CN115548295A - Preparation method of polyaniline composite material for positive electrode of Zn ion battery - Google Patents
Preparation method of polyaniline composite material for positive electrode of Zn ion battery Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
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- 239000011259 mixed solution Substances 0.000 claims description 69
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 30
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 26
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 26
- 239000011701 zinc Substances 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 24
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- 150000002500 ions Chemical class 0.000 claims description 16
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- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 6
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- 239000010405 anode material Substances 0.000 abstract description 6
- 238000011161 development Methods 0.000 abstract description 4
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- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 6
- 239000010406 cathode material Substances 0.000 description 4
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- 230000008569 process Effects 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000011206 ternary composite Substances 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000009396 hybridization Methods 0.000 description 2
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
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Abstract
The invention discloses a preparation method of a polyaniline composite material for a Zn Ion Battery (ZIBs) anode, which relates to the technical field of new energy electronic materials. The PANI, the CNTs and the Zn can be directly prepared into the composite material, the characteristic of complex preparation steps of the anode material is avoided, a large amount of required anode material can be obtained at one time, the manufacturing cost can be greatly reduced, and the development and the industrial development of products are facilitated; CNTs are introduced on the basis of PANI to form a continuous conductive network, and an integrated composite structure has a better electron transfer path and a higher specific surface area; the addition of Zn can change the shape of PANI, enhance the mechanical strength of PANI and prolong the cycle life of ZIBs.
Description
Technical Field
The invention relates to the technical field of new energy electronic materials, in particular to a preparation method of a polyaniline composite material for a Zn ion battery anode.
Background
Since MacDiamid proposed Polyaniline (PANI) to be a promising cathode material for secondary batteries in 1987, zn// PANI secondary batteries have been studied for decades, polyaniline is considered one of the most promising conductive polymers due to its high conductivity and ease of synthesis, and PANI is most typically characterized by its ability to store charge and its reversible electrochemical behavior, making it a good candidate for ZIBs cathode materials. As the anode material, polyaniline is doped with various dopants under certain synthesis conditions, and can obtain high specific capacity. The research on the zinc ion doped polyaniline mainly focuses on the change of the conductivity, the morphology and the molecular structure of the polyaniline.
Polyaniline still has the problems as ZIBs cathode material, namely the electrochemical cycle life of the material is short due to the electrochemical degradation of polyaniline, and the polyaniline can not be in close contact with the electrode and is easy to fall off due to volume expansion and contraction in the charge-discharge process, so that the service life of the ZIBs is greatly reduced.
Disclosure of Invention
The invention aims to provide a preparation method of a polyaniline composite material for a Zn ion battery anode, which aims to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of a polyaniline composite material for a Zn ion battery anode comprises the following specific steps:
1) Mixing and stirring solutions of zinc chloride, aniline and hydrochloric acid for 10min at room temperature, wherein the mass ratio of the zinc chloride to the aniline to the hydrochloric acid is 20:30:500, then continuously stirring under the ice bath condition to obtain a first mixed solution;
2) Mixing the single-walled carbon nanotube with a first solvent, wherein the mass ratio of the carbon nanotube to the first solvent is 30:1500, performing ultrasonic action for 2 hours, mixing the mixture with the first mixed solution, and continuously stirring the mixture under the ice bath condition to obtain a second mixed solution;
3) Mixing ammonium persulfate or potassium persulfate with the second mixed solution, wherein the mass ratio of the ammonium persulfate to the second mixed solution is 10:50, stirring for 10 hours under an ice bath condition to obtain a third mixed solution;
4) And centrifuging the third mixed solution, washing the third mixed solution for a plurality of times by using distilled water, carrying out vacuum drying for 10 hours at the temperature of 80 ℃, grinding the third mixed solution, washing the third mixed solution by using a first solvent which is water or an organic solvent, carrying out vacuum drying for 10 hours at the temperature of 80 ℃, and grinding the third mixed solution to obtain a dark green powder product, namely the Zn-doped PANI and CNTs composite material.
On the basis of the technical scheme, the invention also provides the following optional technical scheme:
in one alternative: in the step 1), the first mixed solution is 0.1-10M hydrochloric acid solution, and the mass ratio of the zinc chloride, the aniline and the hydrochloric acid solution is 0.1-80:0.1-90:500.
in one alternative: in the step 2), the mass ratio of the carbon nanotubes to the first solvent in the second mixed solution is 0.1-100:1500.
in one alternative: in the step 3), the mass ratio of ammonium persulfate to the second mixed solution in the third mixed solution is 0.1-20:50.
in one alternative: in step 4), the first solvent is water or an organic solvent.
In one alternative: in the step 4), the temperature of the two times of vacuum drying is 60-100 ℃, and the drying time is 1-24h.
Compared with the prior art, the invention has the following beneficial effects:
1. the PANI, the CNTs and the Zn can be directly prepared into the composite material by using a simple chemical oxidation synthesis method, the characteristic of complicated preparation steps of the anode material is avoided, a large amount of required anode material can be obtained at one time, the manufacturing cost is reduced, and the development and the industrial development of products are facilitated.
2. CNTs are introduced on the basis of PANI to form a continuous conductive network, an integrated composite structure has a better electron transfer path and a higher specific surface area, the appearance of the PANI can be changed by adding Zn, the mechanical strength of the PANI is enhanced, and the cycle life of ZIBs is prolonged.
3、Zn 2+ The introduction of the polyaniline can also supplement Zn in electrolyte consumed by forming a passivation film on the surface of the polyaniline in the charging and discharging processes 2+ The PANI composite material has the advantages that the amount of the PANI composite material is increased, ion exchange is carried out between the PANI composite material and a passivation film and an electrolyte to reduce ion diffusion resistance, and the capacity, multiplying power and cycle performance of the PANI composite material are remarkably improved under the synergistic effect of the three components.
Drawings
FIG. 1 shows Zn 2+ The synthesis mechanism of the PANI-CNTs doped composite material is shown in the figure.
Fig. 2 is a graph of rate performance of a zinc ion battery.
Fig. 3 is a CV curve of a zinc ion battery.
Fig. 4 shows the cycling performance of a zinc ion battery.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
In the embodiment of the invention, the preparation method of the polyaniline composite material for the Zn ion battery anode comprises the following specific steps:
1) Mixing and stirring solutions of zinc chloride, aniline and hydrochloric acid for 1min at room temperature, wherein the mass ratio of the zinc chloride to the aniline to the hydrochloric acid solution is 0.1:0.1:500, then continuously stirring under the ice bath condition to obtain a first mixed solution;
2) Mixing the single-walled carbon nanotube with a first solvent, wherein the mass ratio of the carbon nanotube to the first solvent is 0.1:1500, performing ultrasonic action for 2 hours, mixing the mixture with the first mixed solution, and continuously stirring the mixture under the ice bath condition to obtain a second mixed solution;
3) Mixing ammonium persulfate or potassium persulfate with the second mixed solution, wherein the mass ratio of the ammonium persulfate to the second mixed solution is 0.1:50, stirring for 1h under an ice bath condition to obtain a third mixed solution;
4) And centrifuging the third mixed solution, washing the third mixed solution for a plurality of times by using distilled water, carrying out vacuum drying for 1h at the temperature of 60 ℃, grinding the third mixed solution, washing the third mixed solution by using a first solvent which is water, carrying out vacuum drying for 1h at the temperature of 60 ℃, and grinding the third mixed solution to obtain a dark green powder product, namely the Zn-doped PANI and CNTs composite material.
Example 2
In the embodiment of the invention, the preparation method of the polyaniline composite material for the Zn ion battery anode comprises the following specific steps:
1) Mixing and stirring solutions of zinc chloride, aniline and hydrochloric acid for 10min at room temperature, wherein the mass ratio of the zinc chloride to the aniline to the hydrochloric acid is 20:30:500, then continuously stirring under the ice bath condition to obtain a first mixed solution;
2) Mixing the single-walled carbon nanotube with a first solvent, wherein the mass ratio of the carbon nanotube to the first solvent is 30:1500, performing ultrasonic action for 2 hours, mixing the mixture with the first mixed solution, and continuously stirring the mixture under the ice bath condition to obtain a second mixed solution;
3) Mixing ammonium persulfate or potassium persulfate with the second mixed solution, wherein the mass ratio of the ammonium persulfate to the second mixed solution is 10:50, stirring for 10 hours under an ice bath condition to obtain a third mixed solution;
4) And centrifuging the third mixed solution, washing the third mixed solution for a plurality of times by using distilled water, carrying out vacuum drying for 10 hours at the temperature of 80 ℃, grinding the third mixed solution, washing the third mixed solution by using a first solvent, wherein the first solvent is an organic solvent, carrying out vacuum drying for 10 hours at the temperature of 80 ℃, and grinding the third mixed solution to obtain a dark green powder product, namely the Zn-doped PANI and CNTs composite material.
Example 3
In the embodiment of the invention, the preparation method of the polyaniline composite material for the Zn ion battery anode comprises the following specific steps:
1) Mixing and stirring solutions of zinc chloride, aniline and hydrochloric acid for 20min at room temperature, wherein the mass ratio of the zinc chloride to the aniline to the hydrochloric acid is 60:70:500, then continuously stirring under the ice bath condition to obtain a first mixed solution;
2) Mixing the single-walled carbon nanotube with a first solvent, wherein the mass ratio of the carbon nanotube to the first solvent is 60:1500, performing ultrasonic action for 2 hours, mixing the mixture with the first mixed solution, and continuously stirring the mixture under the ice bath condition to obtain a second mixed solution;
3) Mixing ammonium persulfate or potassium persulfate with the second mixed solution, wherein the mass ratio of the ammonium persulfate to the second mixed solution is 16:50, stirring for 20 hours under an ice bath condition to obtain a third mixed solution;
4) And centrifuging the third mixed solution, washing the third mixed solution for several times by using distilled water, carrying out vacuum drying for 20 hours at the temperature of 90 ℃, grinding the third mixed solution, washing the third mixed solution by using a first solvent which is an organic solvent, carrying out vacuum drying for 20 hours at the temperature of 90 ℃, and grinding the third mixed solution to obtain a dark green powder product, namely the Zn-doped PANI and CNTs composite material.
Example 4
In the embodiment of the invention, the preparation method of the polyaniline composite material for the Zn ion battery anode comprises the following specific steps:
1) Mixing and stirring solutions of zinc chloride, aniline and hydrochloric acid for 30min at room temperature, wherein the mass ratio of the zinc chloride to the aniline to the hydrochloric acid is 80:90:500, then continuously stirring under the ice bath condition to obtain a first mixed solution;
2) Mixing the single-walled carbon nanotube with a first solvent, wherein the mass ratio of the carbon nanotube to the first solvent is 100:1500, performing ultrasonic action for 2 hours, mixing the mixture with the first mixed solution, and continuously stirring the mixture under the ice bath condition to obtain a second mixed solution;
3) Mixing ammonium persulfate or potassium persulfate with the second mixed solution, wherein the mass ratio of the ammonium persulfate to the second mixed solution is 20:50, stirring for 24 hours under the ice bath condition to obtain a third mixed solution;
4) And centrifuging the third mixed solution, washing the third mixed solution for a plurality of times by using distilled water, carrying out vacuum drying for 24 hours at the temperature of 100 ℃, grinding the third mixed solution, washing the third mixed solution by using a first solvent, wherein the first solvent is an organic solvent, carrying out vacuum drying for 24 hours at the temperature of 100 ℃, and grinding the third mixed solution to obtain a dark green powder product, namely the Zn-doped PANI and CNTs composite material.
As a preferred embodiment of the invention, polyaniline is polymerized from aniline monomer, zinc ions are adsorbed on a part of nitrogen atoms of the polyaniline, and then the polyaniline adsorbed with the zinc ions and the hydroxyl carbon nanotube are connected together through polycondensation reaction to form the PANI-CNTs composite material doped with the zinc ions.
And (3) testing the electrochemical performance of the zinc ion battery: the preparation method selects pure black superfine powder super-p with high conductivity and PVDF (polyvinylidene fluoride) with wear resistance, high mechanical strength and toughness as additive substances, and uses NMP (N-methyl pyrrolidone) as a solvent to prepare anode slurry; 80mg of polyaniline composite powder prepared by the method, 10mg of super-p and 10mg of PVDF are mixed, 750L of NMP is added into the mixture, and the mixture is stirred at room temperature overnight to form uniform and viscous positive electrode slurry for later use. Cutting the titanium foil into a circular sheet with the diameter of 12mm, taking 5-10uL of positive electrode slurry by using a pipette, uniformly coating the positive electrode slurry on the surface of the titanium foil, and drying the positive electrode slurry in vacuum at 60 ℃ for 24 hours to obtain the positive electrode sheet. And assembling the button battery according to the sequence of the negative electrode shell, the punched zinc sheet, the electrolyte, the diaphragm, the electrolyte, the positive electrode sheet, the gasket and the positive electrode shell, and tightly pressing and sealing the button battery by using a battery sealing machine after the assembly is finished to finish the assembly of the button battery. And carrying out electrochemical performance tests on the assembled battery, wherein the electrochemical performance tests comprise a sweep voltammetry Curve (CV) at different sweep speeds, a constant current charge-discharge curve at different current densities and an electrochemical cyclic stability test.
Fig. 2 shows that the zinc ion battery shows a pair of redox peaks corresponding to the intercalation and deintercalation of zinc ions in PANI composite at different sweep rates. In addition, the higher degree of overlap of the redox peaks at different scan rates indicates that reversible redox reactions can proceed.
FIG. 3 shows zinc ion cells at 0.05, 0.1, 0.2, 0.5, 1, 2 and 5 Ag -1 At 0.05 ag of discharge curve at different current densities -1 The hourly capacity can reach 156.7mAh g -1 。
FIG. 4 shows the current density of 2 Ag for a zinc ion battery -1 The capacity retention rate is up to 95% after 800 times of charge and discharge cycles, and the coulombic efficiency in the charge and discharge process is between 97% and 100%. In addition, the calculated PANI-based Zn ion battery prepared by the method has the highest 166.7mWh g -1 Energy density of (2) and 111mW g -1 The power density of (2).
The embodiment of the invention provides a preparation method of a polyaniline composite material for a Zn ion battery anode, which is characterized in that Carbon Nanotubes (CNTs) hybridization and zinc ion doping are carried out on polyaniline by a one-step chemical oxidation synthesis method to prepare a polyaniline-based ternary composite material, and the polyaniline-based ternary composite material can have high capacity, high rate capability and excellent cycle performance when used as the Zn ion battery anode. With prepared Zn 2+ The doped PANI-CNTs composite material is used as a positive electrode to assemble ZIBs, the electrochemical performance of the anode is measured, and the performance improvement mechanism is researched. The result shows that the CNTs hybridization can improve the conductivity and stability of PANI, and the proper amount of Zn 2+ The doping can improve the mechanical strength of the PANI so as to stabilize the contact between the anode material and the electrode and improve the capacity of the PANI, and the ternary coupling comprehensively improves the electrochemical performance of the battery, including improving the capacity, improving the rate performance and prolonging the cycle life. Cells made from polyaniline samples doped with CNTs solution and 0.06M Zinc ions at 0.05A g -1 The discharge specific capacity of the current density is as high as 156.7mAh g -1 The capacity retention rate is up to 95% after 800 times of charge-discharge cycles, the coulombic efficiency in the charge-discharge process is between 97% and 100%, and 166.7mWh g -1 Energy density of (1) and 111mW g -1 The power density of (a). The ternary composite cathode material can provide a valuable reference for future large-scale industrial production of Zn// PANI batteries.
The above description is only for the specific embodiments of the present disclosure, but the scope of the present disclosure is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present disclosure, and all the changes or substitutions should be covered within the scope of the present disclosure. Therefore, the protection scope of the present disclosure shall be subject to the protection scope of the claims.
Claims (6)
1. A preparation method of a polyaniline composite material for a Zn ion battery anode is characterized by comprising the following steps:
1) Under the condition of room temperature, mixing and stirring the solution of zinc chloride, aniline and hydrochloric acid for 1-30 min, and then continuously stirring under the ice bath condition to obtain a first mixed solution;
2) Mixing the single-walled carbon nanotube with a first solvent, performing ultrasonic action for 2 hours, mixing with the first mixed solution, and continuously stirring under an ice bath condition to obtain a second mixed solution;
3) Mixing ammonium persulfate or potassium persulfate with the second mixed solution, and stirring for 1-24h under an ice bath condition to obtain a third mixed solution;
4) And centrifuging the third mixed solution, washing with distilled water, carrying out vacuum drying, grinding, washing with the first solvent, carrying out vacuum drying, and grinding to obtain a dark green powder product, namely the Zn-doped PANI and CNTs composite material.
2. The method for preparing the polyaniline composite material for Zn ion battery positive electrodes as claimed in claim 1, wherein, in step 1), the first mixed solution is 0.1 to 10M hydrochloric acid solution, and the mass ratio of the zinc chloride, aniline, and hydrochloric acid solution is 0.1 to 80:0.1-90:500.
3. the method for preparing a polyaniline composite material for a Zn ion battery positive electrode according to claim 1, wherein in step 2), the mass ratio of carbon nanotubes to the first solvent in the second mixed solution is 0.1 to 100:1500.
4. the preparation method of the polyaniline composite material used for the Zn-ion battery positive electrode according to claim 1, wherein in step 3), the mass ratio of the ammonium persulfate to the second mixed solution in the third mixed solution is 0.1 to 20:50.
5. the method for preparing the polyaniline composite material for a Zn ion battery positive electrode according to claim 1, wherein in step 4), the first solvent is water or an organic solvent.
6. The method for preparing the polyaniline composite material used for the Zn-ion battery anode according to claim 1, wherein in step 4), the temperature for vacuum drying twice is 60 to 100 ℃ and the drying time is 1 to 24 hours.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20120115674A (en) * | 2011-04-11 | 2012-10-19 | 연세대학교 산학협력단 | A complex comprising 50% intrinsically oxidized polyaniline and carbon nanotubes, and method for preparing the same |
| CN106206073A (en) * | 2016-08-10 | 2016-12-07 | 福州大学 | ZnO thin film Polymerization of Polyaniline/carbon Nanotube combination electrode material and preparation method thereof |
| CN106935916A (en) * | 2017-03-01 | 2017-07-07 | 东莞市联洲知识产权运营管理有限公司 | A kind of preparation method of high-performance zinc Polyaniline Secondary Battery |
| CN110854365A (en) * | 2019-10-30 | 2020-02-28 | 同济大学 | Preparation method of polyaniline/carbon composite material for anode material of water-based zinc-ion battery |
| CN113527673A (en) * | 2021-06-24 | 2021-10-22 | 安徽理工大学 | Preparation method and application of graphene oxide/polyaniline composite material |
| CN114085377A (en) * | 2021-11-22 | 2022-02-25 | 南开大学 | Preparation of polyaniline/carbon nanotube composite material and application of polyaniline/carbon nanotube composite material in sodium-based dual-ion battery |
| CN114890479A (en) * | 2022-06-09 | 2022-08-12 | 上海电力大学 | Water-based zinc ion battery positive electrode material and preparation method and application thereof |
-
2022
- 2022-09-23 CN CN202211178126.9A patent/CN115548295A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20120115674A (en) * | 2011-04-11 | 2012-10-19 | 연세대학교 산학협력단 | A complex comprising 50% intrinsically oxidized polyaniline and carbon nanotubes, and method for preparing the same |
| CN106206073A (en) * | 2016-08-10 | 2016-12-07 | 福州大学 | ZnO thin film Polymerization of Polyaniline/carbon Nanotube combination electrode material and preparation method thereof |
| CN106935916A (en) * | 2017-03-01 | 2017-07-07 | 东莞市联洲知识产权运营管理有限公司 | A kind of preparation method of high-performance zinc Polyaniline Secondary Battery |
| CN110854365A (en) * | 2019-10-30 | 2020-02-28 | 同济大学 | Preparation method of polyaniline/carbon composite material for anode material of water-based zinc-ion battery |
| CN113527673A (en) * | 2021-06-24 | 2021-10-22 | 安徽理工大学 | Preparation method and application of graphene oxide/polyaniline composite material |
| CN114085377A (en) * | 2021-11-22 | 2022-02-25 | 南开大学 | Preparation of polyaniline/carbon nanotube composite material and application of polyaniline/carbon nanotube composite material in sodium-based dual-ion battery |
| CN114890479A (en) * | 2022-06-09 | 2022-08-12 | 上海电力大学 | Water-based zinc ion battery positive electrode material and preparation method and application thereof |
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