CN104681299A - Supercapacitor electrode material of cobaltosic oxide porous nanowire array, and preparation method thereof - Google Patents
Supercapacitor electrode material of cobaltosic oxide porous nanowire array, and preparation method thereof Download PDFInfo
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- CN104681299A CN104681299A CN201510136773.7A CN201510136773A CN104681299A CN 104681299 A CN104681299 A CN 104681299A CN 201510136773 A CN201510136773 A CN 201510136773A CN 104681299 A CN104681299 A CN 104681299A
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- cobaltosic oxide
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- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000007772 electrode material Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000002070 nanowire Substances 0.000 title claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 28
- 239000008139 complexing agent Substances 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 239000003990 capacitor Substances 0.000 claims description 12
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical group S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000006260 foam Substances 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 238000011065 in-situ storage Methods 0.000 claims description 5
- 239000011530 conductive current collector Substances 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 230000004888 barrier function Effects 0.000 claims description 2
- 230000006911 nucleation Effects 0.000 claims description 2
- 238000010899 nucleation Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 239000011230 binding agent Substances 0.000 abstract 1
- 230000001276 controlling effect Effects 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 229910044991 metal oxide Inorganic materials 0.000 description 7
- 150000004706 metal oxides Chemical class 0.000 description 7
- 239000004202 carbamide Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000002322 conducting polymer Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000002772 conduction electron Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 210000002569 neuron Anatomy 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
-
- 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
- H01G11/46—Metal oxides
-
- 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
- H01G11/84—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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Manufacturing & Machinery (AREA)
Abstract
The invention discloses a supercapacitor electrode material of a cobaltosic oxide porous nanowire array. The supercapacitor electrode material comprises a cobaltosic oxide porous nanowire array directly growing on a conductive substrate by adopting a hydrothermal method. The preparation method of the supercapacitor electrode material comprises the following steps: firstly controlling the appearance of a product by regulating the usage amount of a complexing agent, and realizing the self-assembled growth process on the smooth conductive substrate by selecting the varieties of the complexing agent. The preparation process is simple and convenient to operate, the appearance of the product is regular, and the addition of a conducting agent and a binder is dispensed as the electrode material directly grows on the conductive substrate, so that the impedance of an electrode is greatly reduced, the contact action together with the conductive substrate can be increased through the array structure electrode material, so that the electronic transmission is accelerated, and the specific capacity of the electrode can be increased.
Description
Technical field
The invention belongs to ultracapacitor device technical field, be specifically related to electrode material for super capacitor of cobaltosic oxide porous nano linear array and preparation method thereof.
Background technology
Along with the arrival of world energy sources crisis, the power supply unit (such as ultracapacitor, lithium ion battery etc.) of production and manufacturing property brilliance becomes more and more important.Transition metal oxide because of its various valence electron structure, abundant physics and chemistry character, and the focus becoming current research in the application in the fields such as photoelectricity, catalysis, magnetic and ultracapacitor.
The electro-chemical activity of electrode material directly determines the capacitive property of device, and therefore, the exploitation of active electrode material just becomes the emphasis of ECs investigation and application.Usually, the electrode material for ECs comprises Carbon Materials, metal oxide and conducting polymer three major types.The electric double layer stored energy (electric double layer capacitance) that carbon material electrode is formed by the interface of electrolyte and electrode; Metal oxide and conducting polymer materials electrode then obtain faraday's electric capacity (fake capacitance) by the redox reaction of Rapid reversible, and this faraday's electric capacity is generally much larger than the electric double layer capacitance that Carbon Materials obtains.As ECs electrode material use metal oxide containing precious metals (as RuO
2) there is very excellent electrochemical capacitance, but the price of costliness and hypertoxicity restrict its application as electrochemical capacitor electrode material and commercialization greatly, and researcher attempts preparing cobalt oxide (Co by distinct methods
3o4), nickel oxide (NiO), tin oxide (SnO
2) and manganese oxide (MnO
x) etc. base metal oxide, as the substitute of metal oxide containing precious metals, the specific capacity of electrode, efficiency for charge-discharge and long circulation life significantly improve.
One dimension (1D) structure nano material is because metal oxide is in air-sensitive, and the fields such as electrochromism, luminescence, Flied emission, ultracapacitor, nanoelectronics have the broad interest that unique function causes material supplier author and electrochemist.The width of this kind of material and thickness are within the scope of 1-100nm, but length can reach several microns even longer, micro-meter scale provides possibility for 1D nano material in macro-test, simultaneously, more be conducive to the assembling synthesis of small size particles, and in electrochemical terminal test, embody distinctive superiority.
In recent years, various method has good pattern and the adjustable cobaltosic oxide nano linear array of function for controlling to synthesize, adopt at conductive substrates surface in situ growing metal oxide electrode material, effectively can improve the diffusion mass transfer performance that active material utilization is high, increase active surface, improve material.On the one hand, the quick transmission keeping the nano-structure array of close contact to can be electronics with base material provides effective passage; Conduction electron promptly can be transferred to collector electrode from reaction active site along this passage, and can not as powder body material, and electronics is at random walked between unordered nano-crystalline granule.On the other hand, growth in situ eliminates the use of additive material, eliminates the suppression process to electrode.This simple process is easy, environmental protection, is expected to become be with a wide range of applications in energy storage field.
Summary of the invention
The cobaltosic oxide porousization nano-wire array of conductive current collector growth in situ is applied to electrode material for super capacitor by the present invention, provides a kind of preparation method simple and the fake capacitance electrode material had compared with height ratio capacity and better stability.
For solving the problems of the technologies described above, the present invention takes following technical scheme: a kind of electrode for super capacitor material based on cobaltosic oxide porousization nano-wire array, the electrode system of described ultracapacitor comprises conductive current collector, electrode active material layers, electrolyte and barrier film, conductive substrates is electro-conductive glass (FTO), nickel sheet and foam nickel screen.
Described nanowire array structure length is the nano wire of 5 μm-20 μm, wherein class " neuron " structure that combines of the end of 5-10 root nano wire.
The preparation method of ultracapacitor cobaltosic oxide of the present invention, adopt hydro thermal method growth in situ cobaltosic oxide nano linear array in conductive substrates, as the negative electrode of ultracapacitor, specifically comprise the steps: that (1) is by the even ultrasonic mixing in distilled water of cobalt salt, complexing agent and alkaline precipitating agent, this solution is moved in the autoclave of polytetrafluoro liner, and the conductive substrates after washing is placed in solution, hydrothermal temperature is 100 DEG C ~ 140 DEG C, and the time is 3 ~ 10h.React rear taking-up substrate and carried out washing and vacuumize, having obtained the precursor of cobaltosic oxide; (2) heat-treated in air atmosphere by cobaltosic oxide precursor, heat treated temperature is 200 DEG C ~ 600 DEG C, namely obtains the described electrode material for super capacitor based on cobaltosic oxide nano linear array.
The pattern of cobaltosic oxide and the stability in conductive substrates not only relevant with preparation method, also closely related with the kind of complexing agent, studies have found that, after adopting ammonium chloride to replace ammonium fluoride, through the hydro-thermal reaction of the same terms, the active material film of gained is unstable and frangible.Cobalt salt in step of the present invention (1) is cobalt nitrate or cobalt acetate, complexing agent is ammonium fluoride, alkaline precipitating agent is urea, mol ratio is 1:(2-4): 5, wherein the effect of ammonium fluoride promotes that crystal seed is in conductive glass surface film forming, and utilize form the corrosiveness of HF, make substrate surface coarse, contribute to crystal nucleation.
Hydro thermal method is prepared in cobaltosic oxide process, in order to obtain regular appearance, in conjunction with firmly array structure, the placement location of conductive substrates and method have larger impact, the conducting surface of conductive substrates is placed in reactor downwards, and is 45 ° ~ 75 ° with the interior angle of bottom.
Accompanying drawing explanation
Fig. 1 is the low power stereoscan photograph of cobaltosic oxide prepared in embodiment 1.
Fig. 2 is the high power stereoscan photograph of cobaltosic oxide prepared in embodiment 1.
Fig. 3 is the cyclic voltammetry curve of cobaltosic oxide electrode prepared in embodiment 1.
Fig. 4 is the charging and discharging curve of cobaltosic oxide electrode prepared in embodiment 1.
Embodiment
Below in conjunction with embodiment, technical scheme of the present invention and effect are further described.But the concrete grammar used, formula and explanation are not limitation of the present invention.
Embodiment 1: by the even ultrasonic mixing in distilled water of 2.5mmol cobalt nitrate, 5mmol ammonium fluoride and 12.5mmol urea, this solution is moved in the autoclave of polytetrafluoro liner, 120 DEG C of reaction 5h, and the conductive substrates nickel foam after washing is placed in solution, react rear taking-up substrate and carried out washing and vacuumize, obtain the precursor of cobaltosic oxide, by cobaltosic oxide precursor 350 DEG C of heat treatment 1.5h in air atmosphere, obtain cobaltosic oxide nano linear array.
Embodiment 2: by the even ultrasonic mixing in distilled water of 2.5mmol cobalt nitrate, 5mmol ammonium fluoride and 12.5mmol urea, this solution is moved in the autoclave of polytetrafluoro liner, 120 DEG C of reaction 5h, and the electro-conductive glass (FTO) after washing is placed in solution, react rear taking-up substrate and carried out washing and vacuumize, obtain the precursor of cobaltosic oxide, by cobaltosic oxide precursor 350 DEG C of heat treatment 1.5h in air atmosphere, obtain cobaltosic oxide nano linear array.
Embodiment 3: by the even ultrasonic mixing in distilled water of 2.5mmol cobalt nitrate, 5mmol ammonium fluoride and 12.5mmol urea, this solution is moved in the autoclave of polytetrafluoro liner, 120 DEG C of reaction 5h, and the conductive substrates pure nickel sheet after washing is placed in solution, react rear taking-up substrate and carried out washing and vacuumize, obtain the precursor of cobaltosic oxide, by cobaltosic oxide precursor 350 DEG C of heat treatment 1.5h in air atmosphere, obtain cobaltosic oxide nano linear array.
Embodiment 4: by the even ultrasonic mixing in distilled water of 2.5mmol cobalt nitrate, 7.5mmol ammonium fluoride and 12.5mmol urea, this solution is moved in the autoclave of polytetrafluoro liner, 120 DEG C of reaction 5h, and the conductive substrates nickel foam after washing is placed in solution, react rear taking-up substrate and carried out washing and vacuumize, obtain the precursor of cobaltosic oxide, by cobaltosic oxide precursor 350 DEG C of heat treatment 1.5h in air atmosphere, obtain cobaltosic oxide nano linear array.
Embodiment 5: by the even ultrasonic mixing in distilled water of 2.5mmol cobalt nitrate, 10mmol ammonium fluoride and 12.5mmol urea, this solution is moved in the autoclave of polytetrafluoro liner, 120 DEG C of reaction 5h, and the conductive substrates nickel foam after washing is placed in solution, react rear taking-up substrate and carried out washing and vacuumize, obtain the precursor of cobaltosic oxide, by cobaltosic oxide precursor 350 DEG C of heat treatment 1.5h in air atmosphere, obtain cobaltosic oxide nano linear array.
Claims (7)
1. the electrode for super capacitor material based on cobaltosic oxide nano linear array, the electrode system of described ultracapacitor comprises conductive current collector, electrode active material layers, electrolyte and barrier film, it is characterized in that, described electrode active material is the porous cobaltosic oxide nano linear array be grown directly upon in conductive current collector.
2. the electrode for super capacitor material based on cobaltosic oxide nano linear array according to claim 1, is characterized in that, described conductive substrates is electro-conductive glass, nickel sheet and foam nickel screen.
3. the electrode for super capacitor material based on cobaltosic oxide nano linear array according to claim 2, it is characterized in that, the pattern of described cobaltosic oxide nano linear array is the pyramid structure that the end of 5-10 root nano wire combines, and wherein array length is 5 μm-20 μm.
4. the electrode for super capacitor material based on cobaltosic oxide nano linear array, it is characterized in that comprising the steps: the even ultrasonic mixing in distilled water of cobalt salt, complexing agent and alkaline precipitating agent, this solution is moved in the autoclave of polytetrafluoro liner, and the conductive substrates after washing is placed in solution, react rear taking-up substrate and carried out washing and vacuumize, obtain the precursor of cobaltosic oxide, cobaltosic oxide precursor is heat-treated in air atmosphere, obtains cobaltosic oxide nano linear array.
5. the preparation method of the electrode for super capacitor material based on cobaltosic oxide nano linear array according to right 3, it is characterized in that complexing agent is ammonium fluoride, its effect promotes that crystal seed is in conductive glass surface film forming, and utilize form the corrosiveness of HF, make substrate surface coarse, contribute to crystal nucleation.
6. the preparation method of the electrode for super capacitor material based on cobaltosic oxide nano linear array according to right 3, is characterized in that the conducting surface of conductive substrates is placed in reactor downwards, and is 45 ° ~ 75 ° with the interior angle of bottom.
7. the cobaltosic oxide nano linear array of growth in situ in conductive substrates according to claim 3 is as the purposes of ultracapacitor fake capacitance electrode material.
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| CN201510136773.7A CN104681299B (en) | 2015-03-27 | 2015-03-27 | Electrode material for super capacitor of cobaltosic oxide porous nano linear array and preparation method thereof |
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| CN201510136773.7A CN104681299B (en) | 2015-03-27 | 2015-03-27 | Electrode material for super capacitor of cobaltosic oxide porous nano linear array and preparation method thereof |
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Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104966834A (en) * | 2015-07-15 | 2015-10-07 | 扬州大学 | Preparation method of squid-tentacle-shaped tricobalt tetraoxide lithium battery negative electrode material |
| CN105097299A (en) * | 2015-07-16 | 2015-11-25 | 安泰科技股份有限公司 | Cobaltosic oxide/NiCoAl dual-layer hydroxide composite material and preparation method thereof |
| CN105126642A (en) * | 2015-07-27 | 2015-12-09 | 北京工业大学 | Preparation of metal organic framework membrane and application in gas separation |
| CN105470000A (en) * | 2016-01-08 | 2016-04-06 | 广东工业大学 | Integrated composite electrode for supercapacitor and preparation method of integrated composite electrode |
| CN105679549A (en) * | 2016-01-13 | 2016-06-15 | 吉林化工学院 | Preparation of Co3O4@NiO core-shell nanowire array electrode material |
| CN105914046A (en) * | 2016-04-14 | 2016-08-31 | 深圳大学 | Preparation method for hydroxyl-cobalt-carbonate thin-film super capacitor electrode material |
| CN106365210A (en) * | 2016-08-29 | 2017-02-01 | 浙江工业大学 | Preparation and application of shape-controlled cobaltosic oxide nano array |
| CN106531465A (en) * | 2016-12-13 | 2017-03-22 | 华南师范大学 | Cobaltosic oxide asymmetric super capacitor used for photovoltaic energy storage and preparation method |
| CN106683894A (en) * | 2016-12-30 | 2017-05-17 | 盐城工学院 | Co3O4 porous nanosheet array preparation method and application thereof |
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| CN107808777A (en) * | 2017-10-18 | 2018-03-16 | 德清鼎兴电子有限公司 | The cobalt nickel combination electrode and its preparation technology that a kind of capacitor uses |
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