CN111105936A - Energy storage system of modified carbon-based electrode in cooperation with redox electrolyte - Google Patents
Energy storage system of modified carbon-based electrode in cooperation with redox electrolyte Download PDFInfo
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 44
- 238000004146 energy storage Methods 0.000 title claims abstract description 30
- 150000001721 carbon Chemical class 0.000 title claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002253 acid Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 8
- 230000004913 activation Effects 0.000 claims abstract description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 238000006056 electrooxidation reaction Methods 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 8
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 8
- 239000002041 carbon nanotube Substances 0.000 claims description 8
- -1 potassium ferricyanide Chemical compound 0.000 claims description 8
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 8
- 235000011152 sodium sulphate Nutrition 0.000 claims description 8
- 230000002195 synergetic effect Effects 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 239000004917 carbon fiber Substances 0.000 claims description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- 239000001103 potassium chloride Substances 0.000 claims description 4
- 235000011164 potassium chloride Nutrition 0.000 claims description 4
- 235000010333 potassium nitrate Nutrition 0.000 claims description 4
- 239000004323 potassium nitrate Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 2
- 238000004458 analytical method Methods 0.000 claims description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 2
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 230000010287 polarization Effects 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 2
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims description 2
- 229940041260 vanadyl sulfate Drugs 0.000 claims description 2
- 229910000352 vanadyl sulfate Inorganic materials 0.000 claims description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 8
- 239000003990 capacitor Substances 0.000 description 6
- 238000002484 cyclic voltammetry Methods 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 4
- 238000000840 electrochemical analysis Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 238000010408 sweeping Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000011800 void material 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
- 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
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
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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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
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Abstract
The invention relates to an energy storage system of a modified carbon-based electrode and a redox electrolyte, which comprises the following components: the method comprises the following steps: preparing an electrode: the carbon-based material prepared by the electrochemical activation method in acid liquor is used as an electrode; step two: constructing an energy storage system: and (4) electrochemically oxidizing the electrode prepared in the step one in an aqueous electrolyte. The activation method adopted by the invention has the advantages of simple process, low cost, recyclable raw materials, safety and environmental protection. In the constructed energy storage system, the carbon-based electrode can show ultrahigh area specific capacitance and has better rate performance and cycle life. The constructed energy storage system is safe and pollution-free, has higher cost advantage and is beneficial to commercial application.
Description
Technical Field
The invention relates to an energy storage system of a modified carbon-based electrode in cooperation with redox electrolyte, belonging to the technical field of electrochemical energy storage.
Background
High performance energy storage devices are widely used in utility-scale grid services, hybrid vehicles, and consumer electronics, and among them, secondary batteries represented by lithium ion batteries and carbon-based supercapacitors are gaining market favor. The current research goal of energy storage devices is to achieve a combination of battery level energy density, capacitor level power density, and long cycle life in a single device.
At present, the super capacitor electrode is mainly made of carbon-based materials, and is beneficial to more static electricity adsorbed on the surface for charge storage due to the ultrahigh specific surface area. However, the specific surface area actually used for physical adsorption of electrolyte ions is far lower than the theoretical value due to the surface properties of the material, and the like, and therefore, it is required to improve the energy storage performance of the carbon-based material from the viewpoint of surface modification of the material.
Redox electrochemical capacitors are a class of enhanced double layer capacitors that utilize a reversible redox reaction with a soluble redox couple in the electrolyte. The redox active electrolyte adds a soluble redox couple to the electrochemically inert electrolyte of a conventional EDLC, increasing the storage of the faraday charge in addition to the electric double layer capacitance. Redox capacitors utilize a fixed load of inert electrolyte and void volume in the electrodes as an energy reservoir for the redox couple to provide additional capacity and increase the energy density of the device. When the redox capacitor is charged, the oxidation-active electrolyte at the positive electrode is oxidized and the oxidation-active electrolyte at the negative electrode is reduced, in the same way the process is reversed at the time of discharge.
In recent years, it has been proposed to enhance the electron conductivity of redox couples by compounding a redox additive with a carbon-based material having good conductivity, and some progress has been made, but most of the reported specific capacities are low and cannot be practically applied commercially. Therefore, it is urgently needed to construct a novel energy storage system by adopting a more effective strategy to further improve the specific capacity of the material.
Disclosure of Invention
In order to solve the technical problems, the invention provides an energy storage system of a modified carbon-based electrode in cooperation with a redox electrolyte, which has the following specific technical scheme:
an energy storage system of a modified carbon-based electrode in cooperation with a redox electrolyte specifically comprises the following steps:
the method comprises the following steps: soaking the carbon-based electrode in acid liquor;
step two: placing the soaked electrode in a three-electrode system for electrochemical oxidation, wherein acid liquor used by the electrolyte is the same as that used in the first step;
step three: cleaning and drying the electrode after electrochemical oxidation by using clean water;
step four: the prepared carbon-based material is used as an electrode, a salt solution of redox electrolyte is added to be used as an aqueous electrolyte, an energy storage system with a synergistic effect is constructed, and electrochemical performance analysis is carried out in the system.
Further, the carbon-based electrode is soaked in the acid solution for 5-30 min.
Further, the acid solution in the first step is one or a combination of more of concentrated nitric acid, concentrated hydrochloric acid, phosphoric acid, perchloric acid and concentrated sulfuric acid.
Further, the acid solution in the step one is a mixture of any two of concentrated nitric acid, concentrated hydrochloric acid, phosphoric acid, perchloric acid and concentrated sulfuric acid, and the mass concentration of each acid solution is as follows: the mixing volume ratio of concentrated nitric acid (> 40%), concentrated hydrochloric acid (> 25%), phosphoric acid (> 70%), perchloric acid (> 50%) and concentrated sulfuric acid (> 70%) is 1: 3-3: 1.
Further, the electrochemical activation method in the first step is constant potential oxidation, and the polarization voltage is 1.5-4 volts.
Further, the time of the electrochemical activation treatment is 1-30 minutes.
Further, the carbon-based material in the first step is any one of activated carbon, graphene, carbon nanotubes and carbon fibers.
Further, the aqueous electrolyte in the second step is a salt solution of a redox electrolyte, and the redox electrolyte is any one of vanadyl sulfate, M-phenylenediamine, potassium ferricyanide or benzenediol, and the concentration of the redox electrolyte is 0.01-0.2M.
Further, the salt solution is an aqueous solution of potassium nitrate, lithium chloride, sodium chloride, potassium chloride, lithium sulfate or sodium sulfate, and the salt concentration is 0.5-3M.
The invention has the beneficial effects that:
the adopted activation method has simple process and low cost, and the raw materials can be recycled, thereby being safe and environment-friendly.
In the constructed energy storage system, the carbon-based electrode can show ultrahigh area specific capacitance and has better rate performance and cycle life.
The constructed energy storage system is safe and pollution-free, has higher cost advantage and is beneficial to commercial application.
Drawings
FIG. 1 is a scanning electron microscope image of the carbon nanotubes treated in example 1,
figure 2 is a cyclic voltammogram of the electrode treated in example 1 in an electrolyte containing an redox electrolyte,
figure 3 is a graph of the rate capability of the electrode treated in example 1 in an electrolyte containing an redox electrolyte,
FIG. 4 is a plot of cyclic voltammetry for the control described in example 1,
FIG. 5 is a graph comparing the rate capability of the control described in example 1.
Detailed Description
The present invention will now be described in further detail with reference to the accompanying drawings. These drawings are simplified schematic views illustrating only the basic structure of the present invention in a schematic manner, and thus show only the constitution related to the present invention.
Example 1
An energy storage system with synergistic effect, which is constructed by treating a carbon nano tube electrode and a sodium sulfate aqueous solution containing potassium ferricyanide by electrochemical oxidation, comprises the following specific operation steps:
the carbon nanotube electrode is placed in a mixed solution (volume ratio is 1:1) of concentrated sulfuric acid (mass fraction is 98%) and concentrated nitric acid (mass fraction is 68%) to be fully soaked, electrochemical oxidation is carried out under the voltage of 3V, and the treatment time is 4 minutes. An electron microscope image of the treated carbon nanotubes is shown in fig. 1. And cleaning and drying the treated electrode by using clean water. Then, the electrode was electrochemically tested, the electrolyte was a 1M sodium sulfate solution containing 0.06M potassium ferricyanide, the voltage interval of the cyclic voltammetry test was-0.1-0.8V, and the scan rate was 5-200mV, with the results shown in FIGS. 2 and 3. In order to better show the influence of the synergistic effect on the electrochemical performance, the electrochemical test is respectively carried out on the treated carbon nano tube and the untreated carbon nano tube in a sodium sulfate solution containing potassium ferricyanide and a sodium sulfate solution not containing potassium ferricyanide, and the obtained results are shown in fig. 4 and 5, and the results show that the synergistic effect of the constructed system can greatly improve the specific area capacity of the electrode.
Example 2
An energy storage system with synergistic effect is constructed by using an electrochemical oxidation treatment carbon fiber electrode and a potassium nitrate aqueous solution containing hydroquinone.
The specific operation steps are as follows:
the carbon fiber electrode is placed in a mixed solution (volume ratio is 1:2) of concentrated sulfuric acid (mass fraction is 98%) and perchloric acid (mass fraction is 70%) to be fully soaked, electrochemical oxidation is carried out under the voltage of 4V, and the treatment time is 15 minutes. And cleaning and drying the treated electrode by using clean water. Then the electrode is tested electrochemically, the electrolyte is 1M potassium nitrate solution containing 0.1M hydroquinone, the voltage interval of the cyclic voltammetry test is 0-1V, and the scanning speed is 5-200 mV. According to the experimental result, the specific area capacity of the carbon fiber electrode obtained under the sweeping speed of 5mV/s is up to 1270mF/cm2。
Example 3
An energy storage system with synergistic effect is constructed by using an electrochemical oxidation treatment active carbon electrode and a sodium sulfate aqueous solution containing potassium ferricyanide. The specific operation steps are as follows:
placing the activated carbon electrode in concentrated sulfuric acid (mass fraction is 98%) and concentrated hydrochloric acid (mass fraction is36%) was thoroughly immersed in a mixed solution (volume ratio 2:1) and electrochemically oxidized at a voltage of 2V for 2 minutes. And cleaning and drying the treated electrode by using clean water. And then carrying out electrochemical test on the electrode, wherein the electrolyte is 0.5M sodium sulfate solution containing 0.05M potassium ferricyanide, the voltage interval of the cyclic voltammetry test is-0.2-0.9V, and the scanning rate is 5-200 mV. According to the experimental result, the specific area capacity of the activated carbon electrode obtained under the sweeping speed of 5mV/s is up to 810mF/cm2。
Example 4
And the energy storage system with synergistic effect is constructed by treating the graphene electrode and the potassium chloride aqueous solution containing the p-dihydroxybenzene through electrochemical oxidation. The specific operation steps are as follows:
the activated carbon electrode is placed in a mixed solution (volume ratio is 1:1) of concentrated sulfuric acid (mass fraction is 98%) and concentrated nitric acid (mass fraction is 68%) to be fully soaked, electrochemical oxidation is carried out under the voltage of 2.5V, and the treatment time is 4 minutes. And cleaning and drying the treated electrode by using clean water. And then carrying out electrochemical test on the electrode, wherein the electrolyte is a 1M potassium chloride solution containing 0.1M hydroquinone, the voltage interval of the cyclic voltammetry test is-0.1-0.8V, and the scanning rate is 5-200 mV. According to the experimental result, the specific area capacity of the graphene electrode obtained at the sweeping speed of 5mV/s is up to 2560mF/cm2。
According to the embodiment, the constructed energy storage system has the advantages that the carbon-based electrode can show ultrahigh area specific capacitance, has better rate performance and cycle life, and is beneficial to commercial application.
Claims (8)
1. An energy storage system of a modified carbon-based electrode in cooperation with a redox electrolyte is characterized by comprising the following steps:
the method comprises the following steps: soaking the carbon-based electrode in acid liquor;
step two: placing the soaked electrode in a three-electrode system for electrochemical oxidation, wherein acid liquor used by the electrolyte is the same as that used in the first step;
step three: cleaning and drying the electrode after electrochemical oxidation by using clean water;
step four: the prepared carbon-based material is used as an electrode, a salt solution of redox electrolyte is added to be used as an aqueous electrolyte, an energy storage system with a synergistic effect is constructed, and electrochemical performance analysis is carried out in the system.
2. The energy storage system of the modified carbon-based electrode in cooperation with a redox electrolyte according to claim 1, wherein: the acid solution in the first step is one or a combination of more of concentrated nitric acid, concentrated hydrochloric acid, phosphoric acid, perchloric acid and concentrated sulfuric acid.
3. The energy storage system of the modified carbon-based electrode in cooperation with a redox electrolyte according to claim 1, wherein: the acid solution in the first step is a mixture of any two of concentrated nitric acid, concentrated hydrochloric acid, phosphoric acid, perchloric acid and concentrated sulfuric acid, and the volume ratio of the mixture is 1: 3-3: 1.
4. The energy storage system of the modified carbon-based electrode in cooperation with a redox electrolyte according to claim 1, wherein: the electrochemical activation method in the first step is constant potential oxidation, and the polarization voltage is 1.5-4 volts.
5. The energy storage system of the modified carbon-based electrode in cooperation with a redox electrolyte according to claim 4, wherein: the time of the electrochemical activation treatment is 1-30 minutes.
6. The energy storage system of the modified carbon-based electrode in cooperation with a redox electrolyte according to claim 1, wherein: the carbon-based material in the first step is any one of activated carbon, graphene, carbon nanotubes and carbon fibers.
7. The energy storage system of the modified carbon-based electrode in cooperation with a redox electrolyte according to claim 1, wherein: the aqueous electrolyte in the second step is a salt solution of a redox electrolyte, and the redox electrolyte is any one of vanadyl sulfate, M-phenylenediamine, potassium ferricyanide or benzenediol, and the concentration of the redox electrolyte is 0.01-0.2M.
8. The energy storage system of the modified carbon-based electrode in cooperation with a redox electrolyte according to claim 7, wherein: the salt solution is an aqueous solution of potassium nitrate, lithium chloride, sodium chloride, potassium chloride, lithium sulfate or sodium sulfate, and the salt concentration is 0.5-3M.
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| CN105632783A (en) * | 2016-01-11 | 2016-06-01 | 河南师范大学 | Manufacturing method for redox activity electrolyte based nitrogen-doped graphene supercapacitor |
| CN105806924A (en) * | 2016-05-10 | 2016-07-27 | 西北师范大学 | 8-OHdG sensor as well as preparation method and application thereof |
| CN107919234A (en) * | 2017-10-26 | 2018-04-17 | 中国科学院福建物质结构研究所 | A kind of enhanced ultracapacitor and preparation method thereof |
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