CN110323080B - Preparation method of water system super capacitor - Google Patents
Preparation method of water system super capacitor Download PDFInfo
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- CN110323080B CN110323080B CN201910599158.8A CN201910599158A CN110323080B CN 110323080 B CN110323080 B CN 110323080B CN 201910599158 A CN201910599158 A CN 201910599158A CN 110323080 B CN110323080 B CN 110323080B
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000003990 capacitor Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 43
- 239000004744 fabric Substances 0.000 claims abstract description 43
- 238000003756 stirring Methods 0.000 claims abstract description 32
- 239000000243 solution Substances 0.000 claims abstract description 28
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 14
- 239000012153 distilled water Substances 0.000 claims abstract description 13
- 239000007772 electrode material Substances 0.000 claims abstract description 10
- 239000002131 composite material Substances 0.000 claims abstract description 9
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 8
- 239000004743 Polypropylene Substances 0.000 claims abstract description 8
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 8
- 239000010439 graphite Substances 0.000 claims abstract description 8
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- -1 polypropylene Polymers 0.000 claims abstract description 8
- 229920001155 polypropylene Polymers 0.000 claims abstract description 8
- 235000010344 sodium nitrate Nutrition 0.000 claims abstract description 8
- 239000004317 sodium nitrate Substances 0.000 claims abstract description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 239000003792 electrolyte Substances 0.000 claims description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 238000004070 electrodeposition Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000000137 annealing Methods 0.000 claims description 7
- 229940075397 calomel Drugs 0.000 claims description 7
- 238000005520 cutting process Methods 0.000 claims description 7
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000007773 negative electrode material Substances 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- 239000007774 positive electrode material Substances 0.000 claims description 7
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 12
- 229910021389 graphene Inorganic materials 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000012286 potassium permanganate Substances 0.000 description 5
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000002070 nanowire Substances 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- 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
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- 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
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- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
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Abstract
The invention discloses a preparation method of a water system super capacitor, which is used for solving the technical problem that the water system super capacitor prepared by the existing method is low in working voltage. The technical scheme is that carbon cloth, graphite and sodium nitrate are mixed, concentrated sulfuric acid is added drop by drop, and KMnO is added4Adding distilled water and stirring, and adding H2O2And adding the solution into the mixture solution, and finally adding hydrazine hydrate into the solution and heating to obtain the reduced graphene coated carbon cloth serving as the cathode of the supercapacitor. Preparation of CO from graphene coated carbon cloth by using electrochemical workstation3O4The NSs/ACC @ RGO composite electrode material is used as the positive electrode of the supercapacitor. A water system super capacitor is assembled by taking a porous polypropylene film as a diaphragm and a water-soluble electrolyte solution as a base. Through tests, the working voltage of the water system super capacitor prepared by the invention is improved to 2.2V from 1.4V of the background technology.
Description
Technical Field
The invention relates to a preparation method of a super capacitor, in particular to a preparation method of a water system super capacitor.
Background
The super capacitor is also called as an electrochemical capacitor, is a novel energy storage device between a traditional capacitor and a storage battery, has excellent reversible charge-discharge performance and high-capacity energy storage performance, and has the advantages that: the power density is high, the cycle life is long, the charging speed is high, the instantaneous heavy current discharge can be realized, the environment is protected, and the application prospect is wide. At present, supercapacitors have the disadvantage of a limited energy density. The main reasons for the low energy density of supercapacitors are: under the corresponding voltage window, the electrochemical stable potential window is narrow and the specific capacitance is small.
In terms of electrode materials, oxide pseudocapacitance has great potential. Cobalt Oxide (CO)3O4) As a typical oxide pseudocapacitance material, the material has been widely researched due to the advantages of high theoretical specific capacitance, low preparation cost and the like.
The literature "xiantong, invitrogen, tan new jade, et al, a preparation method of a water system asymmetric supercapacitor based on cobaltosic oxide" discloses a preparation method of a water system asymmetric supercapacitor based on cobaltosic oxide. The method is characterized in that a cobaltosic oxide nano-wire array is taken as a positive electrode, a cobaltosic oxide/polypyrrole composite nano-wire array is taken as a negative electrode, and a water-soluble electrolyte solution is taken as a basis to assemble the water-system asymmetric supercapacitor.
In the method, the working voltage of the water system asymmetric super capacitor only reaches 1.4V, and the mass specific capacitance only reaches 335.34Fg-1During cycling tests, decomposition of the electrode material can lead to a reduction in capacitance and energy density.
Disclosure of Invention
In order to overcome the defect that the water system super capacitor prepared by the existing method is low in working voltage, the invention provides a preparation method of the water system super capacitor. The method comprises the steps of mixing cleaned and dried carbon cloth, graphite and sodium nitrate, dropwise adding concentrated sulfuric acid and stirring, and slowly adding KMnO4Stirring, adding distilled water, stirring, and adding H dropwise2O2Add to the mixture solution until the solution becomes clear. Finally adding hydrazine hydrate into the solutionAnd heating, washing and vacuum drying the carbon cloth to obtain the reduced graphene coated carbon cloth serving as the cathode of the supercapacitor. Adopting graphene coated carbon cloth as a working electrode, a platinum plate as a counter electrode, a calomel electrode as a reference electrode and Co (NO) for an electrochemical workstation3)2 6H2And O is used as electrolyte for electrochemical deposition. Washing, drying and annealing the deposited carbon cloth to obtain CO3O4The NSs/ACC @ RGO composite electrode material is used as the positive electrode of the supercapacitor. Comparing ACC @ RGO negative electrode material and CO according to working voltage and specific capacitance of the positive electrode and the negative electrode3O4Cutting the/ACC @ RGO positive electrode material, and assembling the water system super capacitor by taking the porous polypropylene film as a diaphragm and taking the water-soluble electrolyte solution as the basis. Through tests, the working voltage of the water system super capacitor prepared by the invention is improved to 2.2V from 1.4V of the background technology.
The technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of a water system super capacitor is characterized by comprising the following steps:
step one, preparing an ACC @ RGO material cathode.
Pre-cleaning the carbon cloth with ethanol and distilled water under ultrasonic condition for 10-30min, and vacuum drying at 60-90 deg.C for 5-8 hr. Adding the graphite flake, the carbon cloth and the sodium nitrate into a beaker according to the mass ratio of 1:40:41, dropwise adding 50-80ml of 98% concentrated sulfuric acid, and stirring at-5 to-8 ℃ for 20-60 min.
KMnO with the mass 5-8 times of that of the carbon cloth4Slowly adding into the mixed solution, stirring vigorously in ice bath for 1-3h, transferring into oil bath, stirring at 20-50 deg.C for 1-3h, slowly mixing the solution with 100 plus 150ml distilled water in ice bath, stirring for 1-3h, and stirring the mixed solution in oil bath at 80-98 deg.C for 20-60 min. Finally, H is dripped dropwise2O2Add to the mixture solution until the solution becomes clear.
Adding 2-5ml of hydrazine hydrate with the concentration of 96.3mmol, and heating the solution in an oil bath at 100-130 ℃ for 20-30h under the condensation effect of a water-cooled condenser. And washing the carbon cloth with deionized water for 3-5 times, and then drying the carbon cloth in vacuum at 60-80 ℃ for 8-12h to obtain ACC @ RGO serving as the cathode of the supercapacitor.
Step two, preparing CO3O4ACC @ RGO material anode
Adopting an electrochemical workstation at a potential of-0.8 to-1.0V, using the ACC @ RGO prepared in the step one as a working electrode, a platinum plate as a counter electrode, a calomel electrode as a reference electrode and a concentration of 0.01 to 10mol L-1Co (NO) of3)2 6H2And performing electrochemical deposition by taking O as an electrolyte, wherein the time of the electrodeposition is 600-3600 s.
Washing the deposited carbon cloth with deionized water, drying in air at 60-90 deg.C for 8-12h, and annealing at 350-400 deg.C for 2-4h to obtain CO3O4The NSs/ACC @ RGO composite electrode material is used as the positive electrode of the supercapacitor.
And step three, assembling the water system super capacitor by taking the electrolyte solution as a base.
With Li2SO4And CoSO4Preparing an aqueous electrolyte for the solute, Li2SO4And CoSO4The concentration of solute is 2-3mol L-1And 0.1 to 2mol L-1。
Comparing ACC @ RGO negative electrode material and CO according to working voltage and specific capacitance of the positive electrode and the negative electrode3O4Cutting the/ACC @ RGO positive electrode material, and assembling the water system super capacitor by taking the porous polypropylene film as a diaphragm and taking the water-soluble electrolyte solution as the basis.
The invention has the beneficial effects that: the method comprises the steps of mixing cleaned and dried carbon cloth, graphite and sodium nitrate, dropwise adding concentrated sulfuric acid and stirring, and slowly adding KMnO4Stirring, adding distilled water, stirring, and adding H dropwise2O2Add to the mixture solution until the solution becomes clear. And finally, adding hydrazine hydrate into the solution, heating, washing and vacuum drying the carbon cloth to obtain the reduced graphene coated carbon cloth serving as the cathode of the supercapacitor. Adopting graphene coated carbon cloth as a working electrode, a platinum plate as a counter electrode, a calomel electrode as a reference electrode and Co (NO) for an electrochemical workstation3)2 6H2O asThe electrolyte is electrochemically deposited. Washing, drying and annealing the deposited carbon cloth to obtain CO3O4The NSs/ACC @ RGO composite electrode material is used as the positive electrode of the supercapacitor. Comparing ACC @ RGO negative electrode material and CO according to working voltage and specific capacitance of the positive electrode and the negative electrode3O4Cutting the/ACC @ RGO positive electrode material, and assembling the water system super capacitor by taking the porous polypropylene film as a diaphragm and taking the water-soluble electrolyte solution as the basis.
Tests prove that the positive electrode of the water system super capacitor prepared by the invention is 1Ag-1Shows that 845Fg-1The supercapacitor shows a high voltage window of 2.2V in an aqueous electrolyte and a power density of 1100W Kg-1It has a weight of 99WhKg-1The ultra-high energy density and the capacity retention rate after 10000 cycles are 168 percent of the ultra-long cycle life, and meanwhile, the price is low and the safety is high.
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
Drawings
FIG. 1 shows Co prepared by the method of example 1 of the present invention3O4XRD patterns of/ACC @ RGO samples.
FIG. 2 shows two-dimensional Co prepared by the method of example 23O4TEM images of the nanoplate samples.
FIG. 3 is CO prepared according to the process of the invention example 13O4GCD profile of/ACC @ RGO electrode in a three-electrode test system.
FIG. 4 is CO prepared according to the method of the invention example 23O4the/ACC @ RGO// ACC @ RGO ASCs device has different scanning rates of 1-10mV s at two electrodes-1CV curve below.
FIG. 5 is CO prepared according to the method of the invention, example 33O4the/ACC @ RGO// ACC @ RGO ASCs device is at 5A g-1Cyclic performance curve of time.
FIG. 6 is CO prepared according to the method of the invention, example 33O4A log plot of power density versus corresponding energy density for the/ACC @ RGO// ACC @ RGO ASCs devices.
Detailed Description
The following examples refer to fig. 1-6.
Example 1:
step one, preparing an ACC @ RGO material cathode:
1. the carbon cloth was previously cleaned with ethanol and distilled water under ultrasonic conditions for 30min, and then vacuum-dried at 60 ℃ for 5 hours. Adding the graphite flake, the carbon cloth and the sodium nitrate into a beaker according to the mass ratio of 1:40:41, dropwise adding 50ml of 98% concentrated sulfuric acid and stirring at-5 ℃ for 20 min.
2. The mass of the carbon cloth is 5 times of that of the KMnO4Slowly adding into the above mixed solution, stirring vigorously in ice bath for 1h, transferring into oil bath, stirring at 20 deg.C for 1h, then slowly mixing the solution with 100ml distilled water in ice bath, stirring for 1h, and stirring the mixed solution in oil bath at 80 deg.C for 20 min. H is added dropwise2O2Add to the mixture solution until the solution becomes clear.
3. 2ml of hydrazine hydrate with a concentration of 96.3mmol are added and the solution is heated in an oil bath at 100 ℃ for 20h under the condensation of a water-cooled condenser. And washing the carbon cloth with deionized water for 3 times, and then drying the carbon cloth at 60 ℃ for 8 hours in vacuum to obtain ACC @ RGO serving as the negative electrode of the supercapacitor.
Step two, preparing CO3O4ACC @ RGO material positive electrode:
1. an electrochemical workstation was used at a potential (compared to SCE) -0.8V using ACC @ RGO as the working electrode, a platinum plate as the counter electrode, a calomel electrode as the reference electrode, and a concentration of 10mol L-1Co (NO) of3)2 6H2And O is used as an electrolyte for electrochemical deposition, and the time for electrodeposition is 600 s.
2. Washing the deposited carbon cloth with deionized water, drying in air at 60 deg.C for 8h, and annealing at 350 deg.C for 2h to obtain CO3O4The NSs/ACC @ RGO composite electrode material is used as the positive electrode of the supercapacitor.
Step three, assembling the water system super capacitor by taking the electrolyte solution as the basis:
1. with Li2SO4And CoSO4Preparing an aqueous electrolyte for the solute, Li2SO4And CoSO4The concentration of solute is 2mol L-1And 0.1mol L-1。
2. Comparing ACC @ RGO negative electrode material and CO according to working voltage and specific capacitance of the positive electrode and the negative electrode3O4Cutting the/ACC @ RGO positive electrode material, and assembling the water system super capacitor by taking the porous polypropylene film as a diaphragm and taking the water-soluble electrolyte solution as the basis.
From FIG. 1, it can be seen that the two-dimensional CO3O4The nano-sheet has a cubic structure of Fd-3m (227) space group and a lattice parameter
Very close to cubic
It can be seen from fig. 3 that the operating voltage window of the electrode is 1.2V, which is much higher than the operating voltage window in alkaline electrolyte. It can also be seen from the figure that the current density is 1Ag-1In the case of (2), the specific capacitance calculated using the formula is 845F g-1. When the current density reaches 10Ag-1When the specific capacitance is still 569Fg-1It shows good reversibility and high specific capacity.
Example 2:
step one, preparing an ACC @ RGO material cathode:
1. the carbon cloth was previously cleaned with ethanol and distilled water under ultrasonic conditions for 10min, and then vacuum-dried at 90 ℃ for 8 hours. Adding the graphite flake, the carbon cloth and the sodium nitrate into a beaker according to the mass ratio of 1:40:41, dropwise adding 80ml of 98% concentrated sulfuric acid, and stirring at-8 ℃ for 60 min.
2. The mass of the carbon cloth is 8 times of that of KMnO4Slowly adding into the above mixed solution, stirring vigorously in ice bath for 3h, transferring into oil bath, stirring at 50 deg.C for 3h, then slowly mixing the solution with 150ml distilled water in ice bath, stirring for 3h, and stirring the mixed solution in oil bath at 98 deg.C for 60 min. H is added dropwise2O2Add to the mixture solution until the solution becomes clear.
3. 5ml of hydrazine hydrate with a concentration of 96.3mmol are added and the solution is heated in an oil bath at 130 ℃ for 30h under the condensation of a water-cooled condenser. And finally, washing the carbon cloth with deionized water for 5 times, and then drying the carbon cloth in vacuum at 80 ℃ for 12 hours to obtain ACC @ RGO serving as the negative electrode of the supercapacitor.
Step two, preparing CO3O4ACC @ RGO material positive electrode:
1. an electrochemical workstation was used at a potential (compared to SCE) of-1.0V, using ACC @ RGO as the working electrode, a platinum plate as the counter electrode, a calomel electrode as the reference electrode, and a concentration of 0.1mol L-1Co (NO) of3)2 6H2And O is used as an electrolyte for electrochemical deposition, and the time for electrodeposition is 2500 s.
2. Washing the deposited carbon cloth with deionized water, drying in air at 90 deg.C for 12h, and annealing at 400 deg.C for 4h to obtain CO3O4The NSs/ACC @ RGO composite electrode material is used as the positive electrode of the supercapacitor.
Step three, assembling the water system super capacitor by taking the electrolyte solution as the basis:
1. with Li2SO4And CoSO4Preparing an aqueous electrolyte for the solute, Li2SO4And CoSO4The concentration of solute is 2mol L-1And 0.3mol L-1。
2. Comparing ACC @ RGO negative electrode material and CO according to working voltage and specific capacitance of the positive electrode and the negative electrode3O4Cutting the/ACC @ RGO positive electrode material, and assembling the water system super capacitor by taking the porous polypropylene film as a diaphragm and taking the water-soluble electrolyte solution as the basis.
From fig. 4 it can be seen that the operating voltage window of the water based supercapacitor is 2.2V, much higher than in the alkaline electrolyte. The CV curve shape remained unchanged, indicating its good rate performance.
Example 3:
step one, preparing an ACC @ RGO material cathode:
1. the carbon cloth was previously cleaned with ethanol and distilled water under ultrasonic conditions for 20min, and then vacuum-dried at 80 ℃ for 6 hours. Adding the graphite flake, the carbon cloth and the sodium nitrate into a beaker according to the mass ratio of 1:40:41, dropwise adding 60ml of 98% concentrated sulfuric acid and stirring at-6 ℃ for 40 min.
2. The mass of the carbon cloth is 6 times of the KMnO4Slowly adding into the above mixed solution, stirring vigorously in ice bath for 2h, transferring into oil bath, stirring at 40 deg.C for 2h, then slowly mixing the solution with 120ml distilled water in ice bath, stirring for 2h, and stirring the mixed solution in oil bath at 90 deg.C for 30 min. H is added dropwise2O2Add to the mixture solution until the solution becomes clear.
3. 3ml of hydrazine hydrate with a concentration of 96.3mmol are added and the solution is heated in an oil bath at 120 ℃ for 24h under condensation in a water-cooled condenser. And finally, washing the carbon cloth with deionized water for 3 times, and then drying the carbon cloth in vacuum at 65 ℃ for 10 hours to obtain ACC @ RGO serving as the negative electrode of the supercapacitor.
Step two, preparing CO3O4ACC @ RGO material positive electrode:
1. an electrochemical workstation was used at a potential (compared to SCE) of-0.9V, using ACC @ RGO as the working electrode, a platinum plate as the counter electrode, a calomel electrode as the reference electrode, and a concentration of 0.01mol L-1Co (NO) of3)2 6H2And performing electrochemical deposition by taking O as an electrolyte, wherein the electrodeposition time is 3600 s.
2. Washing the deposited carbon cloth with deionized water, drying in air at 80 deg.C for 10 hr, and annealing at 380 deg.C for 3 hr to obtain CO3O4The NSs/ACC @ RGO composite electrode material is used as the positive electrode of the supercapacitor.
Step three, assembling the water system super capacitor by taking the electrolyte solution as the basis:
1. with Li2SO4And CoSO4Preparing an aqueous electrolyte for the solute, Li2SO4And CoSO4The concentration of solute is 3mol L-1And 2mol L-1。
2. According to the operating voltage and ratio of the positive electrode and the negative electrodeCapacitor pair ACC @ RGO negative electrode material and CO3O4Cutting the/ACC @ RGO positive electrode material, and assembling the water system super capacitor by taking the porous polypropylene film as a diaphragm and taking the water-soluble electrolyte solution as the basis.
It can be seen from fig. 5 that the capacity retention of the device after 10000 cycles is 168%, and the device has an ultra-long cycle life.
It can be seen from fig. 6 that the device has 99WhKg compared to other water system supercapacitors-1The ultra-high energy density of (1) is 1100W Kg at power density-1Then (c) is performed.
Claims (1)
1. A preparation method of a water system super capacitor is characterized by comprising the following steps:
step one, preparing an ACC @ RGO material cathode;
pre-cleaning the carbon cloth with ethanol and distilled water under ultrasonic condition for 10-30min, and vacuum drying at 60-90 deg.C for 5-8 hr; adding a graphite flake, carbon cloth and sodium nitrate into a beaker according to the mass ratio of 1:40:41, dropwise adding 50-80ml of 98% concentrated sulfuric acid, and stirring at-5 to-8 ℃ for 20-60 min;
KMnO with the mass 5-8 times of that of the carbon cloth4Slowly adding the mixed solution into the ice bath, stirring vigorously for 1-3h, transferring into an oil bath, stirring at 20-50 ℃ for 1-3h, slowly mixing the solution with 100 plus 150ml of distilled water in the ice bath, stirring for 1-3h, and stirring the mixed solution in the oil bath at 80-98 ℃ for 20-60 min; finally, H is dripped dropwise2O2Adding to the mixture solution until the solution becomes clear;
adding 2-5ml of hydrazine hydrate with the concentration of 96.3mmol, and heating the solution in oil bath at the temperature of 100 ℃ and 130 ℃ for 20-30h under the condensation action of a water-cooled condenser; washing the carbon cloth with deionized water for 3-5 times, and then drying the carbon cloth in vacuum at the temperature of 60-80 ℃ for 8-12h to obtain ACC @ RGO serving as a cathode of the supercapacitor;
step two, preparing Co3O4a/ACC @ RGO material positive electrode;
use of ACC @ RGO prepared in step one at a potential of-0.8 to-1.0V using an electrochemical workstationIs a working electrode, a platinum plate is used as a counter electrode, a calomel electrode is used as a reference electrode, and the concentration is 0.01-10mol L-1Co (NO) of3)2· 6H2Performing electrochemical deposition by taking O as electrolyte, wherein the time of the electrochemical deposition is 600-3600 s;
washing the deposited carbon cloth with deionized water, drying in air at 60-90 deg.C for 8-12h, and annealing at 350-400 deg.C for 2-4h to obtain Co3O4The NSs/ACC @ RGO composite electrode material is used as the positive electrode of the super capacitor;
step three, assembling a water system super capacitor by taking the electrolyte solution as a base;
with Li2SO4And CoSO4Preparing an aqueous electrolyte for the solute, Li2SO4And CoSO4The concentration of solute is 2-3mol L-1And 0.1 to 2mol L-1；
Comparing ACC @ RGO negative electrode material and Co according to working voltage and specific capacitance of positive electrode and negative electrode3O4Cutting the/ACC @ RGO positive electrode material, and assembling the water system super capacitor by taking the porous polypropylene film as a diaphragm and taking the water-soluble electrolyte solution as the basis.
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| CN103887076A (en) * | 2014-01-21 | 2014-06-25 | 华侨大学 | Water system asymmetric super capacitor and preparation method thereof |
| CN106531452A (en) * | 2016-11-08 | 2017-03-22 | 西南科技大学 | Preparation method of quaternary carbon fiber cloth/graphene/tricobalt tetraoxide/polyaniline composite electrode material |
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