CN113782346B - Poly 3, 4-ethylenedioxythiophene/nickel cobaltate/carbon cloth flexible electrode - Google Patents
Poly 3, 4-ethylenedioxythiophene/nickel cobaltate/carbon cloth flexible electrode Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 60
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 54
- 239000004744 fabric Substances 0.000 title claims abstract description 53
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 title claims abstract description 47
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 230000020477 pH reduction Effects 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 5
- 239000000178 monomer Substances 0.000 claims abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 4
- 238000011065 in-situ storage Methods 0.000 claims abstract description 4
- 239000007800 oxidant agent Substances 0.000 claims abstract description 4
- 230000003647 oxidation Effects 0.000 claims abstract description 4
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 4
- 230000001590 oxidative effect Effects 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 33
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 238000003760 magnetic stirring Methods 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 239000006185 dispersion Substances 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 17
- 238000009210 therapy by ultrasound Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 15
- 238000001291 vacuum drying Methods 0.000 claims description 14
- 239000002131 composite material Substances 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- 238000000137 annealing Methods 0.000 claims description 6
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 6
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 6
- 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 description 6
- 239000007772 electrode material Substances 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 2
- 238000001035 drying Methods 0.000 claims 1
- 238000011068 loading method Methods 0.000 claims 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 abstract description 11
- 230000008901 benefit Effects 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 13
- 238000001878 scanning electron micrograph Methods 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000010277 constant-current charging Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000006056 electrooxidation reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000123 polythiophene Polymers 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical class [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- -1 ethylenedioxy Chemical group 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical class [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
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Abstract
The invention discloses a poly (3, 4-ethylenedioxythiophene)/nickel cobaltate/carbon cloth flexible electrode and a preparation method thereof, and belongs to the technical field of preparation of electrodes for supercapacitors. The flexible electrode is prepared by taking carbon cloth with the surface subjected to acidification treatment as a carrier, nickel cobaltate prepared by a hydrothermal method as a supporting material, 3, 4-ethylenedioxythiophene as a monomer and ammonium persulfate as an oxidant through an in-situ chemical oxidation method. The flexible electrode prepared by the invention has high specific capacitance and excellent electrochemical cycle stability, is mainly used for manufacturing flexible supercapacitors, and has remarkable economic value and social benefit.
Description
Technical Field
The invention belongs to the technical field of preparation of electrodes for a supercapacitor, and particularly relates to a poly (3, 4-ethylenedioxythiophene)/nickel cobaltate/carbon cloth flexible electrode and a preparation method thereof.
Background
With the development of scientific technology and the improvement of living standard of people, portable electronic devices, such as flexible advertisement screens, smart bracelets, smart folding notebooks, smart folding mobile phones and the like, are developing towards multi-functionalization, light weight, thinness and flexibility. Developing flexible supercapacitors with high power density and large specific capacity is an important task in the development of flexible portable electronic devices. The flexible electrode is an important component of the flexible supercapacitor, and the performance of the flexible electrode directly influences the performance of the supercapacitor. Therefore, the research and development of the electrode for the flexible supercapacitor with large specific capacitance and good cycling stability have important research significance and wide application value. The conductive polymer has the advantages of good conductivity, higher porosity, high energy density, high power density, low resistance, low cost, environmental friendliness and the like, and has great application potential in the aspect of flexible electrodes. The poly 3, 4-ethylenedioxythiophene is an important conductive polymer, has the characteristics of high conductivity, excellent redox activity, good environmental stability, high transparency, safety and no toxicity, and has become a flexible electrode material with wide application prospect. However, the commercial application of poly 3, 4-ethylenedioxythiophene in flexible electrodes is limited due to the low theoretical specific capacitance of poly 3, 4-ethylenedioxythiophene, poor solubility of monomers in water, easy agglomeration during polymerization, and the like.
Disclosure of Invention
The invention provides a poly (3, 4-ethylenedioxythiophene)/nickel cobaltate/carbon cloth flexible electrode and a preparation method thereof, aiming at the problems of easy agglomeration, low specific capacitance and the like of the existing poly (3, 4-ethylenedioxythiophene) when used as a flexible supercapacitor electrode material. The flexible electrode prepared by the invention has high specific capacitance and excellent electrochemical cycle stability, is mainly used for manufacturing flexible supercapacitors, and has remarkable economic value and social benefit.
In order to achieve the purpose, the invention adopts the following technical scheme:
a poly (3, 4-ethylenedioxythiophene)/nickel cobaltate/carbon cloth flexible electrode is prepared by taking carbon cloth with acidized surface as a carrier, taking nickel cobaltate prepared by a hydrothermal method as a supporting material, taking 3, 4-ethylenedioxythiophene as a monomer and ammonium persulfate as an oxidant through an in-situ chemical oxidation method; the method specifically comprises the following steps:
(1) at room temperature, 0.5-2 g of cobalt nitrate hexahydrate and 0.2-0.4 g of nickel nitrate hexahydrate are added into 50-100 mL of organic solution, magnetic stirring is carried out for 10-30 min, 1-2 g of hexamethylenetetramine is added, magnetic stirring is continued for 10-20 min, the temperature is raised to 140-180 ℃, magnetic stirring is carried out for 8-16 h, natural cooling is carried out to the room temperature, centrifugation, washing, vacuum drying at 60 ℃ is carried out for 24 h, annealing treatment is carried out for 2-4 h, and nickel cobaltate is prepared.
(2) Adding 40-80 mg of ammonium persulfate into 10-30 mL of deionized water, magnetically stirring at room temperature for 5-10 min, and dropwise adding 0.5-2 mL of hydrochloric acid solution at a speed of 10-20 drops/min under the magnetic stirring to prepare a mixed solution A; adding 20-80 mg of nickel cobaltate into 10-50 mL of deionized water, magnetically stirring at room temperature for 10-30 min, performing ultrasonic treatment for 10-30 min, adding 50-100 mg of 3, 4-ethylenedioxythiophene, magnetically stirring for 10-30 min, and performing ultrasonic treatment for 30-60 min to prepare a mixed dispersion liquid B; and vertically placing the carbon cloth with the surface subjected to acidification treatment in a dispersion liquid B, dropwise adding the solution A into the dispersion liquid B at the speed of 10-30 drops/min, after dropwise adding, magnetically stirring for 12-24 hours, carrying out suction filtration, washing and vacuum drying at 60 ℃ for 24 hours, and preparing the poly 3, 4-ethylenedioxythiophene/nickel cobaltate/carbon cloth flexible electrode.
The organic solution in the step (1) is any one of methanol or ethanol.
The concentration of the hydrochloric acid solution in the step (2) is 4 mol/L, and the solvent is water.
The carbon cloth with the surface subjected to the acidizing treatment in the step (2) is cut into a strip shape of 1 cm multiplied by 2 cm, the strip-shaped carbon cloth is subjected to ultrasonic treatment for 30 min in 5 mol/L nitric acid solution at room temperature, and the carbon cloth is washed by deionized water and dried for later use.
Compared with the prior art, the invention has the following advantages:
(1) the carbon cloth is a flexible material with light weight, high strength and high conductivity, the carbon cloth is used as a carrier, and the nickel cobaltate and the poly 3, 4-dioxythiophene are loaded on the carbon cloth, so that a flexible electrode which is good in flexibility and easy to fold can be prepared.
(2) Nickel cobaltate is a bimetallic oxide, has more active sites than single nickel oxides and cobalt oxides, and can store more charges through a rapid redox reaction, and thus, the nickel cobaltate can impart high specific capacitance to the flexible electrode.
(3) The poly 3, 4-ethylenedioxythiophene has high conductivity and excellent electrochemical stability. Through electrochemical oxidation polymerization reaction, the poly-3, 4-ethylenedioxythiophene and nickel cobaltate are compounded on the surface of the carbon cloth, so that the defect that the poly-3, 4-ethylenedioxythiophene is easy to agglomerate can be remarkably overcome, and the specific capacitance of the flexible electrode is effectively improved.
(4) The poly 3, 4-ethylenedioxythiophene and nickel cobaltate are compounded on the surface of the flexible carbon cloth by utilizing electrochemical oxidation polymerization reaction to directly prepare the flexible electrode, so that the problems of surface dead gas, complicated traditional slurry coating electrode process and the like caused by polymer binders and conductive additives in the conventional method for preparing the flexible electrode can be effectively avoided.
(5) The flexible electrode prepared by the invention has high specific capacitance and excellent electrochemical cycle stability, when the charge-discharge current densities are 1A/g, 2A/g, 4A/g and 8A/g respectively, the specific capacitances of the flexible electrode are 304-325F/g, 298-314F/g, 286-305F/g and 274-293F/g respectively, and the specific capacitance retention rate after 2000 cycles is 87.6-92.0%, so that the flexible electrode is mainly used for manufacturing flexible supercapacitors and has obvious economic value and social benefit.
Drawings
FIG. 1 is an X-ray diffraction pattern of nickel cobaltate prepared in example 1;
FIG. 2 is a scanning electron micrograph of nickel cobaltate prepared in example 1;
FIG. 3 is an infrared absorption spectrum of the poly-3, 4-ethylenedioxythiophene/nickel cobaltate/carbon cloth flexible electrode prepared in example 1;
FIG. 4 is a scanning electron micrograph of the poly-3, 4-ethylenedioxythiophene/nickel cobaltate/carbon cloth flexible electrode prepared in example 1;
FIG. 5 is a scanning electron micrograph of the poly 3, 4-ethylenedioxythiophene/carbon cloth flexible electrode prepared in comparative example 1;
FIG. 6 is a scanning electron micrograph of a poly-3, 4-ethylenedioxythiophene/nickel cobaltate composite prepared in comparative example 2;
FIG. 7 is a scanning electron micrograph of poly-3, 4-ethylenedioxythiophene prepared in comparative example 3.
Detailed Description
The advantages and effects of the poly (3, 4-ethylenedioxythiophene)/nickel cobaltate/carbon cloth flexible electrode and the preparation method thereof in the present embodiment are further illustrated by three groups of examples and two groups of comparative examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
(1) At room temperature, 1 g of cobalt nitrate hexahydrate and 0.3 g of nickel nitrate hexahydrate are added into 80 mL of methanol, after magnetic stirring is carried out for 20 min, 1.5 g of hexamethylenetetramine is added, magnetic stirring is continued for 15 min, the temperature is increased to 160 ℃, magnetic stirring is carried out for 12 h, natural cooling is carried out to the room temperature, centrifugation, washing, vacuum drying at 60 ℃ is carried out for 24 h, annealing treatment at 330 ℃ is carried out for 3 h, and nickel cobaltate is prepared.
(2) Adding 60 mg of ammonium persulfate into 20 mL of deionized water, magnetically stirring for 8 min at room temperature, and dropwise adding 1 mL of hydrochloric acid solution at the speed of 15 drops/min under the magnetic stirring to prepare a mixed solution A; adding 50 mg of nickel cobaltate into 30 mL of deionized water, magnetically stirring at room temperature for 20 min, performing ultrasonic treatment for 20 min, adding 80 mg of 3, 4-ethylenedioxythiophene, magnetically stirring for 20 min, and performing ultrasonic treatment for 45 min to prepare a mixed dispersion liquid B; vertically placing the carbon cloth with the surface subjected to acidification treatment in a dispersion liquid B, dropwise adding the solution A into the dispersion liquid B at the speed of 20 drops/min, after dropwise adding, magnetically stirring for 18 hours, and performing suction filtration, washing and vacuum drying at 60 ℃ for 24 hours to prepare the poly (3, 4-ethylenedioxythiophene)/nickel cobaltate/carbon cloth flexible electrode.
The concentration of the hydrochloric acid solution is 4 mol/L, and the solvent is water.
FIG. 1 is an X-ray diffraction pattern of nickel cobaltate prepared in this example. In the figure, the diffraction peaks at 18.99 °, 31.4 °, 38.7 °, 44.5 °, 58.9 ° and 64.7 ° of 2 θ correspond to the (220), (311), (400), (511) and (440) crystal planes of nickel cobaltate, respectively, and it is shown that nickel cobaltate has been successfully prepared.
FIG. 2 is a scanning electron micrograph of nickel cobaltate prepared in this example. The result shows that the nickel cobaltate is in a nanometer flower-shaped microsphere structure, which is beneficial to increasing the contact area of the flexible electrode and the electrolyte and improving the specific capacitance of the flexible electrode.
Fig. 3 is an infrared absorption spectrum of the poly-3, 4-ethylenedioxythiophene/nickel cobaltate/carbon cloth flexible electrode prepared in this example. It is shown at 1646 cm-1And 1460 cm-1The absorption peak of (a) is derived from the stretching vibration of C = C, C-C on the thiophene ring, and is located at 1383 cm-1And 724 cm-1The absorption peak of (A) is derived from the stretching vibration of C-O-C in ethylenedioxy and the stretching vibration of C-S in thiophene ring. In addition, the thickness is 600-500 cm-1A number of characteristic absorption peaks for nickel cobaltate appear. This indicates that the poly 3, 4-ethylenedioxythiophene/nickel cobaltate/carbon cloth flexible electrode was successfully prepared.
Fig. 4 is a scanning electron micrograph of the poly-3, 4-ethylenedioxythiophene/nickel cobaltate/carbon cloth flexible electrode prepared in this example. As can be seen in the figure, nickel cobaltate and polythiophene grow uniformly on the surface of the carbon cloth, which is beneficial to increasing the contact area between the flexible electrode and the electrolyte and improving the specific capacitance of the flexible electrode.
Example 2
(1) At room temperature, 0.5 g of cobalt nitrate hexahydrate and 0.2 g of nickel nitrate hexahydrate are added into 50 mL of ethanol, after magnetic stirring is carried out for 10 min, 1 g of hexamethylenetetramine is added, magnetic stirring is continued for 10 min, the temperature is raised to 140 ℃, magnetic stirring is carried out for 16 h, natural cooling is carried out to the room temperature, centrifugation, washing, vacuum drying at 60 ℃ is carried out for 24 h, and annealing treatment at 300 ℃ is carried out for 4 h, so that nickel cobaltate is prepared.
(2) Adding 40 mg of ammonium persulfate into 10 mL of deionized water, magnetically stirring for 5 min at room temperature, and dropwise adding 0.5 mL of hydrochloric acid solution at the speed of 10 drops/min under the magnetic stirring to prepare a mixed solution A; adding 20 mg of nickel cobaltate into 10 mL of deionized water, magnetically stirring at room temperature for 10 min, performing ultrasonic treatment for 10 min, adding 50 mg of 3, 4-ethylenedioxythiophene, magnetically stirring for 10 min, and performing ultrasonic treatment for 30 min to prepare a mixed dispersion liquid B; vertically placing the carbon cloth with the surface subjected to acidification treatment in a dispersion liquid B, dropwise adding the solution A into the dispersion liquid B at the speed of 10 drops/min, after dropwise adding, magnetically stirring for 12 hours, carrying out suction filtration, washing and vacuum drying at 60 ℃ for 24 hours, and preparing the poly 3, 4-ethylenedioxythiophene/nickel cobaltate/carbon cloth flexible electrode.
The concentration of the hydrochloric acid solution in the step (2) is 4 mol/L, and the solvent is water.
Example 3
(1) At room temperature, 2 g of cobalt nitrate hexahydrate and 0.4 g of nickel nitrate hexahydrate are added into 100 mL of ethanol, after magnetic stirring is carried out for 30 min, 2 g of hexamethylenetetramine is added, magnetic stirring is continued for 20 min, the temperature is increased to 180 ℃, magnetic stirring is carried out for 8 h, natural cooling is carried out to the room temperature, centrifugation, washing, vacuum drying at 60 ℃ is carried out for 24 h, and annealing treatment is carried out for 2 h to prepare nickel cobaltate.
(2) Adding 80 mg of ammonium persulfate into 30 mL of deionized water, magnetically stirring for 10 min at room temperature, and dropwise adding 2 mL of hydrochloric acid solution at the speed of 20 drops/min under the magnetic stirring to prepare a mixed solution A; adding 80 mg of nickel cobaltate into 50 mL of deionized water, magnetically stirring at room temperature for 30 min, performing ultrasonic treatment for 30 min, adding 100 mg of 3, 4-ethylenedioxythiophene, magnetically stirring for 30 min, and performing ultrasonic treatment for 60 min to prepare a mixed dispersion liquid B; vertically placing the carbon cloth with the surface subjected to acidification treatment in a dispersion liquid B, dropwise adding the solution A into the dispersion liquid B at the speed of 30 drops/min, after dropwise adding, magnetically stirring for 24 hours, and performing suction filtration, washing and vacuum drying at 60 ℃ for 24 hours to prepare the poly (3, 4-ethylenedioxythiophene)/nickel cobaltate/carbon cloth flexible electrode.
The concentration of the hydrochloric acid solution in the step (2) is 4 mol/L, and the solvent is water.
Comparative example 1
Adding 60 mg of ammonium persulfate into 20 mL of deionized water, magnetically stirring for 8 min at room temperature, and dropwise adding 1 mL of hydrochloric acid solution at a speed of 15 drops/min under magnetic stirring to prepare a mixed solution A; adding 80 mg of 3, 4-ethylenedioxythiophene into 30 mL of deionized water, magnetically stirring for 20 min, and performing ultrasonic treatment for 45 min to prepare a solution B; and vertically placing the carbon cloth with the surface subjected to acidification treatment in the solution B, dropwise adding the solution A into the solution B at the speed of 20 drops/min, magnetically stirring for 18 hours after dropwise adding, performing suction filtration, washing and vacuum drying at 60 ℃ for 24 hours, and preparing the poly (3, 4-ethylenedioxythiophene)/carbon cloth flexible electrode.
The concentration of the hydrochloric acid solution is 4 mol/L, and the solvent is water.
FIG. 5 is a scanning electron micrograph of the poly (3, 4-ethylenedioxythiophene)/carbon cloth flexible electrode prepared by the comparative example. It is shown that poly-3, 4-ethylenedioxythiophene is very unevenly distributed on the carbon cloth, mainly due to the absence of support from nickel cobaltate, and poly-3, 4-ethylenedioxythiophene agglomerates during the polymerization.
Comparative example 2
(1) At room temperature, 1 g of cobalt nitrate hexahydrate and 0.3 g of nickel nitrate hexahydrate are added into 80 mL of methanol, after magnetic stirring is carried out for 20 min, 1.5 g of hexamethylenetetramine is added, magnetic stirring is continued for 15 min, the temperature is increased to 160 ℃, magnetic stirring is carried out for 12 h, natural cooling is carried out to the room temperature, centrifugation, washing, vacuum drying at 60 ℃ is carried out for 24 h, annealing treatment at 330 ℃ is carried out for 3 h, and nickel cobaltate is prepared.
(2) Adding 60 mg of ammonium persulfate into 20 mL of deionized water, magnetically stirring for 8 min at room temperature, and dropwise adding 1 mL of hydrochloric acid solution at the speed of 15 drops/min under the magnetic stirring to prepare a mixed solution A; adding 50 mg of nickel cobaltate into 30 mL of deionized water, magnetically stirring at room temperature for 20 min, performing ultrasonic treatment for 20 min, adding 80 mg of 3, 4-ethylenedioxythiophene, magnetically stirring for 20 min, and performing ultrasonic treatment for 45 min to prepare a mixed dispersion liquid B; dropwise adding the solution A into the dispersion liquid B at the speed of 20 drops/min, after the dropwise adding is finished, magnetically stirring for 18 hours, and carrying out suction filtration, washing and vacuum drying at 60 ℃ for 24 hours to prepare the poly 3, 4-ethylenedioxythiophene/nickel cobaltate composite material.
The concentration of the hydrochloric acid solution is 4 mol/L, and the solvent is water.
FIG. 6 is a scanning electron micrograph of the poly-3, 4-ethylenedioxythiophene/nickel cobaltate composite prepared according to the comparative example. As can be seen from the figure, due to the lack of the carbon cloth carrier, the polythiophene and the nickel cobaltate are agglomerated together, so that the contact area of the composite material and the electrolyte is greatly reduced, and the specific capacitance of the composite material is reduced.
Comparative example 3
Adding 60 mg of ammonium persulfate into 20 mL of deionized water, magnetically stirring for 8 min at room temperature, and dropwise adding 1 mL of hydrochloric acid solution at a speed of 15 drops/min under magnetic stirring to prepare a mixed solution A; adding 80 mg of 3, 4-ethylenedioxythiophene into 30 mL of deionized water, magnetically stirring for 20 min, and performing ultrasonic treatment for 45 min to prepare a solution B; dropwise adding the solution A into the solution B at the speed of 20 drops/min, after the dropwise adding is finished, magnetically stirring for 18 hours, and carrying out suction filtration, washing and vacuum drying at 60 ℃ for 24 hours to prepare the poly (3, 4-ethylenedioxythiophene).
The concentration of the hydrochloric acid solution is 4 mol/L, and the solvent is water.
FIG. 7 is a scanning electron micrograph of poly-3, 4-ethylenedioxythiophene prepared according to this comparative example. As can be seen from the figure, the poly 3, 4-ethylenedioxythiophene is a closely packed solid, and there are few voids on the surface, which are not favorable for the poly 3, 4-ethylenedioxythiophene to contact with the electrolyte, resulting in the poly 3, 4-ethylenedioxythiophene having a low specific capacitance.
The electrodes prepared in the three groups of examples and comparative example 1 are used as working electrodes, platinum wires are used as counter electrodes, saturated calomel electrodes are used as reference electrodes, 1 mol/L sulfuric acid aqueous solution is used as electrolyte, the specific capacitance is tested by using a constant current charging and discharging method, and the electrochemical cycling stability is tested by using a cyclic voltammetry method. Uniformly dispersing the composite material prepared in the comparative example 2, acetylene black and polyvinylidene fluoride in N-methylpyrrolidone according to the mass ratio of 80:15:5 to prepare a paste solution, uniformly coating the paste solution on a stainless steel substrate to serve as a working electrode, taking a platinum wire as a counter electrode, taking a saturated calomel electrode as a reference electrode, taking 1 mol/L sulfuric acid aqueous solution as electrolyte, testing the specific capacitance by using a constant current charging and discharging method, and testing the electrochemical cycling stability by using a cyclic voltammetry method. Wherein the voltage range is-0.2V-0.8V, and the charge-discharge current density is 1A/g, 2A/g, 4A/g and 8A/g respectively. The test results are shown in Table 1.
From the test results of the examples and the comparative examples, it can be seen that the poly 3, 4-ethylenedioxythiophene/nickel cobaltate/carbon cloth flexible electrode with high specific capacitance and excellent electrochemical cycling stability can be prepared by an in-situ chemical oxidation method by using carbon cloth with an acidized surface as a carrier, nickel cobaltate prepared by a hydrothermal method as a supporting material, 3, 4-ethylenedioxythiophene as a monomer and ammonium persulfate as an oxidant.
While the foregoing description shows and describes the preferred embodiments of the present invention, it is to be understood that the invention is not limited to the forms disclosed herein, but is not to be construed as excluding other embodiments and is capable of use in various other combinations, modifications, and environments and is capable of changes within the scope of the inventive concept as described herein, commensurate with the above teachings, or the skill or knowledge of the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (5)
1. The poly 3, 4-ethylenedioxythiophene/nickel cobaltate/carbon cloth composite material is characterized in that: loading nickel cobaltate and poly 3, 4-dioxythiophene on carbon cloth by taking the carbon cloth as a carrier;
the preparation method comprises the following steps: the carbon cloth with the surface subjected to acidizing is taken as a carrier, nickel cobaltate prepared by a hydrothermal method is taken as a supporting material, 3, 4-ethylenedioxythiophene is taken as a monomer, ammonium persulfate is taken as an oxidant, and the poly 3, 4-ethylenedioxythiophene/nickel cobaltate/carbon cloth composite material is prepared by an in-situ chemical oxidation method;
the method comprises the following specific steps:
(1) at room temperature, adding 0.5-2 g of cobalt nitrate hexahydrate and 0.2-0.4 g of nickel nitrate hexahydrate into 50-100 mL of organic solution, magnetically stirring for 10-30 min, adding 1-2 g of hexamethylenetetramine, continuously magnetically stirring for 10-20 min, heating to 140-180 ℃, magnetically stirring for 8-16 h, naturally cooling to room temperature, centrifuging, washing, vacuum drying at 60 ℃ for 24 h, heating to 300-360 ℃, and annealing for 2-4 h to obtain nickel cobaltate;
(2) adding 40-80 mg of ammonium persulfate into 10-30 mL of deionized water, magnetically stirring at room temperature for 5-10 min, and dropwise adding 0.5-2 mL of hydrochloric acid solution at a speed of 10-20 drops/min under the magnetic stirring to prepare a solution A; adding 20-80 mg of nickel cobaltate into 10-50 mL of deionized water, magnetically stirring at room temperature for 10-30 min, performing ultrasonic treatment for 10-30 min, adding 50-100 mg of 3, 4-ethylenedioxythiophene, magnetically stirring for 10-30 min, and performing ultrasonic treatment for 30-60 min to obtain a dispersion liquid B; and vertically placing the carbon cloth with the surface subjected to acidification treatment in a dispersion liquid B, dropwise adding the solution A into the dispersion liquid B at the speed of 10-30 drops/min, after dropwise adding, magnetically stirring for 12-24 hours, carrying out suction filtration, washing and vacuum drying at 60 ℃ for 24 hours to obtain the poly 3, 4-ethylenedioxythiophene/nickel cobaltate/carbon cloth composite material.
2. The poly 3, 4-ethylenedioxythiophene/nickel cobaltate/carbon cloth composite of claim 1, wherein: the organic solution in the step (1) is methanol or ethanol.
3. The poly 3, 4-ethylenedioxythiophene/nickel cobaltate/carbon cloth composite of claim 1, wherein: the concentration of the hydrochloric acid solution in the step (2) is 4 mol/L, and the solvent is water.
4. The poly 3, 4-ethylenedioxythiophene/nickel cobaltate/carbon cloth composite of claim 1, wherein: the preparation method of the carbon cloth with the surface subjected to acidizing in the step (2) comprises the following steps: cutting the carbon cloth into strips of 1 cm multiplied by 2 cm, then carrying out ultrasonic treatment on the strips of carbon cloth in 5 mol/L nitric acid solution for 30 min at room temperature, washing with deionized water, and drying.
5. Use of the poly 3, 4-ethylenedioxythiophene/nickel cobaltate/carbon cloth composite of claim 1, wherein: as an electrode material of a flexible supercapacitor.
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