CN107887173B - Asymmetric super capacitor and preparation method thereof - Google Patents
Asymmetric super capacitor and preparation method thereof Download PDFInfo
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- CN107887173B CN107887173B CN201711016021.2A CN201711016021A CN107887173B CN 107887173 B CN107887173 B CN 107887173B CN 201711016021 A CN201711016021 A CN 201711016021A CN 107887173 B CN107887173 B CN 107887173B
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- 239000003990 capacitor Substances 0.000 title abstract description 54
- 238000002360 preparation method Methods 0.000 title abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 109
- -1 quinone compound Chemical class 0.000 claims abstract description 55
- AZQWKYJCGOJGHM-UHFFFAOYSA-N para-benzoquinone Natural products O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims abstract description 25
- 150000002989 phenols Chemical class 0.000 claims abstract description 21
- 150000001721 carbon Chemical class 0.000 claims abstract description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 50
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 32
- 239000003792 electrolyte Substances 0.000 claims description 16
- 229910002804 graphite Inorganic materials 0.000 claims description 14
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
- 239000002388 carbon-based active material Substances 0.000 claims description 10
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- 238000002791 soaking Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 229930185605 Bisphenol Natural products 0.000 claims description 7
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 7
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- 238000000034 method Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 150000005205 dihydroxybenzenes Chemical class 0.000 claims description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
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- 238000007654 immersion Methods 0.000 claims description 2
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims 5
- JLTFZOLNJALRLP-UHFFFAOYSA-N C1(C(C=CC2=CC=CC=C12)=O)=O.[Na] Chemical compound C1(C(C=CC2=CC=CC=C12)=O)=O.[Na] JLTFZOLNJALRLP-UHFFFAOYSA-N 0.000 claims 1
- AFVAAKZXFPQYEJ-UHFFFAOYSA-N anthracene-9,10-dione;sodium Chemical compound [Na].C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 AFVAAKZXFPQYEJ-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- YFXUVNYTWHTQNF-UHFFFAOYSA-N naphthalene-1,4-dione;sodium Chemical compound [Na].C1=CC=C2C(=O)C=CC(=O)C2=C1 YFXUVNYTWHTQNF-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 25
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- GGCZERPQGJTIQP-UHFFFAOYSA-M sodium 2-anthraquinonesulfonate Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)[O-])=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-M 0.000 description 8
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- 238000011160 research Methods 0.000 description 7
- 238000007600 charging Methods 0.000 description 6
- 238000006479 redox reaction Methods 0.000 description 5
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 4
- 239000013543 active substance Substances 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- 238000010277 constant-current charging Methods 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
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- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 4
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- 239000002390 adhesive tape Substances 0.000 description 3
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 230000033116 oxidation-reduction process Effects 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
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- 239000011149 active material Substances 0.000 description 2
- 150000004056 anthraquinones Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000011530 conductive current collector Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
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- 238000001035 drying Methods 0.000 description 2
- 239000000017 hydrogel Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229930192627 Naphthoquinone Natural products 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
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- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003137 locomotive effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000005055 memory storage Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 125000004151 quinonyl group Chemical group 0.000 description 1
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- 230000002441 reversible effect Effects 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- AURROVOEOKOHQK-UHFFFAOYSA-M sodium;1,4-dioxonaphthalene-2-sulfonate Chemical compound [Na+].C1=CC=C2C(=O)C(S(=O)(=O)[O-])=CC(=O)C2=C1 AURROVOEOKOHQK-UHFFFAOYSA-M 0.000 description 1
- DHQNJUHTJSDCOL-UHFFFAOYSA-M sodium;3,4-dioxonaphthalene-2-sulfonate Chemical compound [Na+].C1=CC=C2C(=O)C(=O)C(S(=O)(=O)[O-])=CC2=C1 DHQNJUHTJSDCOL-UHFFFAOYSA-M 0.000 description 1
- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012360 testing method Methods 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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- 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
-
- 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)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention discloses an asymmetric supercapacitor and a preparation method thereof, and particularly discloses a supercapacitor containing an asymmetric modified carbon-based electrode pair and a preparation method thereof, wherein asymmetric modified carbon-based electrodes in the supercapacitor are paired electrodes, two carbon-based electrodes comprise a current collector and a carbon-based material on the surface of the current collector, one carbon-based electrode also comprises at least one phenolic compound, and the other carbon-based electrode also comprises at least one quinone compound. The invention creatively provides a new system formed by respectively modifying phenols and quinones on the carbon-based electrodes and using the carbon-based electrodes as the electrodes of the super capacitor, and the effective capacitance of the two electrodes of the super capacitor system is obviously improved, so that the capacitance density and the energy density of the super capacitor are obviously improved, and the preparation method is simple and easy for commercial application.
Description
Technical Field
The invention belongs to the technical field of super capacitors, and particularly relates to an asymmetric super capacitor and a preparation method thereof.
Background
The super capacitor is a novel electricity storage device between a secondary battery and a common capacitor, has double functions of the common capacitor and a battery, has power density far higher than that of the common battery (10-100 times), and has energy density far higher than that of the traditional physical capacitor (100 times). Compared with the common capacitor and the battery, the super capacitor has the advantages of small volume, large capacity, high charging speed, long cycle life, high discharge power, wide working temperature range (-25 ℃ -85 ℃), good reliability, low cost and the like, and has very wide application prospects in the fields of energy, communication, electronic power, national defense and the like, for example: portable instrument equipment, data memory storage system, electric automobile power supply, emergent reserve power etc.. At present, the main objective of research in the field of various countries is to prepare supercapacitors which have high power density, high capacity density and stable performance and can be used for power systems (including backup power sources, electric locomotives and the like) and renewable energy systems.
The carbon-based material has the characteristics of porosity, high specific surface area, high porosity, good chemical stability, long service life and the like, and is often used as an electrode material of an electric double layer capacitor, so that higher energy density and power density can be obtained. The activated carbon is more frequently used as an electrode material of most commercial supercapacitors at present due to low price, but the activated carbon has the defect of low capacity density, so that the application of the supercapacitors in many fields requiring high energy density is limited, and therefore, the improvement of the capacity density of the activated carbon-based electrode material becomes one of the key problems to be solved urgently at present.
In order to further improve the performance of the carbon-based electrode material, a great deal of research work is carried out on the carbon-based electrode material through surface modification and various novel preparation processes, and the research mainly comprises the surface modification of activated carbon and the development of novel carbon materials such as carbon gel, carbon nano tubes, graphene, glassy carbon, carbon fibers and carbon foam obtained by pyrolyzing a polymer matrix.
The specific surface area of the currently developed activated carbon can reach 3000m at most2g-1However, the capacity density does not simply increase with the increase of the specific surface area, which is closely related to the porosity and the pore size distribution density, and the proportion of micropores (2nm to 50nm) is found to be one of the key factors for determining the capacity size. However, in the present activated carbon, micropores (C) are common<2nm) is larger, and the electrolyte can not be effectively infiltrated in the micropores, namely the micropores can not effectively form an electric double layer to store energy, so that the micropores existing in larger proportion do not contribute to improving the capacity density of the material, which is one of the main reasons that the capacity density of the active carbon can not be effectively improved at present. For example, a specific surface area of > 2000m for the current common2g-1The utilization ratio of the specific surface of the activated carbon electrode material is generally<30% of the total volume density of the aqueous electrolyte<210F g-1Assembled to form super capacitor with mass specific capacitance < 50F g-1。
Electrochemical active matters in the redox electrolyte can generate Faraday quasi-capacitance on the activated carbon electrode through redox reaction, and the capacitance generated by the Faraday quasi-capacitance is higher than the capacitance of an electric double layer, so that the Faraday quasi-capacitance contribution in the activated carbon-based electrode material is improved, and the capacity density of the carbon-based supercapacitor can be greatly improved. Patent CN 105632783a adopts benzenediol redox active ingredients to improve the specific capacitance of the electrode material of the super capacitor by about 2 times, but the related literature reports that the super capacitor assembled by using hydroquinone alone only shows the faraday's capacitance of phenol hydroxyl redox at the positive electrode and is still an electric double layer capacitance with low capacitance density at the negative electrode during charging and discharging, and the capacitance performance of the whole super capacitor is mainly limited to one electrode of the electric double layer capacitance with low capacitance value due to the influence of the two electrode capacitances connected in series, and the advantage of the other electrode with high faraday's capacitance cannot be fully exerted.
Therefore, it is a research direction to find a solution for increasing the overall specific capacitance of the super capacitor so as to meet the application requirements of the super capacitor in the field of high energy density.
Disclosure of Invention
Based on the defects in the prior art, the inventor researches and discovers that the positive and negative electrodes with good matching property can generate a gain effect on the capacitance based on the finding that the overall specific capacitance of the super capacitor is improved by starting from the matching property of the positive and negative electrodes in the super capacitor; specifically, the invention provides an asymmetric modified carbon-based electrode pair, and the mass specific capacitance of a super capacitor comprising the asymmetric modified carbon-based electrode pair reaches 250F g-1Above, the mass ratio of the super capacitor assembled by the existing carbon-based electrode is almost 5 times of the capacitance, and the super capacitor assembled by the existing carbon-based electrode has the advantage of high capacitance. Meanwhile, the super capacitor provided by the invention has the advantages of power density not lower than that of a super capacitor assembled by the existing carbon-based electrode, simplicity and convenience in implementation, low cost, remarkable improvement on capacitance and energy density and the like, and is easy to commercially apply.
The technical scheme of the invention is as follows:
an asymmetrically modified carbon-based electrode pair for a supercapacitor, wherein one electrode comprises at least one phenolic compound, a current collector and a carbon active material on the surface of the current collector, and the other electrode comprises at least one quinone compound, a current collector and a carbon active material on the surface of the current collector.
According to the invention, the current collector is preferably at least one of a graphite sheet, a platinum foil, a carbon fiber cloth, a graphite tape and a graphene film.
According to the invention, the carbon active material is selected from one or more of activated carbon, graphene, carbon nanotubes, carbon fibers and carbon foam.
According to the invention, the phenolic compound is selected from the group consisting of bisphenol compounds and/or monophenol compounds;
preferably, the bisphenol compound is selected from one or more of benzenediol, halogenated benzenediol, bisphenol a or derivatives thereof; preferably, the diphenol is selected from one or more of hydroquinone, resorcinol and catechol; preferably, the halogen in the halogenated benzenediol is selected from F, Cl, Br or I, and is also preferably bromine.
Preferably, the two phenolic hydroxyl groups of the bisphenol compound are in the para-positions.
Preferably, the bisphenol compound is selected from hydroquinone and/or brominated hydroquinone.
Preferably, the monophenol compound is selected from phenol and/or brominated phenols.
According to the invention, the quinone compound is selected from one or more of anthraquinone compounds and naphthoquinone compounds;
preferably, in the quinone compound, the aromatic ring in which the quinone group is located contains a para-quinone functional group;
preferably, the quinone compound is selected from one or more of sodium 9, 10-anthraquinone sulfonate, sodium 1, 4-dihydroxyanthraquinone sulfonate, sodium 1, 4-naphthoquinone sulfonate, sodium 1, 2-naphthoquinone sulfonate or sodium 2, 6-naphthoquinone sulfonate.
The invention also provides a preparation method of the asymmetric modified carbon-based electrode pair, which comprises the following steps:
coating a carbon active material on a current collector, and soaking the current collector in a solution containing at least one phenolic compound to obtain an electrode;
the carbon active material is coated on a current collector and immersed in a solution containing at least one quinone compound to obtain another electrode.
According to the invention, the immersion time is 12 hours or more, preferably 12 to 24 hours.
According to the invention, the concentration of the solution containing at least one phenolic compound is 0.001mol L-1-0.1molL-1(ii) a The concentration of the solution containing at least one quinone compound is 0.001mol L-1-0.1mol L-1。
According to the invention, the concentration ratio of the solution containing at least one phenolic compound to the solution containing at least one quinone compound is 10: 1-1: 10. Researches find that the phenolic compound or the aldehyde compound can show extra Faraday pseudocapacitance contribution on the carbon-based electrode, and the size of the extra Faraday pseudocapacitance contribution can be adjusted by adjusting the concentration of the solution; specifically, the faradaic capacitance contribution is large, and the concentration of the solution can be appropriately reduced, while the faradaic capacitance contribution is small, and the concentration of the solution can be appropriately increased. By controlling the concentration ratio of the two solutions within the above range, the capacitance of the two electrodes can be made equivalent, and the energy density can be increased, thereby better achieving the object of the present invention.
The invention also provides a supercapacitor which comprises the asymmetric modified carbon-based electrode pair, wherein an electrode containing the phenolic compound is a positive electrode, and an electrode containing the quinone compound is a negative electrode.
According to the invention, the supercapacitor also comprises an electrolyte or gel electrolyte.
Preferably, the electrolyte is an acidic electrolyte, such as sulfuric acid, phosphoric acid or hydrochloric acid; the gel electrolyte is an acidic gel electrolyte.
According to the invention, the supercapacitor is a button supercapacitor or a flexible solid supercapacitor.
The principle and the beneficial effects of the invention are as follows: active substances which can generate electrochemical oxidation reduction in corresponding potential windows are respectively modified on the positive carbon-based electrode and the negative carbon-based electrode, and the capacitance performance of the positive carbon-based electrode and the negative carbon-based electrode is respectively enhanced by the active substances, so that the capacitance performance and the energy performance of the whole super capacitor device are remarkably improved. Further, adopting an acid electrolyte, wherein proton hydrogen ions participate in the oxidation-reduction reaction of the phenolic compound or the quinone compound; and a phenol or quinone electrochemical organic matter with a para-functional group with small steric hindrance during redox reaction is selected, so that the conversion efficiency is further improved, and the redox reversibility is enhanced.
The invention discloses a novel supercapacitor, which is formed by assembling a phenolic modified carbon-based electrode as one electrode, a quinone modified carbon-based electrode as the other electrode and an acidic electrolyte. MakingCarbon-based materials for supercapacitors generally have a high specific surface area and spontaneously adsorb organic materials in solution. By applying the characteristic, the super capacitor which is singly combined with certain electroactive substances such as phenols and quinones can show Faraday quasi-capacitance contribution in the acid electrolyte, and the capacitance of the super capacitor is improved, so that the invention of the first aspect of the application is provided. However, further research finds that the faraday quasi-capacitance of the phenolic or quinone electrochemical active substance is mainly reflected on one electrode, so that the capacitance contribution of the two electrodes is obviously unequal, and the capacitance performance of the whole super capacitor formed by connecting the two electrodes in series is mainly reflected on one electrode of the electric double layer capacitor with low capacitance value, but the advantage of the other extremely high faraday quasi-capacitance can not be fully exerted. Therefore, the invention further creatively provides a novel system which is formed by respectively modifying phenols and quinones on the carbon-based electrodes and using the carbon-based electrodes as a pair of electrodes of the super capacitor. Because the capacitance contributed by the two electrodes is well matched, the advantage of high faradaic capacitance generated by oxidation reduction of two different electrochemical active matters in the electrodes on the electrodes can be played in an electrolyte, so that the assembled novel super capacitor system has much higher specific capacitance than a super capacitor assembled by unmodified carbon-based electrodes. The simple and efficient method is used for enabling the mass specific capacitance of the whole super capacitor to reach 250F g-1Above, a huge advantage of capacitance density is exhibited. The novel super capacitor manufactured by the method is simple and convenient to implement, low in cost, remarkably improved in capacitance density and energy density, and easy to commercially apply.
Drawings
FIG. 1 shows the voltage of 5mV s for a super capacitor SC-4 assembled with a modified activated carbon electrode in example 3 and a super capacitor SC-1 assembled with an unmodified activated carbon electrode in example 1 of the present invention-1Cyclic voltammogram at sweep rate.
FIG. 2 shows that the super capacitor SC-4 assembled by the modified activated carbon electrode in example 3 and the super capacitor SC-1 assembled by the unmodified activated carbon electrode in example 1 are at 1A g-1Charge and discharge curves at current density.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that various changes or modifications can be made by those skilled in the art after reading the disclosure of the present invention, and such equivalents also fall within the scope of the invention.
Comparative example 1
Mixing commercial activated carbon powder as an electrode active material, a conductive agent (conductive carbon black) and a binder (sodium carboxymethyl cellulose: an aqueous dispersion of styrene butadiene rubber) according to a solid mass ratio (85: 10: 2.5: 2.5), performing ball milling to obtain a slurry, uniformly coating the slurry on a graphite sheet to prepare an activated carbon electrode, cutting the electrode into a 16mm circular sheet shape, and enabling the loading capacity of the electrode active material to be 3mg cm-2。
Taking two pieces of the active carbon electrodes prepared in the way above, and keeping the volume of the active carbon electrodes at 1mol L-1And (4) assembling the super capacitor SC-1 in sulfuric acid.
Example 1
Mixing commercial activated carbon powder as an electrode active material, a conductive agent (conductive carbon black) and a binder (sodium carboxymethyl cellulose: an aqueous dispersion of styrene butadiene rubber) according to a solid mass ratio (85: 10: 2.5: 2.5), performing ball milling to obtain a slurry, uniformly coating the slurry on a graphite sheet to prepare an activated carbon electrode, cutting the electrode into a 16mm circular sheet shape, and enabling the loading capacity of the electrode active material to be 3mg cm-2。
Taking two active carbon electrodes, and soaking one electrode in a solution containing 0.006mol L-11mol L of Hydroquinone-1Immersing the other electrode in a solution containing 0.024mol L of sulfuric acid-11mol L of anthraquinone-2-sulfonic acid sodium salt-1And (3) soaking in a sulfuric acid solution for 12 hours, taking out, and absorbing the redundant solution on the surface of the electrode by using filter paper to obtain the hydroquinone modified activated carbon electrode and the anthraquinone-2-sodium sulfonate modified activated carbon electrode.
The hydroquinone modified activated carbon electrode is used as a positive electrode, the anthraquinone-2-sodium sulfonate modified activated carbon electrode is used as a negative electrode, and the activated carbon electrode is separated by cellulose filter paper and then is divided by 1mol L-1And sulfuric acid is assembled into the button type super capacitor SC-2.
Example 2
Two pieces of the activated carbon electrode prepared in example 1 were each immersed in a solution containing 0.006mol L-11mol L of hydroquinone-1Sulfuric acid solution and a solution containing 0.024mol L-11mol L of anthraquinone-2-sulfonic acid sodium salt-1And (3) soaking the sulfuric acid solution for 24 hours, taking out the sulfuric acid solution, and absorbing the redundant solution on the surface of the electrode by using filter paper to obtain the hydroquinone modified activated carbon electrode and the anthraquinone-2-sodium sulfonate modified activated carbon electrode.
The hydroquinone modified activated carbon electrode is used as a positive electrode, the anthraquinone-2-sodium sulfonate modified activated carbon electrode is used as a negative electrode, and the activated carbon electrode is separated by cellulose filter paper and then is divided by 1mol L-1And sulfuric acid is assembled into the button type super capacitor SC-3.
Example 3
Two pieces of the activated carbon electrode prepared in example 1 were each immersed in a solution containing 0.006mol L-11mol L of hydroquinone-1Sulfuric acid solution and a sulfuric acid solution containing 0.012mol L-11mol L of anthraquinone-2-sulfonic acid sodium salt-1And (3) soaking the sulfuric acid solution for 24 hours, taking out the sulfuric acid solution, and absorbing the redundant solution on the surface of the electrode by using filter paper to obtain the hydroquinone modified activated carbon electrode and the anthraquinone-2-sodium sulfonate modified activated carbon electrode.
The hydroquinone modified activated carbon electrode is used as a positive electrode, the anthraquinone-2-sodium sulfonate modified activated carbon electrode is used as a negative electrode, and the activated carbon electrode is separated by cellulose filter paper and then is divided by 1mol L-1And sulfuric acid is assembled into the button type super capacitor SC-4.
Comparing the cyclic voltammetry curves of the super capacitor SC-1 and the super capacitor SC-4 (see figure 1), it can be seen that the cyclic voltammetry curve of the SC-1 is a typical rectangular curve of the double layer capacitance, while the cyclic voltammetry curve of the SC-4 has a pair of obviously symmetrical redox peaks, which indicates that a rapid and reversible redox reaction occurs on the SC-4 electrode, mainly the hydroquinone loaded on the activated carbon electrode oxidizes hydroquinone during positive scan, the anthraquinone-based functional group on the anthraquinone-2-sodium sulfonate is reduced into a corresponding anthraquinone-based functional group during negative scan, and only one pair of redox peaks occurs because both the electrochemical actives generate redox reactions of the phenol group and the quinone-based functional group.
SC-4 has a high faradaic contribution, as seen from the area enclosed by the oxidation-reduction peak curve of SC-4 on the voltage-current density diagram several times as large as the area enclosed by the rectangular curve of the SC-1 electric double layer capacitance. Comparing the constant current charging and discharging curves of the super capacitors SC-1 and SC-4 (see FIG. 2), it can be seen that the SC-1 constant current charging and discharging curve is a typical symmetrical triangular curve of the capacitance of the double electric layers, the discharging time is equal to the charging time, and 100% coulomb charging and discharging efficiency is achieved. And the constant-current charge-discharge curve of the SC-4 is similar to a Mongolian shape, and shows a charge-discharge platform similar to battery behavior in a voltage range of 0.4-0.6V, further showing that the high Fala quasi-capacitance contribution of the SC-4 is provided, the charge-discharge curve is quite symmetrical, and almost 100% of coulomb charge-discharge efficiency is provided, showing that the SC-4 cannot cause the reduction of power density due to the electrochemical active matter. It can also be seen from FIG. 2 that the charging and discharging time of SC-4 is 5 times that of SC-1 at the same charging and discharging current density, which indicates that the discharging capacitance density of SC-4 is 5 times that of SC-1.
Example 4
Two pieces of the activated carbon electrode prepared in example 1 were each immersed in a solution containing 0.006mol L-11mol L of hydroquinone-1Sulfuric acid solution and a solution containing 0.006mol L-11mol L of anthraquinone-2-sulfonic acid sodium salt-1And (3) soaking the sulfuric acid solution for 24 hours, taking out the sulfuric acid solution, and absorbing the redundant solution on the surface of the electrode by using filter paper to obtain the hydroquinone modified activated carbon electrode and the anthraquinone-2-sodium sulfonate modified activated carbon electrode.
The hydroquinone modified activated carbon electrode is used as a positive electrode, the anthraquinone-2-sodium sulfonate modified activated carbon electrode is used as a negative electrode, and the activated carbon electrode is separated by cellulose filter paper and then is divided by 1mol L-1And sulfuric acid is assembled into the button type super capacitor SC-5.
Comparative example 2
Mixing commercial activated carbon powder as electrode active material with conductive agent (conductive carbon black) and binder (sodium carboxymethyl cellulose: styrene butadiene rubber aqueous dispersion) at a solid mass ratio (85: 10: 2.5: 2.5) by ball milling to obtain slurry, uniformly coating the slurry on a graphite adhesive tape conductive current collector, drying at 100 ℃ to obtain the flexible activated carbon powderThe working area of the active carbon slurry coating on the electrode is 1cm × 3cm, and the loading capacity of the active material is 1mg cm-2. The graphite tape is prepared by adhering graphite paper with the thickness of 3mm to a graphite layer with the thickness of dozens of micrometers by using an adhesive tape.
Taking two pieces of the prepared activated carbon flexible electrodes, wherein one piece of the two pieces of the prepared activated carbon flexible electrodes is used as a positive electrode, the other piece of the prepared activated carbon flexible electrodes is used as a negative electrode, sulfuric acid hydrogel (mass ratio of concentrated sulfuric acid: polyvinyl alcohol: water: 1:10) is coated on working areas of the two electrodes, then the two pieces of the activated carbon flexible electrodes are attached together to form a sandwich type flexible solid-state supercapacitor SC-6, and the sandwich type flexible solid-state supercapacitor is cured for 30min at 40 ℃, wherein the sulfuric acid gel plays roles of an electrolyte.
Example 5
Mixing commercial activated carbon powder as an electrode active material, a conductive agent (conductive carbon black) and a binder (sodium carboxymethyl cellulose: an aqueous dispersion of styrene butadiene rubber) according to a solid mass ratio (85: 10: 2.5: 2.5) by ball milling to prepare a slurry, uniformly coating the slurry on a graphite tape conductive current collector, and drying the slurry at 100 ℃ to prepare a flexible activated carbon electrode, wherein the working area of the active carbon slurry coated on the electrode is 1cm × 3cm, and the loading capacity of the active material is 1mg cm-2. The graphite tape is prepared by adhering graphite paper with the thickness of 3mm to a graphite layer with the thickness of dozens of micrometers by using an adhesive tape.
Two pieces of the prepared active carbon flexible electrode are taken, and one piece of the electrode is soaked in a solution containing 0.006mol L-11mol L of Hydroquinone-1The other electrode was immersed in a solution containing 0.012mol L of sulfuric acid-11mol L of anthraquinone-2-sulfonic acid sodium salt-1Soaking in sulfuric acid solution for 24h, taking out, and absorbing the redundant solution on the surface of the electrode by using filter paper to obtain the hydroquinone modified activated carbon flexible electrode and the anthraquinone-2-sodium sulfonate modified activated carbon flexible electrode.
The active carbon flexible electrode modified by hydroquinone is used as a positive electrode, the active carbon flexible electrode modified by anthraquinone-2-sodium sulfonate is used as a negative electrode, sulfuric acid hydrogel (mass ratio is concentrated sulfuric acid: polyvinyl alcohol: water: 1:10) is coated on working areas of the two electrodes, then the two electrodes are attached together to form a sandwich type flexible solid super capacitor SC-7, and the sandwich type flexible solid super capacitor SC-7 is solidified for 30min at 40 ℃, wherein the sulfuric acid gel plays roles of an electrolyte and a diaphragm.
Example 7
The supercapacitor prepared as described above was charged at 1A g-1The specific capacitance of the electrode material and the mass specific capacitance of the active substance of the whole super capacitor are tested by constant current charging and discharging under the current density; and at 1mA cm-2The volume specific capacitance of the flexible super capacitor is tested by constant current charging and discharging under the current density. The specific test results are shown in table 1.
TABLE 1 Performance test Table for super capacitor
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (16)
1. An asymmetrically modified carbon-based electrode pair for a supercapacitor, characterized in that one electrode comprises at least one phenolic compound, a current collector and a carbon active material on the surface of the current collector, and the other electrode comprises at least one quinone compound, a current collector and a carbon active material on the surface of the current collector; wherein the electrode containing the phenolic compound is a positive electrode, and the electrode containing the quinone compound is a negative electrode;
the quinone compound is selected from one or more of 9, 10-anthraquinone sodium sulfonate, 1, 4-dihydroxy anthraquinone sodium sulfonate, 1, 4-naphthoquinone sodium sulfonate, 1, 2-naphthoquinone sodium sulfonate or 2, 6-naphthoquinone sodium sulfonate.
2. The asymmetrically modified carbon-based electrode pair according to claim 1, wherein the current collector is at least one of a graphite sheet, a platinum foil, a carbon fiber cloth, a graphite tape, a graphene film;
the carbon active material is selected from one or more of activated carbon, graphene, carbon nanotubes, carbon fibers and carbon foam.
3. The asymmetrically modified carbon-based electrode pair according to claim 1, wherein the phenolic compound is selected from a bisphenol compound and/or a monophenol compound.
4. The asymmetrically modified carbon-based electrode pair according to claim 3, wherein the bisphenol compound is selected from one or more of benzenediol, halogenated benzenediol, bisphenol A, or derivatives thereof; the monophenol compound is selected from phenol and/or brominated phenol.
5. The asymmetrically modified carbon-based electrode pair according to claim 4, wherein the hydroquinone is selected from one or more of hydroquinone, resorcinol, catechol;
the halogen in the halogenated benzenediol is selected from F, Cl, Br or I.
6. The asymmetrically modified carbon-based electrode pair according to claim 3, wherein two phenolic hydroxyl groups of the bisphenol compound are in para-positions.
7. The asymmetrically modified carbon-based electrode pair according to claim 6, wherein the bisphenol compound is selected from hydroquinone and/or brominated hydroquinone.
8. A method for preparing an asymmetrically modified carbon-based electrode pair for a supercapacitor according to any one of claims 1 to 7, comprising the steps of:
coating a carbon active material on a current collector, and soaking the current collector in a solution containing at least one phenolic compound to obtain an electrode serving as a positive electrode;
the carbon active material is coated on a current collector and immersed in a solution containing at least one quinone compound to obtain another electrode, which serves as a negative electrode.
9. The method according to claim 8, wherein the time for the immersion is 12 hours or more.
10. The process according to claim 8, wherein the solution containing at least one phenolic compound has a concentration of 0.001mol L-1-0.1mol L-1(ii) a The concentration of the solution containing at least one quinone compound is 0.001mol L-1-0.1mol L-1。
11. The production method according to claim 8, wherein the concentration ratio of the solution containing at least one phenolic compound to the solution containing at least one quinone compound is 10:1 to 1: 10.
12. A supercapacitor comprising the asymmetrically modified carbon-based electrode pair according to any one of claims 1 to 7, wherein the electrode containing a phenolic compound is a positive electrode and the electrode containing a quinone compound is a negative electrode.
13. The supercapacitor according to claim 12, further comprising an electrolyte or gel electrolyte.
14. The supercapacitor of claim 13, wherein the electrolyte is an acidic electrolyte and the gel electrolyte is an acidic gel electrolyte.
15. The supercapacitor of claim 14, wherein the acidic electrolyte is sulfuric acid, phosphoric acid, or hydrochloric acid.
16. The supercapacitor according to any one of claims 12 to 15, wherein the supercapacitor is a button supercapacitor or a flexible solid supercapacitor.
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