CN114783788B - Carbon fiber electrode for nitrogen-phosphorus in-situ doped supercapacitor and preparation and application thereof - Google Patents

Carbon fiber electrode for nitrogen-phosphorus in-situ doped supercapacitor and preparation and application thereof Download PDF

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CN114783788B
CN114783788B CN202210175371.8A CN202210175371A CN114783788B CN 114783788 B CN114783788 B CN 114783788B CN 202210175371 A CN202210175371 A CN 202210175371A CN 114783788 B CN114783788 B CN 114783788B
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carbon fiber
hccp
supercapacitor
phosphorus
nitrogen
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CN114783788A (en
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徐海兵
陈少杰
祝颖丹
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Ningbo Institute of Material Technology and Engineering of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
    • H01G11/40—Fibres
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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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Abstract

The invention discloses a carbon fiber electrode for a nitrogen-phosphorus in-situ doped supercapacitor, a preparation method thereof and application thereof in the supercapacitor. The preparation method comprises the following steps: the desized carbon fiber is oxidized by nitric acid, washed and dried to obtain CFO; grafting Hexachlorocyclotriphosphazene (HCCP) on the surface of carbon fiber through a grafting reaction to obtain CFO-HCCP; dissolving HCCP and aliphatic compound with a plurality of nucleophilic groups in a solvent, and coating a large number of cross-linked polyphosphazene micro-nano hybrid coatings on the surface of the carbon fiber through in-situ polymerization to obtain cross-linked polyphosphazene material modified carbon fiber M-CF; and heating the M-CF to 400-600 ℃ under the protection of inert gas, keeping the temperature for 1-10 h, heating to 700-1200 ℃ again, keeping the temperature for 1-10 h, and naturally cooling to obtain the carbon fiber electrode material for the nitrogen-phosphorus in-situ doped supercapacitor.

Description

Carbon fiber electrode for nitrogen-phosphorus in-situ doped supercapacitor and preparation and application thereof
Technical Field
The invention relates to the field of new energy materials, in particular to a carbon fiber electrode for a nitrogen-phosphorus in-situ doped supercapacitor and preparation and application thereof.
Background
With the increasing consumption of a large amount of traditional fossil fuel and the increasing emission of carbon dioxide, the fields of automobiles, rail transit, aerospace and the like face the technical problems of light weight, renewable energy use, novel energy storage equipment development and the like. Super capacitor is widely paid attention to as an energy storage device because of its advantages of high power density, fast charge transmission, fast charge and discharge speed, long cycle life, etc., and has been applied in the above fields.
As a key component of the supercapacitor, development of an electrode material excellent in electrochemical properties has been receiving much attention. Carbon materials, metal oxides and conductive polymers are common electrode materials, wherein carbon fibers not only have excellent electric conductivity and heat conductivity, but also have excellent mechanical strength and electrochemical stability, and are ideal materials for preparing the supercapacitor electrode. However, the carbon fiber has smooth surface and low specific surface area, so that electrolyte has poor wettability, the charge concentration density on the surface of the electrode is low, and the energy storage effect is not ideal. The high specific surface area and the rich pore structure are one of the key factors for realizing the charge storage and the rapid charge migration of the carbon fiber electrode. Therefore, when the carbon fiber is used as an electrode material, the surface treatment is performed in advance, so that a rich pore structure is constructed, and the specific area of the carbon fiber is improved.
The current method for activating and modifying the surface of the carbon fiber electrode mainly comprises etching modification of a liquid strong corrosive medium, modification of a porous active carbon-based coating (active carbon, graphene, carbon nano tube and the like), and the like. However, the mechanical properties of the carbon fiber electrode body may be damaged by chemical etching or the like, and in addition, the internal resistance and wettability of the carbon fiber electrode may be increased by introducing a pure carbon coating with a porous structure.
Heteroatom doping is also one of effective ways for improving the electrochemical performance of the carbon-based supercapacitor electrode material, and the heteroatom-doped porous carbon material is introduced into the surface of the carbon fiber, so that the surface wettability of the carbon fiber electrode material can be improved, the charge balance of the surface of the carbon fiber is changed, the working potential window is widened, and the additional pseudocapacitance performance is endowed, so that the specific capacity of the carbon fiber electrode material is obviously improved. There is a literature that by calcining carbon fiber cloth deposited with urea, boric acid and polyethylene oxide-propylene oxide copolymer, boron and nitrogen doped active carbon fiber electrode materials are introduced on the fiber surface, and supercapacitor electrode materials with high specific surface area, high specific capacitance and long cycle life are obtained (Chemical Engineering Journal,2021, 410:128365). However, the small molecular species heteroatom sources are easily lost during calcination, resulting in less doping of the heteroatoms. Therefore, a new method for constructing a highly doped multi-level porous active carbon material on the surface of the carbon fiber is necessary to be developed, and a solution is provided for preparing the high-performance carbon fiber electrode material.
Disclosure of Invention
Aiming at the technical problems and the defects existing in the field, the invention provides a preparation method of a carbon fiber electrode for a nitrogen-phosphorus in-situ doped supercapacitor, which has the advantages of simple process, high efficiency, strong structure and performance controllability and the like. The invention is based on in-situ polymerization reaction, introduces cross-linked polyphosphazene nano particles containing nitrogen and phosphorus elements on the surface of carbon fiber, constructs micro-nano multi-stage hybrid modified carbon fiber, deposits nitrogen and phosphorus doped micro-nano multi-stage active carbon material on the surface of carbon fiber through high temperature carbonization treatment in inert atmosphere, improves the specific surface area and heteroatom doping amount of carbon fiber, improves the electrochemical performance of carbon fiber electrode, and provides a solution for preparing high-performance carbon fiber electrode material for super capacitor.
A preparation method of a carbon fiber electrode for a nitrogen-phosphorus in-situ doped supercapacitor comprises the following steps:
(1) The desized carbon fiber is oxidized by nitric acid, washed and dried to obtain oxidized carbon fiber which is marked as CFO;
(2) Dissolving hexachlorocyclotriphosphazene in a solvent, adding CFO and an acid binding agent, taking out carbon fibers after sealed ultrasonic reaction, washing with the solvent to obtain HCCP grafted carbon fibers, and marking the HCCP grafted carbon fibers as CFO-HCCP;
(3) Dissolving HCCP and aliphatic compound with a plurality of nucleophilic groups in a solvent, then adding CFO-HCCP and acid binding agent, standing for 0.1-24 h after sealed ultrasonic reaction, taking out carbon fiber, washing with the solvent, and drying to obtain carbon fiber modified by cross-linked polyphosphazene nanomaterial, which is marked as M-CF;
the nucleophilic group comprises-NH 2 At least one of, -NH-;
(4) And (3) heating the M-CF to 400-600 ℃ under the protection of inert gas, keeping the temperature for 1-10 h, heating to 700-1200 ℃ again, keeping the temperature for 1-10 h, and cooling to obtain the carbon fiber modified by the cross-linked polyphosphazene derivative porous carbon, namely the carbon fiber electrode for the nitrogen-phosphorus in-situ doped supercapacitor, namely the C-M-CF.
The invention adopts micron-scale carbon fiber, and under certain conditions, uses a fiber with a plurality of nucleophilic groups (-NH) 2 In-situ polymerizing aliphatic compound (NH-etc.) with HCCP on activated carbon fiber surface to generate cross-linked polyphosphazene hybridized coating with a large amount of cross-linked polyphosphazene nano particles, carbonizing the carbon fiber modified by micro-nano multi-scale cross-linked polyphosphazene hybridized coating at high temperature under the protection of inert gas, and cross-linking polyThe phosphazene is carbonized into a nitrogen and phosphorus doped micro-nano porous carbon material which is tightly coated on the surface of the carbon fiber, so that the carbon fiber electrode material modified by carbon derived from the crosslinked polyphosphazene is prepared.
In a preferred embodiment, in the preparation method of the carbon fiber electrode for the nitrogen-phosphorus in-situ doped supercapacitor, the temperature of nitric acid oxidation in the step (1) is 20-120 ℃ and the time is 0.5-24 h.
In a preferred embodiment, in the preparation method of the carbon fiber electrode for the nitrogen-phosphorus in-situ doped supercapacitor, in the step (2), the solvent is used in an amount of 10-1000 mL and the CFO is used in an amount of 0.1-10 g relative to 0.1-10 g of HCCP.
In a preferred embodiment, in the preparation method of the carbon fiber electrode for the nitrogen-phosphorus in-situ doped supercapacitor, in the step (2), the temperature of the ultrasonic reaction is 20-100 ℃ and the time is 1-10 h.
In a preferred embodiment, in the preparation method of the carbon fiber electrode for the nitrogen-phosphorus in-situ doped supercapacitor, in the step (3), the aliphatic compound is used in an amount of 0.1-10 g, the solvent used for dissolution is used in an amount of 10-1000 mL, and the CFO-HCCP is used in an amount of 0.1-10 g, relative to 0.1-10 g of HCCP.
In a preferred embodiment, in the preparation method of the carbon fiber electrode for the nitrogen-phosphorus in-situ doped supercapacitor, the temperature of the ultrasonic reaction is 20-100 ℃ and the time is 0.5-10 h in the step (3).
In a preferred embodiment, in the preparation method of the carbon fiber electrode for the nitrogen-phosphorus in-situ doped supercapacitor, in the step (2) and the step (3), the solvent is independently selected from one or more of ethanol, diethyl ether, acetone, acetonitrile, tetrahydrofuran and ethyl acetate.
In a preferred embodiment, in the preparation method of the carbon fiber electrode for the nitrogen-phosphorus in-situ doped supercapacitor, in the step (2) and the step (3), the acid binding agent is independently selected from triethylamine, N-diisopropylethylamine, 4-dimethylaminopyridine, triethanolamine, pyridine or potassium carbonate, sodium carbonate, ammonium carbonate and sodium acetate.
In a preferred embodiment, the method for preparing the carbon fiber electrode for the nitrogen-phosphorus in-situ doped supercapacitor comprises the following step (3), wherein the aliphatic compound with a plurality of nucleophilic groups comprises at least one of ethylenediamine, 1, 3-propylenediamine, 1, 2-propylenediamine, butylenediamine, pentylene diamine, hexamethylenediamine, 1, 2-cyclohexanediamine, 1, 4-cyclohexanediamine, tri (2-aminoethyl) amine, piperazine, aminoethylpiperazine, N1- (2-aminoethyl) -1, 4-piperazine diethylamine, N- [2- (1-piperazinyl) ethyl ] -1, 2-ethylenediamine and polyethyleneimine.
In a preferred embodiment, in the preparation method of the carbon fiber electrode for the nitrogen-phosphorus in-situ doped supercapacitor, in the step (4), the heating rate is 1-20 ℃/min.
The invention also provides the carbon fiber electrode for the nitrogen-phosphorus in-situ doped supercapacitor, which is prepared by the preparation method.
The invention also provides application of the carbon fiber electrode for the nitrogen-phosphorus in-situ doped supercapacitor in the supercapacitor.
The beneficial effects of the invention are at least as follows:
1. the modification method for constructing the micro-nano multi-scale hybridization structure with nitrogen and phosphorus elements on the surface of the carbon fiber is provided.
2. Based on in-situ template polymerization, a hybrid polymer coating with nano particles of a cross-linked polyphosphazene structure is introduced on the surface of the carbon fiber, so as to provide a carbon source for the carbonization process.
3. In the carbonization process, nitrogen and phosphorus atoms in the cross-linked polyphosphazene hybrid coating can be doped in a porous carbon material structure on the surface of the carbon fiber, so that the specific surface area, the porosity, the electrolyte wettability and the like of the carbon fiber can be improved, and the electrochemical performance of the modified carbon fiber can be improved.
4. The carbon fiber modified by the cross-linked polyphosphazene derivative carbon can be used as an electrode material of the supercapacitor, and the energy storage performance of the supercapacitor can be effectively improved.
Detailed Description
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. The methods of operation, under which specific conditions are not noted in the examples below, are generally in accordance with conventional conditions, or in accordance with the conditions recommended by the manufacturer.
Example 1
The desized carbon fiber is oxidized for 2 hours at 100 ℃ by concentrated nitric acid, active groups such as carboxyl, hydroxyl and the like are introduced to the surface of the carbon fiber, and the oxidized carbon fiber CFO is obtained after washing and drying. 0.4g of Hexachlorocyclotriphosphazene (HCCP) is weighed and added into a reactor, 40mL of anhydrous acetonitrile is added, 0.3g of CFO is added after stirring and dissolving, 3mL of Triethylamine (TEA) is injected, the mixture is immediately sealed, after ultrasonic reaction is carried out for 3 hours at 40 ℃, the carbon fiber is taken out, and the carbon fiber is respectively washed by acetonitrile and tetrahydrofuran, so that the HCCP grafted carbon fiber (CFO-HCCP) is prepared. 0.4g of HCCP and 0.3g of piperazine are weighed and added into a reactor, 75mL of THF is added, 0.3g of CFO-HCCP is added after stirring and dissolving, 4mL of TEA is injected, the mixture is immediately sealed, ultrasonic reaction is carried out at 25 ℃ for 1.5 hours, carbon fiber is taken out after standing for 24 hours, acetonitrile is used for extraction for 12 hours, and vacuum drying is carried out, thus obtaining polyphosphazene modified carbon fiber (CF-PZPi). And (3) placing the CF-PZPi in a tubular furnace for carbonization treatment, heating to 500 ℃ under the protection of inert gas, keeping for 5 hours, heating to 800 ℃ and keeping for 2 hours, wherein the heating rate is 10 ℃/min, and naturally cooling to room temperature to obtain the polyphosphazene derivative carbon modified carbon fiber (CF-CPZPi). The surface of the polyphosphazene derivative carbon modified carbon fiber prepared in the embodiment is coated by a carbon material with a multi-level pore structure doped with rich nitrogen and phosphorus. The electrode was used as an electrode of a supercapacitor, and the electrochemical properties of the electrode were tested under a 3M KOH electrolyte three-electrode electrochemical test system at different current densities, and the results are shown in Table 1, wherein the current density was 1mA/cm 2 When the area specific capacitance reaches 803.5mF/cm 2 The current density was 10mA/cm 2 When the area specific capacitance reaches 570.2mF/cm 2 . Under the same test conditions, the area specific capacitance of the desized carbon fiber is only 2.5mF/cm 2 (current density was 1 mA/cm) 2 ) The area specific capacitance of the carbon oxide fiber (CFO) was 121.3mF/cm 2 (current density was 1 mA/cm) 2 )。
Example 2
The desized carbon fiber is oxidized for 2 hours at 100 ℃ by concentrated nitric acid, and the oxidized carbon fiber CFO is obtained after washing and drying. 0.4g of HCCP is weighed and added into a reactor, 40mL of anhydrous acetonitrile is added, 0.4g of CFO is added after stirring and dissolving, 3mL of TEA is injected, immediately sealing is carried out, and the temperature is higher than 40 DEG CAfter 3h of acoustic reaction, the carbon fiber was taken out and washed with acetonitrile and tetrahydrofuran, respectively, to prepare HCCP grafted carbon fiber (CFO-HCCP). 0.5g of HCCP and 1.0g of Polyethylenimine (PEI) are weighed and added into a reactor, 75mL of THF is added, 0.4g of CFO-HCCP is added after stirring and dissolving, 4mL of TEA is injected, the mixture is immediately sealed, ultrasonic reaction is carried out for 2 hours at 40 ℃, after standing for 18 hours, carbon fibers are taken out, acetonitrile is used for extraction for 12 hours, and vacuum drying is carried out, thus obtaining polyphosphazene modified carbon fibers (CF-PZPEI). And (3) placing the CF-PZPEI in a tube furnace for carbonization treatment, heating to 500 ℃ under the protection of inert gas, keeping for 5 hours, heating to 800 ℃ and keeping for 2 hours, wherein the heating rate is 10 ℃/min, and naturally cooling to room temperature to obtain the cross-linked polyphosphazene derivative micro-nano multi-scale carbon layer modified carbon fiber (CF-CPZPEI). The porous carbon material doped with rich nitrogen and phosphorus is deposited on the surface of the polyphosphazene derivative carbon modified carbon fiber prepared in the embodiment. Using the same as an electrode of a super capacitor, the electrochemical performance of the super capacitor was tested under a 3M KOH electrolyte three-electrode electrochemical test system according to example 1, and the results are shown in Table 1, wherein the current density is 1mA/cm 2 When the area specific capacitance is up to 752mF/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The current density was 10mA/cm 2 When the area specific capacitance reaches 528.7mF/cm 2 。
Comparative example
The difference from example 1 is that the carbon fiber was directly taken out after the HCCP grafted carbon fiber (CFO-HCCP) and the comonomer (HCCP and piperazine) were polymerized for 1.5 hours under the assistance of ultrasound, and the other steps were the same, so as to prepare a carbon fiber electrode modified with a cross-linked polyphosphazene derivative carbon material, and electrochemical performance test was performed with reference to example 1, and the results are shown in table 1.
TABLE 1
Further, it will be understood that various changes and modifications may be made by those skilled in the art after reading the foregoing description of the invention, and such equivalents are intended to fall within the scope of the claims appended hereto.

Claims (7)

1. The preparation method of the carbon fiber electrode for the nitrogen-phosphorus in-situ doped supercapacitor is characterized by comprising the following steps of:
(1) The desized carbon fiber is oxidized by nitric acid, washed and dried to obtain oxidized carbon fiber which is marked as CFO;
(2) Dissolving hexachlorocyclotriphosphazene in a solvent, adding CFO and an acid binding agent, taking out carbon fibers after sealed ultrasonic reaction, washing with the solvent to obtain HCCP grafted carbon fibers, and marking the HCCP grafted carbon fibers as CFO-HCCP;
(3) Dissolving HCCP and aliphatic compound with a plurality of nucleophilic groups in a solvent, then adding CFO-HCCP and acid binding agent, standing for 0.1-24 h after sealed ultrasonic reaction, taking out carbon fiber, washing with the solvent, and drying to obtain carbon fiber modified by cross-linked polyphosphazene nanomaterial, which is marked as M-CF;
aliphatic compounds having a plurality of nucleophilic groups include at least one of ethylenediamine, 1, 3-propylenediamine, 1, 2-propylenediamine, butylenediamine, pentyldienediamine, hexamethylenediamine, 1, 2-cyclohexanediamine, 1, 4-cyclohexanediamine, tris (2-aminoethyl) amine, piperazine, aminoethylpiperazine, N1- (2-aminoethyl) -1, 4-piperazine diethylamine, N- [2- (1-piperazinyl) ethyl ] -1, 2-ethylenediamine, polyethyleneimine;
(4) And (3) heating the M-CF to 400-600 ℃ under the protection of inert gas, keeping the temperature for 1-10 h, heating the M-CF to 700-1200 ℃ again, keeping the temperature for 1-10 h, wherein the heating rate is 1-20 ℃/min, and cooling to obtain the carbon fiber modified by the cross-linked polyphosphazene derivative porous carbon, namely the carbon fiber electrode for the nitrogen-phosphorus in-situ doped supercapacitor, wherein the carbon fiber electrode is marked as the C-M-CF.
2. The method according to claim 1, wherein in the step (1), the nitric acid is oxidized at 20 to 120 ℃ for 0.5 to 24 hours.
3. The method according to claim 1, wherein in step (2):
the amount of solvent used for dissolution is 10-1000 mL and the amount of CFO is 0.1-10 g relative to 0.1-10 g of HCCP;
the temperature of the ultrasonic reaction is 20-100 ℃ and the time is 1-10 h.
4. The method according to claim 1, wherein in the step (3):
the amount of aliphatic compound is 0.1-10 g, the amount of solvent used for dissolution is 10-1000 mL, and the amount of CFO-HCCP is 0.1-10 g relative to 0.1-10 g of HCCP;
the temperature of the ultrasonic reaction is 20-100 ℃ and the time is 0.5-10 h.
5. The method according to claim 1, wherein in the steps (2) and (3):
the solvent is selected from one or more of ethanol, diethyl ether, acetone, acetonitrile, tetrahydrofuran and ethyl acetate;
the acid binding agent is independently selected from triethylamine, N-diisopropylethylamine, 4-dimethylaminopyridine, triethanolamine, pyridine or potassium carbonate, sodium carbonate, ammonium carbonate and sodium acetate.
6. The carbon fiber electrode for the nitrogen-phosphorus in-situ doped supercapacitor prepared by the preparation method according to any one of claims 1-5.
7. The use of the carbon fiber electrode for the nitrogen-phosphorus in-situ doped supercapacitor according to claim 6 in a supercapacitor.
CN202210175371.8A 2022-02-25 2022-02-25 Carbon fiber electrode for nitrogen-phosphorus in-situ doped supercapacitor and preparation and application thereof Active CN114783788B (en)

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KR102042734B1 (en) * 2018-05-15 2019-11-08 고려대학교 산학협력단 Carbon fiber electrode, wire type supercapacitor comprising the same and manufacturing method of the carbon fiber electrode
CN110453266A (en) * 2019-08-06 2019-11-15 北京化工大学 A kind of method that carbon fiber surface electrophoretic deposition polymer micro-nano particle prepares high-performance composite materials
CN111691188A (en) * 2019-03-14 2020-09-22 中国科学院宁波材料技术与工程研究所 Dendritic phosphazene graft modified carbon fiber and preparation method and application thereof
CN112522956A (en) * 2019-09-19 2021-03-19 中国科学院宁波材料技术与工程研究所 Silica microsphere modified multi-scale hybrid carbon fiber and preparation method and application thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016198550A1 (en) * 2015-06-10 2016-12-15 Centre National De La Recherche Scientifique Metal carbodiimides and metal cyanamides as electrode materials
KR102042734B1 (en) * 2018-05-15 2019-11-08 고려대학교 산학협력단 Carbon fiber electrode, wire type supercapacitor comprising the same and manufacturing method of the carbon fiber electrode
CN108611704A (en) * 2018-05-21 2018-10-02 广东工业大学 A kind of carbon nano-fiber and preparation method thereof
CN111691188A (en) * 2019-03-14 2020-09-22 中国科学院宁波材料技术与工程研究所 Dendritic phosphazene graft modified carbon fiber and preparation method and application thereof
CN110453266A (en) * 2019-08-06 2019-11-15 北京化工大学 A kind of method that carbon fiber surface electrophoretic deposition polymer micro-nano particle prepares high-performance composite materials
CN112522956A (en) * 2019-09-19 2021-03-19 中国科学院宁波材料技术与工程研究所 Silica microsphere modified multi-scale hybrid carbon fiber and preparation method and application thereof

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