CN113299898B - Fluorine doping modification method for enhancing positive electrode of nickel-zinc battery and positive electrode material thereof - Google Patents
Fluorine doping modification method for enhancing positive electrode of nickel-zinc battery and positive electrode material thereof Download PDFInfo
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000011737 fluorine Substances 0.000 title claims abstract description 23
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 23
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 12
- 238000002715 modification method Methods 0.000 title claims abstract description 8
- 230000002708 enhancing effect Effects 0.000 title abstract description 10
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 title abstract description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000011701 zinc Substances 0.000 claims abstract description 29
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- 229910052799 carbon Inorganic materials 0.000 claims description 24
- 239000004744 fabric Substances 0.000 claims description 22
- 239000010405 anode material Substances 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 239000010406 cathode material Substances 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims 1
- 239000007772 electrode material Substances 0.000 abstract description 25
- 230000001276 controlling effect Effects 0.000 abstract description 4
- 230000006872 improvement Effects 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 7
- 238000005520 cutting process Methods 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 5
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 description 3
- 239000011686 zinc sulphate Substances 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- 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
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- B82Y40/00—Manufacture or treatment of nanostructures
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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
- H01M10/00—Secondary cells; Manufacture thereof
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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
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- 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
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Abstract
The invention discloses a fluorine doping modification method for enhancing a nickel-zinc battery positive electrode and a positive electrode material thereof, wherein the shape, electronic structure property and phase composition of the prepared electrode material are regulated and controlled by controlling the fluorine doping amount, so that the fluorine doping has obvious improvement effect on the shape and electronic structure of the electrode material, and after the fluorine doping is utilized, the shape of the electrode material is converted into a one-dimensional and two-dimensional composite structure from a single nano linear structure, thereby being beneficial to enhancing the structural stability of the electrode material and further enhancing the cycle life of the electrode material as a water-based zinc-based battery positive electrode material. In addition, fluorine doping plays a role in improving the valence state of active metal in the electrode material, so that the electronic structure property and the conductivity of the electrode material are influenced, the obvious excellent cycle stability is shown, and the service life is long. In addition, the preparation method is simple, quick and effective, reduces the cost and difficulty of industrial large-scale production, is suitable for large-scale industrial production, and has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of battery anode materials, and particularly relates to a fluorine doping modification method for enhancing an anode of a nickel-zinc battery and an anode material thereof.
Background
With the increasing environmental problems and the increasing consumption of fossil energy, the development of clean and sustainable new energy and new energy storage technology is an urgent matter. Among many energy storage technologies, lithium ion batteries still occupy the dominant position in the current market, but the low storage capacity, high cost and safety problems of lithium limit the further development of lithium batteries. The water system zinc-based battery has the advantages of environmental protection, low cost, rich zinc reserve, safety and the like, but the cycle life of the water system zinc-based battery is low as the main bottleneck for limiting the rapid development of the water system zinc-based battery at present. The reasons for the short cycle life of the zinc-based battery anode material comprise poor stability of zinc anode dendrites and the anode material, and the zinc dendrite problem is effectively solved by means of regulating and controlling electrolyte, controlling morphology and the like at present, so that how to enhance the stability of the anode material of the zinc-based battery is of great importance.
During the cyclic charge and discharge process, the positive electrode material of the zinc-based battery usually has the problems of phase transformation, structural collapse, volume expansion or active metal dissolution, and the like, thereby causing capacity fading. At present, scientists mainly aim to solve the above problems of the cathode material. For example, the Nazar team reported a utilization of Zn2+And crystal water intercalation V2O5By increasing V2O5The interlayer distance of (2) reduces the transmission resistance of electrolyte ions, thereby achieving the effect of stabilizing the electrode material structure. In addition, surface coating on the positive electrode material is also an effective strategy. For example, Yanqing Fu et al report a method of protecting a manganese oxide electrode with a carbon layer. After 120 cycles of charge and discharge, the carbon-coated manganese oxide can still provide higher capacity as the anode material. The anode material is subjected to nano-structure design, so that the circulation stability of the anode material can be effectively improved, and the reasonable structural design can reduce the ion transmission resistance of the electrolyte and the transmission path of the electrolyte, so that the purpose of enhancing the stability of the material is achieved. For example, Jinping Liu et al designed a three-dimensional structured nickel oxide positive electrode material that was able to retain 91% of its initial capacity after 1000 charge-discharge cycles.
As can be seen from the above documents, the above conventional methods can effectively improve the cycle stability of the positive electrode material of the zinc-based battery, but still have problems. Ion intercalation, carbon material coating, and nano-structure design are generally complex in preparation process, which increases process cost. In addition, the regulation and control of the structure or the components cannot be precisely controlled in large-scale preparation, so the application prospect is not clear.
Disclosure of Invention
In view of the above-mentioned shortcomings, the present invention aims to provide a fluorine doping modification method for enhancing a positive electrode of a nickel-zinc battery and a positive electrode material thereof.
In order to realize the purpose, the technical scheme provided by the invention is as follows:
a fluorine doping modification method for enhancing a positive electrode of a nickel-zinc battery comprises the following steps:
(1) adding nitrate, urea and a certain amount of ammonium fluoride dissolved solution into distilled water, and uniformly stirring to obtain a solution, wherein the molar ratio of ammonium fluoride to nitrate is 1: 1-4, the concentration of the nitrate is 10-100 mmol/L, and the molar ratio of the nitrate to the urea is 1: 4-6, preferably 1: 5;
(2) adding the carbon cloth into the solution obtained in the step (1) to fully soak the carbon cloth;
(3) transferring the solution and the carbon cloth into a reaction kettle, and then heating;
(4) and after the hydrothermal reaction is finished, taking out the carbon cloth, cleaning and drying to obtain the cathode material.
As a preferable scheme of the invention, the stirring mode in the step (1) is magnetic stirring, the rotating speed is 200-500 r/min, and the stirring time is 10-60 min.
As a preferable scheme of the invention, the ultrasonic treatment in the step (2) is carried out for 10-40 minutes to fully soak the carbon cloth.
As a preferable mode of the present invention, the volume of the reaction vessel in the step (3) is 1.2 times or more the volume of the solution in the step (1).
As a preferable scheme of the invention, in the step (3), the reaction kettle is positioned in an oven for heating, the heating temperature is 60-140 ℃, and the heating time is 10-20 hours.
As a preferable scheme of the invention, deionized water is adopted to ultrasonically clean the carbon cloth in the step (4).
As a preferable scheme of the invention, the number of times of ultrasonic cleaning of the carbon cloth by deionized water in the step (4) is more than or equal to 3 times, and the ultrasonic cleaning time is more than or equal to 15 minutes each time.
As a preferable embodiment of the present invention, the carbon cloth cleaned in the step (4) is dried in a vacuum drying oven.
As a preferable scheme of the invention, the vacuum degree of the vacuum drying oven is less than 133Pa, the drying temperature is 70-90 ℃, and the drying is carried out for 3-24 hours.
The water system zinc-based battery anode material is prepared by adopting the fluorine doping modification method for enhancing the nickel-zinc battery anode.
The invention has the beneficial effects that: according to the invention, the shape, electronic structure property and phase composition of the prepared electrode material are regulated and controlled by controlling the fluorine doping amount, so that the fluorine doping can obviously improve the shape and electronic structure of the electrode material, and after the fluorine doping is utilized, the shape of the electrode material is converted into a one-dimensional and two-dimensional composite structure from a single nano linear structure, so that the structural stability of the electrode material is favorably enhanced, and the cycle life of the electrode material as the anode material of the water-based zinc-based battery is prolonged. In addition, fluorine doping plays a role in improving the valence state of the active metal in the electrode material, so that the electronic structural property and the conductivity of the electrode material are influenced (increased from 0.22S/cm to 0.37S/cm). Due to the improvement, the fluorine-doped electrode material shows obviously excellent cycle stability in the water-based zinc-based battery and has long service life. In addition, the preparation method is simple, quick and effective, reduces the cost and difficulty of industrial large-scale production, is suitable for large-scale industrial production, and has wide application prospect.
The invention is further illustrated by the following examples in conjunction with the drawings.
Drawings
Figure 1 is the cycle stability data for the samples prepared in comparative example 1.
Fig. 2 is the cycle stability data and coulombic efficiency for the samples prepared in example 1.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the examples are only preferred embodiments of the present invention, and the present invention is not intended to list all the embodiments. The examples are given solely for the purpose of illustrating the invention and are not intended to limit the scope of the invention.
Comparative example 1:
weighing 1.162g Ni (NO)3)2·6H2O,0.581g Co(NO3)2·6H2Dissolving 1.8g of urea in 72mL of deionized water, and stirring for 30 minutes at the rotating speed of 350rpm/min by using a magnetic stirrer to obtain a uniform solution; cutting 5X3cm2And (3) dipping the carbon cloth in the solution, carrying out ultrasonic treatment for 30 minutes, transferring the solution and the carbon cloth to a 100mL hydrothermal reaction kettle, reacting for 12 hours in a 120 ℃ oven, carrying out ultrasonic cleaning for 3 times by using deionized water, cleaning for 15 minutes each time, then placing in the oven, vacuumizing until the vacuum degree is less than 133pa, and carrying out vacuum drying for 12 hours at 80 ℃ to obtain the material. Cut 1x1cm2The prepared material is used as the anode material of the water-based zinc-based battery and adopts 2M KOH +0.02M ZnSO4The solution is electrolyte, and the zinc sheet is a negative electrode to assemble the water-system zinc-based battery for testing. The discharge capacity of the prepared electrode material is 210mAh/g when the current density is 1A/g. As shown in fig. 1, after 5000 charge-discharge cycles, the capacity remained 51.2% of the initial value.
Example 1:
weighing 1.162g Ni (NO)3)2·6H2O,0.581g Co(NO3)2·6H2Dissolving 1.8g of urea and 0.444g of ammonium fluoride in 72mL of deionized water, and stirring for 30 minutes at the rotating speed of 350rpm/min by using a magnetic stirrer to obtain a uniform solution; cutting 5X3cm2And (3) dipping the carbon cloth in the solution, carrying out ultrasonic treatment for 30 minutes, transferring the solution and the carbon cloth to a 100mL hydrothermal reaction kettle, reacting for 12 hours in a 120 ℃ oven, carrying out ultrasonic cleaning for 3 times by using deionized water, cleaning for 15 minutes each time, then placing in the oven, vacuumizing until the vacuum degree is less than 133pa, and carrying out vacuum drying for 12 hours at 80 ℃ to obtain the material. Cutting 1x1cm2The obtained material is used as the anode material of an aqueous zinc-based battery, and2M KOH+0.02M ZnSO4the solution is electrolyte, and the zinc sheet is a negative electrode to assemble the water-system zinc-based battery for testing. The discharge capacity of the prepared electrode material is 245mAh/g when the current density is 1A/g. As shown in fig. 2, after 10000 charge-discharge cycles, the capacity remained 90% of the initial value.
Example 2:
weighing 1.162g Ni (NO)3)2·6H2O,0.581g Co(NO3)2·6H2Dissolving 1.8g of urea and 0.888g of ammonium fluoride in 72mL of deionized water, and stirring for 30 minutes at the rotating speed of 350rpm/min by using a magnetic stirrer to obtain a uniform solution; cutting 5X3cm2And (3) dipping the carbon cloth in the solution, carrying out ultrasonic treatment for 30 minutes, transferring the solution and the carbon cloth into a 100mL hydrothermal reaction kettle, reacting for 12 hours in a drying oven at 120 ℃, then carrying out ultrasonic cleaning for 3 times by using deionized water, cleaning for 15 minutes each time, then placing in the drying oven, vacuumizing until the vacuum degree is less than 133pa, and carrying out vacuum drying for 12 hours at 80 ℃ to obtain the material. Cutting 1x1cm2The prepared material is used as the anode material of the water-system zinc-based battery and takes 2M KOH +0.02M ZnSO4The solution is electrolyte, and the zinc sheet is a negative electrode to assemble the water-system zinc-based battery for testing. The discharge capacity of the prepared electrode material is 155mAh/g when the current density is 1A/g. The capacity remained increased for the first 5000 cycles and then tended to stabilize, with almost no decrease after 10000 cycles of charge-discharge cycles.
Compared with the examples 1 and 2, the comparison example 1 shows that fluorine doping has obvious improvement effect on the appearance and the electronic structure of the electrode material, and the appearance of the electrode material is converted into a one-dimensional and two-dimensional composite structure from a single nanowire-shaped structure after the fluorine element is doped, so that the structural stability of the electrode material is favorably enhanced. In addition, fluorine doping improves the valence state of the active metal in the electrode material, thereby affecting the electronic structure property and the conductivity of the electrode material. Due to the improvement, the fluorine-doped electrode material shows obviously excellent cycling stability in the water-based zinc-based battery.
Variations and modifications to the above-described embodiments may occur to those skilled in the art, which fall within the scope and spirit of the above description. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and modifications and variations of the present invention are also intended to fall within the scope of the appended claims. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation. Other methods and materials, which may be derived from the same or similar methods and components as described in the above examples of the invention, are within the scope of the invention.
Claims (5)
1. A fluorine doping modification method for a positive electrode material of an aqueous zinc-based battery is characterized by comprising the following steps:
(1) dissolving nickel nitrate, cobalt nitrate, urea and a certain amount of ammonium fluoride in distilled water, and uniformly stirring to obtain a solution, wherein the molar ratio of ammonium fluoride to nitrate is (1-4): 1, the concentration of nitrate in the solution is 10-100 mmol/L, and the molar ratio of nitrate to urea is 1: 4-6;
(2) adding the carbon cloth into the solution obtained in the step (1) to fully soak the carbon cloth;
(3) transferring the solution and the carbon cloth into a reaction kettle, and then heating;
(4) after the hydrothermal reaction is finished, taking out the carbon cloth, cleaning, and then drying to obtain a positive electrode material;
performing ultrasonic treatment for 10-40 minutes in the step (2) to fully soak the carbon cloth;
the reaction kettle in the step (3) is positioned in an oven for heating, the heating temperature is 60-140 ℃, and the heating time is 10-20 hours;
drying the carbon cloth cleaned in the step (4) in a vacuum drying oven;
the vacuum degree of the vacuum drying oven is less than 133Pa, the drying temperature is 70-90 ℃, and the drying is carried out for 3-24 hours.
2. The method for modifying the fluorine doping of the anode material of the aqueous zinc-based battery according to claim 1, wherein the stirring manner in the step (1) is magnetic stirring, the rotating speed is 200-500 rpm, and the stirring time is 10-60 minutes.
3. The method for modifying fluorine doping in a positive electrode material of an aqueous zinc-based battery according to claim 1, wherein the volume of the reaction vessel in the step (3) is 1.2 times or more the volume of the solution in the step (1).
4. The method for modifying the fluorine doping of the water-based zinc-based battery cathode material according to claim 1, wherein the step (4) comprises ultrasonically cleaning the carbon cloth with deionized water.
5. The method for modifying the fluorine doping of the anode material of the aqueous zinc-based battery according to claim 4, wherein the carbon cloth is ultrasonically cleaned by deionized water in the step (4) for more than or equal to 3 times, and the ultrasonic cleaning time is more than or equal to 15 minutes each time.
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| Title |
|---|
| Cobalt iron carbonate hydroxide hydrate on 3D porous carbon as active and stable bifunctional oxygen electrode for Zn-air battery;Yan Qi-Jin等;《Journal of Power Sources》;20180924;第402卷;第388-393页 * |
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| CN113299898A (en) | 2021-08-24 |
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