CN111128561A - Flexible asymmetric solid-state supercapacitor with nanostructure and preparation method thereof - Google Patents
Flexible asymmetric solid-state supercapacitor with nanostructure and preparation method thereof Download PDFInfo
- Publication number
- CN111128561A CN111128561A CN201911412538.2A CN201911412538A CN111128561A CN 111128561 A CN111128561 A CN 111128561A CN 201911412538 A CN201911412538 A CN 201911412538A CN 111128561 A CN111128561 A CN 111128561A
- Authority
- CN
- China
- Prior art keywords
- solid
- flexible
- state supercapacitor
- carbon foam
- flexible asymmetric
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 68
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 51
- 239000000463 material Substances 0.000 claims abstract description 34
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003792 electrolyte Substances 0.000 claims abstract description 28
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 19
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 19
- 239000003990 capacitor Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 24
- 239000000758 substrate Substances 0.000 claims description 19
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- KAEHZLZKAKBMJB-UHFFFAOYSA-N cobalt;sulfanylidenenickel Chemical compound [Ni].[Co]=S KAEHZLZKAKBMJB-UHFFFAOYSA-N 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 9
- 229920000877 Melamine resin Polymers 0.000 claims description 8
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229920002799 BoPET Polymers 0.000 claims description 5
- 239000001913 cellulose Substances 0.000 claims description 5
- 229920002678 cellulose Polymers 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical group CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 5
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 5
- 238000009736 wetting Methods 0.000 claims description 5
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000010000 carbonizing Methods 0.000 claims description 2
- 238000004806 packaging method and process Methods 0.000 claims description 2
- 239000007772 electrode material Substances 0.000 abstract description 9
- 238000013461 design Methods 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 20
- 238000001816 cooling Methods 0.000 description 16
- 238000001035 drying Methods 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- -1 polytetrafluoroethylene Polymers 0.000 description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 229910052786 argon Inorganic materials 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 238000004146 energy storage Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000007664 blowing Methods 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 5
- 239000004202 carbamide Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 5
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical group Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 3
- 238000007600 charging Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000010335 hydrothermal treatment Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002135 nanosheet Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 229910003266 NiCo Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical class [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- JTRONPPAUSSTQI-UHFFFAOYSA-N ethane-1,2-diol;ethanol Chemical compound CCO.OCCO JTRONPPAUSSTQI-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- AHKZTVQIVOEVFO-UHFFFAOYSA-N oxide(2-) Chemical compound [O-2] AHKZTVQIVOEVFO-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
Images
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
- H01G11/24—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
- H01G11/30—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
-
- 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
- H01G11/54—Electrolytes
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
-
- 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
-
- 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)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention relates to the technical field of asymmetric super capacitors, in particular to a flexible asymmetric solid-state super capacitor with a nano structure and a preparation method thereof. The flexible asymmetric solid-state supercapacitor comprises a positive electrode, a negative electrode, a diaphragm and an electrolyte, wherein the positive electrode is made of carbon foam/cobalt nickel sulfide materials, the negative electrode is made of carbon foam/bismuth trioxide materials, and the electrolyte is made of polyvinyl alcohol/potassium hydroxide gel. The method of the invention selects the electrode material,The design of a micro-nano structure, the assembly of a macroscopic device, the multilayer compounding and the synergy ensure that the prepared flexible solid-state supercapacitor has good electrochemical performance, the voltage window is expanded to 1.5V, and the current density is 1 mA/cm2When the capacitance of the area reaches 475 mF/cm2At 3.73 mW/cm3Has a power density of 0.74mWh/cm3High energy density. The method is simple and easy to implement, green and environment-friendly, and has excellent performance, so that effective technical support can be provided for the design of the next-generation high-performance flexible super capacitor.
Description
Technical Field
The invention relates to the technical field of asymmetric super capacitors, in particular to a flexible asymmetric solid-state super capacitor with a nano structure and a preparation method thereof.
Background
With the development of flexible electronics, wearable electronic devices are rapidly entering the lives of people. In order to realize the commercialization of wearable devices, the energy supply components of the wearable devices also need to be flexible and have high performance, and therefore, the high-performance flexible energy storage devices will increasingly show potential market values. In recent years, asymmetric supercapacitors are widely applied to flexible energy storage devices due to wide working voltage, ultrahigh power density, fast charging rate and long cycle life, and development of flexible positive and negative electrode materials with both mechanical properties and energy storage properties is a key point for realizing efficient energy storage of the flexible positive and negative electrode materials.
The currently commonly used positive electrode active material is transition metal oxide, wherein nickel-cobalt bimetallic oxide (nickel cobaltate, NiCo)2O4) Have recently been studied extensively. Nickel cobaltates, which have twice the conductivity of single metal oxides, are considered to be more effective electrode materials, however, have poor charging capacity and sustained cycle life, limiting their use in the energy storage field. Nickel cobalt bimetallic sulfide (cobalt nickel sulfide, NiCo)2S4) Compared with nickel-cobalt bimetallic oxide, the nickel-cobalt bimetallic oxide has smaller energy band gap, so that the conductivity of the nickel-cobalt sulfide is at least two times higher than that of the nickel cobaltate; cobalt nickel sulfide, on the other hand, has a higher electrochemical activity and higher capacity than other single metal oxides or sulfides due to its inherent redox reactive sites. Although cobalt nickel sulfide has achieved an improvement in the energy storage performance of nickel cobalt based systems, it has not yet met with large power sourcesThe development of electronic devices, hybrid vehicles and smart grids, and therefore, the increase of the specific area capacity, rate capability and cycling stability of these materials is still a major challenge. An effective method for improving the multiplying power of the cobalt nickel sulfide material is to design a multi-three-dimensional multi-level structure to provide a larger specific surface area and a higher surface loading capacity, so as to promote effective charge and mass exchange in the Faraday redox reaction process.
Bismuth trioxide is widely used as a negative active material due to the advantages of innocuity, easy synthesis, wide band gap, good oxide ion conductivity, proper negative working window, high electrochemical stability, high redox reversibility and the like, but the capacitance of the bismuth trioxide is severely limited due to low conductivity of the bismuth trioxide in the preparation process. Therefore, in order to obtain high energy, the electrode material needs to be selected and optimized, and the micro-nano structure of the material is designed to ensure that the performance of the material is optimal.
In order to improve the mechanical properties of the electrode material, the positive and negative electrode active materials are required to be loaded on a flexible substrate to form a flexible electrode. The melamine foam has flexibility and is rich in three-dimensional structure pore channels, and after carbonization, the pore structure can still keep good mechanical properties and can be used as an ideal carrier of a flexible device. How to optimize the components of the electrode material and construct a functional interface, and realize the effective load of the active electrode material on a flexible substrate, the preparation of the flexible asymmetric supercapacitor with both mechanical properties and energy storage properties still faces huge challenges.
Disclosure of Invention
The invention aims to solve the problems and provides a flexible asymmetric solid-state supercapacitor with a nano structure and a preparation method thereof.
The technical scheme for solving the problems is to provide a flexible asymmetric solid-state supercapacitor with a nano structure, which comprises a positive electrode, a negative electrode, a diaphragm and an electrolyte, wherein the positive electrode is selected from a carbon foam/cobalt nickel sulfide material for growing cobalt nickel sulfide on a porous carbon substrate, the negative electrode is selected from a carbon foam/bismuth trioxide material for growing bismuth trioxide on the porous carbon substrate, and the electrolyte is selected from polyvinyl alcohol/potassium hydroxide gel.
Preferably, the carbon foam/bismuth trioxide material is prepared by growing bismuth trioxide on a porous carbon substrate from a bismuth precursor solution through a hydrothermal method.
Preferably, the carbon foam/bismuth trioxide material is prepared by the following steps: dissolving bismuth nitrate in a solvent with the volume ratio of 2:1, obtaining a precursor solution of bismuth in the ethanol-ethylene glycol mixed solution; and (3) immersing the porous carbon substrate into a bismuth precursor solution, reacting for 3-8h at the temperature of 150-200 ℃, cooling, cleaning and drying to obtain the carbon foam/bismuth trioxide material.
Preferably, the carbon foam/cobalt nickel sulfide material is prepared by growing a cobalt nickel precursor on a porous carbon substrate by a hydrothermal method through a mixed solution of cobalt salt, nickel salt and a pH regulator, and then immersing the cobalt nickel precursor into a vulcanizing agent.
Preferably, the pH regulator is urea.
Preferably, the carbon foam/cobalt nickel sulphide material is prepared by: preparing a mixed solution of nickel salt, cobalt salt and urea; immersing the porous carbon substrate into the mixed solution, reacting for 8-12h at 100-200 ℃, cooling, cleaning and drying to obtain a precursor material; and (3) immersing the precursor material into a vulcanizing agent solution, reacting for 10-15h at the temperature of 80-120 ℃, cooling, cleaning and drying to obtain the carbon foam/cobalt nickel sulfide material.
Preferably, the nickel salt is NiCl2。
Preferably, CoCl is selected as the cobalt salt2。
Preferably, the vulcanizing agent is 0.1-0.5mol/L thioacetamide solution.
Preferably, the polyvinyl alcohol/potassium hydroxide gel is a gel obtained by dissolving PVA in KOH solution and stirring at 90-100 ℃ until the PVA is transparent.
Preferably, the polyvinyl alcohol/potassium hydroxide gel is prepared by: 4-8 g of PVA is dissolved in 40-60 mL of 1-5 mol/L KOH solution and stirred at 90-100 ℃ until the solution is transparent, thus obtaining polyvinyl alcohol/potassium hydroxide gel.
Preferably, the porous carbon substrate is nitrogen-doped porous carbon foam obtained by carbonizing melamine sponge.
Preferably, the carbonization treatment comprises the steps of: the melamine sponge is placed in a high-temperature tube furnace, argon is introduced for 15-40 min at room temperature before pyrolysis, the flow of the argon is 500-1500 standard cubic centimeters per minute, and air in the tube is exhausted. Then keeping the flow rate of the argon gas, raising the temperature to 600-900 ℃ at the speed of 5-20 ℃/min, pyrolyzing for 1-3h, and then slowly cooling to the room temperature.
Preferably, the separator is cellulose paper.
The invention also aims to provide a preparation method of the flexible asymmetric solid-state supercapacitor with the nano structure, which comprises the following steps: and assembling the anode, the cathode, the diaphragm and the electrolyte into a solid capacitor, and then packaging by PET.
Preferably, the assembling comprises the steps of: and soaking the anode and the cathode in an electrolyte, taking out after wetting, assembling the anode, the electrolyte, the diaphragm, the electrolyte and the cathode in sequence, and curing at room temperature for 2-6h to obtain the flexible asymmetric solid supercapacitor.
Preferably, the PET package comprises the steps of: and (4) wrapping the assembled solid capacitor in a PET film, and heating and plasticizing.
The invention has the beneficial effects that:
1. the carbon foam with the three-dimensional interconnection network structure is used as an electrode substrate, and has the advantages of good chemical stability, rich porous structure, open pore channel, large specific surface area, good conductivity and the like, thereby being beneficial to the migration of electrolyte and the uniform growth of transition metal oxide on a carbon foam framework.
2. The positive electrode and the negative electrode respectively adopt cobalt nickel sulfide and bismuth trioxide, and the working voltage window of the super capacitor can be greatly expanded by superposing the absolute complementary voltage windows of the positive electrode and the negative electrode, so that the super capacitor can provide high energy density capability.
3. The high-conductivity nitrogen-doped carbon foam is combined with cobalt nickel sulfide and bismuth trioxide active electrode materials, and the double-layer capacitance of the carbon foam is combined with the Faraday capacitance of metal oxide, so that the super-capacitance is improved, the optimized synergistic effect of the structure and the composition of the nano mixed electrode material is improved, and the performance of the asymmetric solid supercapacitor is greatly improved.
4. The method is simple, practicable, environment-friendly and low in cost, and avoids the use of adhesives and conductive additives, and meanwhile, the flexible asymmetric solid super capacitor device has the advantages of working voltage expansion, large capacitance, high energy density and good rate capability.
Drawings
FIG. 1 is an SEM image of a carbon foam produced in example 1 of the present application;
FIG. 2 is an SEM image of a carbon foam/cobalt nickel sulfide material prepared in example 1 of the present application;
FIG. 3 is an SEM image of a carbon foam/bismuth trioxide material made in example 1 of the present application;
FIG. 4 is an XRD pattern of carbon foam/cobalt nickel sulfide and carbon foam/bismuth trioxide produced in example 1 of the present application;
FIG. 5 is a cyclic voltammogram of a flexible asymmetric solid-state supercapacitor made in example 1 of the present application;
FIG. 6 is a graph showing the charging and discharging curves of the flexible asymmetric solid-state supercapacitor made in example 1 of the present application;
FIG. 7 is a graph of rate capability of a flexible asymmetric solid-state supercapacitor made in example 1 of the present application;
FIG. 8 is a Ragon plot and comparison to a comparative example of a flexible asymmetric solid-state supercapacitor made in example 1 of the present application;
fig. 9 is a structural diagram of a flexible asymmetric solid-state supercapacitor manufactured in example 1 of the present application.
Detailed Description
The following are specific embodiments of the present invention and are further described with reference to the accompanying drawings, but the present invention is not limited to these embodiments.
Example 1
A flexible asymmetric solid-state supercapacitor of a nanostructure is prepared by the following steps:
(1) preparing a porous carbon substrate: placing melamine sponge in a high-temperature tube furnace, firstly introducing argon at room temperature for 25min, wherein the flow of the argon is 1000cm3And/min, exhausting air in the pipe. Then keeping the flow rate of argon gas, raising the temperature to 800 ℃ at the speed of 5 ℃/min, pyrolyzing for 1h, and slowly cooling to room temperature to obtain the carbon foam.
(2) Preparation of the positive electrode: mixing NiCl2，CoCl2And urea were dissolved in deionized water and continuously stirred to form a homogeneous pink solution. And (2) immersing the carbon foam obtained in the step (1) into the solution, transferring the carbon foam into a polytetrafluoroethylene hydrothermal reaction kettle, placing the polytetrafluoroethylene hydrothermal reaction kettle in an air-blowing drying oven, preserving the heat at 100 ℃ for 12 hours, and cooling to room temperature. Then washed with deionized water and dried to obtain the carbon foam/cobalt nickel hydroxide material. And soaking the obtained carbon foam/cobalt nickel hydroxide in 0.2 mol/L thioacetamide solution, carrying out hydrothermal treatment at 95 ℃ for 12 hours, cooling to room temperature, washing with deionized water, and drying to obtain the carbon foam/cobalt nickel sulfide material.
(3) Preparation of a negative electrode: 0.97g of bismuth nitrate pentahydrate is dissolved in a mixed solution of ethanol and ethylene glycol in a volume ratio of 2:1, and the solution is stirred and dissolved to obtain a dispersion liquid. And (2) immersing the carbon foam obtained in the step (1) into the dispersion, transferring the carbon foam into a polytetrafluoroethylene hydrothermal reaction kettle, placing the polytetrafluoroethylene hydrothermal reaction kettle in an air-blowing drying oven, preserving the heat at 160 ℃ for 5 hours, and cooling to room temperature. Then washing with deionized water and drying. And (3) putting the dried sample into a high-temperature tube furnace, and annealing in an argon atmosphere to obtain the carbon foam/bismuth trioxide material.
(4) Preparing an electrolyte: 6 g of PVA was dissolved in 60 mL of a 2mol/L KOH solution and stirred at 95 ℃ until it was transparent, to obtain a polyvinyl alcohol/potassium hydroxide gel.
(5) Cellulose paper is selected as the diaphragm.
(6) And soaking the anode and the cathode in an electrolyte, taking out after wetting, assembling the anode, the electrolyte, the diaphragm, the electrolyte and the cathode in sequence, and curing at room temperature for 5 hours to obtain the flexible asymmetric solid-state supercapacitor.
(7) And (4) wrapping the assembled solid capacitor in a PET film, and heating and plasticizing.
(8) The electrode materials were characterized and the results are shown in fig. 1-4.
Fig. 1 shows the microscopic morphology of the carbon foam material, and it is seen that the carbon foam has a three-dimensional interconnected network structure with a smooth and flat surface, and the interconnected structure is favorable for the migration of electrolyte and the uniform growth of cobalt nickel sulfide nanorods and bismuth trioxide nanosheets on the carbon foam skeleton.
Fig. 2 is a microscopic topography of a carbon foam/cobalt nickel sulfide material, with cobalt nickel sulfide growing uniformly and vertically on the carbon foam skeleton, without significant aggregation, forming a typical pine-twig like structure.
Fig. 3 shows a carbon foam/bismuth trioxide material, and it can be seen from fig. 3 that bismuth nitrate is decomposed into bismuth trioxide nanosheets after simple solvent heat treatment, and under a higher magnification, the bismuth trioxide nanosheets can be observed to densely grow on a carbon foam skeleton, and are assembled into a structure similar to agaric.
FIG. 4 is a phase diagram of carbon foam/cobalt nickel sulfide and carbon foam/bismuth trioxide measured by X-ray diffraction (XRD). By searching JCPDS card database, it can be found that the prepared carbon foam/cobalt nickel sulfide material can easily index to cubic phase of cobalt nickel sulfide (JCPDS, No. 00-020-. In the carbon foam/bismuth trioxide phase, in addition to one diffraction peak from carbon foam, four diffraction peaks at 2 θ values of 28 °, 32.4 °, 46.5 °, and 55.1 ° corresponding to the (111), (200), (220), and (311) crystal planes of carbon foam/bismuth trioxide are well oriented to the cubic phase of carbon foam/bismuth trioxide (JCPDS, No. 27-0052).
And (3) carrying out electrochemical performance test on the prepared flexible asymmetric solid-state supercapacitor: the flexible asymmetric solid-state supercapacitor is connected to an electrochemical workstation, the performance of the flexible asymmetric solid-state supercapacitor is tested through cyclic voltammetry and constant current charging and discharging, and the area capacitance, the power density and the energy density are calculated. The detection results are shown in fig. 5-8.
Fig. 5 is a cyclic voltammogram of a flexible asymmetric solid-state supercapacitor, which is prepared by using carbon foam/cobalt nickel sulfide as a positive electrode, carbon foam/bismuth trioxide as a negative electrode, and polyvinyl alcohol/potassium hydroxide as a gel electrolyte. The operating voltage window of the flexible asymmetric solid-state supercapacitor device can be expanded to 1.5V by superimposing the absolute complementary voltage windows of the positive and negative electrodes, demonstrating its ability to provide high energy density.
FIG. 6 is a graph of the charge and discharge curves of the flexible asymmetric solid-state supercapacitor, and from the GCD curve of FIG. 6, the values of the asymmetric supercapacitor at 1, 2, 4, 6, 8 and 10 mA/cm can be calculated2The area capacitance is 475.5, 340.2, 284.2, 223.4, 207.6 and 152.8 mF/cm2。
Fig. 7 is a graph of rate performance of the flexible asymmetric solid-state supercapacitor, and it can be seen from fig. 7 that the prepared flexible asymmetric solid-state supercapacitor device shows good rate performance.
FIG. 8 is a Ragon graph of a flexible asymmetric solid-state supercapacitor, in FIG. 8, square dots represent asymmetric supercapacitors in the present embodiment, and it can be seen from FIG. 8 that at a power density of 3.73 mW/cm3When the energy density is 0.74mWh/cm3。
Fig. 9 is a construction diagram of a flexible asymmetric solid-state supercapacitor demonstrating the feasibility of the present application.
Example 2
A flexible asymmetric solid-state supercapacitor of a nanostructure is prepared by the following steps:
(1) preparing a porous carbon substrate: placing melamine sponge in a high-temperature tube furnace, firstly introducing argon for 15min at room temperature, wherein the flow of the argon is 500cm3And/min, exhausting air in the pipe. Then keeping the flow rate of argon gas, raising the temperature to 600 ℃ at the speed of 5 ℃/min, pyrolyzing for 1h, and slowly cooling to room temperature to obtain the carbon foam.
(2) Preparation of the positive electrode: mixing NiCl2，CoCl2And urea were dissolved in deionized water and continuously stirred to form a homogeneous pink solution. And (2) immersing the carbon foam obtained in the step (1) into the solution, transferring the carbon foam into a polytetrafluoroethylene hydrothermal reaction kettle, placing the polytetrafluoroethylene hydrothermal reaction kettle into an air-blowing drying oven, preserving the heat at 200 ℃ for 8 hours, and cooling to room temperature. Then washed with deionized water and dried to obtain the carbon foam/cobalt nickel hydroxide material. And soaking the obtained carbon foam/cobalt nickel hydroxide in 0.1 mol/L thioacetamide solution, carrying out hydrothermal treatment at 80 ℃ for 10 hours, cooling to room temperature, washing with deionized water, and drying to obtain the carbon foam/cobalt nickel sulfide material.
(3) Preparation of a negative electrode: 0.9g of bismuth nitrate pentahydrate is dissolved in a mixed solution of ethanol and ethylene glycol in a volume ratio of 2:1, and the mixed solution is stirred and dissolved to obtain a dispersion liquid. And (2) immersing the carbon foam obtained in the step (1) into the dispersion, transferring the carbon foam into a polytetrafluoroethylene hydrothermal reaction kettle, placing the polytetrafluoroethylene hydrothermal reaction kettle in an air-blowing drying oven, preserving the heat at 150 ℃ for 3 hours, and cooling to room temperature. Then washing with deionized water and drying. And (3) putting the dried sample into a high-temperature tube furnace, and annealing in an argon atmosphere to obtain the carbon foam/bismuth trioxide material.
(4) Preparing an electrolyte: 4g of PVA was dissolved in 40 mL of a 1mol/L KOH solution and stirred at 90 ℃ until it was clear, to give a polyvinyl alcohol/potassium hydroxide gel.
(5) Cellulose paper is selected as the diaphragm.
(6) And soaking the anode and the cathode in an electrolyte, taking out after wetting, assembling the anode, the electrolyte, the diaphragm, the electrolyte and the cathode in sequence, and curing at room temperature for 2 hours to obtain the flexible asymmetric solid-state supercapacitor.
(7) And (4) wrapping the assembled solid capacitor in a PET film, and heating and plasticizing.
Example 3
A flexible asymmetric solid-state supercapacitor of a nanostructure is prepared by the following steps:
(1) preparing a porous carbon substrate: placing melamine sponge in a high-temperature tube furnace, firstly introducing the melamine sponge at room temperatureArgon gas flow of 1500cm for 40 min3And/min, exhausting air in the pipe. Then keeping the flow rate of argon gas, raising the temperature to 900 ℃ at the rate of 20 ℃/min, pyrolyzing for 3h, and slowly cooling to room temperature to obtain the carbon foam.
(2) Preparation of the positive electrode: mixing NiCl2，CoCl2And urea were dissolved in deionized water and continuously stirred to form a homogeneous pink solution. And (2) immersing the carbon foam obtained in the step (1) into the solution, transferring the carbon foam into a polytetrafluoroethylene hydrothermal reaction kettle, placing the polytetrafluoroethylene hydrothermal reaction kettle in an air-blowing drying oven, preserving the heat at 150 ℃ for 10 hours, and cooling to room temperature. Then washed with deionized water and dried to obtain the carbon foam/cobalt nickel hydroxide material. And soaking the obtained carbon foam/cobalt nickel hydroxide in 0.5mol/L thioacetamide solution, carrying out hydrothermal treatment at 120 ℃ for 15 hours, cooling to room temperature, washing with deionized water, and drying to obtain the carbon foam/cobalt nickel sulfide material.
(3) Preparation of a negative electrode: dissolving 1.2g of bismuth nitrate pentahydrate in a mixed solution of ethanol and ethylene glycol in a volume ratio of 2:1, and stirring and dissolving to obtain a dispersion liquid. And (2) immersing the carbon foam obtained in the step (1) into the dispersion, transferring the carbon foam into a polytetrafluoroethylene hydrothermal reaction kettle, placing the polytetrafluoroethylene hydrothermal reaction kettle in an air-blowing drying oven, preserving the heat at 200 ℃ for 8 hours, and cooling to room temperature. Then washing with deionized water and drying. And (3) putting the dried sample into a high-temperature tube furnace, and annealing in an argon atmosphere to obtain the carbon foam/bismuth trioxide material.
(4) Preparing an electrolyte: 8 g of PVA was dissolved in 50 mL of a 5mol/L KOH solution and stirred at 100 ℃ until it was transparent, to obtain a polyvinyl alcohol/potassium hydroxide gel.
(5) Cellulose paper is selected as the diaphragm.
(6) And soaking the anode and the cathode in an electrolyte, taking out after wetting, assembling the anode, the electrolyte, the diaphragm, the electrolyte and the cathode in sequence, and curing at room temperature for 6 hours to obtain the flexible asymmetric solid-state supercapacitor.
(7) And (4) wrapping the assembled solid capacitor in a PET film, and heating and plasticizing.
Comparative examples 1 to 4
A flexible asymmetric solid-state supercapacitor was prepared according to the prior art and has the structure shown in table 1 below.
The performance ratio of the supercapacitor of comparative example to the supercapacitor of example 1 is shown in fig. 8, in which a dot with a circle number of 2 indicates the performance result of comparative example 1, a dot with a regular triangle number of 3 indicates the performance result of comparative example 2, a dot with an inverted triangle number of 4 indicates the performance result of comparative example 3, and a dot with a diamond shape number of 5 indicates the performance result of comparative example 4. Fig. 8 shows that the flexible asymmetric solid supercapacitor obtained by the method has better performance than the conventional supercapacitor through reasonable matching between the anode and cathode materials and the substrate.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
Claims (10)
1. The utility model provides a flexible asymmetric solid-state ultracapacitor system of nanostructure, includes positive pole, negative pole, diaphragm and electrolyte, its characterized in that: the anode is selected from a carbon foam/cobalt nickel sulfide material for growing cobalt nickel sulfide on a porous carbon substrate, the cathode is selected from a carbon foam/bismuth trioxide material for growing bismuth trioxide on the porous carbon substrate, and the electrolyte is selected from polyvinyl alcohol/potassium hydroxide gel.
2. The nanostructured flexible asymmetric solid-state supercapacitor according to claim 1, wherein: the carbon foam/bismuth trioxide material is prepared by growing bismuth trioxide on a porous carbon substrate by a hydrothermal method from a bismuth precursor solution.
3. The nanostructured flexible asymmetric solid-state supercapacitor according to claim 1, wherein: the carbon foam/cobalt nickel sulfide material is prepared by growing a cobalt nickel precursor on a porous carbon substrate by a hydrothermal method through a mixed solution of cobalt salt, nickel salt and a pH regulator, and then immersing the cobalt nickel precursor into a vulcanizing agent.
4. The nanostructured flexible asymmetric solid-state supercapacitor according to claim 3, wherein: the vulcanizing agent is thioacetamide solution.
5. The nanostructured flexible asymmetric solid-state supercapacitor according to claim 1, wherein: the porous carbon substrate is nitrogen-doped porous carbon foam obtained by carbonizing melamine sponge.
6. The nanostructured flexible asymmetric solid-state supercapacitor according to claim 1, wherein: the polyvinyl alcohol/potassium hydroxide gel is obtained by dissolving PVA in KOH solution and then stirring at 90-100 ℃ until the PVA is transparent.
7. The nanostructured flexible asymmetric solid-state supercapacitor according to claim 1, wherein: the diaphragm is made of cellulose paper.
8. A method for preparing a nano-structured flexible asymmetric solid-state supercapacitor according to any one of claims 1 to 7, wherein: the method comprises the following steps: and assembling the anode, the cathode, the diaphragm and the electrolyte into a solid capacitor, and then packaging by PET.
9. The method for preparing the flexible asymmetric solid-state supercapacitor with the nano structure according to claim 8, wherein the flexible asymmetric solid-state supercapacitor with the nano structure comprises the following steps: the assembly comprises the following steps: and soaking the anode and the cathode in an electrolyte, taking out after wetting, assembling the anode, the electrolyte, the diaphragm, the electrolyte and the cathode in sequence, and curing at room temperature for 2-6h to obtain the flexible asymmetric solid supercapacitor.
10. The method for preparing the flexible asymmetric solid-state supercapacitor with the nano structure according to claim 8, wherein the flexible asymmetric solid-state supercapacitor with the nano structure comprises the following steps: the PET package comprises the following steps: and (4) wrapping the assembled solid capacitor in a PET film, and heating and plasticizing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911412538.2A CN111128561A (en) | 2019-12-31 | 2019-12-31 | Flexible asymmetric solid-state supercapacitor with nanostructure and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911412538.2A CN111128561A (en) | 2019-12-31 | 2019-12-31 | Flexible asymmetric solid-state supercapacitor with nanostructure and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111128561A true CN111128561A (en) | 2020-05-08 |
Family
ID=70506434
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911412538.2A Pending CN111128561A (en) | 2019-12-31 | 2019-12-31 | Flexible asymmetric solid-state supercapacitor with nanostructure and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111128561A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111540612A (en) * | 2020-05-09 | 2020-08-14 | 晋江瑞碧科技有限公司 | Preparation method of organic/inorganic composite super capacitor |
| CN112599361A (en) * | 2020-12-14 | 2021-04-02 | 湖南大学 | Wide-temperature-range high-performance electrochemical energy storage device based on bismuth-based electrode |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104299797A (en) * | 2014-11-06 | 2015-01-21 | 中南大学 | Water-system asymmetric super-capacitor based on NiCo2S4 and NiCo2S4 composite material |
| CN105551812A (en) * | 2016-01-19 | 2016-05-04 | 南京理工大学 | NiCo2S4 supercapacitor material and preparation method therefor |
| CN106067383A (en) * | 2016-08-23 | 2016-11-02 | 中国科学院重庆绿色智能技术研究院 | A kind of pseudocapacitors positive pole based on cobalt sulfide nickel nucleocapsid three-dimensional multistage nanostructured and preparation method thereof |
| CN205900332U (en) * | 2016-08-23 | 2017-01-18 | 中国科学院重庆绿色智能技术研究院 | Fake capacitance ware is anodal based on three -dimensional multistage nanostructured of cobaltous sulfide nickel nucleocapsid |
| CN107492657A (en) * | 2017-07-12 | 2017-12-19 | 三峡大学 | A kind of preparation method of cobalt sulfide nickel both positive and negative polarity battery and its application on the recyclable battery of alkalescence |
| CN109950050A (en) * | 2019-04-17 | 2019-06-28 | 武汉工程大学 | A kind of preparation method based on carbonization melamine foamed plastic@Bi2O3 nanometer sheet electrode material for super capacitor |
| CN110233058A (en) * | 2019-07-15 | 2019-09-13 | 浙江工业大学 | A kind of self assembly hollow form NiCo2S4 material, preparation method and its application |
| CN110265226A (en) * | 2019-07-12 | 2019-09-20 | 福州大学 | A kind of nickel sulfide/carbonization melamine foamed plastic combination electrode material and preparation method thereof |
-
2019
- 2019-12-31 CN CN201911412538.2A patent/CN111128561A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104299797A (en) * | 2014-11-06 | 2015-01-21 | 中南大学 | Water-system asymmetric super-capacitor based on NiCo2S4 and NiCo2S4 composite material |
| CN105551812A (en) * | 2016-01-19 | 2016-05-04 | 南京理工大学 | NiCo2S4 supercapacitor material and preparation method therefor |
| CN106067383A (en) * | 2016-08-23 | 2016-11-02 | 中国科学院重庆绿色智能技术研究院 | A kind of pseudocapacitors positive pole based on cobalt sulfide nickel nucleocapsid three-dimensional multistage nanostructured and preparation method thereof |
| CN205900332U (en) * | 2016-08-23 | 2017-01-18 | 中国科学院重庆绿色智能技术研究院 | Fake capacitance ware is anodal based on three -dimensional multistage nanostructured of cobaltous sulfide nickel nucleocapsid |
| CN107492657A (en) * | 2017-07-12 | 2017-12-19 | 三峡大学 | A kind of preparation method of cobalt sulfide nickel both positive and negative polarity battery and its application on the recyclable battery of alkalescence |
| CN109950050A (en) * | 2019-04-17 | 2019-06-28 | 武汉工程大学 | A kind of preparation method based on carbonization melamine foamed plastic@Bi2O3 nanometer sheet electrode material for super capacitor |
| CN110265226A (en) * | 2019-07-12 | 2019-09-20 | 福州大学 | A kind of nickel sulfide/carbonization melamine foamed plastic combination electrode material and preparation method thereof |
| CN110233058A (en) * | 2019-07-15 | 2019-09-13 | 浙江工业大学 | A kind of self assembly hollow form NiCo2S4 material, preparation method and its application |
Non-Patent Citations (1)
| Title |
|---|
| ZHIHONG AI等: "Capacitance performance of nanostructured CoNi2S4 with different morphology grown on carbon cloth for supercapacitors", 《CHEMPLUSCHEM》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111540612A (en) * | 2020-05-09 | 2020-08-14 | 晋江瑞碧科技有限公司 | Preparation method of organic/inorganic composite super capacitor |
| CN112599361A (en) * | 2020-12-14 | 2021-04-02 | 湖南大学 | Wide-temperature-range high-performance electrochemical energy storage device based on bismuth-based electrode |
| CN112599361B (en) * | 2020-12-14 | 2023-06-23 | 湖南大学 | Bismuth-based electrode-based wide-temperature-zone high-performance electrochemical energy storage device |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101916857B (en) | Composite cathode material for lithium ion power and energy storage battery and preparation method thereof and battery | |
| CN102664103B (en) | Zinc cobaltate nanorod/foam nickel composite electrode, preparation method thereof and application thereof | |
| CN111199835B (en) | Preparation method of nickel cobalt selenium/nickel cobalt double hydroxide composite electrode material with hierarchical structure | |
| CN108054019B (en) | NiCo of laminated structure2S4@NixCo(1-x)(OH)2Preparation method and application of composite material | |
| CN108922790B (en) | Preparation method and application of composite material | |
| CN109616331B (en) | Core-shell type nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material and preparation method thereof | |
| CN109850866B (en) | Hierarchical porous carbon material for flexible supercapacitor and preparation method thereof | |
| CN109637825B (en) | Nickel sulfide nanosheet/carbon quantum dot composite material and preparation method and application thereof | |
| CN104377040A (en) | Electrode applied to electrochemical energy storage device and preparation method thereof | |
| CN110615487A (en) | CoNiO2Preparation method of nanoflower electrode material | |
| Wang et al. | Construction of flower-like ZnCo 2 S 4/ZnCo 2 O 4 arrays on Ni foam for high-performance asymmetric supercapacitors | |
| CN112018361A (en) | Carbon cloth loaded carbon coated cobalt selenide nanosheet battery cathode material and preparation thereof | |
| CN110844899A (en) | Carbon nano tube composite cobalt sulfide nano material and preparation method and application thereof | |
| CN106299344B (en) | A kind of sodium-ion battery nickel titanate negative electrode material and preparation method thereof | |
| CN112216520B (en) | Preparation method and application of composite electrode with MOF-derived Ni-Co-S nanoparticles growing on carbon cloth | |
| CN111128561A (en) | Flexible asymmetric solid-state supercapacitor with nanostructure and preparation method thereof | |
| CN110033955B (en) | Preparation method for constructing nickel-cobalt-ore binary composite material based on graphene | |
| CN109637824B (en) | CoFe for super capacitor2S4Nano-sheet/foamed nickel composite material and preparation method thereof | |
| CN105591107B (en) | A kind of ultra-thin stratiform V5S8And preparation method thereof with the application in lithium ion/sodium-ion battery | |
| CN112687875B (en) | Preparation method and application of nickel molybdate flexible film composite material | |
| CN112038106B (en) | Electrode material, preparation method thereof and supercapacitor electrode | |
| CN110415993B (en) | Preparation method and application of Mn-Co-S/Co-MOF nano material | |
| CN110993359B (en) | Flexible solid-state asymmetric supercapacitor device and preparation method and application thereof | |
| CN110120520B (en) | Self-supporting flower-shaped Co of conductive carrier3V2O8Lithium ion battery cathode material and preparation | |
| CN109378462B (en) | Three-dimensional Co for lithium ion battery3Sn2/SnO2Negative electrode material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200508 |