CN117638096A - Cu-Zn-ZIF-8-based zinc-free dendrite deposited carbon fiber anode material, battery and method thereof - Google Patents
Cu-Zn-ZIF-8-based zinc-free dendrite deposited carbon fiber anode material, battery and method thereof Download PDFInfo
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 57
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 57
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 210000001787 dendrite Anatomy 0.000 title claims abstract description 39
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 title claims abstract description 39
- 239000010405 anode material Substances 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims abstract description 16
- 239000011701 zinc Substances 0.000 claims abstract description 62
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 53
- 239000000463 material Substances 0.000 claims abstract description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 25
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical group [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000004744 fabric Substances 0.000 claims description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 10
- 239000007773 negative electrode material Substances 0.000 claims description 10
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- SLCITEBLLYNBTQ-UHFFFAOYSA-N CO.CC=1NC=CN1 Chemical compound CO.CC=1NC=CN1 SLCITEBLLYNBTQ-UHFFFAOYSA-N 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 5
- 239000011787 zinc oxide Substances 0.000 claims description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910001431 copper ion Inorganic materials 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- 239000003014 ion exchange membrane Substances 0.000 claims description 3
- 239000012982 microporous membrane Substances 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 230000008021 deposition Effects 0.000 abstract description 15
- 230000006911 nucleation Effects 0.000 abstract description 12
- 238000010899 nucleation Methods 0.000 abstract description 12
- 239000007772 electrode material Substances 0.000 abstract description 6
- 230000004888 barrier function Effects 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 238000011946 reduction process Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 9
- 238000004146 energy storage Methods 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- -1 carbon felt Chemical compound 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- KJYQVRBDBPBZTD-UHFFFAOYSA-N methanol;nitric acid Chemical compound OC.O[N+]([O-])=O KJYQVRBDBPBZTD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000005036 potential barrier Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- GTSHREYGKSITGK-UHFFFAOYSA-N sodium ferrocyanide Chemical group [Na+].[Na+].[Na+].[Na+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] GTSHREYGKSITGK-UHFFFAOYSA-N 0.000 description 1
- 235000012247 sodium ferrocyanide Nutrition 0.000 description 1
- 239000000264 sodium ferrocyanide Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a Cu-Zn-ZIF-8-based zinc-free dendrite deposited carbon fiber anode material, a battery and a method thereof, and belongs to the field of flow battery electrode materials. According to the invention, the surface of the carbon fiber is covered with a layer of Cu-Zn-ZIF-8 material, so that uniform and stable deposition of zinc ions is realized, and zinc dendrite generation is inhibited. Cu-Zn-ZIF-8 grows on the surface of the carbon fiber through hydrothermal reaction, and the nucleation barrier of Zn can be reduced due to higher bonding energy between the Cu-Zn-ZIF-8 and Zn atoms, so that Zn deposition is promoted. The method has simple process and stable performance, and the carbon felt prepared by the method is used as an electrode material of the negative electrode of the zinc-based flow battery, so that the mass transfer rate of zinc ions on the surface of the electrode can be enhanced, the nucleation site of Zn can be increased, the deposition uniformity of the zinc ions in the reduction process is remarkably improved, the generation of zinc dendrites is inhibited, the working current density range of the battery is widened, and the service life and the safety of the zinc-based flow battery are improved.
Description
Technical Field
The invention belongs to the field of electrode materials of flow batteries, and particularly relates to a Cu-Zn-ZIF-8-based zinc-free dendrite deposited carbon fiber anode material, a battery and a method thereof.
Background
The use of renewable energy sources such as solar energy and wind energy is increasing. However, renewable energy generation is difficult to completely replace traditional energy forms due to the intermittent and unstable nature of renewable energy. Thus, with the large-scale utilization of renewable energy sources, the demand for energy storage technology is also increasing. Among them, zinc-based flow battery has the outstanding advantages of abundant raw materials, low cost, high flexibility, high safety, high capacity, etc., which makes zinc-based flow battery one of the solutions for large-scale energy storage.
However, unlike all-vanadium and other liquid-liquid flow batteries, zinc-based flow batteries undergo zinc metal plating and stripping in the redox reaction of the negative electrode, resulting in zinc dendrite generation due to zinc deposition non-uniformity. The zinc dendrite can increase battery polarization loss after generation, reduce battery efficiency and capacity, and can puncture the separator when severe, resulting in short circuit. Dendrite problems seriously affect the service life and safety of zinc-based flow batteries. Thus, alleviating the zinc dendrite problem is of great importance for large-scale application of zinc-based flow batteries.
Disclosure of Invention
The invention aims to provide a Cu-Zn-ZIF-8-based carbon fiber anode material deposited without zinc dendrite, a battery and a method thereof, aiming at the common zinc dendrite problem in zinc-based flow batteries. The invention can reduce zinc nucleation barrier, enhance zinc deposition uniformity, inhibit zinc dendrite generation, enhance the efficiency and capacity of the zinc-based flow battery, and greatly prolong the service life of the zinc-based flow battery.
The specific technical scheme adopted by the invention is as follows:
in a first aspect, the invention provides a zinc dendrite-free deposited carbon fiber anode material based on Cu-Zn-ZIF-8, which is formed by compounding a Cu-Zn-ZIF-8 material and a carbon fiber material, wherein the Cu-Zn-ZIF-8 material is uniformly distributed on the surface of the carbon fiber material in a granular form, and a uniform micro-nano pore structure is formed.
Preferably, the carbon fiber material is carbon felt, graphite felt, carbon cloth or carbon paper.
In a second aspect, the invention provides a preparation method of a Cu-Zn-ZIF-8-based zinc-free dendrite deposited carbon fiber anode material, which comprises the following steps:
adding the 2-methylimidazole methanol solution with the same volume into the copper-zinc solution, and uniformly stirring to obtain a mixed solution; and soaking the pretreated carbon fiber material in the mixed solution, fully reacting for 12-48 hours (preferably 12-24 hours) at room temperature (preferably 25-30 ℃), and washing and drying to obtain the Cu-Zn-ZIF-8-based zinc-free dendrite deposited carbon fiber anode material.
Preferably, in the copper-zinc solution, the concentration of copper ions is 0.01-0.03M (more preferably 0.01M), the concentration of zinc ions is 0.05-0.5M (more preferably 0.1-0.3M), and the solvent is methanol; the solute adopts one of the following combinations: zinc acetate, copper acetate or zinc nitrate, copper nitrate.
Preferably, the concentration of the 2-methylimidazole methanol solution is 0.2-2M.
Preferably, the pretreatment process of the carbon fiber material is as follows: the carbon fiber material was soaked in a 68wt% concentrated nitric acid solution for 24 hours, and after the soaking was completed, washed with deionized water to ph=7.
Preferably, the washing and drying means washing with deionized water and methanol until the solution ph=7, and then drying in a vacuum drying oven at 40-80 ℃ (more preferably 50-70 ℃) for 6 hours.
In a third aspect, the invention provides a zinc-based flow battery, wherein the negative electrode of the battery is the zinc-free dendrite deposited carbon fiber negative electrode material based on Cu-Zn-ZIF-8 in the first aspect or the zinc-free dendrite deposited carbon fiber negative electrode material based on Cu-Zn-ZIF-8 obtained by the preparation method in the second aspect; the positive electrode of the battery is made of carbon fiber material.
Preferably, the thickness of the negative electrode is 0.7 to 6mm (more preferably 1 to 2 mm), and the porosity is 75 to 98% (more preferably 90%).
Preferably, the battery negative electrode electrolyte is zinc oxide solution or zinc ion solution, and the concentration of zinc in the solution is 0.1-0.4M; the battery separator is one of an ion exchange membrane, a porous membrane or a microporous membrane.
Compared with the prior art, the invention has the following beneficial effects:
the invention adopts the carbon fiber negative electrode material for zinc-free dendrite deposition based on Cu-Zn-ZIF-8, has higher binding energy with Zn atoms, can obviously reduce zinc nucleation potential barrier, improve zinc nucleation uniformity and induce zinc ion uniform deposition, thereby effectively inhibiting zinc dendrite growth. The material is successfully applied to the negative electrode of the zinc-based flow battery, so that the efficiency and the capacity of the battery can be remarkably improved, and the working current density range of the battery is widened. Meanwhile, the negative electrode material can avoid the problem of diaphragm penetration caused by zinc dendrite formation, thereby prolonging the service life of the battery and improving the application safety of the battery. In addition, the preparation process is simple and convenient, the cost is low, the material performance is stable and reliable, a feasible solution is provided for the application of the zinc-based flow battery in the large-scale energy storage field, and the wide application of the zinc-based flow battery in the large-scale energy storage field is promoted.
Drawings
FIG. 1 is an electron microscope image of a Cu-Zn-ZIF-8-based zinc-free dendrite deposited carbon fiber negative electrode material;
FIG. 2 is a graph of zinc nucleation overpotential for the examples versus the comparative examples;
FIG. 3 is a scanning electron microscope image of example electrodes and comparative example electrodes at the end of charge of a zinc-based flow battery.
Detailed Description
In order that the invention may be more readily understood, a further description of the invention will be rendered by reference to specific examples that are illustrated in the appended drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
The invention provides a Cu-Zn-ZIF-8-based zinc-free dendrite deposited carbon fiber anode material which is mainly formed by compounding a Cu-Zn-ZIF-8 material and a carbon fiber material, wherein the Cu-Zn-ZIF-8 material is uniformly distributed on the surface of the carbon fiber material in a granular form, and a uniform micro-nano pore structure is formed.
In actual use, the carbon fiber material may be carbon felt, graphite felt, carbon cloth or carbon paper.
For the Cu-Zn-ZIF-8-based zinc-free dendrite deposited carbon fiber anode material, the invention provides a preparation method thereof, which comprises the following steps:
(1) Pretreating carbon fibers: the carbon fiber material was immersed in a 68wt% concentrated nitric acid solution for 24 hours. After the soaking is completed, the mixture is washed by deionized water until the pH value is=7.
(2) Preparing a solution: preparing a copper-zinc mixed solution, wherein the concentration of copper ions is 0.01-0.03M, preferably 0.01M; the zinc ion concentration is 0.05-0.5M, preferably 0.1-0.3M; the solute is zinc acetate, copper acetate or zinc nitrate, copper nitrate, and the solvent is methanol.
(3) Adding the 2-methylimidazole methanol solution with the same volume into the copper-zinc mixed solution, and uniformly stirring to obtain the mixed solution. The concentration of the 2-methylimidazole methanol solution is 0.2 to 2M, preferably 0.4 to 1.2M.
(4) The carbon fiber material is soaked in the mixed solution and reacted for 12-48 hours, preferably 12-24 hours, at room temperature, preferably at a temperature of 25-30 ℃.
(5) The reacted carbon fiber material was washed with deionized water and methanol to ph=7.
(6) And (3) placing the carbon fiber material into a vacuum drying oven, and drying at 40-80 ℃, preferably 50-70 ℃ for 6 hours to obtain the zinc-free dendrite deposited carbon fiber anode material based on Cu-Zn-ZIF-8.
The invention further provides a zinc-based flow battery based on the Cu-Zn-ZIF-8 zinc-free dendrite deposited carbon fiber anode material. In the battery, a zinc-free dendrite deposited carbon fiber anode material of Cu-Zn-ZIF-8 is used as a battery anode; the positive electrode of the battery is common carbon fiber, including carbon felt, graphite felt, carbon cloth or carbon paper, etc.
In actual use, the thickness of the negative electrode is 0.7-6mm, preferably 1-2mm; the porosity is 75% -98%, preferably 90%. The battery negative electrode electrolyte is zinc oxide solution or zinc ion solution, and the concentration of zinc in the solution is 0.1-0.4M; the battery separator is one of an ion exchange membrane, a porous membrane or a microporous membrane.
Examples
The invention provides a Cu-Zn-ZIF-8-based zinc-free dendrite deposited carbon fiber anode material, a scanning electron microscope image of which is shown in figure 1, and the surface of the carbon fiber is covered with granular Cu-Zn-ZIF-8 crystals. The carbon fiber electrode material is specifically a carbon cloth electrode material.
The preparation raw materials of the Cu-Zn-ZIF-8-based zinc-free dendrite deposited carbon fiber material of the embodiment comprise: original common carbon cloth with model of carbon energy WS040, copper nitrate, zinc nitrate, 2-methylimidazole, deionized water and concentrated nitric acid methanol. The preparation method comprises the following steps:
(1) The carbon cloth material was soaked in a 68wt% concentrated nitric acid solution for 24 hours. After the soaking is completed, the mixture is washed by deionized water until the pH value is=7.
(2) 50ml of copper-zinc mixed solution was prepared: wherein the copper ion concentration is 0.01M; zinc ion concentration was 0.05M; the solute is zinc nitrate and copper nitrate, and the solvent is methanol.
(3) 50ml of 2-methylimidazole methanol solution with the concentration of 0.2M is added into the copper-zinc mixed solution, and the mixed solution is obtained after uniform stirring.
(4) The carbon cloth is soaked in the mixed solution and reacts for 24 hours at room temperature.
(5) The reacted carbon fiber was washed with deionized water and methanol to ph=7.
(6) And (3) putting the carbon fiber into a vacuum drying oven, and drying at 50 ℃ for 6 hours to obtain the Cu-Zn-ZIF-8-based zinc-free dendrite deposited carbon fiber anode material.
Comparative example
The model of the raw carbon cloth which is not treated is carbon energy WS040.
The properties of the carbon cloth materials of examples and comparative examples were measured using a three electrode system in which the working electrode was two carbon cloths cut to a size of 1cm x 1cm, the counter electrode was a platinum sheet electrode, the reference electrode was a mercury oxide electrode, the electrolyte was a zinc oxide solution, and the concentration was 0.4mol/L. The zinc nucleation overpotential of both materials was measured under constant current deposition conditions and the results are shown in fig. 2.
The electrodes of the examples and the comparative examples were respectively mounted on the negative electrode of an alkaline zinc-iron flow battery. The positive electrode of the battery is square common carbon felt with the thickness of 3mm, the size of 5cm x 5cm and the porosity of 90%; the cathode electrode is formed by superposing carbon cloth materials in a three-layer embodiment or a comparative embodiment, the size of the cathode electrode is 5cm x 5cm, the anode electrolyte is sodium ferrocyanide solution, and the concentration is 0.8mol/L; the negative electrode electrolyte is zinc oxide solution with the concentration of 0.4mol/L; the membrane is Nafion211 membrane manufactured by DuPont company at 80mA/cm 2 The negative electrode zinc deposition morphology is shown in figure 3 for 24 minutes of charging.
Fig. 2 shows that the nucleation overpotential difference between the examples and the comparative examples is reduced (14 mV) compared with the nucleation overpotential (3 mV) of the examples, which indicates that zinc ions have a lower deposition energy barrier on the electrode surface, uniform nucleation is more easily achieved, and the zinc deposition effect is more uniform, so that zinc dendrites can be effectively prevented from being generated.
Fig. 3 shows the morphology difference of zinc deposited on the surfaces of the example and the comparative example, and it can be seen that the zinc on the surface of the comparative example is agglomerated into balls, and the zinc deposition on the surface of the example is distributed more uniformly and has smoother morphology, so that zinc dendrites are less likely to occur, and the operation safety of the zinc-based flow battery can be effectively improved.
According to the invention, the surface of the carbon fiber is covered with a layer of Cu-Zn-ZIF-8 material, so that uniform and stable deposition of zinc ions is realized, and zinc dendrite generation is inhibited. Cu-Zn-ZIF-8 grows on the surface of the carbon fiber through hydrothermal reaction, and the nucleation barrier of Zn can be reduced due to higher bonding energy between the Cu-Zn-ZIF-8 and Zn atoms, so that Zn deposition is promoted. The method has simple process and stable performance, and the carbon felt prepared by the method is used as an electrode material of the negative electrode of the zinc-based flow battery, so that the mass transfer rate of zinc ions on the surface of the electrode can be enhanced, the nucleation site of Zn can be increased, the deposition uniformity of the zinc ions in the reduction process is remarkably improved, the generation of zinc dendrites is inhibited, the working current density range of the battery is widened, and the service life and the safety of the zinc-based flow battery are improved.
The above embodiment is only a preferred embodiment of the present invention, but it is not intended to limit the present invention. Various changes and modifications may be made by one of ordinary skill in the pertinent art without departing from the spirit and scope of the present invention. Therefore, all the technical schemes obtained by adopting the equivalent substitution or equivalent transformation are within the protection scope of the invention.
Claims (10)
1. The zinc-free dendrite deposited carbon fiber negative electrode material based on Cu-Zn-ZIF-8 is characterized by being formed by compounding a Cu-Zn-ZIF-8 material and a carbon fiber material, wherein the Cu-Zn-ZIF-8 material is uniformly distributed on the surface of the carbon fiber material in a granular form, and a uniform micro-nano pore structure is formed.
2. The Cu-Zn-ZIF-8-based zinc-free dendrite deposited carbon fiber negative electrode material of claim 1 wherein the carbon fiber material is carbon felt, graphite felt, carbon cloth, or carbon paper.
3. The preparation method of the zinc-free dendrite deposited carbon fiber negative electrode material based on Cu-Zn-ZIF-8 is characterized by comprising the following steps of:
adding the 2-methylimidazole methanol solution with the same volume into the copper-zinc solution, and uniformly stirring to obtain a mixed solution; and soaking the pretreated carbon fiber material in the mixed solution, fully reacting at room temperature, washing and drying to obtain the Cu-Zn-ZIF-8-based zinc-free dendrite deposited carbon fiber anode material.
4. The method according to claim 3, wherein the copper-zinc solution has a copper ion concentration of 0.01 to 0.03M and a zinc ion concentration of 0.05 to 0.5M, and the solvent is methanol; the solute adopts one of the following combinations: zinc acetate, copper acetate or zinc nitrate, copper nitrate.
5. A method of preparation according to claim 3, wherein the concentration of the 2-methylimidazole methanol solution is 0.2-2M.
6. A method according to claim 3, characterized in that the pretreatment of the carbon fiber material is as follows: the carbon fiber material was soaked in a 68wt% concentrated nitric acid solution for 24 hours, and after the soaking was completed, washed with deionized water to ph=7.
7. A method according to claim 3, wherein the washing and drying means washing with deionized water and methanol to a solution ph=7, followed by drying at 40-80 ℃ for 6h.
8. A zinc-based flow battery, which is characterized in that the negative electrode of the battery is a zinc-free dendrite deposited carbon fiber negative electrode material based on Cu-Zn-ZIF-8 according to claim 1 or a zinc-free dendrite deposited carbon fiber negative electrode material based on Cu-Zn-ZIF-8 obtained by the preparation method according to any one of claims 3-7; the positive electrode of the battery is made of carbon fiber material.
9. The zinc-based flow battery of claim 8, wherein the negative electrode has a thickness of 0.7-6mm and a porosity of 75% -98%.
10. The zinc-based flow battery of claim 8, wherein the negative electrode electrolyte of the battery is a zinc oxide solution or a zinc ion solution, and the concentration of zinc in the solution is 0.1-0.4M; the battery separator is one of an ion exchange membrane, a porous membrane or a microporous membrane.
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