CN114156451B - Carbon cloth composite material with three-dimensional structure zinc pyrovanadate nanosheets grown on surface, preparation method of carbon cloth composite material and rechargeable battery - Google Patents

Carbon cloth composite material with three-dimensional structure zinc pyrovanadate nanosheets grown on surface, preparation method of carbon cloth composite material and rechargeable battery Download PDF

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CN114156451B
CN114156451B CN202111441252.4A CN202111441252A CN114156451B CN 114156451 B CN114156451 B CN 114156451B CN 202111441252 A CN202111441252 A CN 202111441252A CN 114156451 B CN114156451 B CN 114156451B
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carbon cloth
zinc
composite material
pyrovanadate
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CN114156451A (en
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刘金云
朱亚军
王艳
朱莉影
韩阗俐
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Anhui Normal University
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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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention provides a carbon cloth composite material with a three-dimensional structure zinc pyrovanadate nanosheet grown on the surface, a preparation method thereof and a rechargeable battery, wherein glycine is added into NH 4 VO 3 Stirring the solution for reaction, and adding Zn (NO) into the obtained mixed solution 3 ) 2 ·6H 2 And carrying out hydrothermal synthesis on the O solution and the carbon cloth to obtain the carbon cloth composite material with the zinc pyrovanadate nanosheets grown on the surface. Compared with the prior art, the invention has the advantages of low cost, excellent performance, good stability of cycle performance, long service life and the like by compounding the carbon cloth and the zinc pyrovanadate, and reduces the loss of active substances in the charging/discharging process, thereby improving the electrochemical performance of the anode. The composite material of the invention improves the cycle stability of the battery, has long service life of the battery, good controllability, simple experimental process, low cost and environmental protection.

Description

Carbon cloth composite material with three-dimensional structure zinc pyrovanadate nanosheets grown on surface, preparation method of carbon cloth composite material and rechargeable battery
Technical Field
The invention belongs to the technical field of battery composite materials, and particularly relates to a carbon cloth composite material with zinc pyrovanadate nanosheets grown on the surface, a preparation method thereof, and a water system zinc ion positive electrode and a zinc ion battery prepared by using the carbon cloth composite material.
Background
With the rapid development of electronic technology, the development of flexible electronic devices has received more and more attention from the academia and industry. One of the biggest challenges in developing flexible electronics is developing flexible, lightweight, thin, and safe portable energy storage devices that are compatible with them. Currently, lithium ion batteries are widely used in portable electronic devices. However, due to limited reserves of lithium resources on earth, organic system batteries have serious potential safety hazards, and development of flexible lithium ion batteries faces a plurality of dilemmas. Therefore, it is becoming more attractive to develop new flexible energy storage systems that are safer and cheaper.
In recent years, zinc ion batteries ((ZIBs) have great application prospects in flexible energy storage devices by virtue of the advantages of high safety, easiness in assembly, high capacity, low cost, environmental friendliness, abundant zinc resources and the like, and the ZIBs adopt neutral or weak acid electrolyte, and the energy storage mechanism is that Zn is adopted unlike the traditional alkaline batteries 2+ "rocking chair" batteries as carriers, i.e. by Zn 2+ Dissolution/deposition of Zn in zinc anode 2+ Electrochemical intercalation/deintercalation at the anode, thereby realizing reversible storage and release of electric energy. ZIBs exhibit excellent charge and discharge properties as compared to conventional alkaline batteries. In recent years, the study of ZIBs has become a focus of attention in the field of polyvalent metal ion batteries, and has made great progress, and these studies have made great progress in the development of next-generation high-performance zinc anode materials.
Disclosure of Invention
The invention aims to provide a carbon cloth composite material with a three-dimensional structure zinc pyrovanadate nano sheet grown on the surface, which is a carbon cloth composite material with a zinc pyrovanadate nano sheet grown on the surface, a composite electrode and a zinc pyrovanadate nano sheet grown on the surface.
The invention also aims to provide a preparation method of the carbon cloth composite material with the zinc pyrovanadate nano-sheets of the three-dimensional structure grown on the surface, which is characterized in that the carbon cloth composite material with the zinc pyrovanadate nano-sheets grown on the surface is preliminarily synthesized by a hydrothermal method, and then the carbon cloth composite material with the zinc pyrovanadate nano-sheets grown on the surface is obtained by washing and drying.
The invention also provides a rechargeable battery, and a flexible zinc ion battery manufactured by adopting the carbon cloth composite material with the three-dimensional structure zinc pyrovanadate nanosheets grown on the surface.
The invention aims at achieving the purposes, and the specific technical scheme is as follows:
the preparation method of the carbon cloth composite material with the three-dimensional structure zinc pyrovanadate nanosheets grown on the surface comprises the following steps:
1) Adding glycine to NH under heating 4 VO 3 Stirring the solution to obtain solution A;
2) Dropwise adding a zinc source solution into the solution A in the step 1), adding carbon cloth to perform hydrothermal reaction, washing and drying a product to obtain surface growth Zn 3 (OH) 2 V 2 O 7 ·2H 2 Carbon cloth composite material of O nano-sheet.
NH as described in step 1) 4 VO 3 The preparation method of the solution comprises the following steps: NH is added to 4 VO 3 Placing in water, stirring at 60-100deg.C for 10-120 min;
NH as described in step 1) 4 VO 3 The concentration of the solution is 0.09-0.19M;
in the step 1), glycine is added under the heating condition at 60-100 ℃; stirring for 5-10min after glycine is added, and performing subsequent process.
Glycine and NH as described in step 1) 4 VO 3 NH contained in the solution 4 VO 3 The molar ratio is 2:3.
in the step 1), glycine and ammonium metavanadate are adopted, and the synthesized nano material is of a flaky compact structure, so that the improvement of the charge and discharge capacity of the battery is facilitated; the ammonium metavanadate serves to introduce the V element.
The zinc source in step 2) is a soluble zinc source, preferably Zn (NO) 3 ) 2 ·6H 2 O；
Zn (NO) as described in step 2) 3 ) 2 ·6H 2 The concentration of the O solution is 0.125-0.25M;
NH in step 1) 4 VO 3 NH in solution 4 VO 3 Molar ratio to zinc source in the zinc source solution in step 2) 3:2;
the specification of the carbon cloth WOS1002 in the step 2) is 100mm multiplied by 400mm.
Before the carbon cloth in the step 2) is used, pretreatment is carried out, and the pretreatment method comprises the following steps: and (3) treating the cut carbon cloth with aqua regia, acetone and ethanol in sequence, and finally washing with water.
The hydrothermal reaction in the step 2) means that the reaction is carried out for 8 to 12 hours at 160 to 180 ℃;
the hydrothermal reaction in the step 2) is carried out in a polytetrafluoroethylene high-pressure reaction kettle.
After the hydrothermal reaction in the step 2), washing and drying; the washing is to wash with deionized water for at least 3 times; the drying is carried out at 60-70deg.C for 10-12 hr.
The carbon cloth composite material with the zinc pyrovanadate nanosheets with the three-dimensional structures grown on the surfaces is prepared by the method. Growing zinc pyrovanadate nano-sheets on the surface of the carbon cloth; the zinc pyrovanadate nano sheet is sheet-shaped, the sheet-shaped size is 2-3 microns, the composite material is a small square sheet of 10mm multiplied by 10mm carbon cloth, and sheet-shaped zinc pyrovanadate uniformly grows on the surface.
The invention provides a rechargeable battery, which is prepared by using the carbon cloth composite material with the three-dimensional structure zinc pyrovanadate nanosheets grown on the surface, and the specific preparation method comprises the following steps:
the carbon cloth composite material with the three-dimensional structure zinc pyrovanadate nano-sheet grown on the surface is used as the positive electrode of the zinc ion battery, and the zinc ion battery is dried in a drying oven at 60 ℃ for 10-12 hours; the zinc sheet is used as a counter electrode, the electrolyte is manganese acetate/zinc acetate electrolyte, the hydrogel is PVA/manganese acetate-zinc acetate hydrogel, and the water-based zinc ion battery is obtained through assembly.
In the preparation method of the carbon cloth composite material with the zinc pyrovanadate nanosheets grown on the surface, the carbon cloth substrate is pretreated, the growth of the composite material is not facilitated due to the hydrophobicity of the carbon cloth, and the carbon cloth is sequentially treated by aqua regia, acetone, ethanol and water to make the carbon cloth hydrophilic, so that the growth of the composite material is facilitated; glycine is then added to NH 4 VO 3 Stirring the solution for reaction, adding a zinc source solution into the obtained mixed solution, and finally performing hydrothermal synthesis to obtain the carbon cloth composite material with the zinc pyrovanadate nanosheets grown on the surface.
The raw materials used in the preparation process are glycine, ammonium metavanadate and a zinc source, wherein the zinc source can be prepared from zinc salts with common crystal water, and the glycine and the ammonium metavanadate ensure that the product is of a sheet-shaped compact structure, and the battery assembled by the sheet-shaped nano material has better performance; control of NH 4 VO 3 The concentration of the solution, the concentration of the zinc source solution and the reaction conditions can control the shape and the size, and the battery performance is improved.
In the invention, NH in ammonium metavanadate 4 + Ionization in water makes the solution acidic, and glycine contains-COOH and-OH zwitterions, so that it has strong buffering property, can effectively retain pH stability of solution, and can be reacted with added zinc source to produce Zn 3 (OH) 2 V 2 O 7 ·2H 2 O。Zn 3 (OH) 2 V 2 O 7 ·2H 2 The crystal structure of O is composed of a layer-by-layer stack of Zn-V oxide polyhedral chains, in which zinc oxide layers (ZnO 6 ) By V-O-V bonds (V 2 O 7 4- Groups) are separated, and water molecules are located between the two layers. Such an open frame and a large interlayer spacing (0.715 nm vs. Zn) 2+ Hydrated ion radius of 0.43 nm) is Zn 2+ Providing an ideal insertion (extraction) route.
The carbon cloth is low in price and easy to obtain; the composite material of the zinc pyrovanadate and the carbon cloth improves the cycle stability of the battery, prolongs the service life, increases the capacity, reduces the loss of active substances in the charge and discharge process, and improves the electrochemical performance of the positive electrode material.
According to the invention, the carbon cloth composite material with the three-dimensional structure zinc pyrovanadate nanosheets grown on the surface is used as the anode of the flexible zinc ion battery, so that the zinc ion rechargeable battery is prepared, the cycling stability is good, the battery capacity is stabilized to be more than 100mAh/g after the zinc ion rechargeable battery is cycled for 250 times under the current density of 0.1A, and the average charge-discharge efficiency is maintained to be 95%.
Compared with the prior art, the invention has the advantages of low cost, excellent performance, good stability of cycle performance, long service life and the like by compounding the carbon cloth and the zinc pyrovanadate, and reduces the loss of active substances in the charging/discharging process, thereby improving the electrochemical performance of the anode. The composite material of the invention improves the cycle stability of the battery, has long service life of the battery, good controllability, simple experimental process, low cost and environmental protection.
Drawings
FIG. 1 is an SEM image of carbon cloth after the treatment of step 1) of example 3; the magnification is higher under the scanning electron microscope, so that the growth condition of the nano material is convenient to observe, and the presented cylindrical carbon fiber is single.
FIG. 2 is an SEM image of a carbon cloth composite material with zinc pyrovanadate nanoplatelets grown on the surface obtained in step 6) of example 3;
FIG. 3 is a TEM image of the carbon cloth composite material with zinc pyrovanadate nanoplatelets grown on the surface obtained in the step 6) of example 3;
FIG. 4 is an XRD pattern of the carbon cloth composite material with zinc pyrovanadate nanoplatelets grown on the surface obtained in step 6) of example 3;
FIG. 5 is an SEM image of a carbon cloth composite material with zinc pyrovanadate nanoplatelets grown on the surface obtained in step 6) of example 1;
FIG. 6 is an SEM image of a carbon cloth composite material with zinc pyrovanadate nanoplatelets grown on the surface obtained in step 6) of example 2;
FIG. 7 is an SEM image of a carbon cloth composite material with zinc pyrovanadate nanoplatelets grown on the surface obtained in step 6) of example 4;
FIG. 8 is an SEM image of a carbon cloth composite material with zinc pyrovanadate nanoplatelets grown on the surface obtained in step 6) of example 5;
FIG. 9 is a graph showing the charge and discharge capacity of a zinc ion battery assembled from a zinc ion battery anode prepared from a carbon cloth composite material with zinc pyrovanadate nanoplatelets grown on the surface prepared in example 3 at a current density of 0.1A;
fig. 10 is a charge-discharge curve test chart of a zinc ion battery assembled by a zinc ion battery anode prepared by a carbon cloth composite material with a zinc pyrovanadate nanosheet grown on the surface prepared in example 3 at a current density of 0.1A.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The test materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
Those of skill in the art, without any particular mention of the techniques or conditions, may follow the techniques or conditions described in the literature in this field or follow the product specifications.
In the invention, the stirring device is built: the invention is described in detail below with reference to examples using magnetic stirring.
Example 1
The preparation method of the carbon cloth composite material with the three-dimensional structure zinc pyrovanadate nanosheets grown on the surface comprises the following steps:
1) Pretreating carbon cloth: soaking WOS1002 carbon cloth with the specification of 100mm multiplied by 400mm in aqua regia for 24 hours, respectively carrying out ultrasonic treatment on the carbon cloth for 10 hours by using acetone and ethanol, and finally washing the carbon cloth by using deionized water until no carbon fiber exists, so that the carbon cloth becomes hydrophilic, and the growth of a composite material is facilitated;
2) At 80℃7.5mmol NH 4 VO 3 The powder was dissolved in 40mL deionized water; thermal insulation stirringAfter stirring for 20 minutes, NH was added at 80 ℃ 4 VO 3 Adding 5mmol glycine into the solution, and stirring for 8min;
3) 5mmol Zn (NO) 3 ) 2 ·6H 2 O is added into 20mL of deionized water to obtain a solution;
4) Dropwise adding the solution obtained in the step 3) into the mixed solution obtained in the step 2), and stirring for 10 minutes;
5) Transferring the solution obtained in the step 4) into a 50mL polytetrafluoroethylene high-pressure reaction kettle, adding the carbon cloth treated in the step 1), and reacting for 8 hours at 180 ℃;
6) Washing the product obtained in the step 5) with deionized water for 5 times, and drying in a 60 ℃ oven for 12 hours to obtain the carbon cloth composite material with the zinc pyrovanadate nanosheets grown on the surface.
The prepared carbon cloth composite material with the zinc pyrovanadate nano-sheet grown on the surface has a characterization diagram shown in figure 5, and is a small carbon cloth square sheet with the size of 10mm multiplied by 10mm, and the zinc pyrovanadate nano-sheet grows on the carbon cloth square sheet and has the size of about 2 microns.
Example 2
The preparation method of the carbon cloth composite material with the three-dimensional structure zinc pyrovanadate nanosheets grown on the surface comprises the following steps:
1) Pretreating carbon cloth: soaking WOS1002 carbon cloth with the specification of 100mm multiplied by 400mm in aqua regia for 24 hours, respectively carrying out ultrasonic treatment on the carbon cloth for 10 hours by using acetone and ethanol, and finally washing the carbon cloth by using deionized water until no carbon fiber exists, so that the carbon cloth becomes hydrophilic, and the growth of a composite material is facilitated;
2) At 80℃7.5mmol NH 4 VO 3 The powder was dissolved in 40mL deionized water. After stirring for 20 minutes, NH was brought to 80 ℃ 4 VO 3 Adding 5mmol glycine into the solution, and stirring for 10min;
3) 5mmol Zn (NO) 3 ) 2 ·6H 2 O is added into 20mL of deionized water to obtain a solution;
4) Dropwise adding the solution obtained in the step 3) into the mixed solution obtained in the step 2), and stirring for 10 minutes;
5) Transferring the solution obtained in the step 4) into a 50mL polytetrafluoroethylene high-pressure reaction kettle, adding the carbon cloth treated in the step 1), and reacting at 170 ℃ for 10 hours;
6) Washing the product obtained in the step 5) with deionized water for at least 3 times, and drying in a 60 ℃ oven for 12 hours to obtain the carbon cloth composite material with the zinc pyrovanadate nanosheets grown on the surface.
The prepared carbon cloth composite material with the zinc pyrovanadate nano-sheet grown on the surface is a small carbon cloth square sheet with the size of 10mm multiplied by 10mm, and the zinc pyrovanadate nano-sheet grows on the carbon cloth square sheet and has the size of 2 microns.
Example 3
The preparation method of the carbon cloth composite material with the three-dimensional structure zinc pyrovanadate nanosheets grown on the surface comprises the following steps:
1) Pretreating carbon cloth: soaking WOS1002 carbon cloth with the specification of 100mm multiplied by 400mm in aqua regia for 24 hours, respectively carrying out ultrasonic treatment on the carbon cloth for 10 hours by using acetone and ethanol, and finally washing the carbon cloth by using deionized water until no carbon fiber exists, so that the carbon cloth becomes hydrophilic, and the growth of a composite material is facilitated;
2) At 80℃3.75mmol NH 4 VO 3 The powder was dissolved in 40mL deionized water. After stirring for 20 minutes, NH was brought to 80 ℃ 4 VO 3 Adding 2.5mmol glycine into the solution, and stirring for 8min;
3) 2.5mmol Zn (NO) 3 ) 2 ·6H 2 O is added into 20mL of deionized water to obtain a solution;
4) Dropwise adding the solution obtained in the step 3) into the mixed solution obtained in the step 2), and stirring for 10 minutes;
5) Transferring the solution obtained in the step 4) into a 50mL polytetrafluoroethylene high-pressure reaction kettle, adding the carbon cloth treated in the step 1), and reacting at 170 ℃ for 10 hours;
6) Washing the product obtained in the step 5) with deionized water for 5 times, and drying in a 60 ℃ oven for 12 hours to obtain the carbon cloth composite material with the zinc pyrovanadate nanosheets grown on the surface.
The prepared carbon cloth composite material with the zinc pyrovanadate nano-sheet grown on the surface is a small carbon cloth square sheet with the size of 10mm multiplied by 10mm, and the zinc pyrovanadate nano-sheet grows on the carbon cloth square sheet and has the size of about 2 microns.
Fig. 3 is a TEM image of a carbon cloth composite material with zinc pyrovanadate nanoplatelets grown on the surface obtained in step 6) of example 3, after being peeled from the carbon cloth.
Example 4
The preparation method of the carbon cloth composite material with the three-dimensional structure zinc pyrovanadate nanosheets grown on the surface comprises the following steps:
1) Pretreating carbon cloth: soaking WOS1002 carbon cloth with the specification of 100mm multiplied by 400mm in aqua regia for 24 hours, respectively carrying out ultrasonic treatment on the carbon cloth with the specification of 100mm multiplied by 400mm in acetone and ethanol for 10 hours, and finally washing the carbon cloth with deionized water until no carbon fiber exists, so that the carbon cloth becomes hydrophilic, and the growth of a composite material is facilitated;
2) At 80℃3.75mmol NH 4 VO 3 The powder was dissolved in 40mL deionized water. After stirring for 20 minutes, NH was brought to 80 ℃ 4 VO 3 Adding 2.5mmol glycine into the solution, and stirring for 5min;
3) 2.5mmol Zn (NO) 3 ) 2 ·6H 2 O is added into 20mL of deionized water to obtain a solution;
4) Dropwise adding the solution obtained in the step 3) into the mixed solution obtained in the step 2), and stirring for 10 minutes;
5) Transferring the solution obtained in the step 4) into a 50mL polytetrafluoroethylene high-pressure reaction kettle, adding the carbon cloth treated in the step 1), and reacting for 8 hours at 180 ℃;
6) Washing the product obtained in the step 5) with deionized water for 4 times, and drying in a 60 ℃ oven for 12 hours to obtain the carbon cloth composite material with the zinc pyrovanadate nanosheets grown on the surface.
The prepared carbon cloth composite material with the zinc pyrovanadate nano-sheet grown on the surface is a small carbon cloth square sheet with the size of 10mm multiplied by 10mm, and the zinc pyrovanadate nano-sheet grows on the carbon cloth square sheet and has the size of about 2 microns.
Example 5
The preparation method of the carbon cloth composite material with the three-dimensional structure zinc pyrovanadate nanosheets grown on the surface comprises the following steps:
1) Pretreating carbon cloth: soaking WOS1002 carbon cloth with the specification of 100mm multiplied by 400mm in aqua regia for 24 hours, carrying out acetone and ethanol ultrasonic treatment for 10 hours respectively, and finally washing with deionized water until no carbon fiber exists, so that the carbon cloth becomes hydrophilic, and the growth of a composite material is facilitated;
2) At 80℃4.5mmol NH 4 VO 3 The powder was dissolved in 40mL deionized water. After stirring for 20 minutes, NH was brought to 80 DEG C 4 VO 3 Adding 3mmol glycine to the solution;
3) At the same time, 3mmol Zn (NO 3 ) 2 ·6H 2 O is added into 20mL of deionized water to obtain a solution;
4) Dropwise adding the solution obtained in the step 3) into the mixed solution obtained in the step 2), and stirring for 10 minutes;
5) Transferring the solution obtained in the step 4) into a 50mL polytetrafluoroethylene high-pressure reaction kettle, adding the carbon cloth treated in the step 1), and reacting at 170 ℃ for 10 hours;
6) Washing the product obtained in the step 5) with deionized water for at least 3 times, and drying in a 60 ℃ oven for 12 hours to obtain the carbon cloth composite material with the zinc pyrovanadate nanosheets grown on the surface.
The prepared carbon cloth composite material with the zinc pyrovanadate nano-sheet grown on the surface is a small carbon cloth square sheet with the size of 10mm multiplied by 10mm, and the zinc pyrovanadate nano-sheet grows on the carbon cloth square sheet and has the size of about 2 microns.
Example 6
A zinc ion battery is prepared by adopting the carbon cloth composite material with the zinc pyrovanadate nanosheets grown on the surface prepared in the embodiment 3 as a water-based zinc ion battery anode, and assembling the water-based zinc ion battery anode.
The preparation method comprises the following steps:
taking the carbon cloth composite material with the zinc pyrovanadate nanosheets grown on the surface of the final product obtained in the example 3 as the positive electrode of the water-based zinc ion battery, and drying the water-based zinc ion battery in a drying oven at 60 ℃ for 12 hours; the zinc sheet is used as a counter electrode, the electrolyte is manganese acetate/zinc acetate electrolyte, the hydrogel is PVA/manganese acetate-zinc acetate hydrogel, and the water-based zinc ion battery is obtained through assembly.
The assembled zinc ion battery is subjected to charge and discharge performance test by using a battery tester, the test result of the cycle stability under the current density of 0.1A is shown in figures 9-10, the battery capacity is stabilized to be more than 100mAh/g after the battery is cycled for 250 times under the current density of 0.1A, and the average charge and discharge efficiency is maintained to be more than 95%. Fig. 10 is a charge and discharge curve of the product of example 3 for the first 250 cycles after battery assembly, and it can be seen that there is a significant charge and discharge plateau between 1.0 and 1.4V.
The foregoing detailed description of the carbon cloth composite material for growing zinc pyrovanadate nanosheets, the preparation method thereof, and the aqueous zinc ion battery anode and zinc ion battery described above with reference to the examples is illustrative and not limiting, and several examples can be listed according to the defined scope, so variations and modifications without departing from the general inventive concept shall fall within the scope of protection of the present invention.

Claims (6)

1. The preparation method of the carbon cloth composite material with the three-dimensional structure zinc pyrovanadate nanosheets grown on the surface is characterized by comprising the following steps of:
1) Adding glycine to NH under heating 4 VO 3 Stirring the solution to obtain solution A;
2) Dropwise adding a zinc source solution into the solution A in the step 1), adding carbon cloth to perform hydrothermal reaction, washing and drying a product to obtain surface growth Zn 3 (OH) 2 V 2 O 7 ·2H 2 Carbon cloth composite material of O nano-sheet;
glycine and NH as described in step 1) 4 VO 3 NH contained in the solution 4 VO 3 The molar ratio is 2:3, a step of;
the hydrothermal reaction in the step 2) means that the reaction is carried out for 8-12 hours at 160-180 ℃.
2. The method according to claim 1, wherein the NH in step 1) is selected from the group consisting of 4 VO 3 The concentration of the solution is 0.09-0.19M.
3. The method of claim 1, wherein the concentration of the zinc source solution in step 2) is 0.125-0.25M.
4. According to the weightsThe process according to claim 1, wherein NH in step 1) 4 VO 3 NH in solution 4 VO 3 Molar ratio to zinc source in the zinc source solution in step 2) 3:2.
5. a carbon cloth composite material with three-dimensional structure zinc pyrovanadate nano-sheets grown on the surface prepared by the preparation method of any one of claims 1-4, which is characterized in that the zinc pyrovanadate nano-sheets are grown on the surface of the carbon cloth; the zinc pyrovanadate nano-sheet is sheet-shaped, and the sheet-shaped size is 2-3 microns.
6. A rechargeable battery, which is characterized in that the rechargeable battery is prepared from the carbon cloth composite material with the zinc pyrovanadate nano-sheet with the three-dimensional structure grown on the surface according to claim 5.
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CN114914423B (en) * 2022-05-26 2023-07-14 华东师范大学 Composite material of zinc vanadate coated carbon microsphere, and preparation method and application thereof

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102299312A (en) * 2011-08-08 2011-12-28 浙江大学 Three-dimensional porous lithium vanadate anode material and preparation method thereof
CN103413938A (en) * 2013-04-08 2013-11-27 三峡大学 Pyrovandate cathode material of lithium-ion battery and preparation method of pyrovandate cathode material
CN108217725A (en) * 2018-01-04 2018-06-29 湖北大学 A kind of hydrated basic pyrovanadic acid zinc（Zn3V2O7(OH)2·2H2O）The preparation method and application of material
CN108346795A (en) * 2018-01-25 2018-07-31 三峡大学 A kind of water system Zinc ion battery negative material Zn3(OH)2V2O7·2H2The preparation method of O
CN110444408A (en) * 2019-08-30 2019-11-12 哈尔滨理工大学 A kind of vanadium nitride nanometer sheet flexible composite electrode material and the preparation method and application thereof
CN110492100A (en) * 2019-09-02 2019-11-22 吉林大学 Zinc manganate nanoparticle carbon cloth composite material and preparation method thereof and lithium ion battery
CN110581268A (en) * 2019-09-26 2019-12-17 安徽师范大学 Self-supporting binary metal sulfide composite material and preparation method thereof, lithium ion battery cathode and lithium ion battery
CN112341639A (en) * 2020-11-05 2021-02-09 安徽师范大学 Self-repairing hydrogel, preparation method thereof and flexible self-repairing rechargeable battery
CN112436118A (en) * 2020-11-23 2021-03-02 华中农业大学 VO2(B) Carbon cloth self-supporting material and preparation method and application thereof
CA3155063A1 (en) * 2019-09-20 2021-03-25 Li-S Energy Limited Flexible lithium-sulfur batteries
CN113457663A (en) * 2021-07-28 2021-10-01 东莞市普隆电子有限公司 3D nano flower-shaped Zn3(VO4)2Preparation method and application thereof

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102299312A (en) * 2011-08-08 2011-12-28 浙江大学 Three-dimensional porous lithium vanadate anode material and preparation method thereof
CN103413938A (en) * 2013-04-08 2013-11-27 三峡大学 Pyrovandate cathode material of lithium-ion battery and preparation method of pyrovandate cathode material
CN108217725A (en) * 2018-01-04 2018-06-29 湖北大学 A kind of hydrated basic pyrovanadic acid zinc（Zn3V2O7(OH)2·2H2O）The preparation method and application of material
CN108346795A (en) * 2018-01-25 2018-07-31 三峡大学 A kind of water system Zinc ion battery negative material Zn3(OH)2V2O7·2H2The preparation method of O
CN110444408A (en) * 2019-08-30 2019-11-12 哈尔滨理工大学 A kind of vanadium nitride nanometer sheet flexible composite electrode material and the preparation method and application thereof
CN110492100A (en) * 2019-09-02 2019-11-22 吉林大学 Zinc manganate nanoparticle carbon cloth composite material and preparation method thereof and lithium ion battery
CA3155063A1 (en) * 2019-09-20 2021-03-25 Li-S Energy Limited Flexible lithium-sulfur batteries
CN110581268A (en) * 2019-09-26 2019-12-17 安徽师范大学 Self-supporting binary metal sulfide composite material and preparation method thereof, lithium ion battery cathode and lithium ion battery
CN112341639A (en) * 2020-11-05 2021-02-09 安徽师范大学 Self-repairing hydrogel, preparation method thereof and flexible self-repairing rechargeable battery
CN112436118A (en) * 2020-11-23 2021-03-02 华中农业大学 VO2(B) Carbon cloth self-supporting material and preparation method and application thereof
CN113457663A (en) * 2021-07-28 2021-10-01 东莞市普隆电子有限公司 3D nano flower-shaped Zn3(VO4)2Preparation method and application thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
3D hierarchical Zn3(OH)2V2O7·2H2O and Zn3(VO4)2 microspheres: Synthesis,characterization and photoluminescence;Miao Wang等;Materials Research Bulletin;第47卷(第1期);18-23 *
焦钒酸锌纳米材料的制备;顾媛媛;;化学工程与装备(07);全文 *
碘/碳纤维布正极材料的制备及其电化学性能;孙鸿晨;韩亚娜;柏冲;蔡锋石;;电源技术(第11期);全文 *
纳米钒酸锌的制备及表面特性研究;郑皓心;朱丽伟;左桂鸿;郑友进;;黑龙江科技信息(第31期);全文 *

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