CN114464764B - Preparation method and application of polyaniline-coated ferric vanadate flexible electrode - Google Patents
Preparation method and application of polyaniline-coated ferric vanadate flexible electrode Download PDFInfo
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- 229920000767 polyaniline Polymers 0.000 title claims abstract description 38
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- 239000004744 fabric Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000006056 electrooxidation reaction Methods 0.000 claims abstract description 4
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 4
- 239000000758 substrate Substances 0.000 claims abstract description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 26
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 14
- 229910052697 platinum Inorganic materials 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 9
- 238000000151 deposition Methods 0.000 claims description 9
- 230000008021 deposition Effects 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 9
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 5
- 238000004070 electrodeposition Methods 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- 235000010344 sodium nitrate Nutrition 0.000 claims description 4
- 239000004317 sodium nitrate Substances 0.000 claims description 4
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 6
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 238000009831 deintercalation Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 3
- 239000011247 coating layer Substances 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000011701 zinc Substances 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 239000007772 electrode material Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Abstract
The invention discloses a preparation method and application of a polyaniline-coated ferric vanadate flexible electrode, and belongs to the technical field of water-based zinc ion battery materials. The electrode takes carbon cloth as a flexible substrate, and Fe is prepared by a hydrothermal reaction-electrochemical oxidation polymerization two-step method 5 V 15 O 39 (OH) 9 ·9H 2 The O@PANI three-dimensional conductive network skeleton grows on the surface of the carbon cloth uniformly, and the structure can limit the volume effect in the process of zinc ion deintercalation and promote the transmission speed of ions and electrons. Meanwhile, the introduction of the polyaniline coating layer can further improve the conductivity, specific capacity, platform voltage and structural stability of the electrode, and the obtained polyaniline coated ferric vanadate material has better electrochemical performance compared with a pure ferric vanadate material. The preparation method of the electrode is simple and efficient, low in cost, high in controllability and suitable for large-scale production.
Description
Technical Field
The invention belongs to the technical field of water-based zinc ion battery materials, and particularly relates to a preparation method and application of a polyaniline-coated ferric vanadate flexible electrode.
Background
With the increasing demands of people on lightweight and wearable electronic products, the development of novel flexible energy storage devices becomes an important point of current research. In recent years, lithium ion batteries which are rapidly developed are unsuitable for being applied to the flexible field due to the lack of resource reserves, the human toxicity of organic electrolyte, the flammability and other problems. In contrast, the water-based zinc ion battery adopts safer, environment-friendly and cheaper water-based electrolyte, and has the advantages of simple manufacturing process, abundant zinc resources, high theoretical specific capacity and the like, so that the water-based zinc ion battery has extremely strong application potential of the flexible energy storage device. However, the development of flexible zinc ion batteries is still in the primary stage, and the development of low-cost, high-capacity and high-flexibility cathode materials has been a difficulty in the field.
Vanadium belongs to a typical transition metal element, and a special outermost electron structure causes vanadium to present various valence states (+5, +4, +3, +2) in a compound, and the multiple valence states can induce multiple electron transfer so as to contribute to high theoretical specific capacity, so that vanadium-based materials are attracting attention in the research of zinc ion batteries. Wherein the vanadium iron binary metal oxide Fe 5 V 15 O 39 (OH) 9 ·9H 2 O has higher resource abundance and environmental friendliness in nature, and the large-spacing interlayer space in the crystal structure can accommodate more Zn 2+ And promotes the ion transmission speed, thereby having certain application potential. Chinese patent (CN 112062160A) fully studied Fe 5 V 15 O 39 (OH) 9 ·9H 2 O has application to the electrochemical performance of zinc ion battery anodes, but its study is limited to conventional rigid cathode materials and exhibits ideal long-cycle stability only within 300 turns. The electrode material is expanded to the flexible field, and the conductivity, specific capacity, platform voltage and structural stability of the electrode are obviously improved by coating polyaniline, so that the electrode material has very important significance in promoting commercialization of flexible zinc ion batteries.
Disclosure of Invention
The invention provides a preparation method and application of a polyaniline-coated ferric vanadate flexible electrode. The invention uses Fe 5 V 15 O 39 (OH) 9 ·9H 2 The application of the O positive electrode material is expanded to the field of flexible zinc ion batteries, and the conductivity, specific capacity, platform voltage and structural stability of the electrode are obviously improved by coating polyaniline. The polyaniline coated ferric vanadate flexible electrode has a uniform three-dimensional conductive network skeleton structure, and the structure can limit the volume effect in the zinc ion deintercalation process and accelerate the separationThe electron and electron transport rates, thereby helping the electrode to achieve good electrochemical performance.
The technical scheme of the invention is as follows:
the preparation method of the polyaniline-coated ferric vanadate flexible electrode comprises the following steps: carbon cloth is used as a flexible substrate, and Fe is prepared by a hydrothermal reaction-electrochemical oxidation polymerization two-step method 5 V 15 O 39 (OH) 9 ·9H 2 The O@PANI three-dimensional conductive network skeleton grows on the surface of the carbon cloth uniformly, and the thickness of the obtained network skeleton is about 30-70nm, and specifically comprises the following steps:
(1) Transferring a certain amount of dilute hydrochloric acid into a beaker, and sequentially adding a certain amount of sodium nitrate, ferric chloride and vanadium trichloride into the dilute hydrochloric acid. The above solution was stirred at room temperature for 15min, transferred to an autoclave, and a piece of carbon cloth was added and subjected to hydrothermal reaction. After cooling, repeatedly cleaning the obtained product with deionized water to obtain CC@Fe 5 V 15 O 39 (OH) 9 ·9H 2 O precursor electrode.
(2) CC@Fe obtained in step (1) 5 V 15 O 39 (OH) 9 ·9H 2 The O precursor electrode is clamped by a platinum electrode clamp to be used as a working electrode, a platinum sheet electrode with the same size is used as a counter electrode, and a certain amount of pyrrole monomer is dissolved in 1mol L -1 The uniform solution obtained after further ultrasonic dispersion is electrolyte, and constant current electrodeposition is carried out in an electrode pool. After the deposition is finished, the CC@Fe is obtained by reversely washing with deionized water and drying 5 V 15 O 39 (OH) 9 ·9H 2 O@PANI flexible electrode.
Preferably, the diluted hydrochloric acid used in step (1) has a pH of 1.5 to 3.5.
Preferably, in the step (1), the sodium nitrate is added in an amount of 0.005 to 0.030mol, the ferric chloride is added in an amount of 0.005 to 0.030mol, and the vanadium trichloride is added in an amount of 0.0002 to 0.0010mol.
Preferably, the volume of the hydrothermal reaction solution in step (1) is 50% -80% of the volume of the autoclave.
Preferably, the hydrothermal reaction temperature in the step (1) is 60-140 ℃ and the reaction time is 0.5-3h.
Preferably, the pyrrole monomer is added in the amount of 0.001 to 0.010mol in step (2).
Preferably, the constant current deposition current density in step (2) is 1-5mA cm -2 The deposition time is 10-40min.
The application of the polyaniline-coated ferric vanadate flexible electrode is that the polyaniline-coated ferric vanadate flexible electrode is a positive electrode of a water-based zinc ion battery.
The invention has the beneficial effects that:
(1) The flexible electrode of the carbon cloth polyaniline coated ferric vanadate is synthesized by a simple hydrothermal reaction-electrochemical oxidation polymerization two-step method. The three-dimensional conductive network skeleton structure of the electrode not only can limit the volume effect in the zinc ion deintercalation process, but also can accelerate the transmission speed of ions and electrons. Meanwhile, the introduction of the polyaniline coating layer can further improve the conductivity, specific capacity, platform voltage and structural stability of the electrode, so that the composite electrode has excellent electrochemical performance.
(2) The invention adds Fe to the Chinese patent (CN 112062160A) 5 V 15 O 39 (OH) 9 ·9H 2 The application of the O positive electrode material is expanded to the field of flexible zinc ion batteries. Meanwhile, the acid resistance of the material is skillfully utilized to finish polyaniline proton acid doped coating modification, so that the electrode material has better electrochemical performance. Such as at 0.2mA cm -2 582.2. Mu. Ah cm at current density of (C) -2 High specific discharge capacity of (2); at 2mA cm -2 Can still keep 225.1 mu Ah cm after 1000 circles of circulation under the current density -2 Is a specific discharge capacity of (a).
Drawings
FIGS. 1 and 2 are SEM images of a polyaniline-coated ferric vanadate flexible electrode prepared in example 1 of the present invention;
FIG. 3 is a graph showing that the polyaniline-coated ferric vanadate flexible electrode prepared in example 1 of the present invention was 2mA cm when applied to a zinc ion battery -2 Long cycle performance plot at current density;
Detailed Description
The invention is further described below with reference to examples and figures.
Example 1
(1) Taking 0.02mol NaNO 3 、0.015mol FeCl 3 And 0.00075mol VCl 3 Dissolved in 18ml of diluted hydrochloric acid with a pH of 1.5. The solution was magnetically stirred at room temperature for 15min, then transferred to a 25mL autoclave and a piece of ready-to-use carbon cloth was added. The reaction kettle is screwed up and put into a blast drying oven with the temperature of 120 ℃ for 1h. Naturally cooling for 8h after finishing constant temperature, taking out the obtained product after the reaction kettle is cooled to room temperature, repeatedly cleaning with deionized water, and finally drying for 12h at 60 ℃ to obtain CC@Fe 5 V 15 O 39 (OH) 9 ·9H 2 O precursor electrode.
(2) CC@Fe obtained in step (1) 5 V 15 O 39 (OH) 9 ·9H 2 The O precursor electrode is clamped by a platinum electrode clamp to be used as a working electrode, a platinum sheet electrode with the same size is used as a counter electrode, and 0.007mol of pyrrole monomer is dissolved in 1mol L -1 The uniform solution obtained after further ultrasonic dispersion is electrolyte. At 2mA cm -2 And (3) performing constant current electrodeposition under the current density, and repeatedly cleaning and drying the working electrode after 30min of deposition to obtain the polyaniline-coated ferric vanadate flexible electrode.
Fig. 1 and fig. 2 are scanning electron microscope images of polyaniline-coated iron vanadate grown on carbon cloth prepared in example 1 of the present invention, and it can be seen that the three-dimensional conductive network skeleton is uniformly and tightly arranged on carbon cloth fibers.
The flexible electrode prepared in example 1 was used as the positive electrode, and a zinc sheet held by a platinum electrode holder was used as the negative electrode, 1M ZnSO 4 The zinc ion battery performance test is carried out under a two-electrode system as electrolyte, the test voltage range is 0.2-1.8V, and the test voltage is compared with Zn/Zn 2+ . The electrode material is 0.2mA cm -2 582.2. Mu. Ah cm at a current density of (C) -2 High specific discharge capacity of (2). FIG. 3 is a graph of 2mA cm -2 Long cycle performance at current density for 225.1 muAh cm after 1000 cycles -2 And proved to have excellent long-cycle stability.
Example 2
(1) Taking 0.02mol NaNO 3 、0.015mol FeCl 3 And 0.00075mol VCl 3 Dissolved in 18ml of diluted hydrochloric acid with a pH of 1.5. The solution was magnetically stirred at room temperature for 15min, then transferred to a 25mL autoclave and a piece of ready-to-use carbon cloth was added. The reaction kettle is screwed up and put into a blast drying oven with the temperature of 120 ℃ for 1h. Naturally cooling for 8h after finishing constant temperature, taking out the obtained product after the reaction kettle is cooled to room temperature, repeatedly cleaning with deionized water, and finally drying for 12h at 60 ℃ to obtain CC@Fe 5 V 15 O 39 (OH) 9 ·9H 2 O precursor electrode.
(2) CC@Fe obtained in step (1) 5 V 15 O 39 (OH) 9 ·9H 2 The O precursor electrode is clamped by a platinum electrode clamp to be used as a working electrode, a platinum sheet electrode with the same size is used as a counter electrode, and 0.007mol of pyrrole monomer is dissolved in 1mol L -1 The uniform solution obtained after further ultrasonic dispersion is electrolyte. At 2mA cm -2 And (3) performing constant current electrodeposition under the current density, and repeatedly cleaning and drying the working electrode after 20min of deposition to obtain the polyaniline-coated ferric vanadate flexible electrode.
The flexible electrode prepared in example 1 was used as the positive electrode, and a zinc sheet held by a platinum electrode holder was used as the negative electrode, 1M ZnSO 4 The zinc ion battery performance test is carried out under a two-electrode system as electrolyte, the test voltage range is 0.2-1.8V, and the test voltage is compared with Zn/Zn 2+ . The electrode material is 0.2mA cm -2 565.5 mu Ah cm at a current density of (A) -2 High specific discharge capacity of (2) mA cm -2 Can still keep 221.4 mu Ah cm after 1000 circles of current density -2 Is a specific discharge capacity of (a).
Example 3
(1) Taking 0.02mol NaNO 3 、0.015mol FeCl 3 And 0.00075mol VCl 3 Dissolved in 18ml of diluted hydrochloric acid with a pH of 1.5. The solution was magnetically stirred at room temperature for 15min, then transferred to a 25mL autoclave and a piece of ready-to-use carbon cloth was added. The reaction kettle is screwed up and put into a blast drying oven with the temperature of 120 ℃ for 1.5 hours. Naturally cooling for 8h after finishing constant temperature, taking out the obtained product and repeatedly cleaning with deionized water after the reaction kettle is cooled to room temperature, and finallyDrying at 60deg.C for 12 hr to obtain CC@Fe 5 V 15 O 39 (OH) 9 ·9H 2 O precursor electrode.
(2) CC@Fe obtained in step (1) 5 V 15 O 39 (OH) 9 ·9H 2 The O precursor electrode is clamped by a platinum electrode clamp to be used as a working electrode, a platinum sheet electrode with the same size is used as a counter electrode, and 0.007mol of pyrrole monomer is dissolved in 1mol L -1 The uniform solution obtained after further ultrasonic dispersion is electrolyte. At 2mA cm -2 And (3) performing constant current electrodeposition under the current density, and repeatedly cleaning and drying the working electrode after 30min of deposition to obtain the polyaniline-coated ferric vanadate flexible electrode.
The flexible electrode prepared in example 1 was used as the positive electrode, and a zinc sheet held by a platinum electrode holder was used as the negative electrode, 1M ZnSO 4 The zinc ion battery performance test is carried out under a two-electrode system as electrolyte, the test voltage range is 0.2-1.8V, and the test voltage is compared with Zn/Zn 2+ . The electrode material is 0.2mA cm -2 542.8. Mu.Ah cm at a current density of (A) -2 High specific discharge capacity of (2) mA cm -2 Can still keep 213.8 mu Ah cm after being cycled for 1200 circles under the current density -2 Is a specific discharge capacity of (a).
Claims (9)
1. A preparation method of a polyaniline-coated ferric vanadate flexible electrode is characterized in that the polyaniline-coated ferric vanadate flexible electrode takes carbon cloth as a flexible substrate, and Fe is prepared by a hydrothermal reaction-electrochemical oxidation polymerization two-step method 5 V 15 O 39 (OH) 9 ·9H 2 The O@PANI three-dimensional conductive network skeleton grows on the surface of the carbon cloth uniformly, the thickness of the obtained network skeleton is 30-70nm, and the preparation method comprises the following steps:
(1) Transferring a certain amount of dilute hydrochloric acid into a beaker, sequentially adding a certain amount of sodium nitrate, ferric chloride and vanadium trichloride into the dilute hydrochloric acid, stirring the solution at room temperature for 15min, transferring into an autoclave, adding a piece of carbon cloth, performing hydrothermal reaction, cooling, and repeatedly cleaning the obtained product with deionized water to obtain CC@Fe 5 V 15 O 39 (OH) 9 ·9H 2 An O precursor electrode;
(2) CC@Fe obtained in step (1) 5 V 15 O 39 (OH) 9 ·9H 2 The O precursor electrode is clamped by a platinum electrode clamp to be used as a working electrode, a platinum sheet electrode with the same size is used as a counter electrode, and a certain amount of pyrrole monomer is dissolved in 1mol L -1 The uniform solution obtained after further ultrasonic dispersion is used as electrolyte, constant current electrodeposition is carried out in an electrode pool, deionized water is reversely used for cleaning and drying are carried out after the deposition is completed, and CC@Fe is obtained 5 V 15 O 39 (OH) 9 ·9H 2 O@PANI flexible electrode.
2. The method for preparing the polyaniline-coated ferric vanadate flexible electrode according to claim 1, wherein the pH value of the diluted hydrochloric acid used in the step (1) is 1.5-3.5.
3. The method for preparing the polyaniline-coated ferric vanadate flexible electrode according to claim 1, wherein in the step (1), the sodium nitrate addition amount is 0.005-0.030mol, the ferric chloride addition amount is 0.005-0.030mol, and the vanadium trichloride addition amount is 0.0002-0.0010mol.
4. The method for preparing the polyaniline-coated ferric vanadate flexible electrode according to claim 1, wherein the volume of the solution in the step (1) is 50% -80% of the volume of the high-pressure reaction kettle.
5. The method for preparing the polyaniline-coated ferric vanadate flexible electrode according to claim 1, wherein the hydrothermal reaction temperature in the step (1) is 60-140 ℃ and the reaction time is 0.5-3h.
6. The method for preparing the polyaniline-coated ferric vanadate flexible electrode according to claim 1, wherein the addition amount of the pyrrole monomer in the step (2) is 0.001-0.010mol.
7. A kind of according to claim 1The preparation method of the polyaniline coated ferric vanadate flexible electrode is characterized in that the constant current deposition current density in the step (2) is 1-5mA cm -2 The deposition time is 10-40min.
8. A polyaniline coated ferric vanadate flexible electrode, wherein the electrode is prepared by the preparation method of any one of claims 1-7.
9. The application of the polyaniline-coated ferric vanadate flexible electrode, which is characterized in that the polyaniline-coated ferric vanadate flexible electrode is prepared by the preparation method according to any one of claims 1-7, and the application is the positive electrode of a water-based zinc ion battery.
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