CN112233909B - Zinc oxide-nano vanadium dioxide doped porous carbon composite electrode material and preparation method thereof - Google Patents

Zinc oxide-nano vanadium dioxide doped porous carbon composite electrode material and preparation method thereof Download PDF

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CN112233909B
CN112233909B CN202011111051.3A CN202011111051A CN112233909B CN 112233909 B CN112233909 B CN 112233909B CN 202011111051 A CN202011111051 A CN 202011111051A CN 112233909 B CN112233909 B CN 112233909B
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vanadium dioxide
electrode material
zinc oxide
composite electrode
nano vanadium
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CN112233909A (en
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李道玉
韩慧果
刘波
彭穗
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Chengdu Advanced Metal Materials Industry Technology Research Institute Co Ltd
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Chengdu Advanced Metal Materials Industry Technology Research Institute Co Ltd
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Abstract

The invention belongs to the field of battery materials, and particularly relates to a porous carbon composite electrode material doped with zinc oxide and nano vanadium dioxide and a preparation method thereof. The invention aims to solve the technical problem of providing a preparation method of a porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide, which comprises the following steps: A. adding acrylonitrile, acrylamide, azodiisobutyronitrile, zinc acetate and nano vanadium dioxide into a solvent, uniformly mixing, adding an initiator, and reacting at 55-75 ℃ under inert gas to obtain functional polyacrylonitrile; B. uniformly mixing functional polyacrylonitrile, a polyacrylonitrile solution and a foaming agent, pouring the mixture into a mold for foaming at 160-190 ℃, cooling to room temperature after foaming is finished, and standing to obtain porous polyacrylonitrile; C. and carrying out graphitization reaction on the porous polyacrylonitrile to obtain the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide. The method can prepare the composite electrode material with excellent performance.

Description

Zinc oxide-nano vanadium dioxide doped porous carbon composite electrode material and preparation method thereof
Technical Field
The invention belongs to the field of battery materials, and particularly relates to a porous carbon composite electrode material doped with zinc oxide and nano vanadium dioxide and a preparation method thereof. The electrode material can be used for preparing super capacitor electrodes.
Background
The supercapacitor is an energy storage device with high efficiency, practicality and environmental protection, and has the advantages of high power density, convenient control, high conversion efficiency, wide working temperature range, no pollution and the like. Along with the improvement of the technology, the production cost is gradually reduced, and the energy storage battery is more and more applied to the field of energy storage, so that the energy storage battery can be replaced by the energy storage battery on many occasions in the future. But the super capacitor is expensive at present and cannot be used for large-scale power energy storage. Therefore, reducing the production cost is an essential step for the further development of super capacitors and the replacement of storage batteries in the future.
The super capacitor is composed of an electrode material, an electrolyte, a diaphragm, a collector and the like, each part has great influence on the super capacitor, and the electrode material plays a decisive role in the performance of the super capacitor. Common electrode materials of the super capacitor include carbon materials, metal oxide materials, conductive polymer materials and composite materials. Carbon materials are widely used as electrode materials for supercapacitors because of their low cost and various existing forms, but since they store energy only by means of an electric double layer, there is a limit in performance, and thus electrode development and research of metal oxide materials have been emerging. The metal oxide material is different from a carbon material electrode in an electric double layer capacitor for storing energy, and when the capacitor is charged and discharged, reversible oxidation-reduction reaction occurs at the interface of the metal oxide and a solution, so that higher specific capacity is obtained. The material electrode has larger specific capacity, but is expensive, and is not beneficial to the development of the super capacitor. The composite material is a composite material which is prepared by performing a nano-composite technology by using a carbon material as a matrix and a metal oxide as an active substance to improve the charge utilization rate in order to further increase the energy storage of the supercapacitor and enable the supercapacitor to have capacitance performance and electric double layer characteristics, and is a main direction for developing and researching the electrode material of the supercapacitor in the future.
The macroporous-mesoporous-microporous three-dimensional hierarchical porous carbon is prepared in the composite electrode by a template method and is used as an electrode material of the supercapacitor, so that the electrode material has smaller resistance and shorter diffusion path to promote ion transmission, the main dynamic limitation of the electrochemical process in the porous electrode is overcome, and the rapid diffusion of electrolyte ions at high rate is facilitated.
Pen\2253131of the institute of Material science and engineering of Tianjin university of Industrial science and the like, carbon black and nickel cobaltate nanowires are simultaneously loaded on the carbon nanofibers by a hydrothermal method by taking the carbon nanofibers as a substrate, and NiCo is prepared by further heat treatment2O4The carbon black @ nano carbon fiber self-supporting composite electrode has excellent cycling stability. However, the method is complicated in process due to the use of a hydrothermal method, and cannot be used for large-scale production.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide. The preparation method comprises the following steps:
A. adding acrylonitrile, acrylamide, azodiisobutyronitrile, zinc acetate and nano vanadium dioxide into a solvent, uniformly mixing, adding an initiator, and reacting at 55-75 ℃ under inert gas to obtain functional polyacrylonitrile;
B. uniformly mixing functional polyacrylonitrile, a polyacrylonitrile solution and a foaming agent, pouring the mixture into a mold for foaming at 160-190 ℃, cooling to room temperature after foaming is finished, and standing to obtain porous polyacrylonitrile;
C. and carrying out graphitization reaction on the porous polyacrylonitrile to obtain the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide.
In the step A of the preparation method of the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide, the purity of the nano vanadium dioxide is more than 99%.
In the preparation method step A of the zinc oxide-nano vanadium dioxide doped porous carbon composite electrode material, the mass ratio of acrylonitrile to acrylamide to azobisisobutyronitrile is 85 to 14 to 1 to 98 to 1.
In the preparation method step A of the porous carbon composite electrode material doped with zinc oxide and nano vanadium dioxide, the mass ratio of the zinc acetate to the nano vanadium dioxide is 1: 1-3: 1.
In the step A of the preparation method of the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide, the mass concentration of the total amount of acrylonitrile, acrylamide and azobisisobutyronitrile in the solution is 40-60%.
In the step A of the preparation method of the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide, the total mass of zinc acetate and nano vanadium dioxide is 10-30% of the total mass of acrylonitrile, acrylamide and azobisisobutyronitrile.
In the step A of the preparation method of the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide, the initiator is a persulfate. Potassium persulfate is preferred.
Further, in the step A of the preparation method of the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide, the addition amount of the initiator is 0.3-1.5% of the total mass of acrylonitrile, acrylamide and azobisisobutyronitrile.
In the step A of the preparation method of the zinc oxide-nano vanadium dioxide porous carbon-doped composite electrode material, the solvent is any one of dimethyl sulfoxide, ethanol, acetone or petroleum ether.
In the step A of the preparation method of the zinc oxide-nano vanadium dioxide porous carbon-doped composite electrode material, the inert gas is nitrogen.
In the step A of the preparation method of the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide, the reaction time is 20-30 hours.
In the step A of the preparation method of the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide, uniformly mixing the materials for 10-20 minutes at a rotating speed of 300-500 rpm, and then performing ultrasonic treatment at a frequency of 5-20 KHZ for 5-15 minutes.
In the preparation method step B of the porous carbon composite electrode material doped with zinc oxide and nano vanadium dioxide, the mass ratio of the functional polyacrylonitrile to the polyacrylonitrile solution is 3: 7-5: 5.
Further, in the step B of the preparation method of the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide, the mass concentration of the polyacrylonitrile solution is 70-90%.
In the step B of the preparation method of the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide, the foaming agent is an azo compound or a sulfonyl hydrazine compound. Further, the azo compound is azodicarbonamide, azobisisobutyronitrile or difluorine diisoheptanonitrile. The sulfonyl hydrazide compound is p-toluenesulfonyl hydrazide or 4, 4-oxo-bis-benzenesulfonyl hydrazide.
In the step B of the preparation method of the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide, the addition amount of the foaming agent is 1-5% of the total mass of the functional polyacrylonitrile and the polyacrylonitrile solution.
In the step B of the preparation method of the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide, the foaming time is 15-30 minutes.
In the step B of the preparation method of the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide, the standing time is 24-36 hours.
In the step C of the preparation method of the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide, the graphitization reaction comprises the following steps: pre-oxidizing at 170-280 ℃ for 100-140 minutes, introducing inert gas, reacting at 600 +/-5 ℃, 650 +/-5 ℃, 700 +/-5 ℃, 750 +/-5 ℃ and 800 +/-5 ℃ for 20-40 minutes respectively, and cooling to room temperature under the protection of the inert gas.
Further, in the step C of the preparation method of the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide, the inert gas is high-purity N2。
The invention also provides the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide prepared by the preparation method.
The method takes polyacrylonitrile as a base material, carries out foaming on the polyacrylonitrile to prepare communicated large pores and small pores, prepares micropores by decomposing zinc acetate, and finally prepares the large pores and small pores and microporous three-dimensional hierarchical porous carbon composite electrode material. The metal oxide generated in the decomposition process of the pore-forming agent selected by the method can be partially left in the ring formation process of polyacrylonitrile, so that the reaction active points are increased, and the performance of the capacitor is improved; meanwhile, the added metal oxide can generate chemical bonds when cyclizing with polyacrylonitrile, and is not easy to fall off in long-term use. The method has simple process and low cost, and can be used for industrial large-scale production; and the obtained material has excellent performance.
Detailed Description
The preparation method of the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide comprises the following steps:
A. preparing functional polyacrylonitrile doped with zinc acetate-nano vanadium dioxide:
adding acrylonitrile, acrylamide, azodiisobutyronitrile, zinc acetate and nano vanadium dioxide into a solvent, stirring for 10-20 minutes at a rotating speed of 300-500 rpm by using a stirrer, performing ultrasonic treatment at a frequency of 5-20 KHZ for 5-15 minutes by using ultrasonic waves, adding an initiator, stirring, and heating to 55-75 ℃ under the protection of nitrogen to react for 20-30 hours to obtain functional polypropylene; the content of the monomer (the monomer is a mixture of acrylonitrile, acrylamide and azodiisobutyronitrile) in the solution is 40% -60%, the mass ratio of acrylonitrile to acrylamide to azodiisobutyronitrile is 85: 14: 1-98: 1, the mass ratio of zinc acetate to nano vanadium dioxide is 1: 1-3: 1, the mass ratio of zinc acetate to nano vanadium dioxide is 10% -30% of the total mass of the monomer, and the initiator is 0.3% -1.5% of the total mass of the monomer;
B. foaming polyacrylonitrile:
mixing the functional polyacrylonitrile prepared in the step A with a commercially available polyacrylonitrile solution according to a mass ratio of 3: 7-5: 5, adding a foaming agent (a commercially available azo compound or sulfonyl hydrazide compound foaming agent), uniformly mixing, placing into a mold with a required electrode size and thickness, foaming at 160-190 ℃ for 15-30 minutes, cooling to room temperature, standing at normal temperature for 24-36 hours, and taking out to obtain porous polyacrylonitrile; wherein the addition amount of the foaming agent is 1-5% of the mixed polypropylene solution;
C. preparing a porous carbon composite electrode material:
placing the porous polyacrylonitrile prepared in the step B in a carbonization furnace, pre-oxidizing for 100-140 minutes at the temperature of 170-280 ℃, and then introducing high-purity N2Respectively reacting at 600 +/-5 ℃, 650 +/-5 ℃, 700 +/-5 ℃, 750 +/-5 ℃ and 800 +/-5 ℃ for 20-40 minutes, and then cooling to room temperature under the protection of high-purity nitrogen.
In the step A of the method, if the zinc acetate and the nano vanadium dioxide are directly mixed by adopting the finished polyacrylonitrile, the zinc acetate and the nano vanadium dioxide are inorganic substances, have different polarities from the polyacrylonitrile and cannot be well mixed, and meanwhile, the zinc acetate and the nano vanadium dioxide have small particle size, are easy to agglomerate and are easy to be mixed unevenly, so that the performance of the final material is influenced. In the step A, acrylonitrile, acrylamide and azodiisobutyronitrile are used as raw materials, the acrylonitrile, the acrylamide, the azodiisobutyronitrile, zinc acetate and nano vanadium dioxide are uniformly mixed under ultrasonic waves, then an initiator is added, and the produced polyacrylonitrile wraps the zinc acetate and the nano vanadium dioxide, so that the zinc acetate and the nano vanadium dioxide are uniformly doped in the prepared polyacrylonitrile.
In the step A of the method, because zinc acetate is decomposed to form micropores, if the addition amount of the zinc acetate is too low, the generated micropores are less, and the effect cannot be achieved; if the addition amount of the zinc acetate is too high, too many micropores are generated, and the network structure formed by the polyacrylonitrile can be damaged. Therefore, the mass ratio of the zinc acetate to the nano vanadium dioxide is controlled to be 1: 1-3: 1, the mass ratio of the acrylonitrile to the acrylamide to the azobisisobutyronitrile is controlled to be 85: 14: 1-98: 1, and the total mass of the zinc acetate and the nano vanadium dioxide is 10-30% of the total mass of the acrylonitrile, the acrylamide and the azobisisobutyronitrile.
In step B of the method of the present invention, all the polyacrylonitrile raw materials adopted in the present invention can be prepared by using acrylonitrile, acrylamide, azobisisobutyronitrile as raw materials, but such operation is not economical and increases the operation cost, so that a part of polyacrylonitrile of the present invention is prepared by using acrylonitrile, acrylamide, azobisisobutyronitrile as raw materials, the main purpose is to uniformly dope zinc acetate and nano vanadium dioxide, and another part can be directly prepared by using a commercially available polyacrylonitrile solution. The mass concentration of the polyacrylonitrile solution is 70-90%. The solvent is dimethylformamide or dimethyl sulfoxide.
In the step B of the method, the foaming is not uniform, large holes and small holes can be formed, the large holes and the small holes are influenced by the foaming, and the micropores are influenced by the decomposition of zinc acetate which is a pore-forming agent at the foaming temperature. Therefore, the large and small holes can be controlled by controlling foaming conditions such as the addition amount of the foaming agent, the foaming temperature, the foaming time and the like, for example, the large amount of the foaming agent, the high temperature and the large holes generated in a long time are relatively large; the micropores can be controlled by the amount of zinc acetate added. The corresponding parameters can be controlled by those skilled in the art according to the requirements.
In the step C of the method, the porous polyacrylonitrile obtained in the step B cannot conduct electricity, and the material is used as an electrode material, so that the porous polyacrylonitrile obtained in the step B needs to be subjected to graphitization reaction so as to conduct electricity. The graphitization reaction may be carried out by a conventional method. Preferably, the graphitization reaction of the present invention comprises the steps of: pre-oxidizing at 170-280 ℃ for 100-140 minutes, introducing inert gas, reacting at 600 +/-5 ℃, 650 +/-5 ℃, 700 +/-5 ℃, 750 +/-5 ℃ and 800 +/-5 ℃ for 20-40 minutes, and cooling to room temperature under the protection of the inert gas.
The invention also provides the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide prepared by the method.
Example 1
Uniformly mixing the raw materials in a solvent dimethyl sulfoxide according to the following ratio of 20% of the total mass of acrylonitrile, acrylamide and azodiisobutyronitrile, 55% of the total mass of the acrylonitrile, the acrylamide and the azodiisobutyronitrile, 3: 1 of the zinc acetate and the nano vanadium dioxide, 0.3% of potassium peroxide, and reacting at 65 ℃ for 30 hours to obtain the functional polyacrylonitrile;
uniformly mixing the prepared functional polyacrylonitrile and 75% polyacrylonitrile solution according to the mass ratio of 3: 7 and the foaming amount of 2%, foaming at 160 ℃ for 25 minutes, cooling to room temperature, standing at normal temperature for 24 hours, placing in a carbonization furnace, pre-oxidizing at 170 ℃ for 140 minutes, and introducing high-purity N2Reacting at 600 deg.C, 650 deg.C, 700 deg.C, 750 deg.C and 800 deg.C for 40 min, cooling to room temperature to obtain electrode with specific capacitance of 0.189F-cm-2At a current density of 15mA cm-2Then, the specific capacitance after 2000 cycles was 89.12% of the initial value.
Example 2
Uniformly mixing the raw materials in a solvent dimethyl sulfoxide according to the following ratio of 15% of the total mass of acrylonitrile, acrylamide and azodiisobutyronitrile, 45% of the total mass of the acrylonitrile, the acrylamide and the azodiisobutyronitrile, 2: 1 of the zinc acetate and the nano vanadium dioxide, and 0.5% of potassium peroxide, and reacting at 65 ℃ for 25 hours to obtain the functional polyacrylonitrile;
uniformly mixing the prepared functional polyacrylonitrile and 80 mass percent polyacrylonitrile solution according to the mass ratio of 4: 6 and the foaming dose of 5 percent, foaming at 170 ℃ for 20 minutes, cooling to room temperature, standing at normal temperature for 30 hours, placing in a carbonization furnace, pre-oxidizing at 240 ℃ for 120 minutes, introducing high-purity N2Reacting at 600 deg.C, 650 deg.C, 700 deg.C, 750 deg.C and 800 deg.C for 30 min, cooling to room temperature to obtain electrode with specific capacitance of 0.191F cm-2At a current density of 10mA cm-2Then, the specific capacitance was 89.91% of the initial value after 2000 cycles of charge and discharge.
Example 3
Uniformly mixing the raw materials in a solvent dimethyl sulfoxide according to the following ratio of 25% of the total mass of acrylonitrile, acrylamide and azodiisobutyronitrile, 50% of the total mass of the acrylonitrile, the acrylamide and the azodiisobutyronitrile, 2: 1 of the zinc acetate and the nano vanadium dioxide, and reacting at 65 ℃ for 20 hours to obtain the functional polyacrylonitrile, wherein the mass ratio of the acrylonitrile to the acrylamide to the azodiisobutyronitrile is 95: 4: 1, and the mass ratio of the zinc acetate to the nano vanadium dioxide is 2: 1;
uniformly mixing the prepared functional polyacrylonitrile and a polyacrylonitrile solution with the mass concentration of 85% according to the mass ratio of 5: 5 and the foaming dose of 4%, foaming at 190 ℃ for 15 minutes, cooling to room temperature, standing at normal temperature for 36 hours, placing in a carbonization furnace, pre-oxidizing at 280 ℃ for 100 minutes, introducing high-purity N2Reacting at 600 deg.C, 650 deg.C, 700 deg.C, 750 deg.C and 800 deg.C for 20 min, cooling to room temperature to obtain electrode with specific capacitance of 0.194F cm-2At a current density of 5mA cm-2Then, the specific capacitance was 90.04% of the initial value after 2000 cycles of charge and discharge.

Claims (16)

1. The preparation method of the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide is characterized by comprising the following steps of: the method comprises the following steps:
A. adding acrylonitrile, acrylamide, azodiisobutyronitrile, zinc acetate and nano vanadium dioxide into a solvent, uniformly mixing, adding an initiator, and reacting at 55-75 ℃ under inert gas to obtain functional polyacrylonitrile;
B. uniformly mixing functional polyacrylonitrile, a polyacrylonitrile solution and a foaming agent, pouring the mixture into a mold for foaming at 160-190 ℃, cooling to room temperature after foaming is finished, and standing to obtain porous polyacrylonitrile;
C. and carrying out graphitization reaction on the porous polyacrylonitrile to obtain the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide.
2. The preparation method of the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide according to claim 1, characterized in that: in the step A, the mass ratio of the acrylonitrile to the acrylamide to the azobisisobutyronitrile is 85 to 14 to 1 to 98 to 1.
3. The preparation method of the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide according to claim 2, characterized in that: the mass concentration of the total amount of acrylonitrile, acrylamide and azobisisobutyronitrile in the solution is 40-60%.
4. The preparation method of the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide according to claim 1, characterized in that: in the step A, the mass ratio of the zinc acetate to the nano vanadium dioxide is 1: 1-3: 1.
5. The preparation method of the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide according to claim 4, characterized in that: the total mass of the zinc acetate and the nano vanadium dioxide is 10-30% of the total mass of the acrylonitrile, the acrylamide and the azobisisobutyronitrile.
6. The preparation method of the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide according to claim 1, characterized in that: in step A, the initiator is a persulfate.
7. The preparation method of the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide according to claim 6, characterized in that: the initiator is potassium persulfate.
8. The preparation method of the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide according to claim 7, characterized in that: the addition amount of the initiator is 0.3-1.5% of the total mass of acrylonitrile, acrylamide and azobisisobutyronitrile.
9. The preparation method of the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide according to claim 1, characterized in that: in the step A, the solvent is any one of dimethyl sulfoxide, ethanol, acetone or petroleum ether.
10. The preparation method of the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide according to claim 1, characterized in that: in the step B, the mass ratio of the functional polyacrylonitrile to the polyacrylonitrile solution is 3: 7-5: 5.
11. The preparation method of the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide according to claim 10, characterized in that: the mass concentration of the polyacrylonitrile solution is 70-90%.
12. The preparation method of the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide according to claim 1, characterized in that: in the step B, the foaming agent is an azo compound or a sulfonyl hydrazine compound.
13. The preparation method of the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide according to claim 12, characterized in that: the addition amount of the foaming agent is 1-5% of the total mass of the functional polyacrylonitrile and the polyacrylonitrile solution.
14. The preparation method of the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide according to claim 1, characterized in that: in the step A, the reaction time is 20-30 hours; in the step B, the foaming time is 15-30 minutes; the standing time is 24-36 hours.
15. The preparation method of the porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide according to any one of claims 1 to 14, characterized by comprising the following steps: in step C, the graphitization reaction includes the following steps: pre-oxidizing at 170-280 ℃ for 100-140 minutes, introducing inert gas, reacting at 600 +/-5 ℃, 650 +/-5 ℃, 700 +/-5 ℃, 750 +/-5 ℃ and 800 +/-5 ℃ for 20-40 minutes respectively, and cooling to room temperature under the protection of the inert gas.
16. The porous carbon composite electrode material doped with zinc oxide-nano vanadium dioxide prepared by the preparation method of any one of claims 1 to 15.
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CN104167303A (en) * 2014-07-29 2014-11-26 上海应用技术学院 Mesopore vanadium oxide/carbon composite nano material and preparation method thereof
CN105810955A (en) * 2016-05-05 2016-07-27 攀钢集团研究院有限公司 Preparation method for electrode of vanadium cell
CN109167082A (en) * 2018-08-27 2019-01-08 成都先进金属材料产业技术研究院有限公司 Vanadium cell electrode and vanadium cell
CN110473715A (en) * 2018-05-10 2019-11-19 北京化工大学 A kind of VO2(B) nanobelt/graphene complex thin-film material and its synthetic method and all-solid-state supercapacitor

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104167303A (en) * 2014-07-29 2014-11-26 上海应用技术学院 Mesopore vanadium oxide/carbon composite nano material and preparation method thereof
CN105810955A (en) * 2016-05-05 2016-07-27 攀钢集团研究院有限公司 Preparation method for electrode of vanadium cell
CN110473715A (en) * 2018-05-10 2019-11-19 北京化工大学 A kind of VO2(B) nanobelt/graphene complex thin-film material and its synthetic method and all-solid-state supercapacitor
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