CN109036863B - Selenide @ carbon-based fiber supercapacitor electrode material and preparation method thereof - Google Patents
Selenide @ carbon-based fiber supercapacitor electrode material and preparation method thereof Download PDFInfo
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- UMUKXUYHMLVFLM-UHFFFAOYSA-N manganese(ii) selenide Chemical compound [Mn+2].[Se-2] UMUKXUYHMLVFLM-UHFFFAOYSA-N 0.000 description 3
- QHASIAZYSXZCGO-UHFFFAOYSA-N selanylidenenickel Chemical compound [Se]=[Ni] QHASIAZYSXZCGO-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- CXRFFSKFQFGBOT-UHFFFAOYSA-N bis(selanylidene)niobium Chemical compound [Se]=[Nb]=[Se] CXRFFSKFQFGBOT-UHFFFAOYSA-N 0.000 description 2
- WCQOLGZNMNEYDX-UHFFFAOYSA-N bis(selanylidene)vanadium Chemical compound [Se]=[V]=[Se] WCQOLGZNMNEYDX-UHFFFAOYSA-N 0.000 description 2
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- 229910000480 nickel oxide Inorganic materials 0.000 description 1
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- CADICXFYUNYKGD-UHFFFAOYSA-N sulfanylidenemanganese Chemical compound [Mn]=S CADICXFYUNYKGD-UHFFFAOYSA-N 0.000 description 1
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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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
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- Condensed Matter Physics & Semiconductors (AREA)
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- Microelectronics & Electronic Packaging (AREA)
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Abstract
The invention discloses a selenide @ carbon-based fiber supercapacitor electrode material which is a composite nano material with a core-shell structure, wherein carbon-based fibers are used as a core, selenide is used as a shell, and selenide grows on the surfaces of the carbon-based fibers. Also discloses a cobalt selenide @ carbon nanotube fiber composite nano material and a preparation method thereof. The cobalt selenide @ carbon nanotube fiber composite nano material is prepared by growing a cobalt selenide material on the surface of a carbon nanotube fiber by a hydrothermal method, so that the cobalt selenide @ carbon nanotube fiber composite nano material is formed. The synthesized cobalt selenide @ carbon nanotube fiber supercapacitor electrode material is tested under a three-electrode system and shows 359F g‑1High specific capacity and good cycling stability. The preparation method is simple and low in cost; the prepared cobalt selenide @ carbon nanotube fiber supercapacitor electrode material has the advantages of large specific surface area, high specific capacitance and good cycle performance. In addition, the wearable electronic device has huge application prospect due to the characteristics of high conductivity, strength and flexibility and capability of being woven.
Description
Technical Field
The invention relates to the field of super capacitors, in particular to a preparation method of a fiber super capacitor electrode material.
Background
With the acceleration of global industrialization process, the problems of energy shortage and failure become more and more prominent, and the stability of long-term social development is seriously influenced. Particularly, after the twenty-first century, non-renewable energy such as petroleum, natural gas, coal and the like is continuously consumed, the contradiction between economic development and energy supply becomes more acute, in addition, the environmental problems such as greenhouse effect and the like caused by fossil fuel combustion are more and more serious, and in order to improve the ecological environment and realize the sustainable development of the society, the gravity center of the energy supply structure of the human society gradually turns to a new renewable energy form with clean and environment-friendly property. Although they can alleviate the problems of energy crisis and environmental pollution, they have the limitations of low utilization efficiency, poor continuity of energy supply, and imperfect technology. Based on the defects, the novel energy storage technology is developed at the same time, and the defect of poor continuity of energy supply can be well overcome. The super capacitor is paid much attention to the advantages of high energy density, wide use temperature range, long service life, environmental friendliness and the like, has extremely important and wide application prospect in the aspects of aerospace, national defense science and technology and the like such as solar chargers, standby power supplies of microcomputers, ignition devices of airplanes and the like, and has become a research hotspot of various countries in the world.
Supercapacitors are electrochemical capacitors that can be classified according to charge storage mechanisms into two categories: the electrode materials of the electrochemical double-layer capacitor are mainly carbon materials, and comprise activated carbon, carbon nanotubes, graphene and the like; the other type is a Faraday pseudo capacitor, and electrode materials of the capacitor are mainly transition metal chalcogenide compounds, including oxides such as cobalt oxide, nickel oxide and manganese oxide, sulfides such as cobalt sulfide, nickel sulfide and manganese sulfide, and selenides such as cobalt selenide, nickel selenide and manganese selenide. In order to improve the performance of the device, the electric double layer electrode material and the pseudocapacitance material are generally compounded.
With advances in technology, flexible and wearable electronics are receiving increasing attention. Carbon-based carbon fiber materials generally comprise three types of carbon fibers, carbon nanotube fibers, graphene fibers and the like, and the carbon-based fiber materials have a characteristic of being woven and can be used for portable and wearable supercapacitors, but the carbon-based fiber materials are generally low in specific capacitance value, and the energy density of manufactured supercapacitors is too low, so that the potential application of the supercapacitors is limited.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to compound the transition metal selenide and the carbon-based fiber to form a composite nanofiber material, and solves the problems of low specific capacitance and low energy density of the carbon-based fiber as an electrode material. Based on the purpose of the invention, the technical scheme adopted by the invention is as follows.
The invention provides a selenide @ carbon-based fiber supercapacitor electrode material, which takes carbon-based fibers as a core and selenide as a shell to form a composite nano material with a core-shell structure of selenide and carbon-based fibers. And growing a selenide material on the surface of the carbon-based fiber in situ to form the selenide @ carbon-based fiber composite material with the core-shell structure. Because the shell selenide has a very high capacitance value, the specific capacitance of the composite electrode material is effectively improved.
Furthermore, the carbon-based fiber material is one of carbon fiber, carbon nanotube fiber and graphene fiber.
Further, the selenide is any one of cobalt selenide, nickel selenide, manganese selenide, iron selenide, vanadium selenide, tin selenide, niobium selenide, titanium selenide, and copper selenide.
Furthermore, the electrode material of the selenide @ carbon-based fiber super capacitor is a cobalt selenide @ carbon nanotube fiber composite nano material.
The invention also provides a cobalt selenide @ carbon nanotube fiber composite nanomaterial applied to a supercapacitor electrode material, the composite nanomaterial comprises a shell layer formed by cobalt selenide, carbon nanotube fibers are a core layer, the cobalt selenide uniformly grows on the surfaces of the carbon nanotube fibers, the cobalt selenide is in a nano form, nanosheets are criss-cross and mutually connected to form a three-dimensional network structure, the width of each nanosheet is 100-900 nm, and the thickness of each nanosheet is 5-15 nm.
Further, the cobalt selenide is formed from CoSe2And Co2Se3Two-phase composition of CoSe2And Co2Se3Two phases are uniformly dissolved in solid solution to form a composite material, and CoSe2And Co2Se3An organic whole is formed for the composition of the microscopic crystal domain layer.
The invention also provides a preparation method of the cobalt selenide @ carbon nanotube fiber composite nanomaterial, which comprises the following steps:
(1) mixing 1 m mol of cobalt chloride hexahydrate, 1 m mol of sodium selenite and 40mL of deionized water, stirring for 5-15 min to form a uniform pink solution, and slowly dropwise adding 5 mL of hydrazine hydrate (85% N)2H4·H2O) is taken as a reducing agent, and the mixture is continuously stirred for 5 to 15 minutes to obtain a precursor solution;
(2) placing carbon nanotube fibers in a reaction kettle in a hanging manner, adding a precursor solution, carrying out hydrothermal reaction at the reaction temperature of 120-180 ℃ for 12-15 h, cooling to room temperature, collecting the fibers, washing and drying;
(3) in order to improve the crystallinity of the cobalt selenide on the surface of the fiber, the cobalt selenide is placed in a tube furnace in an Ar atmosphere and annealed at the temperature of 300-600 ℃ for 2 hours, and the cobalt selenide @ carbon nanotube fiber super capacitor electrode material is obtained.
In a three-electrode system test, the specific capacitance value of the prepared cobalt selenide @ carbon nanotube fiber supercapacitor electrode material reaches 288-359F g-1And has high specific capacitance.
The beneficial results of the invention are as follows:
(1) according to the selenide @ carbon-based fiber composite nanomaterial, the carbon-based fiber has excellent thermal conductivity, electrical conductivity and mechanical properties, the selenide has excellent chemical stability and outstanding electrochemical properties, particularly has very high specific capacitance, and the selenide grows on the surface of the carbon-based fiber to form a composite fiber material, so that the specific capacitance of the composite fiber electrode material is effectively improved, and the excellent mechanical properties and the like of the carbon-based material are maintained.
(2) Compared with transition metal oxides and sulfides, the transition metal selenide has very low resistivity, which is beneficial to reducing contact resistance and is very beneficial to preparing all-solid wearable flexible supercapacitors.
(3) The selenide @ carbon-based fiber composite nanomaterial for the supercapacitor prepared by the method disclosed by the invention is composed of selenide and a carbon material, not only has the high conductivity characteristic of transition metal selenide, but also has the structural advantage of the carbon material, and can obviously improve the comprehensive performance of the material.
(4) The invention provides a selenide @ carbon-based fiber composite nano material, wherein cobalt selenide is made of CoSe2And Co2Se3Two-phase composition of CoSe2And Co2Se3Two phases are uniformly dissolved in solid solution to form a composite material, and CoSe2And Co2Se3The composite material forms an organic whole for the composition of microscopic domain layers, not only has the high conductivity characteristic of transition metal selenide, but also has CoSe2And Co2Se3The advantages of two phase structures are favorable for the electrode material electricityAnd (4) transferring the load.
(5) According to the cobalt selenide @ carbon nanotube fiber composite material for the super capacitor, which is prepared by the method, the cobalt selenide uniformly grows on the surface of the carbon nanotube fiber, and the cobalt selenide is in a nano form, and nano sheets are criss-crossed and mutually connected to form a three-dimensional network structure, so that the contact area between an electrode material and an electrolyte is increased, the migration and the diffusion of ions are facilitated, more active points can be obtained, the effect of enhancing the specific capacitance of the electrode material is achieved, and high electrochemical performance is obtained.
(6) The cobalt selenide @ carbon nanotube fiber composite material for the supercapacitor prepared by the method disclosed by the invention has high specific capacitance and conductivity, excellent rate capability and cycle stability, and good electrochemical stability, is an excellent electrode material for the supercapacitor, and can be applied to a supercapacitor product with high energy density.
(7) The method adopts a hydrothermal synthesis method, is simple to operate, short in flow, low in cost, green and environment-friendly, and is suitable for large-scale production.
(8) When the cobalt selenide @ carbon nanotube fiber supercapacitor electrode material prepared by the invention is applied to a supercapacitor, the electrode material not only shows very excellent electrochemical performance, but also has the characteristics of high strength, flexibility and weaving on the premise of ensuring high specific capacity, and has huge application prospect in wearable electronic equipment.
Drawings
Fig. 1 is an X-ray diffraction (XRD) picture of the cobalt selenide @ carbon nanotube fiber supercapacitor electrode material prepared in example 2.
Fig. 2 is a Scanning Electron Microscope (SEM) image of the cobalt selenide @ carbon nanotube fiber supercapacitor electrode material prepared in example 2.
Fig. 3 is a cyclic voltammogram of the cobalt selenide @ carbon nanotube fiber supercapacitor electrode material prepared in example 2.
Fig. 4 is a constant current charge-discharge curve picture of the cobalt selenide @ carbon nanotube fiber supercapacitor electrode material prepared in example 2.
Fig. 5 is an alternating current impedance spectrum of the cobalt selenide @ carbon nanotube fiber supercapacitor electrode material prepared in example 2.
Fig. 6 is a graph showing the cycle stability test of the cobalt selenide @ carbon nanotube fiber supercapacitor electrode material prepared in example 2.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
Preparing carbon-based fibers as cores by a spinning method; growing corresponding selenide on the carbon-based fiber by a hydrothermal method or a magnetron sputtering method to form a shell, and preparing the selenide @ carbon-based fiber composite material. In this embodiment, the inventor selects a plurality of selenides to perform experiments respectively to prepare various selenides @ carbon-based fiber composite materials, and the selenide grown on the carbon-based fiber comprises any one of cobalt selenide, nickel selenide, manganese selenide, iron selenide, vanadium selenide, tin selenide, niobium selenide, titanium selenide, and copper selenide. The specific capacitance of each selenide @ carbon-based fiber composite is shown in table 1. For comparison, the specific capacitance of a single carbon-based fiber is also tabulated.
Example 2
(1) Mixing 1 m mol of cobalt chloride hexahydrate, 1 m mol of sodium selenite and 40mL of deionized water, stirring for 5-15 min to form a uniform pink solution, and slowly dropwise adding 5 mL of hydrazine hydrate (85% N)2H4·H2O) is taken as a reducing agent, and the mixture is continuously stirred for 5 to 15 minutes to obtain a precursor solution;
(2) placing carbon nanotube fibers in a reaction kettle in a hanging manner, adding a precursor solution, carrying out hydrothermal reaction at the reaction temperature of 120-180 ℃ for 12-15 h, cooling to room temperature, collecting the fibers, washing and drying;
(3) in order to improve the crystallinity of the cobalt selenide on the surface of the fiber, the cobalt selenide is placed in a tube furnace in an Ar atmosphere and annealed at the temperature of 300-600 ℃ for 2 hours, and the cobalt selenide @ carbon nanotube fiber super capacitor electrode material is obtained.
The chemical raw materials used in the above examples, cobalt chloride hexahydrate and sodium selenite, were both analytically pure, and the deionized water resistance was 18.0-18.5M Ω.
In a three-electrode system test, the specific capacitance value of the prepared cobalt selenide @ carbon nanotube fiber supercapacitor electrode material reaches 288-359F g-1And has high specific capacitance.
Various tests were performed on the cobalt selenide @ carbon nanotube fiber supercapacitor electrode material prepared in this example. As shown in fig. 1, which is an X-ray diffraction (XRD) pattern of the cobalt selenide @ carbon nanotube fiber supercapacitor electrode material prepared in this example, it can be seen that cobalt selenide is formed by CoSe2And Co2Se3Two phases are solid-dissolved to form a composite. FIG. 2 is a Scanning Electron Microscope (SEM) image thereof, in which: cobalt selenide forms a shell layer, the carbon nanotube fiber is a core layer, the cobalt selenide uniformly grows on the surface of the carbon nanotube fiber, the cobalt selenide is in a nano form, nano sheets are criss-cross and mutually connected to form a three-dimensional network structure, the width of each nano sheet is 100-900 nm, and the thickness of each nano sheet is 5-15 nm.
The cobalt selenide @ carbon nanotube fiber supercapacitor electrode material prepared in the embodiment is subjected to a three-electrode system test, and fig. 3 is a cyclic voltammogram of the cobalt selenide @ carbon nanotube fiber supercapacitor electrode material at 2 mol L-1Under the KOH electrolyte, the electrode material obtains approximately rectangular cyclic voltammetry curve of 10 mV s-1To 100 mV s-1Exhibits good double layer capacitance behavior at scan rates of (a), with no significant faraday current from 0V to 0.5V cyclic voltammograms. FIG. 4 is a constant current charge/discharge curve picture of 2 mol L-1KOH solution of (2) at 1A g-1Shows a current density of 359F g-1The high specific capacity of the catalyst shows good electrochemical performance. FIG. 5 is an AC impedance spectrum at 2 mol L-1In the KOH electrolytic solution, the internal resistance of the composite fiber in the test process is 1.26 Ω, and the charge transfer resistance is 3.75 Ω. FIG. 6 is a graph showing the stability of the cycle, as seen at 1A g−1At current density, 8000 times of charge and dischargeAfter circulation, the composite fiber electrode still retains 86% of the original capacitance value, and shows good circulation stability.
Claims (2)
1. A selenide @ carbon-based fiber supercapacitor electrode material is characterized in that: the selenide @ carbon-based fiber supercapacitor electrode material is a composite nano material with a carbon-based fiber as a core and selenide as a shell, and the selenide is grown on the surface of the carbon-based fiber and has a core-shell structure;
the carbon-based fiber is a carbon nanotube fiber;
the selenide is cobalt selenide;
the electrode material of the selenide @ carbon-based fiber super capacitor is a cobalt selenide @ carbon nanotube fiber composite nano material;
the micro-morphology of the cobalt selenide @ carbon nanotube fiber composite nanomaterial is as follows: cobalt selenide uniformly grows on the surface of the carbon nanotube fiber, the cobalt selenide is in a nano form, nano sheets are criss-cross and mutually connected to form a three-dimensional network structure, the width of each nano sheet is 100-900 nm, and the thickness of each nano sheet is 5-15 nm;
cobalt selenide from CoSe2And Co2Se3Two-phase composition of CoSe2And Co2Se3A composite material formed by uniformly dissolving two phases;
the preparation method of the selenide @ carbon-based fiber supercapacitor electrode material comprises the following steps:
1) mixing 1 m mol of cobalt chloride hexahydrate, 1 m mol of sodium selenite and 40mL of deionized water, stirring for 5-15 min to form a uniform pink solution, slowly dropwise adding 5 mL of hydrazine hydrate serving as a reducing agent, and continuously stirring for 5-15 min to obtain a precursor solution;
2) placing carbon nanotube fibers in a reaction kettle in a hanging manner, adding a precursor solution, carrying out hydrothermal reaction at the reaction temperature of 120-180 ℃ for 12-15 h, cooling to room temperature, collecting the fibers, washing and drying;
3) and (3) annealing for 2 hours at 300-600 ℃ in Ar atmosphere in a tube furnace to obtain the cobalt selenide @ carbon nanotube fiber composite nanomaterial.
2. The selenide @ carbon-based fiber supercapacitor electrode material according to claim 1, wherein: as an electrode material of a super capacitor, the specific capacitance value reaches 359F g in a three-electrode system test-1。
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102225340A (en) * | 2011-04-08 | 2011-10-26 | 安徽大学 | Method for synthesizing catalyst capable of efficiently decomposing hydrazine at room temperature |
| CN105742074A (en) * | 2016-03-31 | 2016-07-06 | 复旦大学 | Poly-dopamine based porous carbon fiber/MoSe2 composite material and preparation method thereof |
| CN106006576A (en) * | 2016-05-31 | 2016-10-12 | 浙江大学 | Nanomaterial used as supercapacitor electrode material, and preparation method thereof |
| CN106098397A (en) * | 2016-08-11 | 2016-11-09 | 浙江大学 | NiSe Ni for ultracapacitor3se2three-dimensional Folium Pini shape nano material and preparation method thereof |
| CN106158420A (en) * | 2016-08-11 | 2016-11-23 | 浙江大学 | A kind of NiSe Ni for ultracapacitor3se2porous nano ball material and preparation method thereof |
| CN106158397A (en) * | 2016-08-11 | 2016-11-23 | 浙江大学 | A kind of NiSe for ultracapacitor poroid nanosphere material and preparation method thereof |
| CN106315522A (en) * | 2016-08-11 | 2017-01-11 | 浙江大学 | NiSe three-dimensional porous nanosheet material used for superconductor and preparation method thereof |
| CN106981377A (en) * | 2017-04-24 | 2017-07-25 | 浙江大学 | A kind of Co3O4The preparation method of@graphene fiber super capacitor electrode materials |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1159211C (en) * | 2002-06-07 | 2004-07-28 | 清华大学 | Synthesis of several metal selenides and tellurides as semiconductor material |
| CN100344531C (en) * | 2005-10-19 | 2007-10-24 | 清华大学 | Process of preparing monodisperse nanometer semiconductor selenide particle |
| US10160906B2 (en) * | 2015-02-24 | 2018-12-25 | Fondazione Istituto Italiano Di Tecnologia | Masked cation exchange lithography |
-
2018
- 2018-07-23 CN CN201810809382.0A patent/CN109036863B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102225340A (en) * | 2011-04-08 | 2011-10-26 | 安徽大学 | Method for synthesizing catalyst capable of efficiently decomposing hydrazine at room temperature |
| CN105742074A (en) * | 2016-03-31 | 2016-07-06 | 复旦大学 | Poly-dopamine based porous carbon fiber/MoSe2 composite material and preparation method thereof |
| CN106006576A (en) * | 2016-05-31 | 2016-10-12 | 浙江大学 | Nanomaterial used as supercapacitor electrode material, and preparation method thereof |
| CN106098397A (en) * | 2016-08-11 | 2016-11-09 | 浙江大学 | NiSe Ni for ultracapacitor3se2three-dimensional Folium Pini shape nano material and preparation method thereof |
| CN106158420A (en) * | 2016-08-11 | 2016-11-23 | 浙江大学 | A kind of NiSe Ni for ultracapacitor3se2porous nano ball material and preparation method thereof |
| CN106158397A (en) * | 2016-08-11 | 2016-11-23 | 浙江大学 | A kind of NiSe for ultracapacitor poroid nanosphere material and preparation method thereof |
| CN106315522A (en) * | 2016-08-11 | 2017-01-11 | 浙江大学 | NiSe three-dimensional porous nanosheet material used for superconductor and preparation method thereof |
| CN106981377A (en) * | 2017-04-24 | 2017-07-25 | 浙江大学 | A kind of Co3O4The preparation method of@graphene fiber super capacitor electrode materials |
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