CN-121769280-B - Micro zinc-iodine battery with wide temperature range and preparation method thereof

CN121769280BCN 121769280 BCN121769280 BCN 121769280BCN-121769280-B

Abstract

The invention discloses a micro zinc-iodine battery with wide temperature range and a preparation method thereof, comprising the following steps of loading iodine on the surface of a microelectrode to form an iodine anode after preparing the microelectrode by 3D printing; the method comprises the steps of preparing a zinc anode matched with an iodine anode in shape by laser engraving, uniformly mixing water, hyaluronic acid, hydrophilic silicon dioxide, zinc perchlorate and zinc bromide to form a gel electrolyte, sequentially laminating the iodine anode, the gel electrolyte and the zinc anode on a substrate, and packaging to obtain the micro zinc-iodine battery with the wide temperature range. The gel electrolyte has the advantages that water is locked by the hydrogen bond formed between the hyaluronic acid and the hydrophilic silicon dioxide and water molecules, evaporation of water at high temperature is inhibited, perchlorate is used for inhibiting solidification of water at low temperature by destroying the hydrogen bond structure between water molecules and water molecules in a gel network, so that a wide temperature range of the miniature battery is realized, meanwhile, bromide ions in the electrolyte are transmitted to a positive electrode through an interface to excite four-electron reaction of iodine, and the energy density of the miniature zinc-iodine battery is improved.

Inventors

NI JIANGFENG
Zhu Junbing
LIANG DANNI
LI LIANG

Assignees

苏州大学

Dates

Publication Date: 20260512
Application Date: 20260228

Claims (7)

1. The preparation method of the miniature zinc-iodine battery with wide temperature range is characterized by comprising the following steps: S1, carrying iodine on the surface of the microelectrode to form an iodine anode after 3D printing preparation, wherein the iodine is carried on the surface of the microelectrode specifically, 1-hexyl-3-methylimidazole bromide and iodine simple substance are dissolved in an organic solvent to form a mixed solution, the microelectrode is placed in the mixed solution for soaking, and then the microelectrode is taken out for drying treatment, wherein the molar ratio of the 1-hexyl-3-methylimidazole bromide to the iodine simple substance is (0.5-1): 1; s2, preparing a zinc anode matched with the iodine anode in shape by laser engraving; S3, uniformly mixing water, hyaluronic acid, hydrophilic silicon dioxide, zinc perchlorate and zinc bromide to form a gel electrolyte, wherein the concentration of the hyaluronic acid in the gel electrolyte is 0.05-0.15g/mL, the concentration of the hydrophilic silicon dioxide is 0.15-0.25g/mL, the concentration of the zinc perchlorate is 3.5-4.5mmol/mL, and the concentration of the zinc bromide is 0.1-0.5mmol/mL; And S4, sequentially laminating the iodine anode, the gel electrolyte and the zinc cathode on a substrate, and packaging to obtain the micro zinc-iodine battery with the wide temperature range.
2. The method for preparing a wide-temperature-range miniature zinc-iodine battery according to claim 1, wherein in S1, the microelectrode prepared by 3D printing is in a grid structure, and the adopted printing ink comprises a conductive material and a binder.
3. The method for preparing a wide-temperature-range miniature zinc-iodine battery according to claim 2, wherein the conductive material is one or more selected from the group consisting of carbon nanotubes, graphene, activated carbon, carbon fibers, conductive carbon black and MXene; the binder is one or more selected from polyvinylidene fluoride, polyacrylonitrile and polyvinylpyrrolidone.
4. The method for preparing a wide temperature range miniature zinc-iodine battery according to claim 1, wherein in S2, the zinc negative electrode is selected from zinc foil, zinc sheet or foam zinc.
5. The method for preparing a wide-temperature-range miniature zinc-iodine battery according to claim 1, wherein in S3, the hyaluronic acid is one or more selected from sodium hyaluronate, potassium hyaluronate and zinc hyaluronate.
6. The method for preparing a wide temperature range micro zinc-iodine battery according to claim 1, wherein in S4, the material of the substrate is one or more selected from the group consisting of polyethylene imine, polyimide and polyethylene terephthalate.
7. A wide temperature range micro zinc-iodine battery prepared by the preparation method of any one of claims 1 to 6.

Description

Micro zinc-iodine battery with wide temperature range and preparation method thereof Technical Field The invention relates to the technical field of zinc-iodine batteries, in particular to a miniature zinc-iodine battery with a wide temperature range and a preparation method thereof. Background The rapid development of autonomous microelectronic devices and microsystems places higher demands on the efficiency and stability of on-chip micro-energy cells. In various micro energy storage technologies, the effective electrode area of a micro battery is in a micro scale (generally less than 1 cm 2 level), and can be integrally packaged with a microelectronic device, and the micro battery becomes an ideal driving power supply of an autonomous microelectronic device due to high energy density and easy integration. Among them, the micro zinc battery exhibits a wide application prospect by virtue of excellent safety and low cost. However, current miniature zinc cells have insufficient energy density and cannot function properly over a wide temperature range of over 0-25 ℃ and cannot meet the energy requirements of autonomous microsystems. In view of the above challenges, researchers have focused on increasing the energy density of miniature zinc cells and their ability to operate at extreme temperatures. In terms of improving energy density, the existing research improves the area specific energy of the miniature zinc battery to more than 2 mWh cm -2 by developing a high-capacity iodine positive electrode, so that the energy requirement of an autonomous micro system is basically met, but the working temperature interval of the miniature zinc battery is limited. Patent CN121319408a expands the operating temperature of the gel electrolyte to-20 ℃ to 25 ℃ by introducing ethylene glycol into the gel electrolyte, but the system has not been applied to micro-cells. In summary, it is difficult to combine the high energy density and wide temperature range working range of the micro zinc cell in the prior art. How to design a miniature zinc cell with high energy density and excellent wide temperature adaptability is still a technical problem to be broken through at present. Disclosure of Invention Aiming at the defects in the prior art, the invention provides a micro zinc-iodine battery with a wide temperature range and a preparation method thereof, optimizes gel electrolyte, inhibits water evaporation at a high temperature by forming hydrogen bond water locking between hyaluronic acid and hydrophilic silicon dioxide and water molecules, inhibits solidification of water at a low temperature by damaging a hydrogen bond structure between water molecules and water molecules in a gel network, realizes the wide temperature range of the micro battery, simultaneously transmits bromide ions in the electrolyte to a positive electrode through an interface to excite four-electron reaction of iodine, improves the energy density of the micro zinc-iodine battery, and solves the problem that the micro battery in the prior art cannot achieve both high energy density and a wide temperature range working range. In order to solve the technical problems, the first aspect of the invention provides a preparation method of a micro zinc-iodine battery with wide temperature range, which comprises the following steps: S1, after a microelectrode is prepared by 3D printing, iodine is loaded on the surface of the microelectrode to form an iodine anode; s2, preparing a zinc anode matched with the iodine anode in shape by laser engraving; S3, uniformly mixing water, hyaluronic acid, hydrophilic silicon dioxide, zinc perchlorate and zinc bromide to form a gel electrolyte; And S4, sequentially laminating the iodine anode, the gel electrolyte and the zinc cathode on a substrate, and packaging to obtain the micro zinc-iodine battery with the wide temperature range. The gel electrolyte is provided with hydrophilic silicon dioxide and zinc perchlorate, water is locked by hydrogen bonds formed between the hyaluronic acid and the hydrophilic silicon dioxide and water molecules, evaporation of water at high temperature is restrained, perchlorate is used for restraining solidification of water at low temperature by destroying a hydrogen bond structure between the water molecules and the water molecules in a gel network, wide temperature range of a miniature battery can be realized, the miniature battery can work at wide temperature range of-40 ℃ to 60 ℃, bromide ions in the electrolyte are transmitted to a positive electrode through an interface to excite four-electron reaction of iodine, so that the energy density of the miniature zinc-iodine battery is improved, and the high energy density and the wide temperature range of the miniature battery are realized. In S1, iodine is loaded on the surface of the microelectrode, namely, 1-hexyl-3-methylimidazole bromide and iodine simple substance are dissolved in an organic solvent to form a mixed solution, and the microe