CN113299928A - Preparation method of high-performance flexible secondary zinc-silver-zinc-air hybrid battery positive electrode material - Google Patents

Preparation method of high-performance flexible secondary zinc-silver-zinc-air hybrid battery positive electrode material Download PDF

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CN113299928A
CN113299928A CN202110567141.1A CN202110567141A CN113299928A CN 113299928 A CN113299928 A CN 113299928A CN 202110567141 A CN202110567141 A CN 202110567141A CN 113299928 A CN113299928 A CN 113299928A
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zinc
silver
carbon cloth
methylimidazole
positive electrode
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乐士儒
温艳迪
迟大钊
张乃庆
李昀隆
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Harbin Institute of Technology
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Harbin Institute of Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9041—Metals or alloys

Abstract

The invention discloses a preparation method of a high-performance flexible secondary zinc-silver-zinc-air hybrid battery positive electrode material, which comprises the following steps: firstly, preparing a cobalt nitrate aqueous solution; secondly, preparing 2-methylimidazole water solution; adding the 2-methylimidazole aqueous solution into a cobalt nitrate aqueous solution to obtain a mixed solution containing 2-methylimidazole and cobalt nitrate; fourthly, putting the carbon cloth subjected to the plasma oxidation treatment into a mixed solution containing 2-methylimidazole and cobalt nitrate, taking out the carbon cloth, washing with deionized water, and drying to obtain the carbon cloth for growing the Co-MOF; fifthly, carbonizing the carbon cloth for growing the Co-MOF at high temperature; sixthly, electrodepositing silver on the surface of the carbonized carbon cloth; and seventhly, oxidizing the silver on the surface of the carbon cloth into monovalent silver oxide. The method is simple and efficient, and the contact area of the positive active material and the matrix is increased and the utilization rate of silver is improved by the triangular nanosheet structure derived from the metal organic complex framework.

Description

Preparation method of high-performance flexible secondary zinc-silver-zinc-air hybrid battery positive electrode material
Technical Field
The invention belongs to the field of new energy materials and electrochemistry, relates to a preparation method of a battery anode, and particularly relates to a method for preparing a zinc-silver-zinc-air hybrid battery anode material by using carbon cloth as a substrate and a metal organic complex frame as a precursor.
Background
With the increasing global energy consumption, the traditional non-renewable energy sources such as coal, oil, natural gas and the like are difficult to meet the future demands. In this context, there is a great interest in developing new renewable energy sources (e.g., solar energy, wind energy, tidal energy, etc.). However, the intermittency and randomness of solar and wind energy limits their application. Electrochemical energy storage technology has become an important development, particularly in order to be able to reliably store and efficiently utilize these intermittent energy sources. With the continuous pursuit of people for portable and wearable electronic products, the development of advanced flexible batteries becomes urgent.
The zinc-based battery has the advantages of high performance, easy assembly, low cost, high safety, environmental protection, rich zinc resources and the like. The zinc-silver battery is one of the most mature battery systems at present, has wide prospect, and is widely and heteroscedasticity in electronic equipment such as watches, hearing aids, calculators, military, aerospace and the like. The zinc-silver battery can provide 300 Wh/kg−1The specific energy and power density of (2) can reach as high as 600 W.kg−1. The zinc-silver battery has the advantages of safety, environmental protection, extremely low self-discharge rate, stable voltage discharge and the like, but the large-scale commercial application of the zinc-silver battery is limited by high cost and the like. The zinc-air battery has the advantages of zero pollution, high energy, safety, low cost, high power, renewable materials and the like, is considered as a new generation of ideal power supply, but the zinc-air battery has low discharge voltage and low positive electrode reaction activity, and needs to use a corresponding catalyst. Therefore, if the hybrid battery can be prepared by combining the characteristics of the zinc-silver battery and the zinc-air battery, the hybrid battery can simultaneously have the characteristics of safety, stable voltage, high discharge voltage and the like.
Paper "An ultra-high end and high-performance quasi-solid-state fiber-shaped Zn-Ag2O battery toharvest wind energy (j. mater. chem. a, 2019 (7)) 2034-. CN103151538A discloses a method for preparing a zinc-air battery catalyst by using silver salt as a raw material and adjusting the ratio of a protective agent, namely polyvinylpyrrolidone, and a carbon carrier to silver, and the utilization rate of silver is not improved by a doping manner.
Disclosure of Invention
Aiming at the problems of low silver utilization rate, poor stability and the like of the existing zinc-silver battery, the invention provides a preparation method of a high-performance flexible secondary zinc-silver-zinc air-air hybrid battery anode material. Silver is uniformly dispersed on the surface of a CoNC triangular nanosheet derived based on a metal organic complex framework, the nanosheet grows on a carbon cloth substrate, the dispersion of an active substance silver, the rapid transportation of electrons and the effective diffusion of ions in a solution are very easy to realize, the utilization rate of an anode active material is improved, the performance of a zinc-silver battery is further improved, and meanwhile, the silver can also be used as a catalyst of an oxygen reduction reaction of an anode of a zinc-air battery, namely Co3O4The zinc-silver/zinc-air hybrid battery can be used as a catalyst for the oxygen precipitation reaction of the positive electrode of the zinc-air battery, can be assembled into a zinc-silver/zinc-air hybrid battery, has wider application, combines the advantages of high voltage of the zinc-silver battery and high capacity of the zinc-air battery, and is assembled into a flexible zinc-silver/zinc-air hybrid battery with the discharge current density of 1 mA cm-2Then, the discharge capacity can reach 2.7 mAh cm-2。
The purpose of the invention is realized by the following technical scheme:
a preparation method of a high-performance flexible secondary zinc-silver-zinc-air hybrid battery anode material takes carbon cloth as a substrate and a metal organic complex frame as a precursor to prepare the zinc-silver-zinc-air hybrid battery anode material, and specifically comprises the following steps:
adding cobalt nitrate into deionized water, and stirring until the cobalt nitrate is uniformly dispersed to obtain a cobalt nitrate aqueous solution with the concentration of 0.05-0.1 mol/L;
adding 2-methylimidazole into deionized water, and stirring at room temperature until the mixture is clear and transparent to obtain a 2-methylimidazole water solution with the concentration of 0.3-0.5 mol/L;
quickly adding the 2-methylimidazole aqueous solution into a cobalt nitrate aqueous solution to obtain a mixed solution containing 2-methylimidazole and cobalt nitrate, wherein: the volume ratio of the 2-methylimidazole to the cobalt nitrate is 1: 1;
step four, putting the carbon cloth subjected to the plasma oxidation treatment into a mixed solution containing 2-methylimidazole and cobalt nitrate for 3-5 hours, taking out the carbon cloth, washing with deionized water, and drying to obtain the carbon cloth for growing the Co-MOF, wherein: the plasma oxidation treatment is to treat the carbon cloth by an oxygen plasma generator;
fifthly, placing the carbon cloth for growing the Co-MOF into a tube furnace for high-temperature carbonization, wherein: the atmosphere of high-temperature carbonization is air or argon; when the atmosphere of high-temperature carbonization is air, the carbonization temperature is 300-400 ℃; when the atmosphere of high-temperature carbonization is argon, the carbonization temperature is 700-900 ℃, and the carbonized carbon is distributed in 3 mol/L FeCl3Soaking in the solution for 5-8 h, taking out the carbon cloth, washing with deionized water, and drying in vacuum;
and step six, electrodepositing silver on the surface of the carbonized carbon cloth by an electrochemical method, wherein: the silver electrodeposition time is 0.5-2 h, and the current density is 5-10 mA/cm2；
Step seven, oxidizing the silver on the surface of the carbon cloth into monovalent silver oxide under the condition that the charge cut-off voltage is 1.8V by an electrochemical method to obtain the metal organic complex-based nano material anode CC-CoNC-Ag2O。
Compared with the prior art, the invention has the following advantages:
the preparation method is simple and efficient, the contact area of the active substance of the positive electrode and the matrix is increased through the triangular nanosheet structure derived from the metal organic complex framework, the utilization rate of silver is improved, and the silver can also be used as a catalyst for the positive electrode oxygen reduction reaction of a zinc-air battery, namely Co3O4As the catalyst for the positive oxygen precipitation reaction of the zinc-air battery, the assembled hybrid battery combines the characteristics of higher discharge voltage and voltage stability of the zinc-silver battery and high capacity of the zinc-air battery, in the presence or absence of oxygenThe air can work in the environment of air, and the use environment is wider.
Drawings
FIG. 1 is a surface SEM photograph of a carbon cloth of example 1 after Co-MOF growth;
fig. 2 is an XRD pattern of the cathode material in an air atmosphere of example 2;
FIG. 3 is a surface SEM photograph of the surface of the carbon cloth after carbonization in air of example 2 before and after silver deposition;
FIG. 4 is an XRD pattern of a positive electrode material prepared under an argon atmosphere in example 6;
FIG. 5 is a surface SEM photograph of the surface of the carbon cloth after carbonization in argon of example 6 before and after deposition of silver;
FIG. 6 is a charge-discharge cycle curve of the assembled aqueous zinc-silver battery of example 6;
fig. 7 is a charge and discharge curve of the assembled flexible zinc silver/zinc air hybrid battery of example 6.
Detailed Description
The technical solutions of the present invention are further described below with reference to the following examples, but the present invention is not limited thereto, and any modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Example 1: preparation of anode material in air atmosphere
Step one, 0.58206 g of Co (NO)3)3·6H2Dissolving O in 40 mL deionized water to prepare Co (NO)3)3An aqueous solution;
step two, dissolving 1.312 g of 2-methylimidazole in 40 mL of deionized water to prepare a 2-methylimidazole water solution;
step three, quickly adding the 2-methylimidazole water solution into Co (NO)3)3Obtaining a mixed solution containing 2-methylimidazole and cobalt nitrate in the aqueous solution;
step four, immersing the carbon cloth subjected to plasma oxidation treatment into the mixed solution, reacting for 4 hours, taking out a sample, washing with deionized water, and vacuum-drying overnight to obtain the carbon cloth for growing the Co-MOF;
step five, annealing the carbon cloth growing the Co-MOF in air at 350 ℃ for 2 h, wherein the heating rate is 2 ℃/min, and naturally cooling to room temperature;
sixthly, placing the carbon cloth carbonized in the air as a working electrode, the graphite rod as a reference electrode and a counter electrode in an electrolytic cell at a constant current density of 5 mA/cm2Is deposited for 0.5 h under the condition of 0.2 mol/L of AgNO electroplating solution30.05 mol/L nitric acid and 0.015 mol/L tartaric acid solution;
step seven, taking silver deposited by carbon cloth containing CoNC nanosheets as a positive electrode, a zinc plate as a negative electrode, 6 mol/L KOH +0.2 mol/L zinc acetate solution as an electrolyte, and performing electrochemical plating at 0.2 mA/cm2The current density of the silver oxide positive electrode was increased to 1.8V, and a monovalent silver oxide positive electrode was obtained.
Example 2: preparation of anode material in air atmosphere
Step one, 0.58206 g of Co (NO)3)3·6H2Dissolving O in 40 mL deionized water to prepare Co (NO)3)3An aqueous solution;
step two, dissolving 1.312 g of 2-methylimidazole in 40 mL of deionized water to prepare a 2-methylimidazole water solution;
step three, quickly adding the 2-methylimidazole water solution into Co (NO)3)3Obtaining a mixed solution containing 2-methylimidazole and cobalt nitrate in the aqueous solution;
step four, immersing the carbon cloth subjected to plasma oxidation treatment into the mixed solution, reacting for 4 hours, taking out a sample, washing with deionized water, and vacuum-drying overnight to obtain the carbon cloth for growing the Co-MOF;
step five, annealing the carbon cloth growing the Co-MOF in air at 350 ℃ for 2 h, wherein the heating rate is 2 ℃/min, and naturally cooling to room temperature;
sixthly, placing the carbon cloth carbonized in the air as a working electrode, the graphite rod as a reference electrode and a counter electrode in an electrolytic cell at a constant current density of 5 mA/cm2Is deposited for 1 hour under the condition of 0.2 mol/L of AgNO electroplating solution30.05 mol/L nitric acid and 0.015 mol/L tartaric acid solution;
step seven, taking silver deposited by carbon cloth containing CoNC nanosheets as a positive electrode, taking a zinc plate as a negative electrode, and dissolving 6 mol/L KOH +0.2 mol/L zinc acetateThe liquid is electrolyte and is at 0.2 mA/cm2The current density of the silver oxide positive electrode was increased to 1.8V, and a monovalent silver oxide positive electrode was obtained.
Example 3: preparation of anode material in air atmosphere
Step one, 0.58206 g of Co (NO)3)3·6H2Dissolving O in 40 mL deionized water to prepare Co (NO)3)3An aqueous solution;
step two, dissolving 1.312 g of 2-methylimidazole in 40 mL of deionized water to prepare a 2-methylimidazole water solution;
step three, quickly adding the 2-methylimidazole water solution into Co (NO)3)3Obtaining a mixed solution containing 2-methylimidazole and cobalt nitrate in the aqueous solution;
step four, immersing the carbon cloth subjected to plasma oxidation treatment into the mixed solution, reacting for 4 hours, taking out a sample, washing with deionized water, and vacuum-drying overnight to obtain the carbon cloth for growing the Co-MOF;
step five, annealing the carbon cloth growing the Co-MOF in air at 350 ℃ for 2 h, wherein the heating rate is 2 ℃/min, and naturally cooling to room temperature;
sixthly, placing the carbon cloth carbonized in the air as a working electrode, the graphite rod as a reference electrode and a counter electrode in an electrolytic cell at a constant current density of 5 mA/cm2Is deposited for 1.5 h under the condition of 0.2 mol/L of AgNO electroplating solution30.05 mol/L nitric acid and 0.015 mol/L tartaric acid solution;
step seven, taking silver deposited by carbon cloth containing CoNC nanosheets as a positive electrode, a zinc plate as a negative electrode, 6 mol/L KOH +0.2 mol/L zinc acetate solution as an electrolyte, and performing electrochemical plating at 0.2 mA/cm2The current density of the silver oxide positive electrode was increased to 1.8V, and a monovalent silver oxide positive electrode was obtained.
Example 4: preparation of anode material in air atmosphere
Step one, 0.58206 g of Co (NO)3)3·6H2Dissolving O in 40 mL deionized water to prepare Co (NO)3)3An aqueous solution;
step two, dissolving 1.312 g of 2-methylimidazole in 40 mL of deionized water to prepare a 2-methylimidazole water solution;
step (ii) ofThirdly, quickly adding the 2-methylimidazole water solution into Co (NO)3)3Obtaining a mixed solution containing 2-methylimidazole and cobalt nitrate in the aqueous solution;
step four, immersing the carbon cloth subjected to plasma oxidation treatment into the mixed solution, reacting for 4 hours, taking out a sample, washing with deionized water, and vacuum-drying overnight to obtain the carbon cloth for growing the Co-MOF;
step five, annealing the carbon cloth growing the Co-MOF in air at 350 ℃ for 2 h, wherein the heating rate is 2 ℃/min, and naturally cooling to room temperature;
sixthly, placing the carbon cloth carbonized in the air as a working electrode, the graphite rod as a reference electrode and a counter electrode in an electrolytic cell at a constant current density of 5 mA/cm2Is deposited for 2 hours under the condition of 0.2 mol/L of AgNO electroplating solution30.05 mol/L nitric acid and 0.015 mol/L tartaric acid solution;
step seven, taking silver deposited by carbon cloth containing CoNC nanosheets as a positive electrode, a zinc plate as a negative electrode, 6 mol/L KOH +0.2 mol/L zinc acetate solution as an electrolyte, and performing electrochemical plating at 0.2 mA/cm2The current density of the silver oxide positive electrode was increased to 1.8V, and a monovalent silver oxide positive electrode was obtained.
Example 5: preparation of anode material in argon atmosphere
Step one, 0.58206 g of Co (NO)3)3·6H2Dissolving O in 40 mL deionized water to prepare Co (NO)3)3An aqueous solution;
step two, dissolving 1.312 g of 2-methylimidazole in 40 mL of deionized water to prepare a 2-methylimidazole water solution;
step three, quickly adding the 2-methylimidazole water solution into Co (NO)3)3Obtaining a mixed solution containing 2-methylimidazole and cobalt nitrate in the aqueous solution;
step four, immersing the carbon cloth subjected to plasma oxidation treatment into the mixed solution, reacting for 4 hours, taking out a sample, washing with deionized water, and vacuum-drying overnight to obtain the carbon cloth for growing the Co-MOF;
step five, keeping the temperature of the carbon cloth for growing the Co-MOF in argon at 700 ℃ for 2 h, raising the temperature at the rate of 1 ℃/min, naturally cooling to room temperature, and then adding 3 mol/L FeCl3Soaking for 6 h, washing with deionized water, and vacuum drying at 60 deg.C;
sixthly, placing the carbon cloth carbonized in the argon as a working electrode, the graphite rod as a reference electrode and a counter electrode in an electrolytic cell at a constant current density of 5 mA/cm2Is deposited for 1 hour under the condition of 0.2 mol/L of AgNO electroplating solution30.05 mol/L nitric acid and 0.015 mol/L tartaric acid solution;
step seven, taking silver deposited by carbon cloth containing CoNC nanosheets as a positive electrode, a zinc plate as a negative electrode, 6 mol/L KOH +0.2 mol/L zinc acetate solution as an electrolyte, and performing electrochemical plating at 0.2 mA/cm2The current density of the silver oxide positive electrode was increased to 1.8V, and a monovalent silver oxide positive electrode was obtained.
Example 6: preparation of anode material in argon atmosphere
Step one, 0.58206 g of Co (NO)3)3·6H2Dissolving O in 40 mL deionized water to prepare Co (NO)3)3An aqueous solution;
step two, dissolving 1.312 g of 2-methylimidazole in 40 mL of deionized water to prepare a 2-methylimidazole water solution;
step three, quickly adding the 2-methylimidazole water solution into Co (NO)3)3Obtaining a mixed solution containing 2-methylimidazole and cobalt nitrate in the aqueous solution;
step four, immersing the carbon cloth subjected to plasma oxidation treatment into the mixed solution, reacting for 4 hours, taking out a sample, washing with deionized water, and vacuum-drying overnight to obtain the carbon cloth for growing the Co-MOF;
step five, keeping the temperature of the carbon cloth for growing the Co-MOF in argon at 800 ℃ for 2 h, raising the temperature at the rate of 1 ℃/min, naturally cooling to room temperature, and then adding 3 mol/L FeCl3Soaking for 6 h, washing with deionized water, and vacuum drying at 60 deg.C;
sixthly, placing the carbon cloth carbonized in the argon as a working electrode, the graphite rod as a reference electrode and a counter electrode in an electrolytic cell at a constant current density of 5 mA/cm2Is deposited for 1 hour under the condition of 0.2 mol/L of AgNO electroplating solution30.05 mol/L nitric acid and 0.015 mol/L tartaric acid solution;
step seven, using the sodium containing CoNCSilver deposited by the rice piece carbon cloth is used as a positive electrode, a zinc piece is used as a negative electrode, 6 mol/L KOH +0.2 mol/L zinc acetate solution is used as electrolyte, and the concentration of the electrolyte is controlled at 0.2 mA/cm2The current density of the silver oxide positive electrode was increased to 1.8V, and a monovalent silver oxide positive electrode was obtained.
Example 7: preparation of anode material in argon atmosphere
Step one, 0.58206 g of Co (NO)3)3·6H2Dissolving O in 40 mL deionized water to prepare Co (NO)3)3An aqueous solution;
step two, dissolving 1.312 g of 2-methylimidazole in 40 mL of deionized water to prepare a 2-methylimidazole water solution;
step three, quickly adding the 2-methylimidazole water solution into Co (NO)3)3Obtaining a mixed solution containing 2-methylimidazole and cobalt nitrate in the aqueous solution;
step four, immersing the carbon cloth subjected to plasma oxidation treatment into the mixed solution, reacting for 4 hours, taking out a sample, washing with deionized water, and vacuum-drying overnight to obtain the carbon cloth for growing the Co-MOF;
step five, preserving the temperature of the carbon cloth for growing the Co-MOF for 2 hours in argon gas at 900 ℃, raising the temperature at 1 ℃/min, naturally cooling to room temperature, and then adding 3 mol/L FeCl3Soaking for 6 h, washing with deionized water, and vacuum drying at 60 deg.C;
sixthly, placing the carbon cloth carbonized in the argon as a working electrode, the graphite rod as a reference electrode and a counter electrode in an electrolytic cell at a constant current density of 5 mA/cm2Is deposited for 1 hour under the condition of 0.2 mol/L of AgNO electroplating solution30.05 mol/L nitric acid and 0.015 mol/L tartaric acid solution;
step seven, taking silver deposited by carbon cloth containing CoNC nanosheets as a positive electrode, a zinc plate as a negative electrode, 6 mol/L KOH +0.2 mol/L zinc acetate solution as an electrolyte, and performing electrochemical plating at 0.2 mA/cm2The current density of the silver oxide positive electrode was increased to 1.8V, and a monovalent silver oxide positive electrode was obtained.
Example 8: preparation of anode material in argon atmosphere
Step one, 0.58206 g of Co (NO)3)3·6H2Dissolving O in 40 mL deionized water to prepare Co (NO)3)3An aqueous solution;
step two, dissolving 1.312 g of 2-methylimidazole in 40 mL of deionized water to prepare a 2-methylimidazole water solution;
step three, quickly adding the 2-methylimidazole water solution into Co (NO)3)3Obtaining a mixed solution containing 2-methylimidazole and cobalt nitrate in the aqueous solution;
step four, immersing the carbon cloth subjected to plasma oxidation treatment into the mixed solution, reacting for 4 hours, taking out a sample, washing with deionized water, and vacuum-drying overnight to obtain the carbon cloth for growing the Co-MOF;
step five, keeping the temperature of the carbon cloth for growing the Co-MOF in argon at 800 ℃ for 2 h, raising the temperature at the rate of 1 ℃/min, naturally cooling to room temperature, and then adding 3 mol/L FeCl3Soaking for 6 h, washing with deionized water, and vacuum drying at 60 deg.C;
sixthly, placing the carbon cloth carbonized in the argon as a working electrode, the graphite rod as a reference electrode and a counter electrode in an electrolytic cell at a constant current density of 5 mA/cm2Is deposited for 0.5 h under the condition of 0.2 mol/L of AgNO electroplating solution30.05 mol/L nitric acid and 0.015 mol/L tartaric acid solution;
step seven, taking silver deposited by carbon cloth containing CoNC nanosheets as a positive electrode, a zinc plate as a negative electrode, 6 mol/L KOH +0.2 mol/L zinc acetate solution as an electrolyte, and performing electrochemical plating at 0.2 mA/cm2The current density of the silver oxide positive electrode was increased to 1.8V, and a monovalent silver oxide positive electrode was obtained.
Example 9: preparation of anode material in argon atmosphere
The method comprises the following steps: 0.58206 g of Co (NO)3)3·6H2Dissolving O in 40 mL deionized water to prepare Co (NO)3)3An aqueous solution;
step two, dissolving 1.312 g of 2-methylimidazole in 40 mL of deionized water to prepare a 2-methylimidazole water solution;
step three, quickly adding the 2-methylimidazole water solution into Co (NO)3)3Obtaining a mixed solution containing 2-methylimidazole and cobalt nitrate in the aqueous solution;
step four, immersing the carbon cloth subjected to plasma oxidation treatment into the mixed solution, reacting for 4 hours, taking out a sample, washing with deionized water, and vacuum-drying overnight to obtain the carbon cloth for growing the Co-MOF;
step five, keeping the temperature of the carbon cloth for growing the Co-MOF in argon at 800 ℃ for 2 h, raising the temperature at the rate of 1 ℃/min, naturally cooling to room temperature, and then adding 3 mol/L FeCl3Soaking for 6 h, washing with deionized water, and vacuum drying at 60 deg.C;
sixthly, placing the carbon cloth carbonized in the argon as a working electrode, the graphite rod as a reference electrode and a counter electrode in an electrolytic cell at a constant current density of 5 mA/cm2Is deposited for 1.5 h under the condition of 0.2 mol/L of AgNO electroplating solution30.05 mol/L nitric acid and 0.015 mol/L tartaric acid solution;
step seven, taking silver deposited by carbon cloth containing CoNC nanosheets as a positive electrode, a zinc plate as a negative electrode, 6 mol/L KOH +0.2 mol/L zinc acetate solution as an electrolyte, and performing electrochemical plating at 0.2 mA/cm2The current density of the silver oxide positive electrode was increased to 1.8V, and a monovalent silver oxide positive electrode was obtained.
Example 10: preparation of anode material in argon atmosphere
Step one, 0.58206 g of Co (NO)3)3·6H2Dissolving O in 40 mL deionized water to prepare Co (NO)3)3An aqueous solution;
step two, dissolving 1.312 g of 2-methylimidazole in 40 mL of deionized water to prepare a 2-methylimidazole water solution;
step three, quickly adding the 2-methylimidazole water solution into Co (NO)3)3Obtaining a mixed solution containing 2-methylimidazole and cobalt nitrate in the aqueous solution;
step four, immersing the carbon cloth subjected to plasma oxidation treatment into the mixed solution, reacting for 4 hours, taking out a sample, washing with deionized water, and vacuum-drying overnight to obtain the carbon cloth for growing the Co-MOF;
step five, keeping the temperature of the carbon cloth for growing the Co-MOF in argon at 800 ℃ for 2 h, raising the temperature at the rate of 1 ℃/min, naturally cooling to room temperature, and then adding 3 mol/L FeCl3Soaking for 6 h, washing with deionized water, and vacuum drying at 60 deg.C;
step six: carbon cloth carbonized in argon gas is used as working electrode and graphiteThe rods as reference electrode and counter electrode were placed in an electrolytic cell at a constant current density of 5 mA/cm2Is deposited for 2 hours under the condition of 0.2 mol/L of AgNO electroplating solution30.05 mol/L nitric acid and 0.015 mol/L tartaric acid solution;
step seven, taking silver deposited by carbon cloth containing CoNC nanosheets as a positive electrode, a zinc plate as a negative electrode, 6 mol/L KOH +0.2 mol/L zinc acetate solution as an electrolyte, and performing electrochemical plating at 0.2 mA/cm2The current density of the silver oxide positive electrode was increased to 1.8V, and a monovalent silver oxide positive electrode was obtained.
Preparing a zinc-silver/zinc-air battery and testing the performance of the zinc-silver/zinc-air battery: taking an electrode prepared by an experiment as a positive electrode, a zinc sheet as a negative electrode and 6 mol/L KOH +0.2 mol/L zinc acetate solution as an electrolyte, and directly carrying out related tests on the zinc-silver battery in an electrolytic cell. The electrode prepared by experiments is used as a positive electrode, a zinc sheet is used as a negative electrode, PVA + KOH gel electrolyte is used as electrolyte and a diaphragm, and the flexible battery is assembled, wherein the positive electrode needs to be sealed when a zinc-silver battery is tested, and the positive electrode is packaged by a breathable adhesive tape when a zinc-air battery is tested.
Fig. 1 is a surface SEM photograph of the carbon cloth prepared in example 1 after Co-MOF is grown on the surface thereof, and it can be seen from the drawing that the structure of the obtained metal-organic complex framework is triangular nanosheet-shaped and uniformly covers the surface of the carbon cloth.
FIG. 2 is an XRD pattern of the positive electrode material prepared in example 2 at each stage in an air atmosphere, and it can be seen from the XRD pattern that Co in Co-MOF is Co-doped after carbonization in air3O4In the form of (a), silver of higher purity is obtained after electrodeposition.
Fig. 3 is a surface SEM photograph of the carbon cloth after carbonization in air and the carbon cloth after deposition of silver prepared in example 2, and it can be seen from the drawings that the structure derived from the obtained metal-organic complex framework is triangular nanosheet-shaped, and after deposition of silver, the silver uniformly covers the surface.
FIG. 4 is an XRD pattern of the cathode material prepared in example 6 at various stages under an argon atmosphere, and it can be seen from the XRD pattern that Co in Co-MOF exists in the form of CoN after carbonization under argon, and FeCl3Soaking with Co3O4Is present, silver is obtained after electrodeposition.
Fig. 5 is a surface SEM photograph of the carbon cloth carbonized in argon prepared in example 6 and a surface SEM photograph of the carbon cloth deposited with silver, and it can be seen from the drawings that the resulting metal-organic complex framework-derived structure is a triangular nanosheet shape, and after silver is deposited, the silver uniformly covers the surface.
FIG. 6 shows the current density of 5 mA cm for the aqueous Zn-Ag battery with the positive electrode prepared in example 6-2And the charge-discharge cycle curve under the voltage of 1.0-1.8V, as can be seen from the figure, the capacity of the zinc-silver battery can reach 0.96 mAh cm-2And the capacity retention rate after 100 cycles is 94.8%.
FIG. 7 shows the current density of a flexible Zn-Ag/Zn-air hybrid battery assembled with a positive electrode prepared in example 6 at 1 mA cm-2And a charge-discharge curve at a voltage of 1.0-1.8V, and it can be seen from the figure that the capacity of the hybrid battery can reach 2.7 mAh cm-2。

Claims (10)

1. A preparation method of a high-performance flexible secondary zinc-silver-zinc-air hybrid battery positive electrode material is characterized by comprising the following steps:
step one, adding cobalt nitrate into deionized water, and stirring until the cobalt nitrate is uniformly dispersed to obtain a cobalt nitrate aqueous solution;
adding 2-methylimidazole into deionized water, and stirring at room temperature until the mixture is clear and transparent to obtain a 2-methylimidazole water solution;
quickly adding the 2-methylimidazole aqueous solution into a cobalt nitrate aqueous solution to obtain a mixed solution containing 2-methylimidazole and cobalt nitrate;
putting the carbon cloth subjected to the plasma oxidation treatment into a mixed solution containing 2-methylimidazole and cobalt nitrate for 3-5 hours, taking out the carbon cloth, washing with deionized water, and drying to obtain the carbon cloth growing the Co-MOF;
putting the carbon cloth with the grown Co-MOF into a tube furnace for high-temperature carbonization;
step six, electrodepositing silver on the surface of the carbonized carbon cloth by an electrochemical method;
and seventhly, oxidizing the silver on the surface of the carbon cloth into monovalent silver oxide by an electrochemical method under the condition that the charge cut-off voltage is 1.8V, and obtaining the metal organic complex-based nano material anode.
2. The preparation method of the high-performance flexible secondary zinc-silver-zinc-air hybrid battery positive electrode material according to claim 1, wherein the concentration of the cobalt nitrate aqueous solution is 0.05-0.1 mol/L.
3. The preparation method of the high-performance flexible secondary zinc-silver-zinc-air hybrid battery positive electrode material according to claim 1, wherein the concentration of the 2-methylimidazole aqueous solution is 0.3-0.5 mol/L.
4. The preparation method of the high-performance flexible secondary zinc-silver-zinc-air hybrid battery positive electrode material according to claim 1, wherein in the mixed solution containing 2-methylimidazole and cobalt nitrate, the volume ratio of 2-methylimidazole to cobalt nitrate is 1: 1.
5. the preparation method of the high-performance flexible secondary zinc-silver-zinc-air hybrid battery cathode material according to claim 1, wherein the atmosphere of high-temperature carbonization is air or argon.
6. The preparation method of the high-performance flexible secondary zinc-silver-zinc-air hybrid battery positive electrode material according to claim 5, wherein the carbonization temperature is 300-400 ℃ when the atmosphere of high-temperature carbonization is air.
7. The preparation method of the high-performance flexible secondary zinc-silver-zinc-air hybrid battery positive electrode material according to claim 5, wherein when the high-temperature carbonization atmosphere is argon, the carbonization temperature is 700-900 ℃, and the carbonized carbon is distributed in 3 mol/L FeCl3Soaking in the solution for 5-8 h, taking out the carbon cloth, washing with deionized water, and drying in vacuum.
8. The high performance flexibility of claim 1The preparation method of the secondary zinc-silver-zinc-air hybrid battery anode material is characterized in that the silver electrodeposition time is 0.5-2 h, and the current density is 5-10 mA/cm2。
9. The metal-organic complex-based nanomaterial positive electrode prepared by the method of any one of claims 1 to 8.
10. The use of a metal-organic complex-based nanomaterial positive electrode prepared by the method of any one of claims 1 to 8 in a zinc-silver/zinc-air hybrid battery.
CN202110567141.1A 2021-05-24 2021-05-24 Preparation method of high-performance flexible secondary zinc-silver-zinc-air hybrid battery positive electrode material Pending CN113299928A (en)

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