CN107768147A - A kind of long-life asymmetric type supercapacitor based on CoFe Prussian blue analogues and preparation method thereof - Google Patents
A kind of long-life asymmetric type supercapacitor based on CoFe Prussian blue analogues and preparation method thereof Download PDFInfo
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- CN107768147A CN107768147A CN201710845870.2A CN201710845870A CN107768147A CN 107768147 A CN107768147 A CN 107768147A CN 201710845870 A CN201710845870 A CN 201710845870A CN 107768147 A CN107768147 A CN 107768147A
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- prussian blue
- pole piece
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- cofe
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- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910003321 CoFe Inorganic materials 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000000463 material Substances 0.000 claims abstract description 38
- 239000000243 solution Substances 0.000 claims abstract description 34
- -1 polypropylene Polymers 0.000 claims abstract description 22
- 239000003792 electrolyte Substances 0.000 claims abstract description 17
- 230000007935 neutral effect Effects 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004743 Polypropylene Substances 0.000 claims abstract description 6
- 230000004888 barrier function Effects 0.000 claims abstract description 6
- 229920001155 polypropylene Polymers 0.000 claims abstract description 6
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims abstract description 4
- 229910052939 potassium sulfate Inorganic materials 0.000 claims abstract description 4
- 235000011151 potassium sulphates Nutrition 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims description 25
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 15
- 239000003990 capacitor Substances 0.000 claims description 14
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 229910020598 Co Fe Inorganic materials 0.000 claims description 11
- 229910002519 Co-Fe Inorganic materials 0.000 claims description 11
- 239000006230 acetylene black Substances 0.000 claims description 10
- 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
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 239000007774 positive electrode material Substances 0.000 claims description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- YWQLEGWLOGTDFU-UHFFFAOYSA-L [Co](Cl)Cl.C(CC(O)(C(=O)O)CC(=O)O)(=O)O Chemical compound [Co](Cl)Cl.C(CC(O)(C(=O)O)CC(=O)O)(=O)O YWQLEGWLOGTDFU-UHFFFAOYSA-L 0.000 claims description 6
- 239000006260 foam Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 239000011258 core-shell material Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000003643 water by type Substances 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical class [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical class [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 2
- 235000019263 trisodium citrate Nutrition 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 238000002242 deionisation method Methods 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000004891 communication Methods 0.000 abstract description 3
- 238000010295 mobile communication Methods 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 239000008151 electrolyte solution Substances 0.000 abstract description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 abstract description 2
- 235000011152 sodium sulphate Nutrition 0.000 abstract description 2
- 238000000975 co-precipitation Methods 0.000 abstract 1
- 238000002484 cyclic voltammetry Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 5
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000003610 charcoal Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000000840 electrochemical analysis Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002152 aqueous-organic solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001055 blue pigment Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical class C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- BYGOPQKDHGXNCD-UHFFFAOYSA-N tripotassium;iron(3+);hexacyanide Chemical compound [K+].[K+].[K+].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] BYGOPQKDHGXNCD-UHFFFAOYSA-N 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
-
- 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
-
- 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 present invention relates to a kind of long-life asymmetric type supercapacitor based on CoFe Prussian blue analogues and preparation method thereof.The Asymmetric Supercapacitor includes anode pole piece, cathode pole piece, the barrier film and electrolyte being arranged between anode pole piece and cathode pole piece；Positive electrode is CoFe Prussian blue analogue nano materials, and negative material is activated carbon, and barrier film is polypropylene diaphragm, and electrolyte is neutral water soluble electrolyte solution；CoFe Prussian blue analogue positive electrodes are prepared using solution coprecipitation, electrolyte is 0.5 1mol/L sodium sulphate or potassium sulfate solution.The ultracapacitor has the charge and discharge circulation life of higher energy density and overlength, and preparation technology is simple, and controllability is good, and cost is low, has huge application prospect in fields such as mobile communication, consumer electronics, communications and transportation and science and techniques of defence.
Description
Technical field
The invention belongs to technical field of capacitor preparation, is related to one kind and is used as positive electrode and work using CoFe Prussian blue analogues
The long-life asymmetric neutral aqueous solution ultracapacitor of property charcoal as negative material and preparation method thereof.
Background technology
Ultracapacitor is a kind of new type of energy storage device occurred in recent years, and ultracapacitor is also known as electrochemical capacitor
Device, it is the model electrochemical energy storage device between traditional capacitor and battery.Compared with traditional capacitor, ultracapacitor
With higher energy density；Compared with battery, it has higher power density, environment-adapting ability is strong, service life is long
And the advantages that green.Thus occupy the critical role increasingly shown in new energy technology, in mobile communication, consumption electricity
The fields such as son, communications and transportation and science and techniques of defence have huge application prospect.
Ultracapacitor is classified according to electrolyte type, can be divided into the aqueous solution and organic solution ultracapacitor.Use
Aqueous solution electrolysis liquid can obtain height ratio capacity and specific power, because aqueous solution resistance (aqueous solution conductance low compared with non-aqueous solution
For~10-2-10-1S/cm, and non-aqueous solution conductance is then~10-4-10-3S/cm)；It can then be obtained from organic solution electrolyte
High voltage, because the height (organic solution decomposition voltage is up to 3.5V) of its electrolyte decomposition voltage ratio aqueous solution, so as to obtain
High ratio energy.But shortcomings be present in organic solution system, such as relatively low specific capacitance, higher viscosity and internal resistance.Relatively
In organic solution ultracapacitor, aqueous solution ultracapacitor have the advantages that it is environment-friendly, nonflammable, safe, but
Because the decomposition electric potential window of water is 1.23V, the operating voltage of aqueous solution ultracapacitor is usually less than 1.2V.In order to improve
The operating voltage of aqueous solution ultracapacitor, 1.4- can be can reach by assembling asymmetric type supercapacitor raising operating voltage
2.0V.Research for electrode material for super capacitor, it is main bottleneck that researchers face that energy density is low, and assembling is non-right
Title type ultracapacitor can expand the potential window of capacitor, so as to increase the energy density of capacitor.Therefore assemble new
Type asymmetric type supercapacitor receives much concern.
The electrode material for ultracapacitor mainly has carbon material, transition metal oxide and conducting polymer at this stage
Thing.A kind of Prussian blue coloring for being navy blue pigment, being mainly used in the industries such as paint, ink, plastics and school supply and stationery.By
In in Prussian blue structure cell, ferrous ion and iron ion occupy two different positions respectively, and all may be used on the two positions
To be substituted with other different transition metal, so the kind of the Prussian blue analogue compound formed has diversity.Class is general
Shandong scholar's oil blackeite compound can be used for the fields such as chemical analysis detection, medical science.Because Prussian blue analogue material has, specific surface area is big,
Porosity is high, and ion insertion and extraction ability is strong and enjoys the pro-gaze of researchers the characteristics of high stability, for alkali metal ion
During the electrode material of battery, chemical property performance is excellent, is also considered as the potential selection of capacitor material.
At present, it is asymmetric about being prepared using CoFe Prussian blue analogues and activated carbon as positive electrode and negative material
The research of type ultracapacitor yet there are no any report.The positive electrode multiselect transition of asymmetric aqueous solution ultracapacitor
Metal oxide, it is non-right because chemical property of the transition metal oxide in electrochemical redox reaction is gradually decayed
The reversible capacity and cycle life of title type aqueous solution ultracapacitor are undesirable.And patent system of the present invention is for the asymmetric of gained
Type aqueous solution ultracapacitor can not only reach higher energy density, and can be kept for the long-life；In addition, the positive pole in the present invention
Material C oFe Prussian blue analogues material uses one-step synthesis, and method is simple.Assemble obtained CoFe Prussian blue analogues material/work
The cyclic voltammetry curve of property charcoal asymmetric type supercapacitor, shows preferable electric double layer capacitance performance, has excellent electricity
Hold characteristic.
The content of the invention
The present invention is directed to the problem of reversible capacity and undesirable cycle life of asymmetric aqueous solution ultracapacitor,
A kind of asymmetric neutrality being prepared using CoFe Prussian blue analogues as positive electrode and activated carbon as negative material is provided
Aqueous solution ultracapacitor and preparation method thereof.
To achieve the above object, the present invention adopts the following technical scheme that, a kind of long-life based on CoFe Prussian blue analogues
Asymmetric neutral aqueous solution ultracapacitor includes positive pole, negative pole, the barrier film being arranged between positive pole and negative pole and electrolysis
Liquid；The positive pole includes positive electrode active materials, acetylene black and polytetrafluoroethylene (PTFE), and the negative pole includes negative active core-shell material, acetylene
Black and polytetrafluoroethylene (PTFE)；The positive electrode active materials are CoFe Prussian blue analogue materials, and the negative active core-shell material is activated carbon；
Described barrier film is polypropylene diaphragm；Described electrolyte is neutral water soluble electrolyte solution.
The above-mentioned asymmetric neutral water of the long-life based on CoFe Prussian blue analogues is claimed in another object of the present invention
The preparation method of solution ultracapacitor, is comprised the following steps that：
(1) preparation of CoFe Prussian blue analogues anode pole piece：By Co-Fe Prussian blue analogues material, acetylene black and polytetrafluoro
Ethene in mass ratio 8：1：1 mixing, adding a small amount of 1-METHYLPYRROLIDONE is sufficiently mixed three, and pulpous state is made, rolls repeatedly
Flakiness, it is pressed in the nickel foam sheared and electrode slice is made, is then dried in vacuo 12h at room temperature in vacuum drying chamber, i.e.,
CoFe Prussian blue analogue anode pole pieces are made；
(2) preparation of activated carbon negative electrode pole piece：By activated carbon, acetylene black and polytetrafluoroethylene (PTFE) in mass ratio 8：1：1 mixing,
Adding a small amount of 1-METHYLPYRROLIDONE is sufficiently mixed three, and pulpous state is made, rolls flakiness repeatedly, is pressed in the foam sheared
Electrode slice is made on nickel, is taken out after being dried in vacuo 12h in 80 DEG C, that is, activated carbon negative electrode pole piece is made；
(3) capacitor is assembled：Take CoFe Prussian blue analogues anode pole piece prepared by step (1) and work prepared by step (2)
Property charcoal cathode pole piece, it is spaced intermediate in anode pole piece and cathode pole piece with polypropylene diaphragm, by anode pole piece and cathode pole piece phase
Superposition is alignd, is immersed in the neutral electrolyte aqueous solution, is assembled into Asymmetric Supercapacitor.
Preferably, the preparation method of the positive electrode active materials is：Weigh 0.6mmol cobalt chlorides and 1mmol citric acids three
Sodium is dissolved in 20mL deionized waters preparation cobalt chloride citric acid three sodium solution, weigh the 0.2mmol potassium ferricyanides be dissolved in 20mL go from
Potassium ferricyanide solution is configured in sub- water；With vigorous stirring, potassium ferricyanide solution is added into cobalt chloride citric acid three sodium solution
In；Precipitation 24 hours are stood at room temperature, sample is collected by centrifugation, and make to be washed with deionized repeatedly, drying to obtain Co-Fe classes are general
Shandong scholar's blue material.
Cube pattern is presented in described CoFe Prussian blue analogues material, and size is 300-400 nanometers.
Preferably, the mass ratio of the CoFe Prussian blue analogues material and activated carbon is 1：(1.0-1.5), preferably 1：
1.2。
Preferably, the described neutral electrolyte aqueous solution is aqueous sodium persulfate solution or potassium sulfate solution.Described neutrality
The concentration of electrolyte aqueous solution is 0.5-1mol/L, preferably 1mol/L.
The electro-chemical test of positive and negative pole material of the present invention is entered using three-electrode system in 1mol/L aqueous sodium persulfate solutions
OK, platinized platinum is as auxiliary electrode, and saturated calomel electrode is as reference electrode, when surveying positive electrode, CoFe Prussian blue analogue electrodes
Pole piece is as working electrode, and when surveying negative material, activated carbon electrodes pole piece is as working electrode.
The electro-chemical test of asymmetric type supercapacitor after assembling is using two electrode systems in 1mol/L sodium sulphate water
Carried out in solution.
It is prepared into the present invention relates to one kind using CoFe Prussian blue analogues as positive electrode and activated carbon as negative material
Asymmetric neutral aqueous solution ultracapacitor arrived and preparation method thereof, preparation technology is simple, is very beneficial for large-scale
Production and application.Compared with prior art, positive electrode active materials Co-Fe Prussian blue analogues only need a step to synthesize, operation
Simply, and there is very superior chemical property；Negative active core-shell material selects activated carbon simultaneously, is assembled into asymmetric water
Solution ultracapacitor, the potential window of capacitor can be effectively widened, improve the energy density of ultracapacitor.Electrochemistry
It can test and show, Asymmetric Supercapacitor of the invention has higher electrochemical capacitor performance, energy density and extremely gone out
The charge and discharge circulation life of color.The ultracapacitor controllability is good, and cost is low, mobile communication, consumer electronics, communications and transportation and
The fields such as science and techniques of defence have huge application prospect.
Brief description of the drawings
Fig. 1 is the SEM figures of Co-Fe Prussian blue analogue nano materials prepared by embodiment 1；
Fig. 2 is Co-Fe Prussian blue analogues anode pole piece prepared by embodiment 1 and activated carbon negative electrode pole piece in 1 mol/L sulphur
Cyclic voltammetry curve (10mV/s) in acid sodium solution；
Fig. 3 be embodiment 1 prepare Co-Fe Prussian blue analogues anode pole piece in 1mol/L metabisulfite solutions electric current be
Constant current charge-discharge curve during 1A/g；
Fig. 4 is that Asymmetric Supercapacitor sweeps cyclic voltammetry curves under speed in 1mol/L metabisulfite solutions in difference,
Wherein (a) be 5,10,20mV/s sweep cyclic voltammetry curve under speed, (b) is 30,50,100mV/s sweep cyclic voltammetric under speed
Curve；
Fig. 5 is that discharge and recharge of the Asymmetric Supercapacitor in 1mol/L metabisulfite solutions under different current strength is bent
Line；Wherein (a) be 300,500, the charging and discharging curve under 800mA/g current strength, (b) is 1,2, under 3A/g current strength
Charging and discharging curve；
Fig. 6 is specific capacitance value of the Asymmetric Supercapacitor under different current densities；
Fig. 7 is the cycle life figure of Asymmetric Supercapacitor.
Embodiment
The present invention is described in detail below by the drawings and specific embodiments, but not limited the scope of the invention.Such as without special
Illustrate, experimental method of the present invention is conventional method, and experiment equipment used, material, reagent etc. can be chemically public
Department's purchase.
Embodiment 1
In actual fabrication process, to reach good chemical property, positive and negative pole material needs to meet Q at work+=
Q-, utilize formula m+/m-=(C-ΔV-)/(C+ΔV+) mass ratio that is calculated optimal positive electrode and negative material is 1/
1.2, the active material on corresponding electrode material is respectively 4.0 and 4.8mg.(wherein, Q+Represent positive pole electricity, Q-Represent negative
Pole electricity, C+Represent the specific capacitance of positive electrode, C-Represent the specific capacitance of negative material, Δ V+Represent the electrochemical window of positive electrode
Mouthful, Δ V-Represent the potential window of negative material, m+Represent the quality of positive active material, m-Represent the matter of negative electrode active material
Amount.)
Prepare CoFe Prussian blue analogue materials：Weigh 0.6mmol cobalt chlorides and 1mmol trisodium citrates be dissolved in 20mL go from
Cobalt chloride citric acid three sodium solution is prepared in sub- water, the 0.2mmol potassium ferricyanides is weighed and is dissolved in 20mL deionized waters and be configured to iron
Potassium cyanide solution；With vigorous stirring, potassium ferricyanide solution is added in cobalt chloride citric acid three sodium solution；It is heavy to stand at room temperature
Change 24 hours, sample is collected by centrifugation, make to be washed with deionized repeatedly, drying to obtain Co-Fe Prussian blue analogue materials, gained
The pattern of product is as shown in Figure 1.
Prepare CoFe Prussian blue analogue anode pole pieces：By prepared Co-Fe Prussian blue analogues nano material (4.0 mg), second
Acetylene black and polytetrafluoroethylene (PTFE) in mass ratio 8：1：1 mixing, adding a small amount of 1-METHYLPYRROLIDONE is sufficiently mixed three, and slurry is made
Shape, flakiness is rolled, is pressed in the nickel foam sheared and electrode slice is made, be then dried in vacuo at room temperature in vacuum drying chamber
12h, that is, CoFe Prussian blue analogue anode pole pieces are made.
Prepare activated carbon negative electrode pole piece：It is 8 according to mass ratio：1：1 ratio weighs activated carbon (4.8mg), acetylene black and
Kynoar, adding a small amount of 1-METHYLPYRROLIDONE is sufficiently mixed three, and pulpous state is made, and rolls flakiness, is pressed in shearing
Electrode slice is made in good nickel foam, is taken out after being dried in vacuo 12h in 80 DEG C, that is, activated carbon negative electrode pole piece is made.
On CHI660E electrochemical workstations, carried out just in 1mol/L metabisulfite solutions using three-electrode system first
Pole and the electro-chemical test of negative material.When testing positive electrode, CoFe Prussian blue analogues electrode plates are as working electrode, Pt
Piece and saturated calomel electrode are respectively as auxiliary electrode and reference electrode；Survey negative material when activated carbon electrodes pole piece directly as
Working electrode, Pt pieces and saturated calomel electrode are respectively as auxiliary electrode and reference electrode.
Electrochemical property test, cyclic voltammetry curve such as Fig. 2 institutes are carried out to products therefrom CoFe Prussian blue analogues material
Show, it is seen that it there are obvious redox peaks, is classical faraday's capacitor.Products therefrom CoFe Prussian blue analogue materials
Constant current charge-discharge curve as shown in figure 3, specific capacitance is up to 481F/g in 1A/g.
Using above-mentioned CoFe Prussian blue analogues as positive electrode, activated carbon is as negative material, positive electrode and negative pole material
The mass ratio of material is 1：1.2, polypropylene diaphragm is used between anode pole piece and cathode pole piece, is immersed in 1 mol/LNa2SO4Solution
In, it is assembled into Asymmetric Supercapacitor.Asymmetric super capacitor performance is tested using two electrode systems.
The cyclic voltammetry curve of Asymmetric Supercapacitor is made as shown in figure 4, potential window is 1.4 V in the present embodiment.
Class rectangle shape is presented in cyclic voltammetry curve as seen from Figure 4, better than transition metal oxide base Asymmetric Supercapacitor.
The constant current charge-discharge curve of Asymmetric Supercapacitor is made as shown in figure 5, in 0.5A/g in the present embodiment,
Specific capacitance is up to 65.5F/g.Its specific capacitance size under different electric currents as shown in fig. 6, when power density is 323W/kg,
Energy density is 15.3Wh/kg.
The cycle life survey that Asymmetric Supercapacitor is made in the present embodiment is carried out on LANHE CT2001A discharge and recharge instrument
Examination, as shown in fig. 7, circulating 6000 times, capacity retention is cyclical stability under conditions of charging and discharging currents density is 1A/g
93%, there is excellent cycle life.
Embodiment 2
The present embodiment and the difference of embodiment 1 are that the mass ratio of CoFe Prussian blue analogues material and activated carbon is 1：
1.5.The neutral electrolyte aqueous solution is concentration 0.5mol/L potassium sulfate solution.
It is described above, the only preferable embodiment of the invention, but the protection domain of the invention is not
This is confined to, any one skilled in the art is in the technical scope that the invention discloses, according to the present invention
The technical scheme of creation and its inventive concept are subject to equivalent substitution or change, should all cover the invention protection domain it
It is interior.
Claims (7)
1. a kind of long-life asymmetric type supercapacitor based on CoFe Prussian blue analogues, it is characterised in that including positive pole, bear
Pole, the barrier film and electrolyte being arranged between positive pole and negative pole；The positive pole includes positive electrode active materials, acetylene black and poly- four
PVF, the negative pole include negative active core-shell material, acetylene black and polytetrafluoroethylene (PTFE)；The positive electrode active materials are that CoFe classes are general
Shandong scholar's blue material, the negative active core-shell material are activated carbon；Described barrier film is polypropylene diaphragm；Described electrolyte is neutrality
Water-soluble electrolytes solution.
A kind of 2. preparation of the long-life asymmetric type supercapacitor based on CoFe Prussian blue analogues as claimed in claim 1
Method, it is characterised in that comprise the following steps that：
(1) preparation of CoFe Prussian blue analogues anode pole piece：By Co-Fe Prussian blue analogues material, acetylene black and polytetrafluoroethylene (PTFE)
In mass ratio 8：1：1 mixing, adding a small amount of 1-METHYLPYRROLIDONE is sufficiently mixed three, and pulpous state is made, and is rolled into repeatedly thin
Piece, it is pressed in the nickel foam sheared and electrode slice is made, be then dried in vacuo 12h at room temperature in vacuum drying chamber, that is, is made
CoFe Prussian blue analogue anode pole pieces；
(2) preparation of activated carbon negative electrode pole piece：By activated carbon, acetylene black and polytetrafluoroethylene (PTFE) in mass ratio 8：1：1 mixing, is added
A small amount of 1-METHYLPYRROLIDONE is sufficiently mixed three, and pulpous state is made, rolls flakiness repeatedly, is pressed in the nickel foam sheared
Electrode slice is made, is taken out after being dried in vacuo 12h in 80 DEG C, that is, activated carbon negative electrode pole piece is made；
(3) capacitor is assembled：Take CoFe Prussian blue analogues anode pole piece prepared by step (1) and activated carbon prepared by step (2)
Cathode pole piece, it is spaced intermediate in anode pole piece and cathode pole piece with polypropylene diaphragm, anode pole piece and cathode pole piece is relatively folded
Add alignment, be immersed in the neutral electrolyte aqueous solution, be assembled into Asymmetric Supercapacitor.
3. according to the method for claim 2, it is characterised in that the preparation method of the Co-Fe Prussian blue analogues material is：
Weigh 0.6mmol cobalt chlorides and 1mmol trisodium citrates be dissolved in preparation cobalt chloride citric acid three sodium solution in 20mL deionized waters,
Weigh the 0.2mmol potassium ferricyanides and be dissolved in 20mL deionized waters and be configured to potassium ferricyanide solution；With vigorous stirring, by iron cyaniding
Potassium solution is added in cobalt chloride citric acid three sodium solution；Precipitation 24 hours are stood at room temperature, and sample is collected by centrifugation, uses deionization
Water washing is multiple, drying to obtain Co-Fe Prussian blue analogue materials.
4. according to the method for claim 2, it is characterised in that described CoFe Prussian blue analogues material presents cube shaped
Looks, size are 300-400 nanometers.
5. according to the method for claim 2, it is characterised in that the quality of the CoFe Prussian blue analogues material and activated carbon
Than for 1：(1.0-1.5).
6. according to the method for claim 2, it is characterised in that the described neutral electrolyte aqueous solution is aqueous sodium persulfate solution
Or potassium sulfate solution.
7. according to the method for claim 2, it is characterised in that the concentration of the described neutral electrolyte aqueous solution is 0.5-
1mol/L。
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108847356A (en) * | 2018-06-28 | 2018-11-20 | 上海交通大学 | A kind of preparation method based on Prussian blue analogue/reduced graphene film Asymmetric Supercapacitor |
| CN110144137A (en) * | 2019-05-06 | 2019-08-20 | 武汉大学 | A kind of nanocube ink, preparation method and application based on CoHCF |
| CN115611379A (en) * | 2022-10-21 | 2023-01-17 | 中国农业大学 | Prussian blue carbon-based composite electrode and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101546650A (en) * | 2009-04-10 | 2009-09-30 | 中南大学 | Electrode material of super capacitor and its preparation method |
| JP2016091699A (en) * | 2014-10-31 | 2016-05-23 | 国立大学法人 筑波大学 | Negative electrode for sodium ion secondary battery, sodium ion secondary battery, negative electrode for lithium ion secondary battery, and lithium ion secondary battery |
| 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 |
| CN106920964A (en) * | 2017-04-05 | 2017-07-04 | 浙江大学 | A kind of prussian blue sodium-ion battery positive material and preparation method thereof |
-
2017
- 2017-09-19 CN CN201711358036.7A patent/CN108109852B/en active Active
- 2017-09-19 CN CN201710845870.2A patent/CN107768147B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101546650A (en) * | 2009-04-10 | 2009-09-30 | 中南大学 | Electrode material of super capacitor and its preparation method |
| JP2016091699A (en) * | 2014-10-31 | 2016-05-23 | 国立大学法人 筑波大学 | Negative electrode for sodium ion secondary battery, sodium ion secondary battery, negative electrode for lithium ion secondary battery, and lithium ion secondary battery |
| 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 |
| CN106920964A (en) * | 2017-04-05 | 2017-07-04 | 浙江大学 | A kind of prussian blue sodium-ion battery positive material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| FENG MA等: "Energy storage materials derived from Prussian blue analogues", 《SCIENCE BULLETIN》 * |
| JINHUI HAO ET AL.: "Metal-organic frameworks derived CoxFe1−xP nanocubes for electrochemical hydrogen evolution", 《NANOSCALE》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108847356A (en) * | 2018-06-28 | 2018-11-20 | 上海交通大学 | A kind of preparation method based on Prussian blue analogue/reduced graphene film Asymmetric Supercapacitor |
| CN110144137A (en) * | 2019-05-06 | 2019-08-20 | 武汉大学 | A kind of nanocube ink, preparation method and application based on CoHCF |
| CN110144137B (en) * | 2019-05-06 | 2020-05-22 | 武汉大学 | CoHCF-based nanocube ink, and preparation method and application thereof |
| CN115611379A (en) * | 2022-10-21 | 2023-01-17 | 中国农业大学 | Prussian blue carbon-based composite electrode and preparation method and application thereof |
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| CN108109852A (en) | 2018-06-01 |
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