CN113496825A - Preparation method, product and application of porous carbon dodecahedron electrode material - Google Patents
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Abstract
The invention discloses a preparation method, a product and application of a porous carbon dodecahedron electrode material, belonging to the technical field of electrode material preparation, wherein the method comprises the following steps: calcining the ZIF-8 nano particles to obtain N-PCD nano particles, mixing the N-PCD nano particles with a sulfur source substance, and calcining again; according to the invention, nitrogen and sulfur are co-doped in the porous carbon electrode material, so that the obtained electrode material has high specific capacity, and the material is applied to the zinc ion hybrid supercapacitor, so that the material has better energy density and excellent cycling stability.
Description
Technical Field
The invention belongs to the technical field of electrode material preparation, and particularly relates to a preparation method, a product and application of a porous carbon dodecahedron electrode material.
Background
With the wide application of intelligent electronic devices, the development of safe, efficient and long-life energy storage devices is urgent. While supercapacitors have high power densities, the lower energy density has always been a bottleneck limiting the development of supercapacitors. In order to accommodate the supercapacitors required in the current generation, designing an assembled hybrid supercapacitor or a zinc-ion hybrid supercapacitor has proven to be an effective approach. Among them, zinc metal is stably present in a neutral aqueous solution, and has attracted much attention because of its high specific capacity and abundant storage capacity, but it is necessary to overcome the problem that the cycle performance is not ideal enough, and therefore, an aqueous zinc ion hybrid supercapacitor having a long cycle life is one of the most promising candidates.
At present, heteroatom-doped carbon is paid much attention as a cathode material of a zinc ion hybrid supercapacitor, and the carbon material has a high specific surface area and is doped with heteroatoms, so that the electrochemical activity can be improved, the electron/ion transmission efficiency can be improved, and a certain effect on maintaining the stability of a structure and prolonging the cycle life can be achieved. Journal of Materials Chemistry a (2020, volume 8, page 11617) discloses that an N/O co-doped hierarchical porous carbon, thanks to its co-doping of N, O, the assembled zinc ion hybrid supercapacitor has excellent specific capacity and capacity retention rate close to one hundred percent under ten thousand cycles. Advanced Functional Materials (2020, volume 31, page 2007843) published reports the synthesis of a range of rGO Materials with different oxygen-containing Functional groups, carboxyl and hydroxyl groups proved to have good performance enhancing effects, which remain stable under twenty thousand cycles, by different types of chemical reduction methods and reducing agents. Chemical Engineering Journal (2021, 421 volume, 129786) discloses that acid treated carbon fibers retain 81% of their capacity after fifty thousand cycles.
Although heteroatom-doped carbon has been widely used, it is a problem to make the cycle performance excellent while maintaining a high specific capacity of the material. The zinc ion mixed capacitor cathode material with N and S common doping, high specific capacity, high energy density and ultrahigh cycle performance prepared by a simple method has not been reported.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method, a product and an application of a porous carbon dodecahedron electrode material.
In order to achieve the purpose, the invention provides the following technical scheme:
the invention provides a preparation method of a porous carbon dodecahedron electrode material, which comprises the following steps: and calcining the ZIF-8 nano particles to obtain N-PCD nano particles, mixing the N-PCD nano particles with a sulfur source substance, and calcining again to obtain the porous carbon dodecahedron electrode material.
Preferably, the preparation method of the ZIF-8 nanoparticles comprises the following steps: dissolving zinc acetate and a surfactant in absolute methanol to obtain a zinc acetate methanol solution; dissolving 2-methylimidazole in anhydrous methanol to obtain a 2-methylimidazole methanol solution; and then adding the obtained zinc acetate methanol solution into a 2-methylimidazole methanol solution, stirring, aging, centrifugally washing generated solid particles, and drying to obtain the ZIF-8 nano particles.
Preferably, the concentration of the zinc acetate methanol solution is 2.5-7.5 g/L; the surfactant is polyvinylpyrrolidone, and the concentration of the surfactant is 16 g/L; the concentration of the 2-methylimidazole methanol solution is 5-10 g/L; the volume ratio of the zinc acetate methanol solution to the 2-methylimidazole methanol solution is 1: 1.
Preferably, the stirring is carried out at room temperature for 1-2 hours; the aging time is 15-30 h; the drying temperature is 80 ℃, and the drying time is 6 h.
Preferably, the calcination is carried out in a nitrogen atmosphere, the temperature is 500-900 ℃, the temperature rise time is 1-3 hours, and the heat preservation time is 1-3 hours.
Preferably, the sulfur source substance is thiourea or sulfur powder, and the mass ratio of the N-PCD nano-particles to the sulfur source substance is (0.05-0.1): (0.2-0.4).
Preferably, the calcination step further comprises a step of acid washing, wherein hydrochloric acid with the concentration of 3mol/L is adopted for acid washing.
The invention also provides the porous carbon dodecahedron electrode material prepared by the preparation method.
The invention also provides application of the porous carbon dodecahedron electrode material in a zinc ion mixed supercapacitor.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, nitrogen and sulfur are co-doped in the porous carbon electrode material, so that the obtained electrode material has high specific capacity, and the material has good energy density and excellent cycling stability when being applied to a zinc ion hybrid supercapacitor, and the specific capacity can reach 133.4mA h g-1The maximum energy density is 107W hkg-1At a current density of 5A g-1The capacity retention rate of one hundred thousand cycles of charge and discharge in time is 97.1 percent;
the invention promotes the research of the heteroatom doped carbon material in the aspect of zinc ion hybrid super capacitor, and plays a certain role in promoting the development of zinc ion energy storage with high cycle performance;
the raw materials of the invention have low price, and the preparation method has the advantages of high repeatability, simple synthesis process, easy control and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is an XRD spectrum of N, S-PCD nanoparticles prepared in example 1;
FIG. 2 is a spectrum of N, S-PCD nanoparticles prepared in example 1;
FIGS. 3(a) - (b) are respectively the SEM images of the N, S-PDC nanoparticles prepared in example 1 at different magnifications;
FIG. 4 is a field emission scanning electron micrograph of N, S-PDC nanoparticles prepared in comparative example 2;
FIG. 5 is a cyclic voltammetry test curve for a coin cell assembled with N, S-PDC nanoparticles prepared in example 1;
FIG. 6 is a constant current charge and discharge curve of the coin cell assembled with N, S-PDC nanoparticles prepared in example 1;
fig. 7 is a graph of the cycle performance test results of the N, S-PDC nanoparticle-assembled coin cells prepared in example 1.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention. It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
Example 1
The preparation method of the nitrogen and sulfur co-doped porous carbon dodecahedron electrode material (N, S-PCD) comprises the following steps:
(1) preparation of ZIF-8:
1.05g of zinc acetate (C)4H6O4Zn·2H2O) and 3.2g of polyvinylpyrrolidone (PVP) are dissolved in 200mL of anhydrous methanol, the obtained solution is poured into 200mL of anhydrous methanol in which 1.31g of 2-methylimidazole (2-MIM) is dissolved, the obtained solution is stirred for 1 hour at room temperature and uniformly mixed, then aging is carried out for 24 hours, the generated white particles are subjected to centrifugal washing, and drying is carried out for 6 hours at 80 ℃ to obtain ZIF-8 nanoparticles.
(2) Preparation of N-PCD
Putting the ZIF-8 nano-particles prepared in the step (1) into a porcelain boat, and putting the porcelain boat into the center of a tube furnace for calcination under the atmosphere of N2The calcining temperature is 800 ℃, the temperature rising time is 2.6 hours, the heat preservation time is 2 hours, and after the temperature of the tubular furnace is naturally reduced, the N-PCD nano-particles are obtained.
And (3) calcining the ZIF-8 nano particles at high temperature in a nitrogen atmosphere, and carbonizing the particles to obtain the carbon material capable of being used as the zinc ion mixed supercapacitor electrode material.
(3) Preparation of N, S-PCD
0.08g of N-PCD nanoparticles from step (2) was mixed with 0.32g of thiourea (CH)4N2S) mixing and grinding, placing the obtained mixture into a porcelain boat, and calcining in a tube furnace in the atmosphere of N2The calcining temperature is 800 ℃, the temperature rise time is 2.6 hours, the heat preservation time is 2 hours, after the temperature of the tube furnace is naturally reduced, the obtained material is washed by 3M hydrochloric acid for 12 hours to remove redundant metal, and the material is washed by water to be neutral after being washed by acid. And drying to obtain N, S-PCD nano particles, namely the nitrogen and sulfur co-doped porous carbon dodecahedron electrode material.
Example 2
Preparing N, S-PCD by the following steps:
(1) preparation of ZIF-8:
0.5g of zinc acetate (C)4H6O4Zn·2H2O) and 3.2g of polyvinylpyrrolidone (PVP) are dissolved in 200mL of anhydrous methanol, the obtained solution is poured into 200mL of anhydrous methanol in which 1.0g of 2-methylimidazole (2-MIM) is dissolved, the obtained solution is stirred for 1.5 hours at room temperature and uniformly mixed, then aging is carried out for 15 hours, the generated white particles are centrifugally washed, and drying is carried out for 6 hours at 80 ℃ to obtain ZIF-8 nanoparticles.
(2) Preparation of N-PCD
Putting the ZIF-8 nano-particles prepared in the step (1) into a porcelain boat, and putting the porcelain boat into the center of a tube furnace for calcination under the atmosphere of N2The calcining temperature is 500 ℃, the temperature rising time is 1 hour, the heat preservation time is 3 hours, and after the tubular furnace is naturally cooled, the N-PCD nano-particles are obtained.
(3) Preparation of N, S-PCD
0.05g of N-PCD nanoparticles from step (2) was mixed with 0.4g of thiourea (CH)4N2S) mixing and grinding, placing the obtained mixture into a porcelain boat, and calcining in a tube furnace in the atmosphere of N2The calcining temperature is 500 ℃, the temperature rising time is 1 hour, the heat preservation time is 3 hours, after the tube furnace is naturally cooled, the obtained material is washed by 3M hydrochloric acid for 12 hours to remove redundant metal, and is washed by water to be neutral after being washed. And drying to obtain N, S-PCD nano particles, namely the nitrogen and sulfur co-doped porous carbon dodecahedron electrode material.
Example 3
Preparing N, S-PCD by the following steps:
(1) preparation of ZIF-8:
1.5g of zinc acetate (C)4H6O4Zn·2H2O) and 3.2g of polyvinylpyrrolidone (PVP) are dissolved in 200mL of anhydrous methanol, the obtained solution is poured into 200mL of anhydrous methanol in which 2.0g of 2-methylimidazole (2-MIM) is dissolved, the obtained solution is stirred for 2 hours at room temperature and uniformly mixed, then aging is carried out for 30 hours, the generated white particles are centrifugally washed, and drying is carried out for 6 hours at 80 ℃ to obtain ZIF-8 nano particlesAnd (4) granulating.
(2) Preparation of N-PCD
Putting the ZIF-8 nano-particles prepared in the step (1) into a porcelain boat, and putting the porcelain boat into the center of a tube furnace for calcination under the atmosphere of N2The calcining temperature is 900 ℃, the temperature rising time is 3 hours, the heat preservation time is 1 hour, and after the tubular furnace is naturally cooled, the N-PCD nano-particles are obtained.
(3) Preparation of N, S-PCD
0.1g of N-PCD nanoparticles from step (2) was mixed with 0.2g of thiourea (CH)4N2S) mixing and grinding, placing the obtained mixture into a porcelain boat, and calcining in a tube furnace in the atmosphere of N2The calcining temperature is 900 ℃, the temperature rising time is 3 hours, the heat preservation time is 1 hour, after the tube furnace is naturally cooled, the obtained material is washed by 3M hydrochloric acid for 12 hours to remove redundant metal, and then washed by water to be neutral. And drying to obtain N, S-PCD nano particles, namely the nitrogen and sulfur co-doped porous carbon dodecahedron electrode material.
Example 4
Preparing N, S-PCD by the following steps:
(1) preparation of ZIF-8:
1.05g of zinc acetate (C)4H6O4Zn·2H2O) and 3.2g of polyvinylpyrrolidone (PVP) are dissolved in 200mL of anhydrous methanol, the obtained solution is poured into 200mL of anhydrous methanol in which 1.31g of 2-methylimidazole (2-MIM) is dissolved, the obtained solution is stirred for 1 hour at room temperature and uniformly mixed, then aging is carried out for 24 hours, the generated white particles are subjected to centrifugal washing, and drying is carried out for 6 hours at 80 ℃ to obtain ZIF-8 nanoparticles.
(2) Preparation of N-PCD
Putting the ZIF-8 nano-particles prepared in the step (1) into a porcelain boat, and putting the porcelain boat into the center of a tube furnace for calcination under the atmosphere of N2The calcining temperature is 800 ℃, the temperature rising time is 2.6 hours, the heat preservation time is 2 hours, and after the temperature of the tubular furnace is naturally reduced, the N-PCD nano-particles are obtained.
(3) Preparation of N, S-PCD
Mixing and grinding 0.08g of N-PCD nano-particles obtained in the step (2) and 0.32g of sulfur powder (S), and mixing and grinding the obtained mixturePlacing the mixture in a porcelain boat, calcining in a tube furnace in the atmosphere of N2The calcining temperature is 800 ℃, the temperature rise time is 2.6 hours, the heat preservation time is 2 hours, after the temperature of the tube furnace is naturally reduced, the obtained material is washed by 3M hydrochloric acid for 12 hours to remove redundant metal, and the material is washed by water to be neutral after being washed by acid. And drying to obtain N, S-PCD nano particles, namely the nitrogen and sulfur co-doped porous carbon dodecahedron electrode material.
Comparative example 1
(1) Preparation of ZIF-8:
1.05g of zinc acetate (C)4H6O4Zn·2H2O) and 3.2g of polyvinylpyrrolidone (PVP) are dissolved in 200mL of anhydrous methanol, the obtained solution is poured into 200mL of anhydrous methanol in which 1.31g of 2-methylimidazole (2-MIM) is dissolved, the obtained solution is stirred for 1 hour at room temperature and uniformly mixed, then aging is carried out for 24 hours, the generated white particles are subjected to centrifugal washing, and drying is carried out for 6 hours at 80 ℃ to obtain ZIF-8 nanoparticles.
(2) Preparation of N-PCD
Putting the ZIF-8 nano-particles prepared in the step (1) into a porcelain boat, and putting the porcelain boat into the center of a tube furnace for calcination under the atmosphere of N2The calcining temperature is 800 ℃, the temperature rising time is 2.6 hours, the heat preservation time is 2 hours, and after the temperature of the tubular furnace is naturally reduced, the N-PCD nano-particles are obtained.
Comparative example 2
(1) Preparation of ZIF-8:
1.05g of zinc acetate (C)4H6O4Zn·2H2O) and 3.2g of polyvinylpyrrolidone (PVP) are dissolved in 200mL of anhydrous methanol, the obtained solution is poured into 200mL of anhydrous methanol in which 1.31g of 2-methylimidazole (2-MIM) is dissolved, the obtained solution is stirred for 1 hour at room temperature and uniformly mixed, then aging is carried out for 24 hours, the generated white particles are subjected to centrifugal washing, and drying is carried out for 6 hours at 80 ℃ to obtain ZIF-8 nanoparticles.
(2) Preparation of N, S-PCD
Mixing 0.08g of ZIF-8 nanoparticles obtained in step (1) with 0.32g of thiourea (CH)4N2S) mixing and grinding, placing the obtained mixture into a porcelain boat, and calcining in a tube furnace in the atmosphere of N2The calcining temperature is 800 ℃, the temperature rise time is 2.6 hours, the heat preservation time is 2 hours, after the temperature of the tube furnace is naturally reduced, the obtained material is washed by 3M hydrochloric acid for 12 hours to remove redundant metal, and the material is washed by water to be neutral after being washed by acid. And drying to obtain N, S-PCD nano particles, namely the nitrogen and sulfur co-doped porous carbon dodecahedron electrode material.
Comparative example 3
The difference from example 1 is that the calcination temperature in step (3) of example 1 was modified to 450 ℃.
Comparative example 4
The difference from example 1 is that "the calcination atmosphere in step (2) of example 1 is N2The modification is that the calcining atmosphere is air.
The final product cannot be obtained due to the direct combustion of the material resulting from calcination in an air atmosphere.
Effect verification
The N, S-PCD nanoparticles obtained in example 1 were subjected to XRD detection using an X-ray diffractometer model D8 from brueck corporation, usa, and EDS using a field emission scanning electron microscope and an X-ray spectrometer model S-4800 from hitachi corporation, japan, and the results are shown in fig. 1 and fig. 2, respectively, where X is a diffraction angle (2 θ) on the abscissa in fig. 1, and Y is a relative diffraction intensity with a diffraction peak corresponding to carbon on the ordinate, as can be seen from fig. 1: the N, S-PCD nanoparticles obtained in example 1 were carbon materials.
As can be seen from fig. 2, the presence of carbon, nitrogen, oxygen, sulfur in the N, S-PCD nanoparticles obtained in example 1 confirms the co-doping of nitrogen and sulfur in the material.
The N, S-PCD nanoparticles prepared in example 1 and comparative example 2 were analyzed by field emission scanning electron microscopy (FE-SEM) using a field emission scanning electron microscope (FE-SEM) of hitachi, japan, and the obtained electron micrographs are shown in fig. 3 and 4, respectively, and it can be seen that the nanoparticle material synthesized in example 1 has a uniform dodecahedral morphology and a diameter in the range of about 550 nm. While the nanoparticle material prepared in comparative example 2 was not of uniform dodecahedral structure, in an agglomerated state.
The above verification was performed for example 2 and example 3, and the obtained results substantially agreed with the above results of example 1.
The performance of the materials prepared in examples 1 to 4 and comparative examples 1 to 3 was analyzed, the materials prepared in each group were taken, uniformly ground with superconducting carbon black (conductive agent) and polyvinylidene fluoride (binder) in a ratio of 8:1:1, 3 drops of 1-methyl-2-pyrrolidone were added dropwise to form a uniform mixture, which was then coated on hydrophilic carbon paper, dried, and then used as a positive electrode, a zinc sheet as a negative electrode, 2M Zn 22SO4And assembling the electrolyte into the button cell. The electrochemical energy storage performance of CHI 660E electrochemical workstation of Shanghai Chenghua corporation is tested at 0.2-1.8V potential window, FIG. 5 is a cyclic voltammetry test curve of zinc ion hybrid super capacitor obtained by using the material of example 1 at different sweep rates, the material is measured from 5mV s-1To 100mV s-1All maintained a consistent rectangular-like shape, indicating good capacitive characteristics. FIG. 6 is a test curve of charge and discharge performance of button cells assembled by the material prepared in example 1 at different current densities, measured at CT3001A electrochemical workstation of Wuhan blue electric company, from current density 0.2A g-1To 20A g-1The maximum capacitance performance is 133.4mA h g-1The rate retention rate is 63%; at a current density of 5A g-1The cycle performance of the zinc ion battery using the N, S-PCD nanomaterial prepared in the previous test was tested, and fig. 7 is a cycle performance of the zinc ion battery using the N, S-PCD nanomaterial prepared in example 1, which was continuously operated for hundreds of thousands of cycles, and the battery capacity was still maintained at 97.1%, and the current density of the battery assembled using the materials prepared in examples 1 to 4 and comparative examples 1 to 3 was 0.2A g-1To 20A g-1Maximum capacity performance, rate retention and at a current density of 5A g-1The capacity retention after one hundred thousand cycles of continuous operation is shown in table 1:
TABLE 1
Therefore, the zinc ion hybrid supercapacitor assembled by the N, S-PCD nano materials prepared by the method has super excellent battery cycling stability. As can be seen from the comparison of the performances of the cells assembled from the materials prepared in example 1 and comparative example 1 in table 1, the performance of co-doping N and S in the material is significantly improved compared to the performance of doping N alone, since the doping of sulfur brings about more optimal performance; as can be seen from the comparison of the performances of the batteries assembled by the materials prepared in example 1 and comparative example 2 in table 1, the performance of the obtained material is poor when ZIF-8 and thiourea are directly calcined, while the performance of the obtained material is good when ZIF-8 is calcined first and then calcined with thiourea, because the ZIF-8 nanoparticles and thiourea are directly mixed and calcined, the obtained material has a non-uniform dodecahedral structure but is agglomerated together, and the structure results in poor material performance; as can be seen from the comparison of the performances of the batteries assembled by using the materials prepared in example 1 and comparative example 3 in table 1, the calcination temperature also has an important influence on the final performances of the materials, and when the calcination temperature is lower, the vulcanization process is incomplete, resulting in poor performances of the finally obtained materials.
The results show that the N, S-PCD nano material prepared by the method has high specific capacity, and the material has better energy density and excellent cycling stability when being applied to a zinc ion hybrid super capacitor. The invention promotes the research of the heteroatom doped carbon material on the zinc ion hybrid supercapacitor, and plays a certain role in promoting the development of zinc ion energy storage with high cycle performance.
The above description is only for the preferred embodiment of the present invention, and the protection scope of the present invention is not limited thereto, and any person skilled in the art should be able to cover the technical scope of the present invention, the technical solution and the inventive concept of the present invention equivalent or change within the technical scope of the present invention.
Claims (9)
1. A preparation method of a porous carbon dodecahedron electrode material is characterized by comprising the following steps: and calcining the ZIF-8 nano particles to obtain N-PCD nano particles, mixing the N-PCD nano particles with a sulfur source substance, and calcining again to obtain the porous carbon dodecahedron electrode material.
2. The method of manufacturing according to claim 1, wherein the ZIF-8 nanoparticles are manufactured by: dissolving zinc acetate and a surfactant in absolute methanol to obtain a zinc acetate methanol solution; dissolving 2-methylimidazole in anhydrous methanol to obtain a 2-methylimidazole methanol solution; and then adding the obtained zinc acetate methanol solution into a 2-methylimidazole methanol solution, stirring, aging, centrifugally washing generated solid particles, and drying to obtain the ZIF-8 nano particles.
3. The preparation method according to claim 2, wherein the concentration of the methanol solution of zinc acetate is 2.5 to 7.5 g/L; the surfactant is polyvinylpyrrolidone; the concentration of the 2-methylimidazole methanol solution is 5-10 g/L; the volume ratio of the zinc acetate methanol solution to the 2-methylimidazole methanol solution is 1: 1.
4. The preparation method according to claim 2, wherein the stirring is performed at room temperature for 1-2 hours; the aging time is 15-30 h; the drying temperature is 80 ℃, and the drying time is 6 h.
5. The method according to claim 1, wherein the calcination is carried out in a nitrogen atmosphere at a temperature of 500 to 900 ℃, for a temperature rise time of 1 to 3 hours, and for a temperature maintenance time of 1 to 3 hours.
6. The production method according to claim 1, wherein the sulfur source substance is thiourea or sulfur powder; the mass ratio of the N-PCD nano-particles to the sulfur source substance is (0.05-0.1) to (0.2-0.4).
7. The method of claim 1, further comprising a step of acid washing after the re-calcination; the acid washing adopts hydrochloric acid with the concentration of 3 mol/L.
8. A porous carbon dodecahedral electrode material prepared by the preparation method according to any one of claims 1 to 7.
9. Use of the porous carbon dodecahedral electrode material of claim 8 in zinc ion hybrid supercapacitors.
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| CN114784299A (en) * | 2022-05-27 | 2022-07-22 | 中国第一汽车股份有限公司 | Nitrogen-sulfur doped carbon material and preparation method and application thereof |
| CN115744867A (en) * | 2022-09-26 | 2023-03-07 | 江苏大学 | Preparation method and application of oxygen-containing functional group carbon material for zinc ion supercapacitor |
| CN116525317A (en) * | 2023-06-14 | 2023-08-01 | 中国矿业大学 | Boron-nitrogen co-doped dodecahedron layered porous carbon, preparation method thereof and layered porous carbon electrode |
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| CN116903880A (en) * | 2023-09-16 | 2023-10-20 | 山东海化集团有限公司 | Flake porous Bi 2 O 3 Preparation method and application of ZnO-ZIF-8 heterojunction material |
| CN116903880B (en) * | 2023-09-16 | 2024-01-02 | 山东海化集团有限公司 | Flake porous Bi 2 O 3 Preparation method and application of ZnO-ZIF-8 heterojunction material |
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