CN114530334B - Asphalt-based carbon/manganese dioxide composite electrode material and preparation method and application thereof - Google Patents
Asphalt-based carbon/manganese dioxide composite electrode material and preparation method and application thereof Download PDFInfo
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- CN114530334B CN114530334B CN202210201356.6A CN202210201356A CN114530334B CN 114530334 B CN114530334 B CN 114530334B CN 202210201356 A CN202210201356 A CN 202210201356A CN 114530334 B CN114530334 B CN 114530334B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/44—Raw materials therefor, e.g. resins or coal
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
- Y02E60/13—Energy storage using capacitors
Abstract
The invention provides an asphalt-based carbon/manganese dioxide composite electrode material, and a preparation method and application thereof, and belongs to the technical field of electric energy storage. The preparation method of the invention adopts green and efficient laser-induced carbonization. Asphalt is used as a carbon source, manganese dioxide powder is mixed, and the asphalt is carbonized by using a semiconductor blue-violet laser as a laser light source, so that the asphalt is oxidized into gas under the action of laser light and heat to be released, porous carbon with three-dimensional conductive network interconnection is formed, and a synergistic effect is formed with manganese dioxide nano sheets inserted in the porous carbon to obtain the self-supporting electrode material without a binder, so that the specific capacity and the cycle stability of the composite material are effectively improved, the electrode preparation cost is reduced, and the electrode preparation flow is simplified.
Description
Technical Field
The invention relates to the technical field of electric energy storage, in particular to an asphalt-based carbon/manganese dioxide composite electrode material, and a preparation method and application thereof.
Background
With the exhaustion of petrochemical energy and the deterioration of the environment, the demand for sustainable clean power is increasing, and efficient storage of power has become a problem that is urgently needed to be solved in the world today. Zinc ion hybrid supercapacitors are considered to be promising next-generation energy storage devices because of their high energy density of the battery and high power density of the supercapacitors. In general, a zinc ion hybrid supercapacitor uses metallic zinc as an anode and a carbon material as a cathode, and the energy storage performance of the supercapacitor is determined by a cathode electrode material, so that a perfect electrode structure is required for constructing an ideal zinc ion hybrid supercapacitor with high charge storage performance, and the cathode electrode material becomes an important point for research of the zinc ion hybrid supercapacitor.
Carbon materials with higher specific surface area and layered porosity structure are considered as ideal positive electrode replacement materials according to the energy storage characteristics of reversible ion adsorption/desorption of the carbon materials. In addition, considering the structural stability and charge storage capacity of the electrode in combination, a single carbon material often cannot meet the requirement of efficient energy storage, so that it is necessary to combine redox electrode materials with higher energy density to improve the charge storage of the electrode. Manganese dioxide is considered as one of the most promising electrode materials due to the characteristics of being rich, low in cost, safe and environment-friendly, high in theoretical specific capacitance and the like, but electrochemical reaction only occurs on the surface of an electrode due to the characteristic of poor conductivity, so that the utilization rate of the electrode material is greatly limited, and the large specific surface area and excellent conductivity of the carbon material are utilized to disperse manganese dioxide to improve the capacitance utilization rate. Although research on improving the electrochemical performance of an electrode by compounding a carbon material with manganese dioxide has been reported, the electrode material is mixed powder, a binder is required to be added for fixation, and the addition of the binder also reduces the conductivity of the electrode, thereby affecting the electrochemical performance of the electrode.
Disclosure of Invention
In view of the above, the invention aims to provide an asphalt-based carbon/manganese dioxide composite electrode material, and a preparation method and application thereof. The composite electrode material prepared by the invention has no adhesive, and is a self-supporting composite electrode material.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of an asphalt-based carbon/manganese dioxide composite electrode material, which comprises the following steps:
asphalt solution and delta-MnO 2 Mixing and forming a film to obtain a film;
and (3) performing laser-induced carbonization on the film to obtain the asphalt-based carbon/manganese dioxide composite electrode material.
Preferably, the delta-MnO 2 The weight ratio of the asphalt to the asphalt in the asphalt solution is 1-4:20.
Preferably, the delta-MnO 2 The weight ratio of the asphalt to the asphalt in the asphalt solution is 1:10.
Preferably, the delta-MnO 2 The nano-sheet is a flower-shaped structure formed by stacking nano-sheets, and the diameter of the flower-shaped structure is 100-500 nm.
Preferably, the wavelength of the laser induced carbonization is 400-465 nm, the power is 1.5-15W, and the scanning speed is 1-50 mm/s.
Preferably, the wavelength of the laser induced carbonization is 450nm, the power is 4.5W, and the scanning speed is 5mm/s.
The invention also provides the asphalt-based carbon/manganese dioxide composite electrode material prepared by the preparation method.
The invention also provides application of the asphalt-based carbon/manganese dioxide composite electrode material in the zinc ion mixed super capacitor.
Preferably, the anode of the zinc ion mixed super capacitor is zinc foil, the cathode is the asphalt-based carbon/manganese dioxide composite electrode material according to the technical scheme, and the electrolyte comprises zinc sulfate and manganese sulfate.
Preferably, the molar ratio of zinc sulfate to manganese sulfate is 5:1.
The invention provides a preparation method of an asphalt-based carbon/manganese dioxide composite electrode material, which comprises the following steps: asphalt solution and delta-MnO 2 Mixing and forming a film to obtain a film; and (3) performing laser-induced carbonization on the film to obtain the asphalt-based carbon/manganese dioxide composite electrode material.
The invention firstly mixes the materials into films, then uses the method of laser induced carbonization, can maintain the three-dimensional structure of the composite material, has self-supporting performance, can be directly used as an electrode, does not need to use a binder, and can further improve the conductivity of the electrode. In the invention, under the action of laser-induced carbonization, the asphalt oxidizes carbon and sulfur elements into gas to release, so as to form porous carbon with three-dimensional conductive network interconnection, and simultaneously the porous carbon is connected with delta-MnO inserted therein 2 The synergistic effect is formed, the specific surface area and the conductivity of the carbon material are effectively improved, the dispersed manganese dioxide improves the capacitance, the self-supporting electrode material without the binder is obtained, the specific capacity and the cycling stability of the composite material are effectively improved, the electrode preparation cost is reduced, and the electrode preparation process is simplified.
Drawings
FIG. 1 is a scanning electron micrograph of pitch-based carbon prepared in comparative example;
FIG. 2 is a scanning electron micrograph of the pitch-based carbon/manganese dioxide composite prepared in example 2;
FIG. 3 is a cyclic voltammogram of the pitch-based carbon/manganese dioxide composite electrode prepared in example 2 at various scan rates of 1-15 mV/s;
FIG. 4 is a constant current charge-discharge diagram of the pitch-based carbon/manganese dioxide composite electrode prepared in example 2 at different current densities of 0.5-10A/g;
FIG. 5 is a graph of the cycling stability of the pitch-based carbon/manganese dioxide composite electrode prepared in example 2 at a current density of 6A/g;
FIG. 6 is a graph of mass specific capacities of pitch-based carbon/manganese dioxide composites prepared in examples 1-3 and pitch-based carbon prepared in comparative example as electrodes at different current densities.
Detailed Description
The invention provides a preparation method of an asphalt-based carbon/manganese dioxide composite electrode material, which comprises the following steps:
asphalt solution and delta-MnO 2 Mixing and forming a film to obtain a film;
and (3) performing laser-induced carbonization on the film to obtain the asphalt-based carbon/manganese dioxide composite electrode material.
In the present invention, all materials used are commercial products in the art unless otherwise specified.
The invention uses asphalt solution and delta-MnO 2 Mixing and forming a film to obtain the film.
In the present invention, the delta-MnO 2 The weight ratio to asphalt in the asphalt solution is preferably 1 to 4:20, more preferably 1:10.
In the present invention, the delta-MnO 2 The nano-sheets are preferably stacked to form a flower-like structure, and the diameter of the flower-like structure is preferably 100-500 nm.
In the invention, asphalt is preferably dissolved in chloroform to obtain the asphalt solution.
In the present invention, the mass concentration of the asphalt solution is preferably 40g/L.
In the present invention, the delta-MnO 2 Preferably made by a process comprising the steps of:
dissolving 2.217g of potassium permanganate in 60mL of deionized water, adding 2mL of 37% hydrochloric acid solution by mass concentration, stirring for 5min, transferring the solution into a polytetrafluoroethylene liner of a 100mL stainless steel reaction kettle, reacting for 6h at 140 ℃, separating out reactants by vacuum filtration, and drying in a vacuum drying oven at 60 ℃ for 12h to obtain delta-MnO 2 。
In the present invention, the film is preferably formed by volatilization in a polytetrafluoroethylene mold.
In the present invention, the inner dimensions of the polytetrafluoroethylene mold are preferably 10mm×20mm×5mm.
After the thin film is obtained, the thin film is subjected to laser induced carbonization, and the asphalt-based carbon/manganese dioxide composite electrode material is obtained.
In the present invention, the wavelength of the laser-induced carbonization is preferably 400 to 465nm, more preferably 450nm, the power is preferably 1.5 to 15W, more preferably 4.5W, and the scanning rate is preferably 1 to 50mm/s, more preferably 5mm/s.
In the present invention, the laser-induced carbonization is preferably performed in a semiconductor laser.
After the laser-induced carbonization is completed, the obtained laser-induced carbonized product is preferably washed with water and dried in vacuum in sequence to obtain the asphalt-based carbon/manganese dioxide composite electrode material.
In the present invention, the temperature of the vacuum drying is preferably 45℃and the time is preferably 12 hours.
The invention also provides the asphalt-based carbon/manganese dioxide composite electrode material prepared by the preparation method.
The invention also provides application of the asphalt-based carbon/manganese dioxide composite electrode material in the zinc ion mixed super capacitor.
In the invention, the anode of the zinc ion mixed super capacitor is zinc foil, the cathode is the asphalt-based carbon/manganese dioxide composite electrode material according to the technical scheme, and the electrolyte comprises zinc sulfate and manganese sulfate.
In the present invention, the molar ratio of zinc sulfate to manganese sulfate is preferably 5:1.
In the present invention, the concentration of zinc sulfate in the electrolyte is preferably 2mol/L, and the concentration of manganese sulfate is preferably 0.4mol/L.
For further explanation of the present invention, the pitch-based carbon/manganese dioxide composite electrode material provided by the present invention, and the preparation method and application thereof will be described in detail with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Taking 50mL of asphalt solution with the concentration of 40 g/L; 0.1g delta-MnO is added 2 Powder, fully dispersing; transferring the mixed solution into a polytetrafluoroethylene mould with the inner dimension of 10mm multiplied by 20mm multiplied by 5mm, and volatilizing the mixed solution to form a film; and (3) placing the film under a semiconductor laser, carbonizing by adopting laser parameters with the wavelength of 450nm, the power of 4.5W and the scanning speed of 5mm/s, cleaning the carbonized film with deionized water for multiple times, and vacuum drying at 45 ℃ for 12 hours to obtain the asphalt-based carbon/manganese dioxide composite material.
Example 2
Taking 50mL of asphalt solution with the concentration of 40 g/L; 0.2g delta is added-MnO 2 Powder, fully dispersing; transferring the mixed solution into a polytetrafluoroethylene mould with the inner dimension of 10mm multiplied by 20mm multiplied by 5mm, and volatilizing the mixed solution to form a film; and (3) placing the film under a semiconductor laser, carbonizing by adopting laser parameters with the wavelength of 450nm, the power of 4.5W and the scanning speed of 5mm/s, cleaning the carbonized film with deionized water for multiple times, and vacuum drying at 45 ℃ for 12 hours to obtain the asphalt-based carbon/manganese dioxide composite material.
Example 3
Taking 50mL of asphalt solution with the concentration of 40 g/L; 0.4g delta-MnO is added 2 Powder, fully dispersing; transferring the mixed solution into a polytetrafluoroethylene mould with the inner dimension of 10mm multiplied by 20mm multiplied by 5mm, and volatilizing the mixed solution to form a film; and (3) placing the film under a semiconductor laser, carbonizing by adopting laser parameters with the wavelength of 450nm, the power of 4.5W and the scanning speed of 5mm/s, cleaning the carbonized film with deionized water for multiple times, and vacuum drying at 45 ℃ for 12 hours to obtain the asphalt-based carbon/manganese dioxide composite material.
Comparative example
Taking 50mL of asphalt solution with the concentration of 40 g/L; transferring the solution into a polytetrafluoroethylene mould to volatilize the solution into a film; and (3) placing the film under a semiconductor laser, carbonizing by adopting laser parameters with the wavelength of 450nm, the power of 4.5W and the scanning speed of 5mm/s, cleaning the carbonized film with deionized water for multiple times, and vacuum drying at 45 ℃ for 12 hours to obtain the asphalt-based carbon material.
Electrochemical performance test of electrode material:
cutting an asphalt-based carbon/manganese dioxide composite electrode material into a size of 10mm multiplied by 15mm to serve as a working electrode, taking zinc foil with the same size as a counter electrode, wherein the electrolyte is a mixed solution of 2mol/L zinc sulfate and 0.4mol/L manganese sulfate, the mol ratio of the zinc sulfate to the manganese sulfate is 5:1, and carrying out electrochemical performance test on the asphalt-based carbon/manganese dioxide composite electrode material on a CHI660E electrochemical workstation through a two-electrode system.
Fig. 1 is a scanning electron micrograph of the pitch-based carbon material prepared in the comparative example, and fig. 2 is a scanning electron micrograph of the pitch-based carbon/manganese dioxide composite material prepared in example 2. It can be seen by combining fig. 1 and fig. 2 that the pitch-based carbon/manganese dioxide composite material prepared by the invention has a hierarchical porous structure, and manganese dioxide nano sheets are inserted between the pitch-based carbon structures, so that the pitch-based carbon/manganese dioxide composite material has good structural stability.
FIG. 3 is a CV chart of the asphalt-based carbon/manganese dioxide composite material prepared in example 2 as a cathode of a zinc ion hybrid supercapacitor at different scanning rates, and it can be seen from the chart that the asphalt-based carbon/manganese dioxide composite material prepared in the invention has good electrochemical performance.
FIG. 4 is a GCD graph of the asphalt-based carbon/manganese dioxide composite material prepared in example 2 as a cathode of a zinc ion hybrid supercapacitor at different current densities, and it can be seen from the graph that the asphalt-based carbon/manganese dioxide composite material prepared in the invention has a longer discharge time.
FIG. 5 is a graph showing the cycling stability of the pitch-based carbon/manganese dioxide composite material prepared in example 2 as a cathode of a zinc ion hybrid supercapacitor at a current density of 6A/g, from which it can be seen that an electrode prepared using the pitch-based carbon/manganese dioxide composite material prepared in accordance with the present invention has stable charge-discharge cycles.
FIG. 6 is a graph showing the mass specific capacity of asphalt-based carbon/manganese dioxide composites prepared in examples 1 to 3 and asphalt-based carbon prepared in comparative example as cathodes of zinc ion hybrid supercapacitors, as can be seen from the graph, delta-MnO was added 2 The specific capacity of the electrode is obviously improved, when delta-MnO 2 When the mass ratio of the composite electrode to asphalt is 2:20, the composite electrode has the optimal mass ratio capacity under each current density.
The foregoing is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. It should be noted that modifications and adaptations to the present invention may occur to one skilled in the art without departing from the principles of the present invention and are intended to be comprehended within the scope of the present invention.
Claims (7)
1. The preparation method of the asphalt-based carbon/manganese dioxide composite electrode material is characterized by comprising the following steps of:
asphalt solution and delta-MnO 2 Mixing and forming a film to obtain a film; the delta-MnO 2 The weight ratio of the asphalt to the asphalt in the asphalt solution is 1:10; the delta-MnO 2 The nano-sheet is a flower-shaped structure formed by stacking nano-sheets, and the diameter of the flower-shaped structure is 100-500 nm;
and (3) performing laser-induced carbonization on the film to obtain the asphalt-based carbon/manganese dioxide composite electrode material.
2. The method according to claim 1, wherein the laser induced carbonization has a wavelength of 400-465 nm, a power of 1.5-15W, and a scanning rate of 1-50 mm/s.
3. The method of claim 1 or 2, wherein the laser induced carbonization has a wavelength of 450nm, a power of 4.5W, and a scanning rate of 5mm/s.
4. A pitch-based carbon/manganese dioxide composite electrode material produced by the production method according to any one of claims 1 to 3.
5. The use of the pitch-based carbon/manganese dioxide composite electrode material of claim 4 in a zinc ion hybrid supercapacitor.
6. The use according to claim 5, wherein the anode of the zinc ion hybrid supercapacitor is zinc foil and the cathode is the pitch-based carbon/manganese dioxide composite electrode material according to claim 4, and the electrolyte comprises zinc sulfate and manganese sulfate.
7. The use according to claim 6, wherein the molar ratio of zinc sulphate to manganese sulphate is 5:1.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210201356.6A CN114530334B (en) | 2022-03-03 | 2022-03-03 | Asphalt-based carbon/manganese dioxide composite electrode material and preparation method and application thereof |
| ZA2022/03320A ZA202203320B (en) | 2022-03-03 | 2022-03-22 | Pitch-based carbon/manganese dioxide composite electrode material as well as preparation method and application thereof |
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| CN202210201356.6A CN114530334B (en) | 2022-03-03 | 2022-03-03 | Asphalt-based carbon/manganese dioxide composite electrode material and preparation method and application thereof |
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| CN114530334B true CN114530334B (en) | 2023-08-15 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102683037A (en) * | 2012-05-10 | 2012-09-19 | 中国第一汽车股份有限公司 | Manganese dioxide asymmetric super capacitor and manufacturing method thereof |
| CN103500815A (en) * | 2013-09-26 | 2014-01-08 | 深圳市贝特瑞新能源材料股份有限公司 | Soft-carbon composite cathode material of lithium ion battery and preparation method thereof |
| KR101580892B1 (en) * | 2014-09-29 | 2015-12-30 | 인하대학교 산학협력단 | Method for manufacturing manganese oxides-doped pitch-based carbon for supercapacitor |
| CN105977490A (en) * | 2016-05-18 | 2016-09-28 | 河南田园新能源科技有限公司 | Method for preparing graphene composite negative electrode material from modified graphene oxide |
| CN109065861A (en) * | 2018-08-01 | 2018-12-21 | 桑德集团有限公司 | Asphaltic base porous carbon materials and preparation method thereof, silicon-carbon cathode material and secondary cell |
-
2022
- 2022-03-03 CN CN202210201356.6A patent/CN114530334B/en active Active
- 2022-03-22 ZA ZA2022/03320A patent/ZA202203320B/en unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102683037A (en) * | 2012-05-10 | 2012-09-19 | 中国第一汽车股份有限公司 | Manganese dioxide asymmetric super capacitor and manufacturing method thereof |
| CN103500815A (en) * | 2013-09-26 | 2014-01-08 | 深圳市贝特瑞新能源材料股份有限公司 | Soft-carbon composite cathode material of lithium ion battery and preparation method thereof |
| KR101580892B1 (en) * | 2014-09-29 | 2015-12-30 | 인하대학교 산학협력단 | Method for manufacturing manganese oxides-doped pitch-based carbon for supercapacitor |
| CN105977490A (en) * | 2016-05-18 | 2016-09-28 | 河南田园新能源科技有限公司 | Method for preparing graphene composite negative electrode material from modified graphene oxide |
| CN109065861A (en) * | 2018-08-01 | 2018-12-21 | 桑德集团有限公司 | Asphaltic base porous carbon materials and preparation method thereof, silicon-carbon cathode material and secondary cell |
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| High energy density capacitor using coal tar pitch derived nanoporous carbon/MnO2 electrodes in aqueous electrolytes;Timothy Tomko;Journal or Power Sources;第196卷(第4期);2380-2386 * |
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| CN114530334A (en) | 2022-05-24 |
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