CN-122025864-A - Water-based zinc ion battery and preparation method thereof

CN122025864ACN 122025864 ACN122025864 ACN 122025864ACN-122025864-A

Abstract

The application provides a water-based zinc ion battery and a preparation method thereof, and belongs to the technical field of energy storage systems. The electrolyte comprises a positive electrode, a negative electrode, electrolyte and a diaphragm, wherein the active material of the positive electrode is a cyclic azo organic compound, the active material of the negative electrode is a zinc-based material, and the electrolyte is a water-based electrolyte containing zinc salt. According to the application, the azo organic compound with the annular conjugated structure is introduced as the positive electrode active material, so that the dissolution of the organic positive electrode in the aqueous electrolyte is effectively inhibited, the reversibility of the zinc ion intercalation/deintercalation reaction is improved, and the cycle stability and the rate capability of the aqueous zinc ion battery are obviously improved.

Inventors

ZHANG KAI
SHEN YONGMIAO
ZHAO FUGANG
JIANG SHANGXU
LI WENBIAO

Assignees

浙江理工大学嵊州创新研究院有限公司
绍兴绿泽新能源科技发展有限责任公司

Dates

Publication Date: 20260512
Application Date: 20260410

Claims (10)

1. A water-based zinc ion battery comprises a positive electrode, a negative electrode, electrolyte and a diaphragm, and is characterized in that an active material of the positive electrode is a cyclic azo organic compound with a cyclic conjugated structure, an active material of the negative electrode is a zinc-based material, and the electrolyte is a water-based electrolyte containing zinc salt.
2. The aqueous zinc ion battery according to claim 1, wherein the cyclic azo-based organic compound is a cyclic azobenzene compound.
3. The aqueous zinc ion battery according to claim 2, wherein the cyclic azobenzene compound is obtained by introducing an azo group into a benzene ring to obtain a diaminodiazo precursor, and subjecting the diaminodiazo precursor to a molecular cyclization reaction to form the azobenzene compound having a cyclic structure.
4. The aqueous zinc-ion battery according to claim 1, wherein the zinc-based material is zinc metal plate/foil/powder, porous zinc electrode or zinc alloy.
5. The aqueous zinc ion battery according to claim 1, wherein the zinc salt is at least one of zinc sulfate, zinc perchlorate, zinc acetate, zinc tetrafluoroborate, zinc fluoride, zinc chloride, zinc bromide, zinc iodide, zinc trifluoromethane sulfonate, and zinc bis (trifluoromethane sulfonyl imide).
6. The aqueous zinc-ion battery according to claim 1, wherein the zinc salt concentration is 1-5 mmol/L.
7. The aqueous zinc-ion battery according to claim 1, wherein the separator is a hydrophilic dendrite preventing composite battery separator.
8. A method for preparing the aqueous zinc ion battery according to claim 1, which is characterized by comprising the following steps: Firstly, mixing a cyclic azo organic compound with a conductive material and a binder, adding nitrogen methyl pyrrolidone, dissolving and grinding to prepare positive electrode slurry, coating the positive electrode slurry on the surface of graphite paper, paving, drying and cutting to obtain a positive electrode plate; And secondly, taking the positive plate as a positive electrode, and combining a negative electrode, a diaphragm and electrolyte to assemble the water-based zinc ion battery.
9. The method for preparing a water-based zinc ion battery according to claim 8, wherein the mass ratio of the cyclic azo organic compound to the conductive material to the binder is 3:6:1.
10. The method of claim 8, wherein the conductive material is carbon black or carbon nanotubes, and the binder is polyvinylidene fluoride or PTFE emulsion.

Description

Water-based zinc ion battery and preparation method thereof Technical Field The application relates to a water system zinc ion battery and a preparation method thereof, and belongs to the technical field of energy storage systems. Background The water-based zinc ion battery is a novel electrochemical energy storage technology and is generally composed of key parts such as a zinc metal anode, a zinc metal cathode, an electrolyte, a diaphragm and the like. The core working principle of the method can be simply summarized as that zinc metal generates reversible deposition/stripping reaction on the negative electrode side, and active substances and zinc ions generate reversible intercalation/deintercalation or coordination reaction on the positive electrode side, so that the mutual conversion of electric energy and chemical energy is realized. Therefore, the zinc ion battery has the advantages of high theoretical capacity, high safety of the water-based electrolyte, abundant sources of raw materials and the like, but the traditional water-based zinc ion battery still has a plurality of defects in aspects of positive electrode materials, electrolyte composition, interface stability and the like, and the further improvement of the electrochemical performance and the expansion of the application range of the traditional water-based zinc ion battery are limited. Therefore, it is of great importance to develop a water-based zinc ion battery with high stability, long cycle life and controllable cost. Disclosure of Invention In view of the above, the present application firstly provides a water-based zinc ion battery, in which an azo organic compound having a cyclic conjugated structure is introduced as a positive electrode active material, so as to effectively inhibit the dissolution of an organic positive electrode in a water-based electrolyte, and improve the reversibility of zinc ion intercalation/deintercalation reaction, thereby significantly improving the cycle stability and rate capability of the water-based zinc ion battery. Specifically, the application is realized by the following scheme: the water-based zinc ion battery comprises a positive electrode, a negative electrode, electrolyte and a diaphragm, wherein an active material of the positive electrode is a cyclic azo organic compound with a cyclic conjugated structure, an active material of the negative electrode is a zinc-based material, and the electrolyte is a water-based electrolyte containing zinc salt. The application takes the cyclic azo organic compound as the active substance of the positive electrode, has stable cyclic conjugated structure and excellent reversible oxidation-reduction performance, can effectively inhibit the dissolution of the active substance in the water-based electrolyte, takes the negative electrode active substance formed by zinc-based materials to generate reversible zinc deposition/stripping reaction in the charge-discharge process, cooperates with the positive electrode active substance to complete electrochemical reaction, and combines the water-based electrolyte containing zinc salt to endow the battery with good electrochemical stability and circularity, and effectively improves the power density and service life of the battery. Further, as preferable: the cyclic azo organic compound is a cyclic azobenzene compound. More preferably: The annular azobenzene compound is obtained by taking a benzene ring as a raw material, introducing azo groups on the benzene ring through mills reaction to obtain a diaminodiazo precursor, and carrying out molecular cyclization reaction on the diaminodiazo precursor to form the azobenzene compound with an annular structure. The zinc-based material is zinc metal plate, zinc foil, zinc powder, porous zinc electrode or zinc alloy, and zinc metal (zinc metal plate, zinc foil, zinc powder) is preferable. The zinc salt is at least one of zinc sulfate (ZnSO 4), zinc perchlorate, zinc acetate, zinc tetrafluoroborate, zinc fluoride, zinc chloride, zinc bromide, zinc iodide, zinc triflate and zinc bis (trifluoromethylsulfonyl imide), and preferably zinc sulfate. In the electrolyte, the concentration of zinc salt is 1-5 mmol/L. The diaphragm is a hydrophilic dendrite-preventing composite battery diaphragm. The aqueous zinc ion battery can be prepared by the following method: Firstly, mixing a cyclic azo organic compound with a conductive material and a binder, adding nitrogen methyl pyrrolidone, dissolving and grinding to prepare positive electrode slurry, coating the positive electrode slurry on the surface of graphite paper, paving, drying and cutting to obtain a positive electrode plate; And secondly, taking the positive plate as a positive electrode, and combining a negative electrode, a diaphragm and electrolyte to assemble the water-based zinc ion battery. The mass ratio of the cyclic azo organic compound to the conductive material to the binder is 3:6:1. The conductive material is carbon blac