembled and packaged with the positive electrode sheet to obtain the component-interface-device integrated zinc cell.

Description

Preparation method of zinc negative electrode of in-situ coupled hydrogel electrolyte and application of zinc negative electrode in zinc battery Technical Field The invention belongs to the technical field of batteries, and particularly relates to a preparation method of a zinc negative electrode of an in-situ coupled hydrogel electrolyte and application of the zinc negative electrode in a zinc battery. Background Based on the strategic requirement of the new energy system for advanced safety, reliability and sustainable depth evolution, the bottleneck of the existing energy storage technology in aspects of resource constraint, safety risk, environmental influence and the like is urgently needed to be broken through. The problems of high external dependency, outstanding thermal runaway hidden trouble and the like of lithium resources are solved, and urgent requirements of a large-scale renewable energy grid connection, long-time energy storage at the power grid side and an intrinsically safe energy storage device of a distributed energy system are difficult to meet. Under the background, the water-based zinc battery is listed as the important development direction of the novel energy storage technology of the state by virtue of the advantages of abundant zinc resources, low cost, no explosion risk and the like. However, the traditional water-based liquid electrolytic solution system has the key problems of uncontrollable zinc dendrite, serious hydrogen evolution corrosion, short cycle life and the like, and severely restricts the application of the traditional water-based liquid electrolytic solution to Anshi engineering. The hydrogel electrolyte is used as a quasi-solid ion conductor, effectively limits free water molecules through a three-dimensional cross-linked network structure, remarkably inhibits side reactions, can directionally regulate and control a Zn 2+ solvation structure, realizes compact and dendrite-free Zn 2+ deposition, and greatly improves the cycling stability of the battery. However, in the prior art, the hydrogel electrolyte and the zinc cathode are often simply assembled in a physical stacking manner, so that the interface impedance is large, a stable interface state of the zinc battery cannot be obtained, and the contradiction between the ionic conductivity and the mechanical property in the hydrogel electrolyte is difficult to be considered. Disclosure of Invention In view of the above problems, it is an object of the present invention to provide a method for preparing a zinc anode with in-situ coupled hydrogel electrolyte, and at the same time, to provide an application of the zinc anode prepared by the preparation method to a zinc battery. Based on the above purpose, the invention adopts the following technical scheme: the preparation method of the zinc cathode of the in-situ coupled hydrogel electrolyte comprises the following steps: 1) Placing a zinc anode in a coupling agent solution, soaking for 0.5-5 h at 30-50 ℃, taking out, drying for 4-8 h at 40-60 ℃ to form a chelate layer linked by coordination bonds on the surface of the zinc anode, wherein the coupling agent solution is prepared from a coupling agent with a polar functional group and an active functional group and a solvent of the coupling agent, the polar functional group of the coupling agent is amino, hydroxyl or thiol, and the active functional group of the coupling agent is alkene, alkyne, thiol or epoxy; 2) And (3) placing the zinc cathode subjected to chelate modification in the step (1) into a hydrogel precursor solution for reaction to obtain the zinc cathode of which the surface is in-situ coupled with the hydrogel electrolyte through a covalent bond. The coupling agent is 4-ethynylaniline, hydroxyethyl methacrylate, N- (2-hydroxyethyl) acrylamide, 3-butine-1-alcohol, glycidol, propylene mercaptan, pentaerythritol tetra (3-mercaptopropionic acid), 3, 6-dioxa-1, 8-octanedithiol or ethylene glycol bis (mercaptoacetic acid), the mol ratio of the coupling agent to the coupling agent is 1:1-10, the hydrogel precursor solution consists of a monomer solution, zinc salt and an initiator, wherein the monomer solution is prepared from a hydrogel monomer, a main solvent for dissolving the monomer and a cosolvent for dissolving the monomer according to the mol ratio of 1:5-20:0.5-2, and the mol concentration of the zinc salt in the monomer solution is 0.4-4 mol.L –1. The coupling agent is 4-ethynylaniline (CAS 14235-81-5, the click reaction type between the coupling agent and the monomer is thiol-alkyne), hydroxyethyl methacrylate (CAS 868-77-9, the click reaction type between the coupling agent and the monomer is thiol-alkene), N- (2-hydroxyethyl) acrylamide (CAS 7646-67-5, the click reaction type between the coupling agent and the monomer is thiol-alkene), 3-butyn-1-ol (CAS 927-74-2, the click reaction type between the coupling agent and the monomer is thiol-alkyne), glycidol (CAS 556-52-5, the click reaction type betw