CN-119400795-B - Preparation method and application of negative electrode coating material of water-based zinc ion battery

Abstract

The invention belongs to the technical field of negative electrode materials of water-based zinc ion batteries, and discloses a preparation method and application of a negative electrode coating material of a water-based zinc ion battery. According to the invention, graphite-phase carbon nitride is used as a matrix material, and the enzymolysis lignin is loaded in the graphite-phase carbon nitride to synthesize the enzymolysis lignin graphite-phase carbon nitride composite material, so that the synthesized material has strong mechanical property and chemical stability, and can also effectively inhibit the corrosion of electrolyte to the surface of a zinc negative electrode. The required zinc cathode coating material is prepared by loading enzymolysis lignin on graphite phase carbon nitride. The coating material is used as a protective layer of the water-based zinc ion battery cathode material, so that the problems generated in the charge and discharge process of the zinc ion battery cathode can be solved, hydrogen evolution, corrosion, side reaction and dendrite of the zinc cathode are inhibited, and the stability and charge and discharge cycle efficiency of the water-based zinc ion battery are effectively improved.

Inventors

• ZHANG XIAOLIN
• LUO ZIHAN
• LI WEN
• LIU XUDONG

Assignees

• 大连大学

Dates

Publication Date

20260508

Application Date

20241030

Claims (7)

1. 1. The preparation method of the negative electrode coating material of the water-based zinc ion battery is characterized by comprising the following steps of: (1) The method comprises the steps of taking urea as a raw material, and obtaining pale yellow solid powder by heat treatment, wherein the pale yellow solid powder is graphite phase carbon nitride; (2) And ball-milling and mixing graphite phase carbon nitride, enzymolysis lignin and polyvinylidene fluoride according to a mass ratio, dropwise adding N-methyl pyrrolidone, and stirring to be in a paint shape to obtain the anode coating material.
2. 2. The method for preparing a negative electrode coating material of an aqueous zinc-ion battery according to claim 1, wherein urea is placed in a crucible in the step (1) and is subjected to heat treatment in a muffle furnace under the conditions of a temperature rise rate of 4-5 ℃ per minute, a calcination temperature of 500-600 ℃ and a calcination time of 2-3 hours.
3. 3. The preparation method of the negative electrode coating material of the water-based zinc ion battery according to claim 1, wherein in the step (2), graphite-phase carbon nitride, enzymolysis lignin and polyvinylidene fluoride are mixed according to the mass ratio of 1-5:1:1, the ball milling mixing rotating speed is 600-650r/min, the time is 30-60min, and the dropwise added N-methyl pyrrolidone is 5-7 drops.
4. 4. The method for preparing a negative electrode coating material of an aqueous zinc-ion battery according to claim 1, wherein urea is placed in a crucible in the step (1) and is subjected to heat treatment in a muffle furnace under the conditions of a temperature rise rate of 4.6 ℃ per minute, a calcination temperature of 550 ℃ and a calcination time of 2 hours.
5. 5. The method for preparing a negative electrode coating material of a water-based zinc ion battery according to claim 1, wherein the graphite phase carbon nitride, the enzymolysis lignin and the polyvinylidene fluoride in the step (2) are mixed in a mass ratio of 5:1:1, and ball milling time is 30min.
6. 6. Use of a negative electrode coating material prepared by the preparation method according to any one of claims 1 to 5 for preparing a zinc negative electrode material.
7. 7. The use according to claim 6, wherein the zinc anode material is prepared by coating the coating material on a zinc foil using a coater.

Description

Preparation method and application of negative electrode coating material of water-based zinc ion battery Technical Field The invention belongs to the technical field of negative electrode materials of water-based zinc ion batteries, and relates to a preparation method and application of a negative electrode coating material of a water-based zinc ion battery. Specifically, the composite material of graphite phase carbon nitride loaded with enzymolysis lignin is used as a coating material of a negative electrode of a water-based zinc ion battery, and is applied to the preparation of the negative electrode material of the water-based zinc ion battery. Background The rapid development of wearable electronics and electric vehicles has stimulated an increasing demand for exploring emerging energy storage systems, but lithium ion batteries have limited energy density and potential safety issues with organic electrolytes, while aqueous multivalent ion batteries have great promise due to the high energy supply through multiple electron transfer and aqueous electrolyte use. In the main metals, the theoretical specific capacity of Zn (5855 mAh cm -3) exceeded the theoretical specific capacity of lithium metal (2061 mAh cm -3). In addition, zn has a high redox potential (0.76V versus standard hydrogen electrode), which enables it to operate in aqueous electrolytes with higher ionic conductivity than organic electrolytes, which will ultimately lead to a significant rate performance. Other advantages of Zn also relate to non-flammability, low cost and high safety, all of which are particularly beneficial for practical wearable technologies. Although significant progress has been made in the discovery of zinc storage materials and devices so far, some problems have hindered commercial application of aqueous zinc ion batteries, mainly problems such as dendrite growth, hydrogen evolution, surface corrosion and by-product formation of the negative electrode. Currently, most of the research is applied in various fields in the form of lignin sulfonate, for example, sodium lignin sulfonate is applied in electrolyte additives. In the prior art, graphite-phase carbon nitride is directly used as a zinc anode coating of a water-based zinc ion battery to be modified, but the graphite-phase carbon nitride cannot effectively inhibit corrosion of the electrolyte on the surface of the zinc anode, so that the battery has poor cyclic charge and discharge effects. Disclosure of Invention Aiming at the problems of growth, hydrogen evolution, corrosion and the like of zinc negative dendrites, the invention provides a preparation method and application of a negative electrode coating material of a water-based zinc ion battery. The coating material is used as a protective layer of the water-based zinc ion battery cathode material, so that the problems generated in the charge and discharge process of the zinc ion battery cathode can be solved, hydrogen evolution, corrosion, side reaction and dendrite of the zinc cathode are inhibited, and the stability and charge and discharge cycle efficiency of the water-based zinc ion battery are effectively improved. The above object of the present invention is achieved by the following technical solutions: the preparation method of the negative electrode coating material of the water-based zinc ion battery comprises the following steps: (1) Taking urea as a raw material, and performing heat treatment to obtain pale yellow solid powder; (2) Ball-milling and mixing light yellow solid powder, enzymolysis lignin and polyvinylidene fluoride (PVDF) according to a mass ratio, dripping N-methyl pyrrolidone (NMP), and stirring to be in a paint shape to obtain the anode coating material. Further, in the step (1), urea is placed in a crucible and is subjected to heat treatment in a muffle furnace, wherein the heat treatment condition is that the temperature rising rate is 4-5 ℃ per minute, the calcining temperature is 500-600 ℃ and the calcining time is 2-3 hours. Further, in the step (2), graphite phase carbon nitride, enzymolysis lignin and polyvinylidene fluoride (PVDF) are mixed according to the mass ratio of 1-5:1:1, the ball milling mixing rotating speed is 600-650r/min, the time is 30-60min, and the dropwise added N-methylpyrrolidone (NMP) is 5-7 drops. Preferably, in step (1), urea is placed in a crucible and subjected to heat treatment in a muffle furnace under the conditions of a heating rate of 4.6 ℃ per minute, a calcination temperature of 550 ℃ and a calcination time of 2 hours. Preferably, the graphite phase carbon nitride, the enzymolysis lignin and polyvinylidene fluoride (PVDF) in the step (2) are mixed in a mass ratio of 5:1:1, and the ball milling time is 30min. The enzymatically hydrolyzed lignin is preferably purchased from Shandong Longli group. The invention also discloses application of the negative electrode coating material prepared by the preparation method in preparation of zinc negative