CN107887173A - A kind of Asymmetric Supercapacitor and preparation method thereof - Google Patents
A kind of Asymmetric Supercapacitor and preparation method thereof Download PDFInfo
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- CN107887173A CN107887173A CN201711016021.2A CN201711016021A CN107887173A CN 107887173 A CN107887173 A CN 107887173A CN 201711016021 A CN201711016021 A CN 201711016021A CN 107887173 A CN107887173 A CN 107887173A
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- Prior art keywords
- carbon
- ultracapacitor
- electrode
- quinones
- compound
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 101
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 47
- 230000004048 modification Effects 0.000 claims abstract description 35
- 238000012986 modification Methods 0.000 claims abstract description 35
- 150000002989 phenols Chemical class 0.000 claims abstract description 26
- 150000004053 quinones Chemical class 0.000 claims abstract description 24
- 239000003990 capacitor Substances 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 40
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 32
- 229910052708 sodium Inorganic materials 0.000 claims description 21
- 239000011734 sodium Substances 0.000 claims description 21
- 230000000694 effects Effects 0.000 claims description 20
- -1 bisphenol compound Chemical class 0.000 claims description 14
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 12
- 229910002804 graphite Inorganic materials 0.000 claims description 12
- 239000010439 graphite Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 11
- 230000005611 electricity Effects 0.000 claims description 9
- 229930185605 Bisphenol Natural products 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 8
- 239000003292 glue Substances 0.000 claims description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 125000000524 functional group Chemical group 0.000 claims description 5
- 239000011245 gel electrolyte Substances 0.000 claims description 5
- 229910021389 graphene Inorganic materials 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 125000004151 quinonyl group Chemical group 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
- 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 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000005868 electrolysis reaction Methods 0.000 claims description 4
- 230000026030 halogenation Effects 0.000 claims description 4
- 238000005658 halogenation reaction Methods 0.000 claims description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- YTWHNPHXSILERV-UHFFFAOYSA-N 1,2-dihydroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CCC2 YTWHNPHXSILERV-UHFFFAOYSA-N 0.000 claims description 2
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 claims description 2
- PKFLXWBXGRAUKU-UHFFFAOYSA-N 3,4-dioxonaphthalene-2-sulfonic acid Chemical class C1=CC=C2C(=O)C(=O)C(S(=O)(=O)O)=CC2=C1 PKFLXWBXGRAUKU-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- 229930192627 Naphthoquinone Natural products 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 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 claims description 2
- 150000004056 anthraquinones Chemical class 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 229940106691 bisphenol a Drugs 0.000 claims description 2
- 230000031709 bromination Effects 0.000 claims description 2
- 238000005893 bromination reaction Methods 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 2
- 125000000687 hydroquinonyl group Chemical class C1(O)=C(C=C(O)C=C1)* 0.000 claims 3
- YIMXKLOZWQFWHK-UHFFFAOYSA-N [S].C1(C=CC(C2=CC=CC=C12)=O)=O Chemical compound [S].C1(C=CC(C2=CC=CC=C12)=O)=O YIMXKLOZWQFWHK-UHFFFAOYSA-N 0.000 claims 1
- 239000003575 carbonaceous material Substances 0.000 abstract description 3
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 18
- 239000007772 electrode material Substances 0.000 description 15
- 230000008901 benefit Effects 0.000 description 7
- 239000002002 slurry Substances 0.000 description 6
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000011149 active material Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000006479 redox reaction Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000005034 decoration Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical class OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000011530 conductive current collector Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- MUVQKFGNPGZBII-UHFFFAOYSA-N 1-anthrol Chemical compound C1=CC=C2C=C3C(O)=CC=CC3=CC2=C1 MUVQKFGNPGZBII-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- IDIFPUPZOAXKOV-UHFFFAOYSA-N azane ruthenium Chemical compound N.[Ru] IDIFPUPZOAXKOV-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000005205 dihydroxybenzenes Chemical class 0.000 description 1
- 238000005183 dynamical system Methods 0.000 description 1
- 239000011263 electroactive material Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- 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
Landscapes
- 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 a kind of Asymmetric Supercapacitor and preparation method thereof, specifically disclose a kind of ultracapacitor containing asymmetric modification carbon-based electrode pair and preparation method thereof, wherein, asymmetric modification carbon-based electrode inside ultracapacitor is paired electrode, carbon-based material of two carbon-based electrodes comprising collector and the collection liquid surface, wherein, at least one phenolic compound is also included in a carbon-based electrode, and at least one quinones is also included in another carbon-based electrode.Innovative proposition of the invention modifies phenols and quinones on carbon-based electrode respectively, and new system is formed as electrode of super capacitor, significantly improve two electrode effective capacitance amounts of super capacitor system, so as to significantly improve the capacitance density of ultracapacitor and energy density, and preparation method is simple, is easy to business application.
Description
Technical field
The invention belongs to supercapacitor technologies field, has and is related to a kind of Asymmetric Supercapacitor and its preparation side
Method.
Background technology
Ultracapacitor is a kind of new storing up electricity device between secondary cell and ordinary capacitor, has common electricity concurrently
The dual-use function of container and battery, its power density are far above common batteries (10~100 times), and energy density is far above traditional thing
Reason electric capacity (>100 times).Compared with ordinary capacitor and battery, ultracapacitor have small volume, capacity are big, charging rate is fast,
Have extended cycle life, discharge power height, operating temperature wide (- 25 DEG C~85 DEG C), the advantages that good reliability and cost are cheap, in energy
The fields such as source, communication, electron electric power, national defence suffer from very wide application prospect, such as：Portable instrument equipment, data note
Recall storage system, electric car power supply, emergent back-up source etc..Various countries are to prepare height in the main target of the area research at present
Power density, high capacity density and stable performance can be used for dynamical system (including back-up source and electric motor car etc.), can be again
The ultracapacitor of raw energy resource system.
Carbon-based material is because with porous, high-specific surface area, high porosity, chemical stability be good and the spy such as service life length
Point, the electrode material of double layer capacitor is often used as, higher energy density and power density can be obtained.Wherein activated carbon
It is even more the electrode material for being frequently used as current most of business ultracapacitors because its is cheap, but activated carbon exists in itself
The shortcomings that capacity density is relatively low, and then limit ultracapacitor and require the application in high-energy-density field many, therefore carry
The capacity density of high activity charcoal base electrode material turns into one of key issue urgently to be resolved hurrily at present.
In order to further improve the performance of carbon-based electrode material, it is modified by surface and various novel preparation process is to carbon-based
Electrode material has carried out numerous studies work, mainly include ruthenium ammonia synthesis catalyst and carbon gel, CNT, graphene,
The development of the new carbons such as the carbon foam obtained by vitreous carbon, carbon fiber and pyrolyzed-polymer matrix.
The specific surface area for the activated carbon developed at present is maximum up to 3000m2g-1More than, but its capacity density is not with than table
The increase of area and present it is simple be incremented by, this is closely related with its porosity and pore-size distribution density, and micro- in finding
Ratio shared by hole (2nm~50nm) is one of key factor for determining its amount of capacity.But in current activated carbon, typically
Micropore (<2nm) proportion is larger, and electrolyte can not be effectively infiltrated in the micropore, i.e., micropore can not be effectively formed double
Electric layer and store energy, therefore, account for micropore existing for larger proportion for improve material capacity density do not contribute, this is mesh
One of the main reason for capacity density of preceding activated carbon can not effectively improve.For example, for specific surface area ＞ common at present
2000m2g-1Active carbon electrode material, it is more usual than the utilization rate on surface<30%, capacity density is general in its aqueous electrolyte
<210F g-1, it is assembled into the quality specific capacitance ＜ 50F g of ultracapacitor-1。
Electro-chemical activity thing can produce farad on activated carbon electrodes by redox reaction in redox electrolytes liquid
Pseudo-capacitance, the capacitance as caused by pseudo capacitance is higher than electric double layer capacitance amount, therefore improves activated carbon base electrode material
Pseudo capacitance contribution in material, the capacity density of Carbon-based supercapacitor can be increased substantially.Patent CN 105632783A
The electrode material specific capacitance of ultracapacitor is improved 2 times or so using benzenediol class redox active composition, but it is related
The ultracapacitor of hydroquinones assembling is used alone in discharge and recharge in document report, only shows phenolic hydroxyl group oxidation in positive pole
The pseudo capacitance of reduction, it is still the low electric double layer capacitance of capacitance density in negative pole, whole ultracapacitor capacitive character energy
Due to being influenceed by two electrode capacitance series connection, become to be primarily limited on low one electrode of electric double layer capacitance of capacitance, and
The advantage of the high pseudo capacitance of another electrode can not be given full play to.
Therefore, searching can improve ultracapacitor entirety specific capacitance, to meet ultracapacitor in high-energy-density
The solution of the application demand in field is our research direction.
The content of the invention
Based on the shortcomings of the prior art, inventor, which studies, to be found, to improve ultracapacitor entirety specific capacitance, can
Started with the matching from the both positive and negative polarity in ultracapacitor, it is found that the good both positive and negative polarity of matching can produce gain to specific capacitance
Effect, based on the discovery that proposing the present invention；Specifically, the present invention provides a kind of asymmetric modification carbon-based electrode pair,
The quality specific capacitance of ultracapacitor comprising this asymmetric modification carbon-based electrode pair reaches 250F g-1More than, it is almost existing
5 times of the quality specific capacitance of the ultracapacitor of carbon-based electrode assembling, show high capacitance advantage.It is meanwhile of the invention
Ultracapacitor has the power density of the ultracapacitor not less than the assembling of existing carbon-based electrode simultaneously, is easy to implement, cost
Cheap, capacitance and energy density improve many advantages, such as notable, are easy to business application.
Technical solution of the present invention is as follows：
A kind of asymmetric modification carbon-based electrode pair of ultracapacitor, wherein, an electrode includes at least one phenols
The carbon activity material of compound, collector and the collection liquid surface, another electrode include at least one quinones, collection
The carbon activity material of fluid and the collection liquid surface.
According to the present invention, the collector is preferably in graphite flake, platinum foil, carbon cloth, graphite glue band, graphene film
It is at least one.
According to the present invention, the carbon activity material is in activated carbon, graphene, CNT, carbon fiber, foamy carbon
It is one or more.
According to the present invention, the phenolic compound is selected from bisphenol compound and/or single phenolic compounds；
Preferably, one kind in benzenediol, halogenation benzenediol, bisphenol-A or derivatives thereof of the bisphenol compound or
It is a variety of；Preferably, one or more of the benzenediol in hydroquinones, resorcinol, catechol；Preferably, institute
The halogen stated in halogenation benzenediol is selected from F, Cl, Br or I, also preferably bromine.
Preferably, two phenolic hydroxyl groups of the bisphenol compound are in contraposition.
Preferably, the bisphenol compound is selected from hydroquinones and/or bromination hydroquinones.
Preferably, the single phenolic compounds are selected from phenol and/or brominated phenol.
According to the present invention, the one kind or more of the quinones in anthraquinone analog compound and naphthoquinone compound
Kind；
Preferably, in the quinones, residing for quinonyl on aromatic rings, contraposition quinonyl functional group is contained；
Preferably, the quinones is selected from 9,10- sodium anthraquinone sulfonates, Isosorbide-5-Nitrae-sodium dihydro-anthraquinone sulfonate, Isosorbide-5-Nitrae-naphthalene
One or more in quinone sodium sulfonate, 1,2- naphthoquinone sulfonic acids sodium or 2,6- naphthoquinone sulfonic acid sodium.
The present invention also provides a kind of preparation method of above-mentioned asymmetric modification carbon-based electrode pair, and methods described includes following step
Suddenly：
Carbon activity material is coated on collector, and is impregnated in the solution containing at least one phenolic compound,
Obtain an electrode；
Carbon activity material is coated on collector, and is impregnated in the solution containing at least one quinones,
Obtain another electrode.
According to the present invention, the time of the dipping is more than 12h, preferably 12h~24h.
According to the present invention, the concentration of the solution containing at least one phenolic compound is 0.001mol L-1-0.1mol
L-1；The concentration of the solution containing at least one quinones is 0.001mol L-1-0.1mol L-1。
According to the present invention, the solution containing at least one phenolic compound is with containing at least one quinones
The concentration ratio of solution is 10:1~1:10.Research finds that the phenolic compound or aldehyde compound show on carbon-based electrode
The big I of extra pseudo capacitance contribution is adjusted by adjusting the concentration of above-mentioned solution；Specifically, faraday is accurate
Capacitance contribution is big, can suitably reduce the concentration of solution, and pseudo capacitance contribution is small, then can suitably increase solution
Concentration.By controlling the concentration ratio of two kinds of solution make it that the capacitance of two electrodes is suitable in above range, and energy
Metric density increased, so as to which the purpose of the present invention be better achieved.
The present invention also provides a kind of ultracapacitor, and the ultracapacitor includes the asymmetric modification carbon-based electrode
It is right, wherein, the electrode containing phenolic compound is positive electrode, and the electrode containing quinones is negative electrode.
According to the present invention, the ultracapacitor also includes electrolyte or gel electrolyte.
Preferably, the electrolyte is acidic electrolysis bath, for example, sulfuric acid, phosphoric acid or hydrochloric acid；The gel electrolyte is
Acid gel electrolyte.
According to the present invention, the ultracapacitor is button ultracapacitor or flexible solid-state supercapacitor.
The present invention principle and beneficial effect be：It can be sent out on positive and negative carbon-based electrode is modified respectively in corresponding potential window
The active material of raw electrochemical redox, the active material strengthens positive and negative carbon-based electrode electric capacity performance respectively, so as to significantly carry
The electric capacity performance and energy performance of high whole ultracapacitor device.Further, using acidic electrolysis bath, proton hydrogen therein
Ion participates in the redox reaction of phenolic compound or quinones；Also, redox reaction space-time is occurring for selection
Between the small contraposition functional group of steric hindrance phenols or quinones electrochemistry organic matter, further improve transformation efficiency, strengthen redox
Invertibity.
Specifically, the invention discloses a kind of Novel super capacitor, have and disclose a kind of carbon-based electricity of phenols modification
An extremely electrode, quinones modification carbon-based electrode is another electrode, the ultracapacitor being assembled into acidic electrolyte bath.As
The carbon-based material of ultracapacitor typically has a high-specific surface area, can organic matter in Spontaneous adsorption solution.With this feature,
Individually the quasi- electricity of faraday can be shown with reference to the ultracapacitor of phenols and quinones certain electroactive material in acidic electrolysis bath
Hold contribution, lift the electric capacity of ultracapacitor, the invention of the application first aspect is proposed based on this.But further research
It was found that phenols or the general major embodiment of quinones electro-chemical activity thing pseudo capacitance are on one of the electrodes, two electrodes are caused
Capacitance contribution amount is significantly unequal, and the whole ultracapacitor capacitive character that two electrodes are composed in series can become to be mainly reflected in electricity
On low one electrode of electric double layer capacitance of capacitance, and the advantage of another high pseudo capacitance can not be given full play to.Therefore, this
Further innovative proposition modifies phenols and quinones on carbon-based electrode respectively for invention, and as the one of ultracapacitor
New system is formed to electrode.Due to preferably have matched the capacitance of two electrodes contribution, two kinds of different electrochemistry in electrode are allowed
Active matter redox and advantage of caused high pseudo capacitance on electrode can be played in a kind of electrolyte,
So that the new super capacitor system of assembling has the specific capacitance more much higher than the ultracapacitor of unmodified carbon-based electrode assembling.
Whole ultracapacitor quality specific capacitance is allowed to reach 250F g with this simple efficient method-1More than, show huge electric capacity
Density advantages.The Novel super capacitor that this method makes is easy to implement, and cost is cheap, and capacitance density and energy density significantly carry
Height, it is easy to business application.
Brief description of the drawings
Fig. 1 is the ultracapacitor SC-4 of modification activities carbon resistance rod assembling in the embodiment of the present invention 3 with not repaiied in embodiment 1
The ultracapacitor SC-1 of activated carbon electrodes assembling is adornd in 5mV s-1Sweep the cyclic voltammetry curve under speed.
Fig. 2 is the ultracapacitor SC-4 of modification activities carbon resistance rod assembling in the embodiment of the present invention 3 with not repaiied in embodiment 1
The ultracapacitor SC-1 of activated carbon electrodes assembling is adornd in 1A g-1Charging and discharging curve under current density.
Embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limit the scope of the invention.Furthermore, it is to be understood that after content disclosed in this invention has been read, ability
Field technique personnel can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the protection that the present invention is limited
Within the scope of.
Comparative example 1
It is electrode active material to take commercial activated carbon powder, with conductive agent (conductive black), binding agent (carboxymethyl cellulose acid
Sodium：The aqueous dispersions of butadiene-styrene rubber) press solid masses ratio (85：10：2.5：2.5) slurry is made in mixing and ball milling, is coated uniformly on
On graphite flake, activated carbon electrodes are made, electrode is cut into 16mm wafer type, and electrode active material load capacity is 3mg cm-2。
The activated carbon electrodes of the above-mentioned preparation of two panels are taken in 1mol L-1Ultracapacitor SC-1 is assembled into sulfuric acid.
Embodiment 1
It is electrode active material to take commercial activated carbon powder, with conductive agent (conductive black), binding agent (carboxymethyl cellulose acid
Sodium：The aqueous dispersions of butadiene-styrene rubber) press solid masses ratio (85：10：2.5：2.5) slurry is made in mixing and ball milling, is coated uniformly on
On graphite flake, activated carbon electrodes are made, electrode is cut into 16mm wafer type, and electrode active material load capacity is 3mg cm-2。
Activated carbon electrodes two panels is taken, a plate electrode is impregnated in containing 0.006mol L-1The 1mol L of hydroquinones-1Sulfuric acid
Solution, another plate electrode are impregnated in containing 0.024mol L-1The 1mol L of anthraquinone-2-sodium-1In sulfuric acid solution, during dipping
Between be 12h, suck the unnecessary solution of electrode surface with filter paper after taking-up, obtain hydroquinones modification activated carbon electrodes and anthracene
The activated carbon electrodes of quinone -2- sodium sulfonates modification.
Using the activated carbon electrodes of hydroquinones modification as positive pole, the activated carbon electrodes conduct of anthraquinone-2-sodium modification
Negative pole, after being separated with cellulosic filter paper, with 1mol L-1Sulfuric acid is assembled into button ultracapacitor SC-2.
Embodiment 2
Activated carbon electrodes two panels prepared by Example 1, is impregnated in containing 0.006mol L respectively-1The 1mol of hydroquinones
L-1Sulfuric acid solution and contain 0.024mol L-1The 1mol L of anthraquinone-2-sodium-1Sulfuric acid solution, dip time 24h, take out
The unnecessary solution of electrode surface is sucked with filter paper afterwards, the activated carbon electrodes and anthraquinone-2-sodium for obtaining hydroquinones modification are repaiied
The activated carbon electrodes of decorations.
Using the activated carbon electrodes of hydroquinones modification as positive pole, the activated carbon electrodes conduct of anthraquinone-2-sodium modification
Negative pole, after being separated with cellulosic filter paper, with 1mol L-1Sulfuric acid is assembled into button ultracapacitor SC-3.
Embodiment 3
Activated carbon electrodes two panels prepared by Example 1, is impregnated in containing 0.006mol L respectively-1The 1mol of hydroquinones
L-1Sulfuric acid solution and contain 0.012mol L-1The 1mol L of anthraquinone-2-sodium-1Sulfuric acid solution, dip time 24h, take out
The unnecessary solution of electrode surface is sucked with filter paper afterwards, the activated carbon electrodes and anthraquinone-2-sodium for obtaining hydroquinones modification are repaiied
The activated carbon electrodes of decorations.
Using the activated carbon electrodes of hydroquinones modification as positive pole, the activated carbon electrodes conduct of anthraquinone-2-sodium modification
Negative pole, after being separated with cellulosic filter paper, with 1mol L-1Sulfuric acid is assembled into button ultracapacitor SC-4.
Compare ultracapacitor SC-1 and ultracapacitor SC-4 cyclic voltammetry curve (see Fig. 1), it can be seen that SC-1
Cyclic voltammetry curve be typical electric double layer capacitance rectangular curve, and then have on SC-4 cyclic voltammetry curve a pair it is obvious
Symmetrical redox peaks, show that the redox reaction of Rapid reversible occurs on SC-4 electrodes, this is mainly supported on activity
Hydroquinones aoxidizes benzoquinone when just sweeping on carbon resistance rod, the anthraquinonyl functional group on anthraquinone-2-sodium in negative sweep also
Original is into corresponding anthrol base functional group, due to being that phenolic group and the redox of quinonyl functional group occurs on two electro-chemical activity things
Reaction, therefore only there are a pair of redox peaks.
From the area that SC-4 redox peaks curve surrounds on voltage-current density figure times over SC-1 electric double layers electricity
The area that the rectangular curve of appearance surrounds sees there is high faraday's pseudo-capacitive contribution in SC-4.Compare ultracapacitor SC-1 and SC-
4 constant current charge-discharge curve (see Fig. 2), it can be seen that SC-1 constant current charge-discharges curve is typical electric double layer capacitance symmetric triangular
Shape curve, discharge time are equal to the charging interval, the coulomb efficiency for charge-discharge for having 100%.And SC-4 constant current charge-discharge curve
Similar yurt shape is presented, the charge and discharge platform of similar battery behavior, further table are shown in 0.4-0.6V voltage ranges
Bright SC-4 high faraday's pseudo-capacitive contribution, and charging and discharging curve is very symmetrical, the coulomb discharge and recharge for also having almost 100%
Efficiency, show that SC-4 will not be because of the decline that power density is caused containing electro-chemical activity thing.Can be with from figure 2, it is seen that same
Under one charging or discharging current density, the time of SC-4 discharge and recharge is 5 times of SC-1, also indicates that SC-4 discharge capacity density is SC-1
5 times.
Embodiment 4
Activated carbon electrodes two panels prepared by Example 1, is impregnated in containing 0.006mol L respectively-1The 1mol of hydroquinones
L-1Sulfuric acid solution and contain 0.006mol L-1The 1mol L of anthraquinone-2-sodium-1Sulfuric acid solution, dip time 24h, take out
The unnecessary solution of electrode surface is sucked with filter paper afterwards, the activated carbon electrodes and anthraquinone-2-sodium for obtaining hydroquinones modification are repaiied
The activated carbon electrodes of decorations.
Using the activated carbon electrodes of hydroquinones modification as positive pole, the activated carbon electrodes conduct of anthraquinone-2-sodium modification
Negative pole, after being separated with cellulosic filter paper, with 1mol L-1Sulfuric acid is assembled into button ultracapacitor SC-5.
Comparative example 2
It is electrode active material to take commercial activated carbon powder, with conductive agent (conductive black), binding agent (carboxymethyl cellulose acid
Sodium：The aqueous dispersions of butadiene-styrene rubber) press solid masses ratio (85：10：2.5：2.5) slurry is made in mixing and ball milling, is evenly coated with
In in graphite glue band conductive current collector, after 100 DEG C of drying, the activated carbon electrodes of flexibility are made.Activated carbon slurry applies on electrode
The work area covered is 1cm × 3cm, and active material load capacity is 1mg cm-2.The graphite glue band is by by stone thick 3mm
Black paper stick next tens microns of layer with adhesive tape after graphite linings made from.
The activated carbon flexible electrode two panels of above-mentioned preparation is taken, one is used as positive pole, and another is as negative pole, with sulfuric acid water-setting
(quality proportioning is the concentrated sulfuric acid to glue：Polyvinyl alcohol：Water=1:1:10) on the working region coated on two electrodes, then it is fitted in
Sandwich style flexible solid-state supercapacitor SC-6 is assembled into together, and solidifies 30min at 40 DEG C, and wherein sulfogel plays electricity
Solve the effect of matter and barrier film.
Embodiment 5
It is electrode active material to take commercial activated carbon powder, with conductive agent (conductive black), binding agent (carboxymethyl cellulose acid
Sodium：The aqueous dispersions of butadiene-styrene rubber) press solid masses ratio (85：10：2.5：2.5) slurry is made in mixing and ball milling, is evenly coated with
In in graphite glue band conductive current collector, after 100 DEG C of drying, the activated carbon electrodes of flexibility are made.Activated carbon slurry applies on electrode
The work area covered is 1cm × 3cm, and active material load capacity is 1mg cm-2.The graphite glue band is by by stone thick 3mm
Black paper stick next tens microns of layer with adhesive tape after graphite linings made from.
The activated carbon flexible electrode two panels of above-mentioned preparation is taken, a plate electrode is impregnated in containing 0.006mol L-1Hydroquinones
1mol L-1Sulfuric acid solution, another plate electrode are impregnated in containing 0.012mol L-1The 1mol L of anthraquinone-2-sodium-1Sulfuric acid
In solution, dip time is 24h, and the unnecessary solution of electrode surface is sucked with filter paper after taking-up, obtains hydroquinones modification
Activated carbon flexible electrode and the activated carbon flexible electrode of anthraquinone-2-sodium modification.
Activated carbon flexible electrode after hydroquinones is modified is soft as positive pole, the activated carbon of anthraquinone-2-sodium modification
Property electrode is as negative pole, and with sulfuric acid hydrogel, (quality proportioning is the concentrated sulfuric acid：Polyvinyl alcohol：Water=1:1:10) two electricity are coated on
On the working region of pole, then fit together and be assembled into sandwich style flexible solid-state supercapacitor SC-7, and it is solid at 40 DEG C
Change 30min, wherein sulfogel plays a part of electrolyte and barrier film.
Embodiment 7
By the ultracapacitor of above-mentioned preparation, in 1A g-1Current density under constant current charge-discharge test electrode material
Specific capacitance and whole ultracapacitor active material quality specific capacitance；And in 1mA cm-2Current density under constant current charge-discharge come
Test the volumetric capacitance of flexible super capacitor.Specific test result is shown in Table 1.
The performance test table of the ultracapacitor of table 1
More than, embodiments of the present invention are illustrated.But the present invention is not limited to above-mentioned embodiment.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution and improvements done etc., it should be included in the guarantor of the present invention
Within the scope of shield.
Claims (10)
1. the asymmetric modification carbon-based electrode pair of a kind of ultracapacitor a, it is characterised in that electrode includes at least one phenol
The carbon activity material of class compound, collector and the collection liquid surface, another electrode include at least one quinones, collection
The carbon activity material of fluid and the collection liquid surface.
2. it is according to claim 1 it is asymmetric modification carbon-based electrode pair, it is characterised in that the collector be graphite flake,
At least one of platinum foil, carbon cloth, graphite glue band, graphene film；
One or more of the carbon activity material in activated carbon, graphene, CNT, carbon fiber, foamy carbon.
3. asymmetric modification carbon-based electrode pair according to claim 1 or 2, it is characterised in that the phenolic compound choosing
From bisphenol compound and/or single phenolic compounds；
Preferably, one or more of the bisphenol compound in benzenediol, halogenation benzenediol, bisphenol-A or derivatives thereof；
Preferably, one or more of the benzenediol in hydroquinones, resorcinol, catechol；
Preferably, the halogen in the halogenation benzenediol is selected from F, Cl, Br or I, also preferably bromine；
Preferably, two phenolic hydroxyl groups of the bisphenol compound are in contraposition；
Preferably, the bisphenol compound is selected from hydroquinones and/or bromination hydroquinones；
Preferably, the single phenolic compounds are selected from phenol and/or brominated phenol.
4. the asymmetric modification carbon-based electrode pair according to claim any one of 1-3, it is characterised in that the quinones chemical combination
One or more of the thing in anthraquinone analog compound and naphthoquinone compound；
Preferably, in the quinones, residing for quinonyl on aromatic rings, contraposition quinonyl functional group is contained；
Preferably, the quinones is selected from 9,10- sodium anthraquinone sulfonates, Isosorbide-5-Nitrae-sodium dihydro-anthraquinone sulfonate, 1,4-naphthoquinone sulphur
One or more in sour sodium, 1,2- naphthoquinone sulfonic acids sodium or 2,6- naphthoquinone sulfonic acid sodium.
A kind of 5. preparation method of the asymmetric modification carbon-based electrode pair described in any one of claim 1-4, it is characterised in that institute
The method of stating comprises the following steps：
Carbon activity material is coated on collector, and is impregnated in the solution containing at least one phenolic compound, is obtained
One electrode；
Carbon activity material is coated on collector, and is impregnated in the solution containing at least one quinones, is obtained
Another electrode.
6. preparation method according to claim 5, it is characterised in that the time of the dipping is more than 12h, is preferably
12h~24h.
7. the preparation method according to claim 5 or 6, it is characterised in that described containing at least one phenolic compound
The concentration of solution is 0.001mol L-1-0.1mol L-1；The concentration of the solution containing at least one quinones is
0.001mol L-1-0.1mol L-1。
Preferably, solution of the solution containing at least one phenolic compound with containing at least one quinones is dense
Degree is than being 10:1~1:10.
8. a kind of ultracapacitor, it is characterised in that the ultracapacitor includes non-right described in claim any one of 1-4
Claim modification carbon-based electrode pair, wherein, the electrode containing phenolic compound is positive electrode, and the electrode containing quinones is negative electricity
Pole.
9. ultracapacitor according to claim 8, it is characterised in that the ultracapacitor is also comprising electrolyte or solidifying
Glue electrolyte.
Preferably, the electrolyte is acidic electrolysis bath, for example, sulfuric acid, phosphoric acid or hydrochloric acid；The gel electrolyte is acidity
Gel electrolyte.
10. ultracapacitor according to claim 8 or claim 9, it is characterised in that the ultracapacitor is that button is super
Capacitor or flexible solid-state supercapacitor.
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