CN115440509A - Preparation method of array type nickel-cobalt-nitrogen nanosheet/carbon felt for supercapacitor - Google Patents
Preparation method of array type nickel-cobalt-nitrogen nanosheet/carbon felt for supercapacitor Download PDFInfo
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- CN115440509A CN115440509A CN202211086532.2A CN202211086532A CN115440509A CN 115440509 A CN115440509 A CN 115440509A CN 202211086532 A CN202211086532 A CN 202211086532A CN 115440509 A CN115440509 A CN 115440509A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 50
- RMKJDGIKQWEFFT-UHFFFAOYSA-N [N].[Co].[Ni] Chemical compound [N].[Co].[Ni] RMKJDGIKQWEFFT-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 239000002135 nanosheet Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000002131 composite material Substances 0.000 claims abstract description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 15
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims abstract description 10
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 7
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 238000000151 deposition Methods 0.000 claims description 6
- 229910052573 porcelain Inorganic materials 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000011888 foil Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 239000003990 capacitor Substances 0.000 abstract description 9
- 239000007772 electrode material Substances 0.000 abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 3
- 229910017052 cobalt Inorganic materials 0.000 abstract description 2
- 239000010941 cobalt Substances 0.000 abstract description 2
- 238000004070 electrodeposition Methods 0.000 abstract description 2
- 229910021389 graphene Inorganic materials 0.000 abstract description 2
- 229910052759 nickel Inorganic materials 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract 2
- 239000002086 nanomaterial Substances 0.000 abstract 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract 1
- 229910052757 nitrogen Inorganic materials 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000004767 nitrides Chemical class 0.000 description 4
- -1 transition metal nitrides Chemical class 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000003623 transition metal compounds Chemical class 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 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
- H01G11/84—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
-
- 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
-
- 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
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
A preparation method of an array type nickel-cobalt-nitrogen nanosheet/carbon felt for a supercapacitor belongs to the field of electrode materials of supercapacitors, and the nanomaterial is a sheet array structure growing on the surface of the carbon felt. The array type nickel-cobalt-nitrogen nano material adopts a synthesis method of electrodeposition and ammonia nitridation, a pretreated carbon felt is used as a substrate, nickel chloride hexahydrate is used as a nickel source, cobalt chloride hexahydrate is used as a cobalt source, and ammonia is used as a nitrogen source, and the prepared nickel-cobalt-nitrogen nanosheets uniformly and vertically grow on the surface of the carbon felt. The nano-silver/graphene composite material is directly used as an electrode of a super capacitor, and the current density is 3A/m as can be known from a three-electrode test 2 When it is used, its specific capacity is 21710F/m 2 . The array type nickel-cobalt-nitrogen nanosheet/carbon felt prepared by the invention has the characteristics of high specific capacity, simple preparation method, low cost and the like.
Description
Technical Field
A preparation method of an array type nickel-cobalt-nitrogen nanosheet/carbon felt for a supercapacitor belongs to the field of electrode materials of supercapacitors.
Technical Field
With the large consumption and price rise of traditional energy sources (such as petroleum, coal, natural gas and the like), the cost of daily production and life is increased and environmental problems are increasingly highlighted, so that people are urgently required to develop green new energy sources (such as solar energy, wind energy and the like) and novel energy storage devices. The super capacitor is one of novel energy storage devices, has the characteristics of high power density, short charging and discharging time, long service life, wide applicable temperature range, safety and the like, and is widely applied to smart grid systems, industrial energy-saving systems, power supply systems and numerous electronic devices. Therefore, the super capacitor becomes one of the hot research directions of the novel energy storage device. Wherein the electrode material is one of the main factors influencing the performance of the super capacitor.
The transition metal compound has higher theoretical specific capacity, so that the transition metal compound is one of hot spot directions for researching pseudo-capacitor electrode materials at present. Compared with transition metal oxides, the metal nitride has higher conductivity, and is more favorable for improving the energy density of the super capacitor and ensuring higher power density of the super capacitor, but the conductivity of the existing metal nitride is still difficult to meet the requirement. In order to improve the conductivity of transition metal nitrides, most of the prior documents are compounded with carbon, wherein most of the prior documents are based on single metal nitride/carbon composite materials, while the reports of double metal nitride/carbon composite materials are less, and the prepared composite materials are mainly in powder form. In addition, although both carbon nanotubes and graphene can improve the conductivity, the cost is high, and the method is not suitable for commercial application. In contrast, the commercialized graphite carbon felt has not only higher electrical conductivity but also larger specific surface area, and the price is relatively low, especially the self-supporting array type nickel-cobalt nitride/carbon felt composite material is reported less.
Disclosure of Invention
The invention provides a method which is low in cost, simple in preparation process, short in period and simple and convenient to operate, utilizes a synthetic method of electrodeposition and ammonia nitridation to successfully prepare a self-supported array type nickel-cobalt-nitrogen nanosheet/carbon felt compound, and shows good electrochemical performance when the self-supported array type nickel-cobalt-nitrogen nanosheet/carbon felt compound is directly used as an electrode of a supercapacitor.
The invention provides a preparation method of a self-supporting array type nickel-cobalt-nitrogen nanosheet/carbon felt for a supercapacitor, which comprises the following steps:
a) Putting a carbon felt with the thickness of 3mm into a plasma cleaning machine, setting the power to be 80W under the condition of air atmosphere, and cutting the carbon felt into a shape with the length and width of 2 x 1cm for later use after 5min of treatment;
b) Sequentially adding deionized water, nickel chloride hexahydrate, cobalt chloride hexahydrate and thiourea into a 100mL beaker, and stirring for 10min for later use;
c) Placing the beaker with the precursor solution in the step b in a water bath kettle at a certain temperature, simultaneously connecting the carbon felt cut in the step a into a working electrode, respectively taking a foil and a saturated calomel electrode as a counter electrode and a reference electrode to jointly form three electrodes, then placing the three electrodes into the precursor solution, depositing for a period of time under a specific voltage, taking out the carbon felt, and carrying out washing and drying treatment;
d) And c, placing the carbon felt dried in the step c in a porcelain boat, transferring the carbon felt into a tube furnace, heating to a preset temperature, carrying out heat preservation treatment in an ammonia atmosphere for a period of time, cooling along with the furnace to room temperature, and obtaining the self-supporting array type nickel-cobalt-nitrogen nanosheet/carbon felt composite material.
e) The self-supporting array type nickel-cobalt-nitrogen nanosheet/carbon felt composite material is directly used as an electrode to be applied to a super capacitor.
The adding amount of the deionized water, the nickel chloride hexahydrate, the cobalt chloride hexahydrate and the thiourea in the step b) is respectively 80ml, 0.08mmol, 0.16mmol and 1.6mmol;
c) depositing for 9min at the water bath temperature of 40 ℃ and the deposition voltage of-0.8V;
in the step d), under the atmosphere of ammonia gas, heating from room temperature to 420 ℃ at the heating rate of 8 ℃/min, and carrying out heat preservation treatment for 3h;
in the step e), in the performance test of the three electrodes of the super capacitor, the electrolyte is 1mol/L sodium hydroxide solution, and when the current density is 3A/m2, the specific capacity of the electrode is 21710F/m 2 。
Compared with other methods for preparing the nickel-cobalt-nitrogen/carbon composite material, the method has the advantages that the array-type nickel-cobalt-nitrogen nanosheets are prepared on the surface of the commercialized carbon felt, in addition, the preparation process is simple, the raw materials are cheap and easy to obtain, the method is suitable for large-scale production, the production cost is reduced, and the production period is shortened; and the composite material can be directly used as a supercapacitor electrode and has better specific capacity.
A Bruker Advance D8X-ray powder diffractometer (Cu ka radiation,
2 θ =10-80 °) the structure of the prepared material was determined. And observing the surface appearance of the prepared material by using a Hitachi S-4800 scanning electron microscope. The electrochemical workstation (CHI 660E) was used for the measurement of the supercapacitive properties.
As can be seen from curve 1 of FIG. 1, when the amount of nickel chloride hexahydrate was 0.24mmol and the amount of cobalt chloride hexahydrate was 0, the material prepared was a nickel nitride/carbon felt composite material (JCPDS card No. 10-0280); as can be seen from curve 3 in FIG. 1, when the amount of nickel chloride hexahydrate is 0 and the amount of cobalt chloride hexahydrate is 0.24mmol, the prepared material is a cobalt nitride/carbon felt composite material (JCPDS card No. 06-0647); as can be seen from the curve 2 of FIG. 1 and FIG. 2, when the addition amount of nickel chloride hexahydrate is 0.08mmol and the addition amount of cobalt chloride hexahydrate is 0.16mmol, the prepared material is a nickel-cobalt-nitrogen/carbon felt composite material. As can be seen from fig. 3, the obtained product nickel-cobalt-nitrogen is mainly of a sheet structure and grows on the surface of the carbon felt in an array state, but the sizes of the nanosheets are different. As shown in FIG. 4, when the self-supporting array type nickel-cobalt-nitrogen nanosheet/carbon felt composite material is used as a supercapacitor electrode to perform a cyclic voltammetry test, the area of a CV curve is increased along with the increase of the sweep rate from 2mV/s to 20mV/s, and the peak position is also shifted. As can be seen from FIG. 5, the current density was 3A/m 2 The specific capacity of the electrode was 21710F/m 2 。
Drawings
FIG. 1 is an X-ray diffraction chart of the resulting product when the molar ratios of nickel chloride hexahydrate and cobalt chloride hexahydrate are 0.24/0 (1), 0.08/0.16 (2) and 0/0.24 (3), respectively.
FIG. 2 is a general X-ray diffraction diagram of the three products of FIG. 1
FIG. 3 is a scanning electron micrograph of the product.
Fig. 4 is a CV curve graph of the self-supporting array type nickel-cobalt-nitrogen nanosheet/carbon felt composite material prepared by the embodiment.
Fig. 5 is a charge-discharge curve diagram of the self-supporting array type nickel-cobalt-nitrogen nanosheet/carbon felt composite material prepared by the embodiment.
Detailed Description
1. Putting a carbon felt with the length of 10cm, the width of 5cm and the thickness of 3mm into a plasma cleaning machine, setting the power to be 80W, treating for 5min under the air atmosphere condition, taking out, and shearing the carbon felt into a shape with the length and the width of 2 x 1cm for later use;
2. adding 80mL of deionized water, 0.08mmol of nickel chloride hexahydrate, 0.16mmol of cobalt chloride hexahydrate and 1.6mmol of thiourea into a 100mL beaker in sequence, and stirring for 10min for later use;
3. placing a beaker filled with 80ml of precursor solution in a water bath kettle at 40 ℃, simultaneously connecting the cut carbon felt into a working electrode, respectively connecting a foil and a saturated calomel electrode into a counter electrode and a reference electrode circuit to jointly form a three electrode, then placing the three electrode into the precursor solution, depositing for 8min under the voltage of-0.8V, taking out the carbon felt, and washing and drying the carbon felt;
4. and then placing the dried carbon felt in a porcelain boat, transferring the porcelain boat into a tubular furnace, performing heat preservation treatment at the temperature rising rate of 8 ℃/min from room temperature to 420 ℃ in an ammonia atmosphere, cooling the porcelain boat to room temperature along with the furnace after heat preservation treatment for 3h, and obtaining the self-supporting array type nickel-cobalt-nitrogen nanosheet/carbon felt composite material (see figures 1, 2 and 3).
Claims (4)
1. A preparation method of an array type nickel-cobalt-nitrogen nanosheet/carbon felt for a supercapacitor comprises the following steps:
a) Putting a carbon felt with the thickness of 3mm into a plasma cleaning machine, setting the power to be 80W under the condition of air atmosphere, and cutting the carbon felt into a shape with the length and width of 2 x 1cm for later use after 5min of treatment;
b) Adding deionized water, nickel chloride hexahydrate, cobalt chloride hexahydrate and thiourea into a 100mL beaker in sequence, and stirring for 10min for later use;
c) Placing the beaker with the precursor solution in the step b in a water bath kettle at a certain temperature, simultaneously connecting the carbon felt cut in the step a into a working electrode, respectively taking a foil and a saturated calomel electrode as a counter electrode and a reference electrode to jointly form three electrodes, then placing the three electrodes into the precursor solution, depositing for a period of time under a specific voltage, taking out the carbon felt, and carrying out washing and drying treatment;
d) And c, transferring the dried carbon felt in the step c into a porcelain boat, placing the porcelain boat in a tubular furnace, heating to a preset temperature, carrying out heat preservation treatment in an ammonia atmosphere for a period of time, cooling to room temperature along with the furnace, and obtaining the self-supporting array type nickel-cobalt-nitrogen nanosheet/carbon felt composite material.
2. The method for preparing array type nickel-cobalt-nitrogen nanosheet/carbon felt for the supercapacitor according to claim 1, wherein the amounts of deionized water, nickel chloride hexahydrate, cobalt chloride hexahydrate and thiourea added in step b) are 80ml, 0.08mmol, 0.16mmol and 1.6mmol, respectively.
3. The method for preparing the array type nickel cobalt nitrogen nanosheet/carbon felt for the supercapacitor according to claim 1, wherein the step c) is carried out at a deposition voltage of-0.8V for 9min at a water bath temperature of 40 ℃.
4. The method for preparing array type nickel cobalt nitrogen nanosheet/carbon felt for the supercapacitor according to claim 1, wherein the temperature rising rate of 8 ℃/min in step d) is from room temperature to 420 ℃ under an ammonia atmosphere, and the heat preservation treatment is carried out for 3 hours.
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| CN202211086532.2A CN115440509B (en) | 2022-08-26 | 2022-08-26 | Preparation method of array type nickel cobalt nitrogen nanosheet/carbon felt for super capacitor |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030143453A1 (en) * | 2001-11-30 | 2003-07-31 | Zhifeng Ren | Coated carbon nanotube array electrodes |
| US20180083331A1 (en) * | 2016-09-19 | 2018-03-22 | David Mitlin | Supercapattery Employing Carbon Nanosheets In The Electrodes |
| CN110642304A (en) * | 2019-10-09 | 2020-01-03 | 上海师范大学 | Trimetal nitride material for super capacitor and preparation method thereof |
| CN113270274A (en) * | 2021-04-23 | 2021-08-17 | 中国科学院合肥物质科学研究院 | Flexible honeycomb-shaped bimetal nitride supercapacitor electrode and preparation method thereof |
| CN113410062A (en) * | 2021-06-17 | 2021-09-17 | 大连理工大学 | Carbon nanocoil stack/nickel-cobalt compound supercapacitor composite electrode material and preparation method thereof |
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2022
- 2022-08-26 CN CN202211086532.2A patent/CN115440509B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030143453A1 (en) * | 2001-11-30 | 2003-07-31 | Zhifeng Ren | Coated carbon nanotube array electrodes |
| US20180083331A1 (en) * | 2016-09-19 | 2018-03-22 | David Mitlin | Supercapattery Employing Carbon Nanosheets In The Electrodes |
| CN110642304A (en) * | 2019-10-09 | 2020-01-03 | 上海师范大学 | Trimetal nitride material for super capacitor and preparation method thereof |
| CN113270274A (en) * | 2021-04-23 | 2021-08-17 | 中国科学院合肥物质科学研究院 | Flexible honeycomb-shaped bimetal nitride supercapacitor electrode and preparation method thereof |
| CN113410062A (en) * | 2021-06-17 | 2021-09-17 | 大连理工大学 | Carbon nanocoil stack/nickel-cobalt compound supercapacitor composite electrode material and preparation method thereof |
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