CN112409028A - CC-NiO-CuCoS composite material and preparation method and application thereof - Google Patents
CC-NiO-CuCoS composite material and preparation method and application thereof Download PDFInfo
- Publication number
- CN112409028A CN112409028A CN202011171824.7A CN202011171824A CN112409028A CN 112409028 A CN112409028 A CN 112409028A CN 202011171824 A CN202011171824 A CN 202011171824A CN 112409028 A CN112409028 A CN 112409028A
- Authority
- CN
- China
- Prior art keywords
- nio
- composite material
- cuco
- cucos
- drying
- 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.)
- Granted
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 137
- 238000002360 preparation method Methods 0.000 title abstract description 19
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 35
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002135 nanosheet Substances 0.000 claims abstract description 24
- 238000004140 cleaning Methods 0.000 claims abstract description 19
- 230000001351 cycling effect Effects 0.000 claims abstract description 16
- 239000002105 nanoparticle Substances 0.000 claims abstract description 16
- 239000007772 electrode material Substances 0.000 claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 14
- 239000003990 capacitor Substances 0.000 claims abstract description 11
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 claims abstract description 11
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004202 carbamide Substances 0.000 claims abstract description 10
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 claims abstract description 10
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000003213 activating effect Effects 0.000 claims abstract description 6
- 230000009286 beneficial effect Effects 0.000 claims abstract description 4
- 239000011248 coating agent Substances 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 230000000087 stabilizing effect Effects 0.000 claims abstract description 3
- 229910016507 CuCo Inorganic materials 0.000 claims description 37
- 239000000463 material Substances 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000000137 annealing Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 230000004913 activation Effects 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- 238000010335 hydrothermal treatment Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 239000003054 catalyst Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 16
- 229910052799 carbon Inorganic materials 0.000 description 16
- 239000013078 crystal Substances 0.000 description 16
- 239000004744 fabric Substances 0.000 description 11
- 238000011068 loading method Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000000840 electrochemical analysis Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 3
- 238000003487 electrochemical reaction Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- 238000003491 array Methods 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000002055 nanoplate Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- VMKYLARTXWTBPI-UHFFFAOYSA-N copper;dinitrate;hydrate Chemical compound O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O VMKYLARTXWTBPI-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000011263 electroactive material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000009432 framing Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
-
- 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
-
- 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)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Ceramic Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a CC-NiO-CuCoS composite material, which is prepared from CC, NiO and CuCo2S4Forming; the NiO nano-sheet is not stacked and the conductive substrate is beneficial to ultra-high-speed transportation of electrons; the microstructure of NiO is a nano-sheet structure, is loaded on the surface of the CC and is used for providing an additional pseudo-capacitor; CuCo2S4The microstructure of (a) is a nanoparticle structure, attached to CC andthe NiO nano sheet surface is used for stabilizing the sheet structure of NiO and coating the exposed CC of a part. The catalyst is prepared by two-step hydrothermal preparation by using CC, nickel nitrate hexahydrate, ammonium fluoride, urea, copper acetate monohydrate, cobalt acetate tetrahydrate and thiourea as starting raw materials. The preparation method comprises the following steps: 1) cleaning and activating CC; 2) preparing a CC-NiO composite material; 3) CC-NiO-CuCo2S4And (4) preparing the composite material. The specific capacitance is 840F g as the application of the electrode material of the super capacitor‑1(ii) a The cycling stability after 3000 cycles was 100%.
Description
Technical Field
The invention relates to a preparation technology of carbon cloth as a matrix material and metal oxide, in particular to a carbon-based Super Capacitor (SCs) composite material and a preparation method and application thereof.
Background
Supercapacitors (SCs) have attracted considerable attention for their superior power density, ultra-long cycle stability, and fast charge and discharge rates, and have become the power sources for portable electronic products and electric/hybrid vehicles. The electrode material is one of the key elements of the SCs, and plays an important role in improving the electrochemical performance of the SCs. In order to meet the increasing energy/power density requirements, great efforts are made to find advanced electrode materials.
The construction of self-supporting arrays on conductive substrates is an effective method to improve the electrochemical performance of transition metal oxides as electrode materials, which not only reduces the agglomeration of active species and provides more electroactive sites without the use of polymeric binders and conductive additives, but also constructs nanoscale arrays for electron transport and buffers structural stresses during electrochemical reactions. Especially in recent years, with the rapid development of flexible/wearable electronic devices and the increasing demand for flexible energy storage devices, flexible conductive substrates for direct growth of electroactive materials are receiving increasing attention. Carbon Cloth (CC) with high conductivity, good flexibility and excellent mechanical properties has become an ideal conductive substrate for supporting active materials and has been widely used in the field of flexible energy storage.
In the prior art, S.D. Dhas et al successfully coated NiO on CC by hydrothermal method as electrode material of super capacitor (Synthesis of NiO nanoparticles for supercapacitor application as an electrode material [ J]Vacuum, volume 181 of 2020.). However, the specific capacitance of the resulting material in a 1M KOH aqueous electrolyte was 132F g-1(ii) a After 500 cycles, the final capacity was 75% of the initial capacity. It is clear that the cycle performance obtained by this prior art is very low. According to the experimental procedures described in the literature, the inventor finds that the reason that the cycle performance of the material obtained by the technical scheme is low is that the NiO nano-sheets are hydrothermally prepared into powder and coated on the carbon cloth through the polyvinylidene fluoride binder, the powder prepared by the method is easy to stack among nano-layers, the adhesion between the powder and the carbon cloth is not high, the problem of falling of a load is caused, and the electrochemical stability of the NiO nano-sheet layer is seriously lost. However, when CC is used as a base material, it is effective to increase the specific capacitance of the composite material by supporting another material.
The problems of specific capacitance and cycle performance can be solved, the microstructure of the composite material can be controlled, and for example, in the prior art, the composite electrode material of NiO nano-sheets with the diameter of about 200nm and the thickness of about 25nm and controllable size and thickness is prepared on CC by a chemical precipitation method in Liu, QX and the like (Rsc Adv, 737 volume in 2017, page number: 23143-. Is realized at 1A g−1Specific capacitance of 600.3F g at the discharge current density of-1(ii) a At 2A g-1After 3000 cycles at current density of (c), the final capacity was 98.1% of the initial capacity. Although this technique improves the specific capacitance performance of the composite, the cycling performance still does not meet the application requirements of supercapacitors.
The performance of the super capacitor is improved by loading metal sulfide on the surface of the CC, such as the prior art Xie, T and the like (EUR J ORG CHEM, 43 years 2018, page numbers 4711-2S4And (3) microspheres. Is realized at 1A g-1Can provide 166.67 mAh g-1At 5A g-1After 3000 cycles at current density of (c), the final capacity was 91.25% of the initial capacity. This technique also suffers from a rapid decay in cycle performance.
Therefore, the morphology of the material is controlled by a reasonable preparation method, the CC material and the transition metal oxide composite electrode material are obtained, and the method is an effective way for improving the material performance.
Disclosure of Invention
The invention aims to provide a stable carbon-based composite material, and a preparation method and application thereof.
In order to improve the electrochemical performance and the electrochemical cycling stability of the carbon-based composite material, NiO nano sheets are loaded on a CC (carbon composite) substrate material, and CuCo is coated on the surfaces of the CC and the NiO nano sheets2S4The technical method of the nano-particles is used for preparing the CC-NiO-CuCoS composite material with stable structure.
Wherein, the load NiO has the following advantages: NiO itself belongs to a pseudo-capacitance electrode material; 2. the metal oxide has high theoretical specific capacitance, high chemical and thermal stability and easy use; 3, the NiO material has low cost.
By loading NiO on the carbon-based material, the electrochemical reaction active sites of the composite material can be increased, the ion exchange rate of the composite material in the electrochemical reaction process is accelerated, and an additional pseudo-capacitance is provided for the composite material, so that the purpose of improving the electrochemical performance of the composite material is achieved.
Coated with CuCo2S4Has the advantages that: excellent electrochemical performance, low cost and non-toxicity, and it has better electronic conductivity than copper or cobalt oxide alone, at least two orders of magnitude higher.
By coating CuCo on CC material2S4The specific surface area of the composite material can be effectively increased, and the lamellar structure collapses in the charge and discharge process, so that the aim of improving the electrochemical cycle stability of the composite material is fulfilled.
In conclusion, the CC load can provide NiO with additional pseudo-capacitance and coated CuCo2S4The two materials of the nano-particles can generate good synergistic effect while exerting own unique advantages, and the purpose of greatly improving the electrochemical performance and the cycling stability of the CC composite material with stable structure can be achieved at the same time.
In addition, the CC is introduced as a substrate material, so that on one hand, the loading material has the effect of less sheet accumulation, on the other hand, the contact area of the carbon-based composite material and the electrolyte is enlarged, and the diffusion of ions can be accelerated, thereby achieving the purpose of improving the overall super-capacitor performance and the electrochemical stability of the composite material.
In order to achieve the purpose of the invention, the invention adopts the technical scheme that:
the CC-NiO-CuCoS composite material is formed from CC, NiO and CuCo2S4Forming; the NiO nano-sheet is not stacked and the conductive substrate is beneficial to ultra-high-speed transportation of electrons; the microstructure of NiO is a nano-sheet structure, is loaded on the surface of the CC and is used for providing an additional pseudo-capacitor; CuCo2S4The microstructure of the composite material is a nanoparticle structure and is attached to the surfaces of the CC and the NiO nano-sheets, and the function of stabilizing the flaky structure of the NiO and coating the partially exposed CC is realized, so that the electrochemical performance of the material is prevented from being influenced by structural collapse in the test process.
The substrate material is prepared by a two-step hydrothermal method by taking CC, nickel nitrate hexahydrate, ammonium fluoride, urea, copper acetate monohydrate, cobalt acetate tetrahydrate and thiourea as starting raw materials.
The preparation method of the CC-NiO-CuCoS composite material comprises the following steps:
step 1) activating CC, namely ultrasonically cleaning CC in an ether solution and absolute ethyl alcohol deionized water respectively, activating the CC in concentrated nitric acid with a certain mass fraction under a certain condition, and then cleaning the CC with deionized water and absolute ethyl alcohol and drying the CC to obtain activated CC;
the mass fraction of the concentrated nitric acid solution in the step 1 is 69%; the activation condition of the step 1 is that the activation temperature is 80-90 ℃ and the activation time is 3-4 h; the cleaning condition in the step 1 is ultrasonic for 15-20 min; the drying condition of the step 1 is that the drying temperature is 60-100 ℃, and the drying time is 12-24 h.
Step 2) preparing a CC-NiO composite material, namely putting the activated CC obtained in the step 1, nickel nitrate hexahydrate, ammonium fluoride and urea into water according to the certain substance quantity ratio, carrying out hydrothermal reaction under certain conditions, cleaning and drying after the reaction is finished, and annealing under certain conditions to obtain the CC-NiO composite material;
in the step 2, the mass ratio of the nickel nitrate hexahydrate, the ammonium fluoride and the urea is 1:6: 12; the hydrothermal reaction condition of the step 2 is that the hydrothermal reaction temperature is 120 ℃, and the hydrothermal reaction time is 12 h; the cleaning conditions of the step 2 are the same as the cleaning conditions of the step 1; the drying condition of the step 2 is that the drying temperature is 60-100 ℃, and the drying time is 20-24 h; the annealing condition of the step 2 is that the annealing temperature is 350 ℃ and the annealing time is 2 h.
And 3) preparing the CC-NiO-CuCoS composite material, namely dissolving copper acetate monohydrate, cobalt acetate tetrahydrate and thiourea in glycol to prepare a mixed solution, stirring the mixed solution for a certain time, adding thiourea into the mixed solution, stirring the mixed solution for a certain time, adding the CC-NiO composite material obtained in the step 2 into the mixed solution after the mixing is finished, carrying out secondary hydrothermal treatment under a certain condition, washing the mixed solution by deionized water and absolute ethyl alcohol after the reaction is finished, and drying the washed solution to obtain the CC-NiO-CuCo composite material2S4A composite material.
In the step 3, the mass ratio of the copper acetate monohydrate to the cobalt acetate tetrahydrate to the thiourea is 1:2: 20; in the step 3, when the copper acetate monohydrate and the cobalt acetate tetrahydrate are dissolved in the ethylene glycol, the stirring time is 30-60min, and then the thiourea is added and stirred for 30-60 min; the conditions of the secondary hydrothermal in the step 3 are that the hydrothermal temperature is 180 ℃ and the hydrothermal time is 24 hours; the cleaning conditions of the step 3 are the same as the cleaning conditions of the step 1; the drying condition of the step 3 is that the drying temperature is 80 ℃ and the drying time is 12 h.
The application of the CC-NiO-CuCoS composite material as the electrode material of the super capacitor can realize the charging and discharging within the range of 0-0.4V and the discharging current density of 1A g-1At the time, the specific capacitance is 600-900F g-1。
Discharging in the range of 0-0.4V and at a discharge current density of 2A g-1While, circulating after 3000 cyclesThe stability was 100%.
The obtained CC-NiO-CuCoS composite material with stable structure is subjected to experimental detection, and the result is as follows:
the CC-NiO-CuCoS composite material with stable structure is tested by X-ray diffraction (XRD) and can be obtained from diffraction crystal faces corresponding to different diffraction peaks, and the composite material is prepared from C, NiO and CuCo2S4The three substances are formed;
the CC-NiO-CuCoS composite material with stable structure is tested by a scanning electron microscope, and the flaky NiO can be seen to be distributed on the CC fiber strip-shaped surface structure; CuCo2S4The nano particles are distributed on the NiO nano sheet and the CC, which shows that the CC-NiO-CuCoS composite material with stable structure is successfully prepared;
and (3) carrying out electrochemical test and electrochemical cycling stability test on the structurally stable CC-NiO-CuCoS composite material:
discharging in the range of 0-0.4V and at a discharge current density of 1A g-1The specific capacitance of the structurally stable CC-NiO-CuCoS composite material is 840F g-1；
At a discharge current density of 2A g-1In the process, the CC-NiO-CuCoS composite material supercapacitor electrode with a stable structure is charged and discharged for 3000 circles within the range of 0-0.4V, and the cycle stability is 100%.
Therefore, compared with the prior art, the CC-NiO-CuCoS composite material has the following advantages:
1. the invention adopts CC, nickel nitrate hexahydrate, ammonium fluoride, urea, copper nitrate monohydrate, cobalt acetate tetrahydrate and thiourea as initial raw materials, and the CC-NiO-CuCo with stable structure is prepared by two-step hydrothermal preparation2S4The composite material realizes the effect of improving the stability of the super capacitor, and the specific capacitance is 840F g-1；
2, modifying the CC by the NiO nano-sheet, increasing the specific surface area of the CC-NiO-CuCoS composite material, and providing an additional pseudo-capacitance for the base material so as to improve the integral specific capacitance of the composite material;
3. coated CuCo2S4The nano particles increase the specific surface area of the NiO nano sheetsThe interlayer spacing is reduced, the ion migration rate is accelerated, and the collapse of a lamellar structure of the material in the long-time charge and discharge process is prevented, so that the cycling stability of the material is improved;
4. supported NiO and coated CuCo2S4Not only play a corresponding role respectively, but also NiO and CuCo2S4The synergistic effect exists between the two components, so that the CC-NiO-CuCoS composite material obtains high specific capacitance performance and cycle stability;
5. fibrous CC is introduced as a substrate material, so that on one hand, the overall appearance of the material is effectively controlled, on the other hand, the contact area of the CC-NiO-CuCoS composite material and an electrolyte is enlarged, and the diffusion of ions is accelerated, thereby improving the overall super-capacitor performance of the composite material.
Therefore, the invention has wide application prospect in the field of super capacitor materials.
Description of the drawings:
FIG. 1 is an XRD of the CC-NiO composite prepared in step 2 of example 1;
FIG. 2 is a scanning electron micrograph of the CC-NiO composite material prepared in step 2 of example 1 with a ruler length of 2 μm;
FIG. 3 is a graph showing the charge and discharge curves of the structurally stable CC-NiO-CuCoS composite prepared in example 1 and the CC-NiO composite prepared in step 2 of example 1;
FIG. 4 is an XRD of the structurally stable CC-NiO-CuCoS composite prepared in example 1;
FIG. 5 is a scanning electron microscope image of the CC-NiO-CuCoS composite material with stable structure prepared in example 1 under the condition that the length of a ruler is 500 nm;
FIG. 6 is a graph showing the charge and discharge curves of the structurally stable CC-NiO-CuCoS composite prepared in example 1;
FIG. 7 is a cycle life curve for the structurally stable CC-NiO-CuCoS composite prepared in example 1;
FIG. 8 is a SEM of the post-cycle of the structurally stable CC-NiO-CuCoS composite prepared in example 1;
FIG. 9 is a CC-CuCo prepared in comparative example 12S4XRD of the composite material;
FIG. 10 is a view showing CC-CuCo prepared in comparative example 12S4Scanning electron microscope images of the composite material under the length of the ruler of 3 mu m;
FIG. 11 shows the structurally stable CC-NiO-CuCoS composite prepared in example 1 and CuCo prepared in comparative example 12S4A charge-discharge curve graph of the composite material;
FIG. 12 is a NiO-CuCo prepared in comparative example 22S4XRD of the composite material;
FIG. 13 shows NiO-CuCo prepared in comparative example 22S4Scanning electron microscope images of the composite material under the length of the ruler of 1 micron;
FIG. 14 shows the structurally stable CC-NiO-CuCoS composite prepared in example 1 and the NiO-CuCo composite prepared in comparative example 22S4And (3) a charge-discharge curve diagram of the composite material.
Detailed Description
The CC-NiO-CuCoS composite material is described in detail by the embodiment and the attached drawings in the specification, and the CC-NiO composite material and the CC-CuCo composite material are respectively provided by the step 2 of the embodiment 1 and the comparative examples 1 and 22S4Composite material, NiO-CuCo2S4The preparation method and the performance characterization of the composite material prove that the invention has CC, NiO and CuCo2S4The three components have synergistic effect. The examples are not intended to limit the invention.
Example 1
A preparation method of a CC-NiO-CuCoS composite material comprises the following steps:
step 1) activating CC, namely ultrasonically cleaning CC with the size of 2cm X2 cm in 40mL of diethyl ether solution with the mass fraction of 99%, 40mL of absolute ethyl alcohol and 40mL of deionized water for 15min, boiling the CC in 40mL of concentrated nitric acid with the mass fraction of 69% in water bath at 80-90 ℃ for 4 hours for activation, cleaning the CC with the deionized water and the absolute ethyl alcohol for three times after the water bath is finished, and drying the CC at 60 ℃ for 12 hours to obtain the activated CC;
and 2) preparing the CC-NiO composite material, namely putting the activated CC obtained in the step 1, nickel nitrate hexahydrate, ammonium fluoride and urea into 60mL of water according to the mass ratio of the nickel nitrate hexahydrate, the ammonium fluoride and the urea being 1:6:12, carrying out hydrothermal reaction in a high-pressure kettle at the reaction temperature of 120 ℃ for 12h, cooling to room temperature after the reaction is finished, drying at the temperature of 60 ℃ for 20h, and finally annealing at the temperature of 350 ℃ for 2h to obtain the CC-NiO composite material, namely CC-NiO for short.
The method for calculating the load on the carbon cloth comprises the following steps: 1. testing the mass and the area of the carbon cloth before loading; 2. testing the mass of the loaded carbon cloth, and calculating to obtain the mass difference; 3. dividing the mass difference by the area of the carbon cloth to obtain the loading capacity of unit area; 4. under the same conditions, the average unit area load capacity is obtained by a plurality of sample tests.
The average load capacity of the NiO nano-sheets on the carbon cloth is 0.5mg cm through experiments and calculation-2。
In order to compare with the CC-NiO-CuCoS composite material and prove the influence of NiO on the performance of the composite material, XRD, SEM and electrochemical tests are carried out on the CC-NiO composite material obtained in the step 2.
In order to prove that the CC-NiO composite material obtained in the step 2 successfully prepares NiO, an XRD test is carried out. The test results are shown in fig. 1, in which the corresponding (002) crystal plane at 2 θ =26.110 ° belongs to the diffraction crystal plane of CC; the corresponding (200) crystal plane at 2 θ =43.472 ° belongs to the diffraction crystal plane of NiO, so it can be demonstrated that the composition of the CC-NiO composite contains CC and NiO, i.e., NiO was successfully prepared on CC through step 2.
In order to prove the micro morphology of NiO in the CC-NiO composite material obtained in the step 2, SEM test is carried out. The test result is shown in fig. 2, NiO is a nano-sheet structure and is uniformly distributed on the surface of the CC, so that it can be proved that NiO nano-sheets are successfully loaded on the CC.
In order to prove the electrochemical performance of the CC-NiO composite material obtained in the step 2, an electrochemical test is carried out. The electrochemical test of all the materials of the invention adopts the following method: the prepared composite material is used as a working electrode, and a calomel electrode and a platinum electrode are respectively used as a reference electrode and a counter electrode, and are immersed in 3M KOH solution to test the specific capacitance of the composite material under a three-electrode system. The test results are shown in FIG. 3, and are in the range of 0-0.4VDischarging at a discharge current density of 1A g-1The specific capacitance of the CC-NiO composite material is 13.625F g-1In the comparative literature, the specific capacitance when NiO nano-plate is loaded on CC by chemical precipitation method is 600.3F g-1In the present study, the specific capacitance of CC-NiO was small, and it was analyzed that the specific capacitance was small due to the difference in the preparation method and experimental conditions.
Step 3) CC-NiO-CuCo2S4Preparing a composite material, dissolving copper acetate monohydrate, cobalt acetate tetrahydrate and thiourea in ethylene glycol according to the mass ratio of 1:2:20 to prepare a mixed solution, stirring for 60min, adding thiourea, stirring for 30min, adding the CC-NiO composite material obtained in the step 2 into the mixed solution after mixing, carrying out secondary hydrothermal treatment at the reaction temperature of 180 ℃ for 24h, respectively washing with deionized water and absolute ethyl alcohol for three times after the reaction is finished, and carrying out vacuum drying at the temperature of 80 ℃ for 12h to obtain the CC-NiO-CuCo composite material2S4Composite material, CC-NiO-CuCo for short2S4。
NiO-CuCo on the carbon cloth is obtained through experiments and calculation2S4Average loading of 1.25mg cm-2。
In order to prove that the CC-NiO-CuCoS composite material obtained in the step 3 successfully prepares CuCo2S4XRD test was performed. The test results are shown in fig. 4, in which the corresponding (002) crystal plane at 2 θ =26.110 ° belongs to the diffraction crystal plane of CC; the corresponding (200) crystal plane at 2 θ =43.472 ° belongs to the diffractive crystal plane of NiO; the (111), (311), (400), (511) and (440) crystal planes at 2 θ =16.190 °, 31.249 °, 37.933 °, 49.931 °, and 54.793 °, respectively, belong to CuCo2S4Thus, it can be confirmed that CC-NiO-CuCo2S4The composite material comprises CC, NiO and CuCo2S4Namely, the CuCo is successfully prepared on the CC-NiO composite material through the step 32S4。
In order to prove that CuCo in the CC-NiO-CuCoS composite material obtained in the step 32S4The microscopic properties of (a) were subjected to SEM test. Test knotAs shown in FIG. 5, CuCo2S4Is in a nano-particle structure and is distributed on the surfaces of the CC and the NiO nano-sheets, so that the CC-NiO composite material is successfully coated with CuCo on the surface2S4And (3) nanoparticles.
In order to prove the electrochemical performance of the CC-NiO-CuCoS composite material obtained in the step 3, an electrochemical test is carried out. The test results are shown in FIG. 6, where the discharge current density is 1A g when the discharge is charged in the range of 0-0.4V-1The specific capacitance of the CC-NiO-CuCoS composite material is 840F g-1。
In order to prove the structural stability and the cycling stability of the CC-NiO-CuCoS composite material obtained in the step 3, an electrochemical cycling stability test is carried out on the CC-NiO-CuCoS composite material, and an SEM test is carried out on the electrode material after cycling.
The electrochemical cycling stability test result is shown in FIG. 7, and the CC-NiO-CuCoS composite material has a discharge current density of 2A g in a voltage range of 0-0.4V-1When the material is charged and discharged for 3000 circles, the cycling stability is 100 percent;
the SEM test of the electrode material after cycling showed no significant change in the structure of the material after cycling and before cycling, as shown in fig. 8.
The experiment proves that the CC-NiO-CuCoS composite material has good structural stability and cycling stability.
To prove NiO and CuCo2S4The respective roles played in the composite materials were to provide comparative example 1, CuCo alone loaded on CC2S4Nanoparticles, i.e. CC-CuCo2S4The preparation method and test results of the composite material of (1).
Comparative example 1
Preparation method of CC-CuCoS composite material, steps not specifically described and example 1 CC-NiO-CuCo2S4The preparation method of the composite material is the same, except that: only the step 1 and the step 3 are carried out, the step 2 is omitted, the CC-NiO composite material is prepared, namely, the process of loading NiO nano sheets is not carried out, and the obtained material is named as CC-CuCo2S4Composite materials, CC-CuCo for short2S4。
CuCo on carbon cloth is obtained by experiment and calculation2S4Average loading of 0.55mg cm-2。
To demonstrate the CC-CuCo obtained in comparative example 12S4The composite material successfully prepares CuCo2S4XRD test was performed. The test results are shown in fig. 9, in which the corresponding (002) crystal plane at 2 θ =26.110 ° belongs to the diffraction crystal plane of CC; the (311), (400), (551) and (440) crystal planes respectively corresponding to 2 θ =31.249 °, 2 θ =37.933 °, 2 θ =49.931 ° and 2 θ =54.793 ° belong to CuCo2S4So that CC-CuCo can be demonstrated2S4The composite material comprises CC and CuCo2S4I.e. the successful preparation of CuCo on CC by comparative example 12S4。
To demonstrate the CC-CuCo obtained in comparative example 12S4CuCo in composite material2S4The microscopic morphology of (a) was subjected to SEM test. The test results are shown in FIG. 10, CuCo2S4Is of a nano-particle structure and is uniformly distributed on the surface of the CC, so that the CC can be proved to be successfully coated with CuCo2S4And (3) nanoparticles.
To demonstrate the CC-CuCo obtained in comparative example 12S4The electrochemical performance of the composite material is tested electrochemically. The test results are shown in FIG. 11, where the discharge current density is 1A g when the discharge is charged in the range of 0-0.4V-1When it is CC-CuCo2S4The specific capacitance of the composite material is 315.25F g-1。
To demonstrate the role of the CC substrate in the composite, comparative example 2 was provided, in which CuCo was supported on NiO nanosheets2S4Nanoparticles, i.e. NiO-CuCo2S4Preparation method and test result of composite material.
Comparative example 2
Preparation method of NiO-CuCoS composite material, steps not specifically described and example 1 CC-NiO-CuCo2S4The composite material is prepared by the same method except that: only the step 2 and the step 3 are carried out, the step 1 CC activation is omitted, namely the NiO nano sheet is directly prepared and CuCo is loaded without adopting the CC as a substrate2S4Nano particles, and the obtained material is named NiO-CuCo2S4Composite materials, NiO-CuCo for short2S4。
To demonstrate that the NiO-CuCo obtained in comparative example 22S4The composite material successfully prepares NiO and CuCo2S4XRD test was performed. The test results are shown in fig. 12, in which the corresponding (200) crystal plane at 2 θ =43.253 ° belongs to the diffractive crystal plane of NiO; the (111), (311), (400), (551) and (440) crystal planes respectively corresponding to 2 θ =16.19 °, 2 θ =31.249 °, 2 θ =37.933 °, 2 θ =49.931 ° and 2 θ =54.793 ° belong to CuCo2S4So that NiO-CuCo can be confirmed2S4The composite material comprises NiO and CuCo2S4Namely, CuCo was successfully prepared on NiO by comparative example 12S4。
To demonstrate that the NiO-CuCo obtained in comparative example 22S4NiO and CuCo in composite material2S4The microscopic morphology of (a) was subjected to SEM test. The test result is shown in FIG. 13, the NiO nano-plate has obvious stacking structure, CuCo2S4The nanoparticle structure is not evident.
To demonstrate that the NiO-CuCo obtained in comparative example 22S4The electrochemical performance of the composite material is tested electrochemically. The test results are shown in FIG. 14, where the discharge current density was 1A g when the discharge was charged in the range of 0-0.4V-1When the specific capacitance is 164F g-1。
According to the results obtained from the foregoing experimental tests,
1. the specific capacitance of the CC-NiO composite obtained in step 2 and the CC-NiO-CuCoS composite obtained in step 3 in example 1 can be seen as follows: is coated with CuCo2S4Then, the specific capacitance is from 13.625F g-1Is lifted to 840F g-1The cycle performance is improved from 75% in the literature to 100% in the study; it can be further demonstrated that CuCo is added2S4Rear endNiO and CuCo2S4The method has a synergistic effect, and finally, ultrahigh specific capacitance performance and cycle stability are obtained.
2. Comparative example 1 CC-CuCo2S4As can be seen from the specific capacitance of the CC-NiO-CuCoS composite material obtained in example 1, the NiO nano-sheets are constructed to support CuCo2S4Specific capacitance from 315.25F g after internal framing of the nanoparticles-1Is lifted to 840F g-1It turns out that these nanoplatelets are interconnected with each other and form a network with spaced voids, which results in a large surface area and an effective buffering of volume changes.
3. Comparative example 2 NiO-CuCo2S4The specific capacitance of the composite material with the CC-NiO-CuCoS obtained in the example 1 is from 164F g-1Is lifted to 840F g-1. The test result shows that: CC as base material pair CC-NiO-CuCo2S4The overall appearance of the composite material can play a decisive role, and the CC is taken as a conductive substrate, thereby being beneficial to the ultra-high speed transportation of electrons and ensuring that the CC-NiO-CuCo2S4The contact area of the composite material and the electrolyte is increased, so that the diffusion of ions is accelerated.
Claims (8)
1. A CC-NiO-CuCoS composite material is characterized in that: consisting of CC, NiO and CuCo2S4Forming; the NiO nano-sheet is not stacked and the conductive substrate is beneficial to ultra-high-speed transportation of electrons; the microstructure of NiO is a nano-sheet structure, is loaded on the surface of the CC and is used for providing an additional pseudo-capacitor; CuCo2S4The microstructure of (2) is a nanoparticle structure, is attached to the surfaces of the CC and the NiO nano-sheets and has the functions of stabilizing the flaky structure of NiO and coating the partially exposed CC.
2. The CC-NiO-CuCoS composite of claim 1, wherein: the substrate material is prepared by a two-step hydrothermal method by taking CC, nickel nitrate hexahydrate, ammonium fluoride, urea, copper acetate monohydrate, cobalt acetate tetrahydrate and thiourea as starting raw materials.
3. The method for preparing the CC-NiO-CuCoS composite material according to claim 1, characterized by comprising the following steps:
step 1) activating CC, namely ultrasonically cleaning CC in an ether solution and absolute ethyl alcohol deionized water respectively, activating the CC in concentrated nitric acid with a certain mass fraction under a certain condition, and then cleaning the CC with deionized water and absolute ethyl alcohol and drying the CC to obtain activated CC;
step 2) preparing a CC-NiO composite material, namely putting the activated CC obtained in the step 1, nickel nitrate hexahydrate, ammonium fluoride and urea into water according to the certain substance quantity ratio, carrying out hydrothermal reaction under certain conditions, cleaning and drying after the reaction is finished, and annealing under certain conditions to obtain the CC-NiO composite material;
step 3) CC-NiO-CuCo2S4Preparing a composite material, namely dissolving copper acetate monohydrate, cobalt acetate tetrahydrate and thiourea in glycol to obtain a mixed solution, stirring the mixed solution for a certain time, adding thiourea into the mixed solution, stirring the mixed solution for a certain time, adding the thiourea into the mixed solution, adding the CC-NiO composite material obtained in the step (2) into the mixed solution after the mixing is finished, carrying out secondary hydrothermal treatment under a certain condition, washing the mixed solution by deionized water and absolute ethyl alcohol after the reaction is finished, and drying the washed solution to obtain the CC-NiO-CuCo composite material2S4A composite material.
4. The production method according to claim 3, characterized in that: the mass fraction of the concentrated nitric acid solution in the step 1 is 69%; the activation condition of the step 1 is that the activation temperature is 80-90 ℃ and the activation time is 3-4 h; the cleaning condition in the step 1 is ultrasonic for 15-20 min; the drying condition of the step 1 is that the drying temperature is 60-100 ℃, and the drying time is 12-24 h.
5. The production method according to claim 3, characterized in that: in the step 2, the mass ratio of the nickel nitrate hexahydrate, the ammonium fluoride and the urea is 1:6: 12; the hydrothermal reaction condition of the step 2 is that the hydrothermal reaction temperature is 120 ℃, and the hydrothermal reaction time is 12 h; the cleaning conditions of the step 2 are the same as the cleaning conditions of the step 1; the drying condition of the step 2 is that the drying temperature is 60-100 ℃, and the drying time is 20-24 h; the annealing condition of the step 2 is that the annealing temperature is 350 ℃ and the annealing time is 2 h.
6. The production method according to claim 3, characterized in that: in the step 3, the mass ratio of the copper acetate monohydrate to the cobalt acetate tetrahydrate to the thiourea is 1:2: 20; in the step 3, when the copper acetate monohydrate and the cobalt acetate tetrahydrate are dissolved in the ethylene glycol, the stirring time is 30-60min, and then the thiourea is added and stirred for 30-60 min; the conditions of the secondary hydrothermal in the step 3 are that the hydrothermal temperature is 180 ℃ and the hydrothermal time is 24 hours; the cleaning conditions of the step 3 are the same as the cleaning conditions of the step 1; the drying condition of the step 3 is that the drying temperature is 80 ℃ and the drying time is 12 h.
7. The use of the CC-NiO-CuCoS composite material as claimed in claim 1 as a supercapacitor electrode material, wherein: discharging in the range of 0-0.4V and at a discharge current density of 1A g-1At the time, the specific capacitance is 600-900F g-1。
8. The use of the CC-NiO-CuCoS composite material as claimed in claim 1 as a supercapacitor electrode material, wherein: discharging in the range of 0-0.4V and at a discharge current density of 2A g-1The cycling stability after 3000 cycles was 100%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011171824.7A CN112409028B (en) | 2020-10-28 | 2020-10-28 | CC-NiO-CuCoS composite material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011171824.7A CN112409028B (en) | 2020-10-28 | 2020-10-28 | CC-NiO-CuCoS composite material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112409028A true CN112409028A (en) | 2021-02-26 |
| CN112409028B CN112409028B (en) | 2022-10-11 |
Family
ID=74841744
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011171824.7A Active CN112409028B (en) | 2020-10-28 | 2020-10-28 | CC-NiO-CuCoS composite material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112409028B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115440503A (en) * | 2022-08-22 | 2022-12-06 | 桂林电子科技大学 | Cobalt copper sulfide nanosheet and preparation method thereof |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009155417A1 (en) * | 2008-06-18 | 2009-12-23 | Board Of Trustees Of The University Of Arkansas | Microwave-assisted synthesis of carbon and carbon-metal composites from lignin, tannin and asphalt derivatives and applications of same |
| KR20150004640A (en) * | 2013-07-03 | 2015-01-13 | 주식회사 포스코 | Wire rod having excellent cold forging characteristics and method for manufacturing the same |
| CN107154486A (en) * | 2017-05-17 | 2017-09-12 | 厦门大学 | A kind of cupric multi-element metal sulfide is the sodium-ion battery of negative material |
| WO2018036001A1 (en) * | 2016-08-24 | 2018-03-01 | 福州大学 | Waxberry-shaped nickel cobalt oxide nanomaterial and preparation method therefor |
| CN108365210A (en) * | 2018-04-12 | 2018-08-03 | 桂林电子科技大学 | A kind of activated carbon carbon-sulfur materials and its preparation method and application |
| CN108455592A (en) * | 2018-04-28 | 2018-08-28 | 福州大学 | A kind of preparation method of N doping porous charcoal/carbon mano-tube composite of inierpeneirating network structure |
| CN108530109A (en) * | 2018-03-23 | 2018-09-14 | 西北工业大学 | A kind of 1500 ~ 1700 DEG C of antioxidant coatings of surface of carbon/carbon composite and preparation method |
| CN109216707A (en) * | 2018-09-12 | 2019-01-15 | 成都理工大学 | CuCo2S4@Ni composite material and preparation method and application |
| WO2019019412A1 (en) * | 2017-07-26 | 2019-01-31 | 中能中科（天津）新能源科技有限公司 | Carbon nanoparticle-porous framework composite material, lithium metal complex of carbon nanoparticle-porous framework composite material, preparation methods therefor, and applications thereof |
| CN109678133A (en) * | 2019-01-14 | 2019-04-26 | 桂林电子科技大学 | A kind of C-base composte material and its preparation method and application of nickel oxide doping |
| CN110407605A (en) * | 2019-08-07 | 2019-11-05 | 哈尔滨师范大学 | A kind of preparation process of porous super capacitor material |
| CN111777069A (en) * | 2020-07-20 | 2020-10-16 | 桂林电子科技大学 | MXene composite material with stable structure and preparation method and application thereof |
| CN111785526A (en) * | 2020-06-10 | 2020-10-16 | 桂林电子科技大学 | Polypyrrole-coated Ni-Co-S nanoneedle array composite material and preparation method and application thereof |
| CN111825127A (en) * | 2020-07-07 | 2020-10-27 | 江苏大学 | Preparation method and application of metal nickel-based nano material |
-
2020
- 2020-10-28 CN CN202011171824.7A patent/CN112409028B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009155417A1 (en) * | 2008-06-18 | 2009-12-23 | Board Of Trustees Of The University Of Arkansas | Microwave-assisted synthesis of carbon and carbon-metal composites from lignin, tannin and asphalt derivatives and applications of same |
| KR20150004640A (en) * | 2013-07-03 | 2015-01-13 | 주식회사 포스코 | Wire rod having excellent cold forging characteristics and method for manufacturing the same |
| WO2018036001A1 (en) * | 2016-08-24 | 2018-03-01 | 福州大学 | Waxberry-shaped nickel cobalt oxide nanomaterial and preparation method therefor |
| CN107154486A (en) * | 2017-05-17 | 2017-09-12 | 厦门大学 | A kind of cupric multi-element metal sulfide is the sodium-ion battery of negative material |
| WO2019019412A1 (en) * | 2017-07-26 | 2019-01-31 | 中能中科（天津）新能源科技有限公司 | Carbon nanoparticle-porous framework composite material, lithium metal complex of carbon nanoparticle-porous framework composite material, preparation methods therefor, and applications thereof |
| CN108530109A (en) * | 2018-03-23 | 2018-09-14 | 西北工业大学 | A kind of 1500 ~ 1700 DEG C of antioxidant coatings of surface of carbon/carbon composite and preparation method |
| CN108365210A (en) * | 2018-04-12 | 2018-08-03 | 桂林电子科技大学 | A kind of activated carbon carbon-sulfur materials and its preparation method and application |
| CN108455592A (en) * | 2018-04-28 | 2018-08-28 | 福州大学 | A kind of preparation method of N doping porous charcoal/carbon mano-tube composite of inierpeneirating network structure |
| CN109216707A (en) * | 2018-09-12 | 2019-01-15 | 成都理工大学 | CuCo2S4@Ni composite material and preparation method and application |
| CN109678133A (en) * | 2019-01-14 | 2019-04-26 | 桂林电子科技大学 | A kind of C-base composte material and its preparation method and application of nickel oxide doping |
| CN110407605A (en) * | 2019-08-07 | 2019-11-05 | 哈尔滨师范大学 | A kind of preparation process of porous super capacitor material |
| CN111785526A (en) * | 2020-06-10 | 2020-10-16 | 桂林电子科技大学 | Polypyrrole-coated Ni-Co-S nanoneedle array composite material and preparation method and application thereof |
| CN111825127A (en) * | 2020-07-07 | 2020-10-27 | 江苏大学 | Preparation method and application of metal nickel-based nano material |
| CN111777069A (en) * | 2020-07-20 | 2020-10-16 | 桂林电子科技大学 | MXene composite material with stable structure and preparation method and application thereof |
Non-Patent Citations (6)
| Title |
|---|
| JAE-HUN KIM等: ""Ni–NiO core–shell inverse opal electrodes for supercapacitors"", 《CHEM. COMMUN.》 * |
| SHUNXIANG WANG等: ""Growth of yolk-shell CuCo2S4 on NiO nanosheets for high-performance flexible supercapacitors"", 《CERAMICS INTERNATIONAL》 * |
| YUQIAO WANG等: ""Oriented CuCo2S4 nanograss arrays/Ni foam as an electrode for a high-performance all-solid-state supercapacitor"", 《NANOTECHNOLOGY》 * |
| 毛小琦: ""过渡金属Co-X(X=Mo, Cu)硫化物和氧化物的协同耦合及其超级电容性能研究"", 《中国优秀硕士学位论文全文数据库 (工程科技Ⅰ辑)》 * |
| 潘利敏等: "水热共沉积C/C复合材料的Ni催化石墨化及性能研究", 《陕西科技大学学报》 * |
| 牟从普等: ""碳包覆NiO@Ni纳米复合物微波吸收性能研究"", 《燕山大学学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115440503A (en) * | 2022-08-22 | 2022-12-06 | 桂林电子科技大学 | Cobalt copper sulfide nanosheet and preparation method thereof |
| CN115440503B (en) * | 2022-08-22 | 2023-05-12 | 桂林电子科技大学 | Cobalt copper sulfide nanosheets and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112409028B (en) | 2022-10-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Dai et al. | MOF-derived Co3O4 nanosheets rich in oxygen vacancies for efficient all-solid-state symmetric supercapacitors | |
| Pan et al. | Interlayer spacing regulation of NiCo-LDH nanosheets with ultrahigh specific capacity for battery-type supercapacitors | |
| Cai et al. | Three-dimensional Co3O4@ NiMoO4 core/shell nanowire arrays on Ni foam for electrochemical energy storage | |
| Abouali et al. | Electrospun carbon nanofibers with in situ encapsulated Co3O4 nanoparticles as electrodes for high-performance supercapacitors | |
| Shen et al. | Synthesis of Nb2C MXene-based 2D layered structure electrode material for high-performance battery-type supercapacitors | |
| Qiu et al. | MXenes nanocomposites for energy storage and conversion | |
| Yao et al. | Nanostructured transition metal vanadates as electrodes for pseudo-supercapacitors: a review | |
| Shi et al. | 3D mesoporous hemp-activated carbon/Ni3S2 in preparation of a binder-free Ni foam for a high performance all-solid-state asymmetric supercapacitor | |
| Li et al. | NiCo2S4 combined 3D hierarchical porous carbon derived from lignin for high-performance supercapacitors | |
| CN111777069B (en) | MXene composite material with stable structure and preparation method and application thereof | |
| Pu et al. | Hydrothermal synthesis of N-doped graphene/Fe2O3 nanocomposite for supercapacitors | |
| CN109411238B (en) | Layered double hydroxide composite electrode material and preparation method and application thereof | |
| Wang et al. | Facile preparation of Ni–Mn layered double hydroxide nanosheets/carbon for supercapacitor | |
| Fan et al. | Hollow carbon microspheres/MnO 2 nanosheets composites: hydrothermal synthesis and electrochemical behaviors | |
| Yang et al. | Hierarchical NiCo LDH–rGO/Ni foam composite as electrode material for high-performance supercapacitors | |
| CN113690429A (en) | Carbon-coated graphene/metal oxide composite material and preparation method thereof | |
| Han et al. | Temperature-induced hierarchical Tremella-like and Pinecone-like NiO microspheres for high-performance supercapacitor electrode materials | |
| He et al. | NiGa2O4 nanosheets in a microflower architecture as anode materials for li-ion capacitors | |
| CN113539699A (en) | ACNFs @ Ni-Mn-P nanosheet array composite material and preparation method and application thereof | |
| Zhang et al. | 3D Hierarchical urchin-like Ni0. 3Co0. 6Cu0. 1 (CO3) 0.5 (OH) microspheres for supercapacitors with high specific capacitance | |
| Li et al. | Unique 3D bilayer nanostructure basic cobalt carbonate@ NiCo–layered double hydroxide nanosheets on carbon cloth for supercapacitor electrode material | |
| CN112409028B (en) | CC-NiO-CuCoS composite material and preparation method and application thereof | |
| Chen et al. | Graphitic carbon nitride nanomaterials for high‐performance supercapacitors | |
| KR20130047885A (en) | Method for fabrication of charge storage in multi-walled carbon nanotube-niooh nano composites | |
| Zhao et al. | Co-electrodeposition of MnO 2/graphene oxide coating on carbon paper from phosphate buffer and the capacitive properties |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |