CN104576082A - Asymmetric supercapacitor with potassium ferricyanide and potassium ferrocyanide added to two electrode chambers respectively and preparation method thereof - Google Patents
Asymmetric supercapacitor with potassium ferricyanide and potassium ferrocyanide added to two electrode chambers respectively and preparation method thereof Download PDFInfo
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- CN104576082A CN104576082A CN201510023879.6A CN201510023879A CN104576082A CN 104576082 A CN104576082 A CN 104576082A CN 201510023879 A CN201510023879 A CN 201510023879A CN 104576082 A CN104576082 A CN 104576082A
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- potassium
- supercapacitor
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- potassium ferricyanide
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- -1 potassium ferricyanide Chemical compound 0.000 title claims abstract description 41
- 239000000276 potassium ferrocyanide Substances 0.000 title claims abstract description 29
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000003990 capacitor Substances 0.000 claims abstract description 48
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims abstract description 19
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 claims description 48
- 239000003792 electrolyte Substances 0.000 claims description 44
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 41
- 239000000463 material Substances 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 31
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 27
- 229910052759 nickel Inorganic materials 0.000 claims description 25
- 230000008569 process Effects 0.000 claims description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000006260 foam Substances 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 150000007522 mineralic acids Chemical class 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 12
- 238000004070 electrodeposition Methods 0.000 claims description 11
- 239000012535 impurity Substances 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 239000007800 oxidant agent Substances 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 8
- 238000004062 sedimentation Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000002484 cyclic voltammetry Methods 0.000 claims description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 6
- 239000011707 mineral Substances 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000008151 electrolyte solution Substances 0.000 claims description 5
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 239000004917 carbon fiber Substances 0.000 claims description 4
- 239000003575 carbonaceous material Substances 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- 239000006258 conductive agent Substances 0.000 claims description 4
- 239000000356 contaminant Substances 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000010306 acid treatment Methods 0.000 claims description 2
- 239000011149 active material Substances 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
- 238000002848 electrochemical method Methods 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 239000006261 foam material Substances 0.000 claims description 2
- 238000005259 measurement Methods 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 abstract description 8
- 239000003014 ion exchange membrane Substances 0.000 abstract 1
- 239000011244 liquid electrolyte Substances 0.000 abstract 1
- 239000007787 solid Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 11
- 239000011259 mixed solution Substances 0.000 description 10
- 230000004888 barrier function Effects 0.000 description 8
- 238000007599 discharging Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 230000033116 oxidation-reduction process Effects 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 2
- CMWORGPVIRCICO-UHFFFAOYSA-I [OH-].[OH-].[OH-].[OH-].[OH-].[Co++].[Ce+3] Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Co++].[Ce+3] CMWORGPVIRCICO-UHFFFAOYSA-I 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000010345 tape casting Methods 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010409 thin film Substances 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
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/64—Liquid electrolytes characterised by additives
-
- 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
-
- 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
- H01G11/52—Separators
-
- 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
-
- 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)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
Abstract
The invention relates to an asymmetric supercapacitor with potassium ferricyanide and potassium ferrocyanide added to two electrode chambers respectively and a preparation method of the asymmetric supercapacitor. According to the asymmetric supercapacitor and the preparation method of the asymmetric supercapacitor, the potassium ferricyanide is added to the positive electrode chamber, the potassium ferrocyanide is added to the negative electrode chamber, and the positive electrode chamber and the negative electrode chamber are separated by an ion exchange membrane and assembled into a single supercapacitor or a multi-body supercapacitor bank. Solid electrodes and liquid electrolyte provide capacitance simultaneously to achieve organic combination of the supercapacitor and a flow battery. The positive electrode of the capacitor achieves pseudocapacitance overlapping of cobaltous hydroxide and the potassium ferricyanide; the negative electrode of the capacitor achieves pseudocapacitance overlapping of an activated carbon electrical double-layer capacitor and the potassium ferrocyanide. Thus, the asymmetric supercapacitor has quite high energy density. In the negative electrode chamber, K4Fe(CN)6 is selected as a reducing agent, so self discharge is reduced, and the stability of the capacitive performance of the capacitor is improved.
Description
Technical field:
The invention belongs to technical field of chemical power, especially Asymmetric Supercapacitor aspect, be specifically related to add the potassium ferricyanide (K respectively in the electrolyte of a kind of the two poles of the earth
3fe (CN)
6) and potassium ferrocyanide (K
4fe (CN)
6) Asymmetric Supercapacitor and preparation method thereof.
Background technology:
The excessive use of traditional energy material causes serious problem of environmental pollution, continuable development of clean energy with utilize imperative, energy and environment have become the significant problem of 21 century facing mankind.Ultracapacitor has the advantages such as power density is high, environmental protection, long service life, good temp characteristic, use it for startup power supply, the smooth startup of high-power military installation can be ensured, vehicle also can be it can be used as to draw the energy, for electric automobile, trolley coach etc.Ultracapacitor is used in electronic device, can uses as the power supply of long-time stable.Along with greatly developing of the regenerative resource such as wind energy, solar energy, huge and effective utilization of the novel energy of less pollution seems more important for these reserves.Ultracapacitor is as the storage of these energy and conversion equipment, be electric energy by solar energy, wind energy transformation, produced electric energy stored, when needs by these fault offset, improve the stability of renewable energy system and transmission system, play the effect of Effective Regulation.
For battery, there is the low defect of energy density in ultracapacitor, and the energy density how improving ultracapacitor becomes the key of ultracapacitor development.The advantages such as water system Asymmetric Supercapacitor has environmental protection, power density is high, cost is low, easy and simple to handle, are subject to the extensive concern of researcher.Positive pole many employings metal oxide, metal hydroxides or conducting polymer are as electrode active material, negative pole employing active carbons etc. are as electrode active material, this unsymmetric structure can expand the operating potential window of ultracapacitor, improves the energy density of ultracapacitor.Research finds, in this electrolytic solution for super capacitor, add redox materials, by the regulation and control of volume and concentration, electrode can be made to produce different contributions from electrolyte to electric capacity, thus can increase substantially the energy density of ultracapacitor.
The application number that applicant has applied for is 2014106901745, and patent that name is called " the two poles of the earth electrolyte adds Asymmetric Supercapacitor of the potassium ferricyanide and p-phenylenediamine (PPD) and preparation method thereof respectively ", at cobalt hydroxide (Co (OH)
2in)-active carbon (AC) Asymmetric Supercapacitor, cathode chamber adds K
3fe (CN)
6, with Co (OH)
2coexist, stability and compatibility are all fine.Due to K
3fe (CN)
6high activity and good redox reversible be well select as catholyte.But the selection of anode chamber reducing agent has very large difficulty, applicant in the above application cathodic reduction material select be organic substance p-phenylenediamine (PPD), its advantage is that oxidation-reduction potential is more negative, with K
3fe (CN)
6oxidation-reduction potential have larger gap, to electric discharge favourable.But for amberplex, be difficult to avoid neutral organic molecule p-phenylenediamine (PPD) through, its self discharge increases, and organic molecule solubility is in aqueous lower, is unfavorable for the capacitive property of capacitor.
K
4fe (CN)
6as reducing agent, not easily through amberplex, the electrolyte of capacitor two Room is not easily mixed mutually, thus reduces self discharge, improve the stability of condenser capacitance performance.And K
4fe (CN)
6in water, solubility is higher, is conducive to the lifting of electrolyte to capacitance contribution.Because K
3fe (CN)
6and K
4fe (CN)
6just be a pair oxidation-reduction pair, reactant and product each other, makes the process of electrolyte simplify.
Summary of the invention:
Technical problem to be solved by this invention adds Asymmetric Supercapacitor of the potassium ferricyanide and potassium ferrocyanide and preparation method thereof, to provide the energy density of capacitor respectively for providing a kind of the two poles of the earth electrolyte.
In order to solve above technical problem, technical scheme provided by the invention is as follows:
The two poles of the earth electrolyte adds an Asymmetric Supercapacitor for the potassium ferricyanide and potassium ferrocyanide respectively, comprises positive pole, negative pole, amberplex and electrolyte, and the cathode chamber of capacitor and anode chamber, between both positive and negative polarity, separate by described amberplex;
Described electrolyte is alkaline aqueous solution, and is added with potassium ferricyanide solution in the electrolyte of cathode chamber, and potassium ferricyanide solution concentration is 0.01 ~ 0.5mol/L; Be added with potassium ferrocyanide solution in the electrolyte of anode chamber, potassium ferrocyanide solution concentration is 0.01 ~ 0.5mol/L.
The two poles of the earth electrolyte adds a preparation method for the Asymmetric Supercapacitor of the potassium ferricyanide and potassium ferrocyanide respectively, and concrete steps are as follows:
Step 1: by material with carbon element through the ultrasonic process of organic solvent, removing organic impurities; By material with carbon element through persalt or sulfuric acid acidation process, removing inorganic impurity improves material with carbon element specific area, adopts constant potential or constant current electrochemical deposition, treated material with carbon element grows cobalt hydroxide film, obtain cobalt hydroxide electrode, it can be used as supercapacitor positive electrode to use;
Step 2: using nickel foam or material with carbon element as substrate, through organic solvent, inorganic acid and deionized water process, removing organic substance and oxide-film, active carbon is mixed with conductive agent, binding agent, blade coating or be sprayed in treated substrate, obtain activated carbon electrodes, it can be used as super capacitor anode to use;
Step 3: by amberplex through hydrogen peroxide and mineral acid treatment, removing surface organic matter, inorganic metal ion impurity, put into used alkaline solution soak stand-by with deionized water after cleaning;
Step 4: by supercapacitor positive electrode, negative pole, amberplex, seal gasket and end plate, become ultracapacitor monomer by bolt combination, or multiple positive pole, negative pole, amberplex, seal gasket and end plate are assembled into the bank of super capacitors of multiple electrode; Adopt injector for medical purpose or vacuum pump mode, electrolyte is injected cathode chamber, anode chamber respectively along reserving hole channel, sealing after fixing;
Step 5: ultracapacitor monomer, the bank of super capacitors of assembling in use step 4 are as required carried out serial or parallel connection, thus reached required electric current and voltage;
Step 6: adopt three-electrode system or two electrode systems to carry out electrochemical measurement to single electrode, single ultracapacitor or bank of super capacitors and many group ultracapacitors, method of measurement is cyclic voltammetry, constant current charge-discharge method or AC impedence method.
Further, in step 1, material with carbon element substrate comprises carbon cloth, carbon fiber felt, carbon fiber paper or graphite, processes above-mentioned carbon material surface, obtains clean material with carbon element substrate; Be specially, soak 1 ~ 5 hour in organic solvent, then ultrasonic 5 ~ 60 minutes, described organic solvent was acetone or alcohol; Soak 1 ~ 5 hour in mineral acid, then ultrasonic 5 ~ 60 minutes, described inorganic acid was hydrochloric acid or sulfuric acid; Finally, soak 1 ~ 5 hour in deionized water, then ultrasonic 5 ~ 60 minutes, removing inorganic acid.
Further, in step 1, adopt electrochemical deposition technique, obtain material with carbon element/cobalt hydroxide electrode, use as supercapacitor positive electrode; In electrochemical deposition process, sedimentation time is 10min ~ 2h, and electrolyte cobalt nitrate concentration is 0.1 ~ 2mol/L, and depositing temperature is 30 ~ 60 DEG C, and sedimentation potential selects-0.6V ~-1.3V, and deposited per area unit size of current is 0.01A ~ 2A/cm
2, unit are active material cobalt hydroxide quality is 0.5 ~ 15mg/cm
2.
Further, in step 2, nickel foam or carbon material surface are processed, obtain the nickel foam that cleans or material with carbon element substrate; Nickel foam or material with carbon element soak 1 ~ 5 hour respectively in organic solvent, and then ultrasonic 5 ~ 60 minutes, organic solvent comprised acetone or alcohol; Soak 1 ~ 5 hour in mineral acid, then ultrasonic 5 ~ 60 minutes, inorganic acid was mainly hydrochloric acid or sulfuric acid; Finally, soak 1 ~ 5 hour in deionized water, then ultrasonic 5 ~ 60 minutes, removing inorganic acid.
Further, in step 2, adopt blade coating or spraying method, obtain nickel foam or material with carbon element/activated carbon electrodes, use as super capacitor anode, active carbon mixes according to the ratio of 80 ~ 90:5 ~ 15:3 ~ 7 with conductive agent, binding agent, and in unit are, blade coating or the quality that is sprayed at the mixture on nickel foam or material with carbon element are 1 ~ 50mg/cm
2.
Further, in step 3, process, be specially diaphragm of supercapacitor amberplex, hydrogen peroxide volume fraction is 2 ~ 10%, and treatment temperature is 60 ~ 80 DEG C, and the processing time is 0.5 ~ 3 hour, removing organic impurities; Inorganic acid comprises watery hydrochloric acid or dilute sulfuric acid, and treatment temperature is 60 ~ 80 DEG C, and the processing time is 0.5 ~ 3 hour, removing inorganic contaminants.
Further, in step 4, end plate, bolt and rubber cushion is adopted to carry out assembling to capacitor and seal; Ultracapacitor shell is square, rectangle or circle, and electrolyte volume changes according to the change of shell sizes and number of electrodes, and monomer electrolytic solution for super capacitor volume is 5ml ~ 2000ml.
Further, in step 4, electrolyte is alkaline aqueous solution, and containing the alkali solute of potassium hydroxide, NaOH or lithium hydroxide, concentration is 0.5 ~ 6mol/L; Add the oxidizing substance potassium ferricyanide in cathode chamber, its concentration is 0.01 ~ 0.5mol/L; Add reducing substances potassium ferrocyanide in anode chamber, its concentration is 0.01 ~ 0.5mol/L.
Further, in steps of 5, ultracapacitor comprises different size electrode area ultracapacitor and multiple or many groups ultracapacitor assembling; Electrode area is 1cm
2~ 2500cm
2; Bank of super capacitors is composed in parallel by multiple ultracapacitor, and its quantity is 2 ~ 100 or more, by the mode built-up circuit of serial or parallel connection, and the electric current required by acquisition and voltage.
Further, in step 6, adopt different scanning speed to carry out cyclic voltammetry to electrode, ultracapacitor, sweep speed scope is 0.1 ~ 100mV/s.Adopt different current density to carry out charge-discharge test to electrode, ultracapacitor, current density range is 0.5A/g ~ 100A/g or 0.1mA/cm
2~ 100mA/cm
2.
Beneficial effect of the present invention is:
1, this patent selects K in anode chamber
4fe (CN)
6as reducing agent, its solubility in water is higher, is conducive to the lifting of electrolyte confrontation capacitance contribution.And not easily through amberplex, the electrolyte of capacitor two Room is not easily mixed mutually, thus reduces self discharge, improve the stability of condenser capacitance performance.Fe (CN)
6 3-with Fe (CN)
6 4-be a pair oxidation-reduction pair, the reactant of room, the two poles of the earth and product each other, electrolyte process is simpler.
2, the pure cerium hydroxide cobalt thin film electrode adopting electro-deposition method to prepare in the present invention, has high specific capacitance and excellent cyclical stability, for high-energy ultracapacitor provides key element.
3, adopt pure cerium hydroxide cobalt electrode to mate with activated carbon electrodes in the present invention, two electrode capacitances are functional, and cyclical stability is high.This capacitor can not only work long-term and stably, and has wider electrochemical operation window, has higher energy density.
4, in the present invention, reversible for height redox electrolytes matter is introduced in electrolytic solution for super capacitor, make electrolyte and electrode material simultaneously, non-interferingly provide electric capacity, super capacitor energy density is increased substantially.Such an approach achieves the combination of electrode and electrolyte solution in ultracapacitor, the capacitive property of ultracapacitor is improved significantly.
5, in the present invention in this novel ultracapacitor, use amberplex as barrier film, the effect of barrier film is not merely separated by both positive and negative polarity, make both positive and negative polarity electric insulation, and the electrolyte of both positive and negative polarity room is different, the oxidizing substance that cathode chamber contains and the reducing substances that anode chamber contains can not mix, and guarantee that the electric charge of two material storage can not the loss because of self discharge.
6, in the present invention, catholyte adds oxidizing substance, and anolyte adds reducing substances, makes in charge and discharge process, and electrode and electrolyte have contribution to the electric capacity of capacitor jointly, achieves the combination of ultracapacitor and flow battery.Because ultracapacitor has higher power density, and flow battery has larger energy density, therefore this device has ultracapacitor and flow battery advantage separately, has the ultracapacitor of higher energy density, more can meet current needs of production.
Accompanying drawing illustrates:
The structural representation of Fig. 1 capacitor of the present invention;
Fig. 2 electrode area is 1cm
20.2mol/L K is added respectively in the electrolyte of the two poles of the earth
3fe (CN)
6with 0.2mol/L K
4fe (CN)
6the cyclic voltammetry curve of Asymmetric Supercapacitor when sweep speed is 25mV/s;
Fig. 3 electrode area is 1cm
20.2mol/L K is added respectively in the electrolyte of the two poles of the earth
3fe (CN)
6with 0.2mol/L K
4fe (CN)
6asymmetric Supercapacitor be 5mA/cm in current density
2time charging and discharging curve;
Fig. 4 electrode area is 100cm
20.1mol/L K is added respectively in the electrolyte of the two poles of the earth
3fe (CN)
6with 0.1mol/L K
4fe (CN)
6asymmetric Supercapacitor difference sweep speed cyclic voltammetry curve;
Fig. 5 electrode area is 100cm
20.1mol/L K is added respectively in the electrolyte of the two poles of the earth
3fe (CN)
6with 0.1mol/L K
4fe (CN)
6the different current density of Asymmetric Supercapacitor under charging and discharging curve.
Fig. 6 electrode area is 100cm
2the K of variable concentrations is added respectively in the electrolyte of the two poles of the earth
3fe (CN)
6and K
4fe (CN)
6the comparison diagram of Asymmetric Supercapacitor charging and discharging curve.
Embodiment:
Below in conjunction with Figure of description, the specific embodiment of the present invention is further described in detail:
As shown in Figure 1, a kind of the two poles of the earth electrolyte adds the Asymmetric Supercapacitor of the potassium ferricyanide and potassium ferrocyanide respectively, comprise positive pole, negative pole, amberplex and electrolyte, the cathode chamber of capacitor and anode chamber, between both positive and negative polarity, separate by described amberplex;
Described electrolyte is alkaline aqueous solution, and is added with potassium ferricyanide solution in the electrolyte of cathode chamber, and potassium ferricyanide solution concentration is 0.01 ~ 0.5mol/L; Be added with potassium ferrocyanide solution in the electrolyte of anode chamber, potassium ferrocyanide solution concentration is 0.01 ~ 0.5mol/L.
The two poles of the earth electrolyte adds a preparation method for the Asymmetric Supercapacitor of the potassium ferricyanide and potassium ferrocyanide respectively, and specific embodiment is as follows:
Embodiment 1:
(1) area 1cm is adopted
2carbon paper is substrate, to soak respectively after 2 hours ultrasonic 30 minutes in acetone, ethanol, deionized water.Adopt constant potential electrodeposition process, prepare carbon paper/cobalt hydroxide electrode.In electrochemical deposition process, cobalt nitrate concentration is 1.2mol/L, and sedimentation time is 1h, and sedimentation potential is-0.9V, and temperature is 45 DEG C.
(2) area 1cm is adopted
2nickel foam is substrate, to soak respectively after 2 hours ultrasonic 30 minutes in acetone, ethanol, deionized water.Knife coating is adopted to prepare nickel foam/activated carbon electrodes.Active carbon, electrically conductive graphite and Nafion solution are mixed according to the ratio that mass ratio is 85:10:5, blade coating is in nickel foam.
(3) process diaphragm of supercapacitor amberplex, be specially, hydrogen peroxide volume fraction is 5%, and treatment temperature is 80 DEG C, and the processing time is 1 hour, removing organic impurities; Adopt dilute sulfuric acid process, treatment temperature is 80 DEG C, and the processing time is 1 hour, removing inorganic contaminants.Using carbon paper/cobalt hydroxide electrode as positive pole, nickel foam/activated carbon electrodes, as negative pole, take amberplex as barrier film, assembling electrode Asymmetric Supercapacitor.
(4) 50ml 1mol/L KOH and 0.2mol/L K is prepared
3fe (CN)
6mixed solution as catholyte, inject cathode chamber; Preparation 50ml 1mol/L KOH and 0.2mol/LK
4fe (CN)
6mixed solution as anolyte, being assembled into electrode area is 1cm
2asymmetric, the asymmetrical Novel asymmetric ultracapacitor of electrolyte of electrode.
(5) cyclic voltammetric (as shown in Figure 2) and charge-discharge test (as shown in Figure 3) are carried out to above-mentioned Novel asymmetric ultracapacitor, when current density is 5mA/cm
2time, ratio capacitance and the energy density of this Novel super capacitor are respectively 256.1F/g and 80Wh/kg.
Embodiment 2:
(1) area 100cm is adopted
2carbon paper is substrate, to soak respectively after 2 hours ultrasonic 30 minutes in acetone, ethanol, deionized water.Adopt constant potential electrodeposition process, prepare carbon paper/cobalt hydroxide electrode.In electrochemical deposition process, cobalt nitrate concentration is 1.2mol/L, and sedimentation time is 1h, and sedimentation potential is-0.9V, and temperature is 45 DEG C.
(2) area 100cm is adopted
2nickel foam is substrate, to soak respectively after 2 hours ultrasonic 30 minutes in acetone, ethanol, deionized water.Knife coating is adopted to prepare nickel foam/activated carbon electrodes.Active carbon, electrically conductive graphite and Nafion solution are mixed according to the ratio that mass ratio is 85:10:5, blade coating is in nickel foam.
(3) process diaphragm of supercapacitor amberplex, be specially, hydrogen peroxide volume fraction is 5%, and treatment temperature is 80 DEG C, and the processing time is 1 hour, removing organic impurities; Adopt dilute sulfuric acid process, treatment temperature is 80 DEG C, and the processing time is 1 hour, removing inorganic contaminants.
(4) cyclic voltammetric and charging/discharging thereof is adopted to test above-mentioned electrode.When charging and discharging currents density is 1mA/cm
2time, the ratio capacitance of carbon paper/cobalt hydroxide electrode is 513F/g, and the ratio capacitance of nickel foam/activated carbon electrodes is 211F/g.
(5) using carbon paper/cobalt hydroxide electrode as positive pole, nickel foam/activated carbon electrodes, as negative pole, with modified polypropene film for barrier film, is assembled into Asymmetric Supercapacitor, adds 1mol/L KOH solution as electrolyte.When current density is 1mA/cm
2time, ratio capacitance and the energy density of this Asymmetric Supercapacitor are respectively 77.2F/g and 27.4Wh/kg.(as Suo Shi Fig. 6 (a)) embodiment 3:
(1) identical with embodiment 2 (1).
(2) identical with embodiment 2 (2).
(3) identical with embodiment 2 (3).
(4) using carbon paper/cobalt hydroxide electrode as positive pole, nickel foam/activated carbon electrodes, as negative pole, take amberplex as barrier film, and positive pole injects the K of 50ml 1mol/L KOH and 0.05mol/L
3fe (CN)
6mixed solution, negative pole injects the K of 50ml 1mol/LKOH and 0.05mol/L
4fe (CN)
6mixed solution, be assembled into that room, the two poles of the earth adds Oxidizing and Reducing Agents respectively, electrode area is 100cm
2new Hydrogen cobalt oxide-active carbon asymmetric capacitor.Carry out charge-discharge test to above-mentioned Novel asymmetric capacitor, maximum potential window 1.6V, current density is 1mA/cm
2, ratio capacitance and the energy density of this novel capacitor are respectively 90.2F/g and 32.1Wh/kg.(as Suo Shi Fig. 6 (b))
Embodiment 4:
(1) identical with embodiment 2 (1).
(2) identical with embodiment 2 (2).
(3) identical with embodiment 2 (3).
(4) using carbon paper/cobalt hydroxide electrode as positive pole, nickel foam/activated carbon electrodes, as negative pole, take amberplex as barrier film, and positive pole injects the K of 50ml 1mol/L KOH and 0.08mol/L
3fe (CN)
6mixed solution, negative pole injects the K of 50ml 1mol/LKOH and 0.08mol/L
4fe (CN)
6mixed solution, be assembled into that room, the two poles of the earth adds Oxidizing and Reducing Agents respectively, electrode area is 100cm
2new Hydrogen cobalt oxide-active carbon asymmetric capacitor.Carry out charge-discharge test to above-mentioned Novel asymmetric capacitor, maximum potential window 1.6V, current density is 1mA/cm
2, ratio capacitance and the energy density of this novel capacitor are respectively 99.4F/g and 35.3Wh/kg.(shown in Fig. 6 (c))
Embodiment 5:
(1) identical with embodiment 2 (1).
(2) identical with embodiment 2 (2).
(3) identical with embodiment 2 (3).
(4) using carbon paper/cobalt hydroxide electrode as positive pole, nickel foam/activated carbon electrodes, as negative pole, take amberplex as barrier film, and positive pole injects the K of 50ml 1mol/L KOH and 0.1mol/L
3fe (CN)
6mixed solution, negative pole injects the K of 50ml 1mol/LKOH and 0.1mol/L
4fe (CN)
6mixed solution, be assembled into that room, the two poles of the earth adds Oxidizing and Reducing Agents respectively, electrode area is 100cm
2new Hydrogen cobalt oxide-active carbon asymmetric capacitor.
Above-mentioned Asymmetric Supercapacitor difference sweeps the cyclic voltammetry curve of speed, as shown in Figure 4;
Charging and discharging curve under the different current density of above-mentioned Asymmetric Supercapacitor, as shown in Figure 5; As can be seen from charging and discharging curve, this Asymmetric Supercapacitor is when containing redox materials, and its multiplying power property needs to improve further.
Carry out charge-discharge test to above-mentioned Novel asymmetric capacitor, maximum potential window 1.6V, current density is 1mA/cm
2, ratio capacitance and the energy density of this novel capacitor are respectively 107F/g and 38Wh/kg.(shown in Fig. 6 (d))
Embodiment 6:
(1) identical with embodiment 2 (1).
(2) identical with embodiment 2 (2).
(3) identical with embodiment 2 (3).
(4) using carbon paper/cobalt hydroxide electrode as positive pole, nickel foam/activated carbon electrodes, as negative pole, take amberplex as barrier film, and positive pole injects the K of 50ml 1mol/L KOH and 0.4mol/L
3fe (CN)
6mixed solution, negative pole injects the K of 50ml 1mol/LKOH and 0.4mol/L
4fe (CN)
6mixed solution, be assembled into that room, the two poles of the earth adds Oxidizing and Reducing Agents respectively, electrode area is 100cm
2new Hydrogen cobalt oxide-active carbon asymmetric capacitor.Carry out charge-discharge test to above-mentioned Novel asymmetric capacitor, maximum potential window 1.6V, current density is 1mA/cm
2, ratio capacitance and the energy density of this novel capacitor are respectively 320F/g and 113.8Wh/kg.(with Fig. 6 (e) Suo Shi).
To sum up, in embodiment 1-6, the impact of redox materials concentration on capacitive property of ultracapacitor is summarized as follows:
Table 1
Embodiment 1 and 2 from table, can find out and add K respectively in capacitor both positive and negative polarity
3fe (CN)
6and K
4fe (CN)
6with do not dose any redox materials, the difference of capacitor ratio capacitance and energy density, is added with K
3fe (CN)
6and K
4fe (CN)
6ultracapacitor ratio capacitance and energy density obviously raise.
Embodiment 3 to 6 from table, can find out the ratio capacitance of ultracapacitor and energy density and K
3fe (CN)
6and K
4fe (CN)
6the variation relation of concentration, along with K
3fe (CN)
6and K
4fe (CN)
6the increase of concentration, the discharge and recharge time all increases, and ultracapacitor ratio capacitance and energy density obviously raise (as shown in Figure 6).
Claims (10)
1. room, the two poles of the earth adds the potassium ferricyanide and a potassium ferrocyanide Asymmetric Supercapacitor respectively, comprises positive pole, negative pole, amberplex and electrolyte, it is characterized in that:
The cathode chamber of capacitor and anode chamber, between both positive and negative polarity, separate by described amberplex;
Described electrolyte is alkaline aqueous solution, and is added with potassium ferricyanide solution in the electrolyte of cathode chamber, and potassium ferricyanide solution concentration is 0.01 ~ 0.5mol/L; Be added with potassium ferrocyanide solution in the electrolyte of anode chamber, potassium ferrocyanide solution concentration is 0.01 ~ 0.5mol/L.
2. room, the two poles of the earth adds a preparation method for the potassium ferricyanide and potassium ferrocyanide Asymmetric Supercapacitor respectively, it is characterized in that:
Step 1: by material with carbon element through the ultrasonic process of organic solvent, removing organic impurities; By material with carbon element through persalt or sulfuric acid acidation process, removing inorganic impurity, improves material with carbon element specific area, adopt constant potential or constant current electrochemical deposition, treated material with carbon element grows cobalt hydroxide film, obtains cobalt hydroxide electrode, it can be used as supercapacitor positive electrode to use;
Step 2: using nickel foam or material with carbon element as substrate, through organic solvent, inorganic acid and deionized water process, removing organic substance and oxide-film, active carbon is mixed with conductive agent, binding agent, blade coating or be sprayed in treated substrate, obtain activated carbon electrodes, it can be used as super capacitor anode to use;
Step 3: by amberplex through hydrogen peroxide and mineral acid treatment, removing surface organic matter, inorganic metal ion impurity, put into used alkaline solution soak stand-by with deionized water after cleaning;
Step 4: by supercapacitor positive electrode, negative pole, amberplex, seal gasket and end plate, become ultracapacitor monomer by bolt combination, or multiple positive pole, negative pole, amberplex, seal gasket and end plate are assembled into the bank of super capacitors of multiple electrode; Adopt injector for medical purpose or vacuum pump mode, electrolyte is injected cathode chamber, anode chamber respectively along reserving hole channel, sealing after fixing;
Step 5: ultracapacitor monomer, the bank of super capacitors of assembling in use step 4 are as required carried out serial or parallel connection, thus reached required electric current and voltage;
Step 6: adopt three-electrode system or two electrode systems to carry out electrochemical measurement to single electrode, single ultracapacitor or bank of super capacitors and many group ultracapacitors, method of measurement is cyclic voltammetry, constant current charge-discharge method or AC impedence method etc.
3. room, a kind of the two poles of the earth as claimed in claim 2 adds the preparation method of the potassium ferricyanide and potassium ferrocyanide Asymmetric Supercapacitor respectively, it is characterized in that: in step 1, material with carbon element substrate comprises carbon cloth, carbon fiber felt, carbon fiber paper or graphite, above-mentioned carbon material surface is processed, obtains clean material with carbon element substrate; Be specially, soak 1 ~ 5 hour in organic solvent, then ultrasonic 5 ~ 60 minutes, described organic solvent was acetone or alcohol; Soak 1 ~ 5 hour in mineral acid, then ultrasonic 5 ~ 60 minutes, described inorganic acid was hydrochloric acid or sulfuric acid; Finally, soak 1 ~ 5 hour in deionized water, then ultrasonic 5 ~ 60 minutes, removing inorganic acid.
4. room, a kind of the two poles of the earth as claimed in claim 2 adds the preparation method of the potassium ferricyanide and potassium ferrocyanide Asymmetric Supercapacitor respectively, it is characterized in that: in step 1, adopt electrochemical deposition technique, obtain material with carbon element/cobalt hydroxide electrode, use as supercapacitor positive electrode; In electrochemical deposition process, sedimentation time is 10min ~ 2h, and electrolyte cobalt nitrate concentration is 0.1 ~ 2mol/L, and depositing temperature is 30 ~ 60 DEG C, and sedimentation potential selects-0.6V ~-1.3V, and deposited per area unit size of current is 0.01A ~ 2A/cm
2, unit are active material cobalt hydroxide quality is 0.5 ~ 15mg/cm
2.
5. room, a kind of the two poles of the earth as claimed in claim 2 adds the preparation method of the potassium ferricyanide and potassium ferrocyanide Asymmetric Supercapacitor respectively, it is characterized in that: in step 2, to nickel foam or carbon material surface process, obtain cleaning foam nickel or material with carbon element substrate; Nickel foam or material with carbon element soak 1 ~ 5 hour respectively in organic solvent, and then ultrasonic 5 ~ 60 minutes, organic solvent comprised acetone or alcohol; Soak 1 ~ 5 hour in mineral acid, then ultrasonic 5 ~ 60 minutes, inorganic acid was mainly hydrochloric acid or sulfuric acid; Finally, soak 1 ~ 5 hour in deionized water, then ultrasonic 5 ~ 60 minutes, removing inorganic acid.
6. room, a kind of the two poles of the earth as claimed in claim 2 adds the preparation method of the potassium ferricyanide and potassium ferrocyanide Asymmetric Supercapacitor respectively, it is characterized in that: in step 2, adopt blade coating or spraying method, obtain nickel foam or material with carbon element/activated carbon electrodes, use as super capacitor anode, active carbon mixes according to the ratio of 80 ~ 90:5 ~ 15:3 ~ 7 with conductive agent, binding agent, and in unit are, blade coating or the quality that is sprayed at the mixture on nickel foam or material with carbon element are 1 ~ 50mg/cm
2.
7. room, a kind of the two poles of the earth as claimed in claim 2 adds the preparation method of the potassium ferricyanide and potassium ferrocyanide Asymmetric Supercapacitor respectively, it is characterized in that: in step 3, diaphragm of supercapacitor amberplex is processed, be specially, hydrogen peroxide volume fraction is 2 ~ 10%, treatment temperature is 60 ~ 80 DEG C, and the processing time is 0.5 ~ 3 hour, removing organic impurities; Inorganic acid comprises watery hydrochloric acid or dilute sulfuric acid, and treatment temperature is 60 ~ 80 DEG C, and the processing time is 0.5 ~ 3 hour, removing inorganic contaminants.
8. room, a kind of the two poles of the earth as claimed in claim 2 adds the preparation method of the potassium ferricyanide and potassium ferrocyanide Asymmetric Supercapacitor respectively, it is characterized in that: in step 4, adopts end plate, bolt and rubber cushion carry out assembling to capacitor and seal; Ultracapacitor shell is square, rectangle or circle, and electrolyte volume changes according to the change of shell sizes and number of electrodes, and monomer electrolytic solution for super capacitor volume is 5ml ~ 2000ml.
9. room, a kind of the two poles of the earth as claimed in claim 2 adds the preparation method of the potassium ferricyanide and potassium ferrocyanide Asymmetric Supercapacitor respectively, its preparation method is characterised in that, in step 4, electrolyte is alkaline aqueous solution, containing the alkali solute of potassium hydroxide, NaOH or lithium hydroxide, concentration is 0.5 ~ 6mol/L; Add the oxidizing substance potassium ferricyanide in cathode chamber, its concentration is 0.01 ~ 0.5mol/L; Add reducing substances potassium ferrocyanide in anode chamber, its concentration is 0.01 ~ 0.5mol/L.
10. room, a kind of the two poles of the earth as claimed in claim 2 adds the preparation method of the potassium ferricyanide and potassium ferrocyanide Asymmetric Supercapacitor respectively, it is characterized in that: in steps of 5, ultracapacitor comprises different size electrode area ultracapacitor and multiple or many groups ultracapacitor assembling; Electrode area is 1cm
2~ 2500cm
2; Bank of super capacitors is composed in parallel by multiple ultracapacitor, and its quantity is 2 ~ 100 or more, by the mode built-up circuit of serial or parallel connection, and the electric current required by acquisition and voltage.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106206059A (en) * | 2016-09-22 | 2016-12-07 | 福州大学 | NiCo2s4the preparation method and application of/graphite felt combination electrode material |
| CN106356203A (en) * | 2016-10-31 | 2017-01-25 | 福州大学 | Nickel cobaltate nano-sheet/graphite felt composite material and preparation and application thereof |
| CN106449137A (en) * | 2016-09-06 | 2017-02-22 | 吉林大学 | Preparation method for asymmetric super capacitor with cobalt hydroxide and active carbon as anode and cathode respectively |
| CN106486296A (en) * | 2016-11-22 | 2017-03-08 | 福州大学 | A kind of preparation method of nitrogen/nickel cobalt codope graphite felt electrode material |
| CN106601497A (en) * | 2016-09-05 | 2017-04-26 | 吉林大学 | Preparation method of two-pole chamber cobalt hydroxide symmetric type super capacitor comprising potassium ferricyanide and p-phenylenediamine |
| CN106898499A (en) * | 2017-02-23 | 2017-06-27 | 武汉科技大学 | A kind of dual chamber pseudocapacitors for adding fuel and preparation method thereof |
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| CN113415811A (en) * | 2021-05-20 | 2021-09-21 | 哈尔滨工业大学 | Preparation method of ferrocyanide and application of ferrocyanide in flow battery |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090190286A1 (en) * | 2006-06-05 | 2009-07-30 | Xiamen University | Supercapacitor |
| CN102176380A (en) * | 2011-01-26 | 2011-09-07 | 中国海洋大学 | Oxidation-reduction reaction electrochemical capacitor |
| CN104269281A (en) * | 2014-09-24 | 2015-01-07 | 吉林大学 | Method for manufacturing asymmetric super capacitor |
-
2015
- 2015-01-16 CN CN201510023879.6A patent/CN104576082B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090190286A1 (en) * | 2006-06-05 | 2009-07-30 | Xiamen University | Supercapacitor |
| CN102176380A (en) * | 2011-01-26 | 2011-09-07 | 中国海洋大学 | Oxidation-reduction reaction electrochemical capacitor |
| CN104269281A (en) * | 2014-09-24 | 2015-01-07 | 吉林大学 | Method for manufacturing asymmetric super capacitor |
Non-Patent Citations (2)
| Title |
|---|
| LING-HAO SU等: "Improvement of the capacitive performances for Co–Al layered double hydroxide by adding hexacyanoferrate into the electrolyte", 《PHYSICAL CHEMISTRY CHEMICAL PHYSICS》 * |
| YING TIAN等: "Capacitive Properties of Activated Carbon in K4Fe(CN)6", 《JOURNAL OF THE ELECTROCHEMICAL SOCIETY》 * |
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