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CN-118515258-B - Zinc ion battery positive electrode material based on starch and zinc carbonate and preparation method thereof

CN118515258BCN 118515258 BCN118515258 BCN 118515258BCN-118515258-B

Abstract

The invention discloses a zinc ion battery anode material based on starch and zinc carbonate and a preparation method thereof, and relates to the field of zinc ion battery electrode materials. The preparation method comprises the specific steps of ball milling and mixing starch and zinc carbonate in a ball milling tank, sintering in a tube furnace, performing plasma treatment and modification, then washing with absolute ethyl alcohol, vacuum drying, uniformly mixing the starch and zinc carbonate with hexafluorobutyl acrylate, 1-amino-5-mercaptoanthraquinone, tetramethylguanidine and tetrahydrofuran, fully reacting, collecting a solid product through vacuum filtration, repeatedly washing with tetrahydrofuran to remove unreacted substances, and drying in a vacuum oven to constant weight to obtain the cathode material. The method effectively improves the first discharge specific capacity and the cyclic 500-time capacity retention rate of the zinc ion battery, and solves the problems of low energy density and short cycle life of the zinc ion battery.

Inventors

  • HUANG BIYING
  • HUANG GUOQIANG
  • HUANG YAOZE
  • LIU ZUXIONG

Assignees

  • 苏州泽世新能源科技有限公司

Dates

Publication Date
20260512
Application Date
20240529

Claims (8)

  1. 1. A preparation method of a zinc ion battery positive electrode material based on starch and zinc carbonate comprises the following operation steps: weighing 20-50 parts of starch and 5-10 parts of zinc carbonate according to parts by weight, ball-milling and mixing in a ball-milling tank, and sintering mixed powder in a tube furnace to form a carbon-based material; Step two, taking 25-35 parts of the carbon-based material prepared in the step one, placing the carbon-based material into a plasma treatment device, maintaining the temperature at a room temperature level, placing the carbon-based material subjected to plasma treatment in air for 1-4 hours to stabilize the surface property of the carbon-based material, then washing the carbon-based material with absolute ethyl alcohol to remove unreacted ammonia gas residues, and drying the carbon-based material overnight under a vacuum condition; Step three, uniformly mixing 120-140 parts of the carbon-based material containing the amino group after plasma treatment, 4-8 parts of hexafluorobutyl acrylate, 0.2-2 parts of 1-amino-5-mercaptoanthraquinone, 1-3 parts of tetramethyl guanidine and 1000-1300 parts of tetrahydrofuran, and fully reacting; and step four, collecting a solid product through vacuum filtration, repeatedly washing with tetrahydrofuran to remove unreacted substances, and drying in a vacuum oven to constant weight to obtain the positive electrode material.
  2. 2. The preparation method of the zinc ion battery anode material based on the starch and the zinc carbonate is characterized in that a planetary ball mill is adopted in the ball milling process, the ball milling tank is made of agate or polytetrafluoroethylene, the ball milling balls are made of zirconium balls or corundum, the ball milling rotating speed is 350-500 r/min, and the ball milling time is 0.5-2 hours.
  3. 3. The preparation method of the zinc ion battery positive electrode material based on the starch and the zinc carbonate is characterized in that the calcination condition of a tube furnace in the first step is inert atmosphere filling, the calcination temperature is 600-900 ℃, and the calcination time is 2-4 hours.
  4. 4. The preparation method of the zinc ion battery positive electrode material based on the starch and the zinc carbonate is characterized in that the heating speed of the tube furnace is 1-10 ℃ per minute.
  5. 5. The method for preparing a zinc ion battery positive electrode material based on starch and zinc carbonate according to claim 3, wherein the inert atmosphere is at least one of nitrogen, argon and helium.
  6. 6. The method for preparing the zinc ion battery positive electrode material based on the starch and the zinc carbonate, which is characterized in that a low-temperature plasma treatment device is used in the second step, the power is set to be 50-100W, the working air pressure is controlled to be 20-30Pa, the flow rate of ammonia gas is set to be 10-20sccm, and the treatment time is 20-40 minutes.
  7. 7. The preparation method of the zinc ion battery positive electrode material based on the starch and the zinc carbonate, which is disclosed in claim 1, is characterized in that the reaction condition of the step three is that the reaction temperature is 50-60 ℃, the reaction pressure is normal pressure, and the reaction time is 2-4 hours.
  8. 8. The method for preparing the positive electrode material of the zinc ion battery based on the starch and the zinc carbonate, which is disclosed in claim 1, is characterized in that the temperature of a vacuum oven in the fourth step is 70-80 ℃.

Description

Zinc ion battery positive electrode material based on starch and zinc carbonate and preparation method thereof Technical Field The invention relates to the field of zinc ion battery electrode materials, in particular to a zinc ion battery anode material based on starch and zinc carbonate and a preparation method thereof. Background As a new secondary battery, zinc ion batteries (Zinc-ionbatteries, ZIBs) have been receiving a great deal of attention in the energy storage field in recent years due to their advantages of safety, environmental protection, low cost, and abundant resources. The positive electrode material is used as a key component of the zinc ion battery, and has a decisive influence on the overall performance of the battery. A process for preparing the doped positive electrode material of Zn ion battery, the doped positive electrode material of Zn ion battery and the doped positive electrode material of Zn ion battery (Chinese patent application number: CN 202111066997.7) includes such steps as dissolving vanadium source, oxidant, fuel and doped cationic raw material in water, mixing to obtain mixed phase, and low-temp combustion reaction. The vanadium source includes NH 4VO3. The oxidizing agent includes NH 4NO3. The fuel includes at least one of CO (NH 2)2, C2H5O 2N. The cation doping raw material includes M (NO 3) N, and M includes at least one of Li, na, K, ag, ca, mg, zn, al, ni, mn, cu. A zinc ion battery positive electrode material, a preparation method and application thereof, and a chemical composition of the zinc ion battery positive electrode material provided by a zinc ion battery (China patent application number: CN 202110080348.6) is AMF 3, wherein A is Li +、Na+ or K +, M is one or two or three of Mn 2+、Co2+ and Ni 2+, and the zinc ion battery positive electrode material has a perovskite structure. The perovskite structure of the zinc ion battery anode material provided by the invention can provide a crystal structure with larger space and stable structure, is favorable for rapid migration of zinc ions in crystal lattices of the zinc ion battery anode material, and has small volume effect of the anode material in the process of ion deintercalation. A method for preparing anode material of Mn-based Zn ion battery includes using obtained carbon fiber product treated by conducting agent to deposit MnO 2 on carbon fiber product as substrate by electrodeposition method to obtain anode material of MnO2 treated by conducting agent. The preparation method provided by the invention can complete the synthesis of the manganese-based zinc ion battery anode material of the flexible zinc ion battery, and can ensure that the MnO 2 structure is porous sheet-shaped and relatively compact. Currently, the electrochemical energy storage field is increasingly in need of high-performance cathode materials. The traditional materials have the problems of low energy density, short cycle life and the like, and development and application of novel materials are urgently needed. Disclosure of Invention The invention mainly aims to provide a preparation method of a zinc ion battery anode material based on starch and zinc carbonate, which aims to overcome the defects in the prior art. The invention also aims to provide the zinc ion battery anode material prepared by the method. In order to achieve the purpose of the invention, the technical scheme adopted by the invention comprises the following steps: The embodiment of the invention provides a zinc ion battery anode material based on starch and zinc carbonate and a preparation method thereof, and the operation steps are as follows: weighing 20-50 parts of starch and 5-10 parts of zinc carbonate according to parts by weight, ball-milling and mixing in a ball-milling tank, and sintering mixed powder in a tube furnace to form a carbon-based material; Step two, taking 25-35 parts of the carbon-based material prepared in the step one, placing the carbon-based material into a plasma treatment device, maintaining the temperature at a room temperature level, placing the carbon-based material subjected to plasma treatment in air for 1-4 hours to stabilize the surface property of the carbon-based material, then washing the carbon-based material with absolute ethyl alcohol to remove unreacted ammonia gas residues, and drying the carbon-based material overnight under a vacuum condition; Step three, uniformly mixing 120-140 parts of the carbon-based material containing the amino group after plasma treatment, 4-8 parts of hexafluorobutyl acrylate, 0.2-2 parts of 1-amino-5-mercaptoanthraquinone, 1-3 parts of tetramethyl guanidine and 1000-1300 parts of tetrahydrofuran, and fully reacting; and step four, collecting a solid product through vacuum filtration, repeatedly washing with tetrahydrofuran to remove unreacted substances, and drying in a vacuum oven to constant weight to obtain the positive electrode material. In some embodiments of the present invention, the ball mill