CN1529334A - Polyaniline/carbon nano tube hybrid super capacitor - Google Patents
Polyaniline/carbon nano tube hybrid super capacitor Download PDFInfo
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- CN1529334A CN1529334A CNA2003101004675A CN200310100467A CN1529334A CN 1529334 A CN1529334 A CN 1529334A CN A2003101004675 A CNA2003101004675 A CN A2003101004675A CN 200310100467 A CN200310100467 A CN 200310100467A CN 1529334 A CN1529334 A CN 1529334A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/48—Conductive polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention relates to structural design of hybrid type super capacitor. In the invention, conducting polyaniline and Nano carbon tube are as active materials of positive and negative poles of super capacitor respectively. The structure of the super capacitor is positive pole current collector/polyaniline pole/electrolyte and membrane Nano carbon tube pole/negartive current collector. Polyaniline/nano carbon tube hybrid type super capacitor can gave play to potential of pole material fully, forming function of coordination and complementation, and possessing higher specific energy and specific power. Comparing with super capacitor made from Nano carbon tube, specific energy of hybrid type super capacitor is raised 135 %, and average specific power is raised 7%. Comparing with super capacitor made from polyaniline specific energy of hybrid type super capacitor is raised30%, and average specific power is raised 100%.
Description
Technical field
The present invention relates to a kind of energy-storage travelling wave tube, the structural design of particularly a kind of polyaniline/carbon nano tube hybrid type ultra-capacitor.
Background technology
Recent two decades comes, and along with the rapid generation and the development of new technology in the fields such as information technology, electronic product, the automobile-used energy, people pay close attention to the research and development of novel ultra-capacitor more.Ultra-capacitor is electrochemical capacitor again, is a kind of novel energy-storing element between ordinary capacitor and secondary cell.Compare with conventional batteries, ultra-capacitor have specific power height, charge and discharge cycles often, advantage such as the time that discharges and recharges is short; Compare with traditional electrolytic capacitor, it has, and specific capacity is big, the specific energy advantages of higher.Ultra-capacitor has many potential application, and high-power ultra-capacitor can be as the load balancing device of motor vehicle, provides auxiliary power in the stages such as the startup of motor vehicle, acceleration, climbings, the big electric current that can the quick storage generator when brake produces.Can make battery be in best power supply state with it and battery coupling, thus prolong battery useful life, improve efficiency of energy utilization, reduce cost.In, low power ultra-capacitor also can be used as accessory power supply of electric welding machine, photoflash lamp, notebook computer, hand-hold electronic device etc.
Electrically conductive polyaniline electrode ultra-capacitor have specific energy height, cost low, can select different advantages such as polymer architecture by MOLECULE DESIGN, people's extensive concern extremely.Electrically conductive polyaniline electrode ultra-capacitor is by the redox reaction that reversible fast p type mixes or goes to mix takes place in the electron conduction polymer film on electrode, make polyaniline electrode store highdensity electric charge, have very high pseudo capacitance, thereby realize highdensity Charge Storage.But polyaniline is stored the main voltage range of electric charge below 1V, as: " the Symmetricredox supercapacitor with conducting polyaniline electrodes " that Kwang Sun Ryu etc. delivers on " Journal of Power Sources " (2002,103 volumes, the 305-309 page or leaf), the main voltage range that also shows polyaniline storage electric charge is below 1V, and this has just limited the raising of specific energy.Because specific energy E=1/2 CV
2So,, just can improve the specific energy of ultra-capacitor greatly if can manage to improve operating voltage.
In November, 1991, the Electronic Speculum expert Iijima of NEC has at first found carbon nano-tube under high resolution transmission electron microscopy (HRTEM), caused people's extensive concern.The one dimension tubulose material with carbon element that carbon nano-tube is made up of the hexagonal mesh of similar graphite, it can be an individual layer, also can be multilayer, diameter in several nanometers between tens nanometers, length can reach several microns, and its lamellar spacing is 0.34nm, and is bigger slightly than the lamellar spacing (0.335nm) of graphite.Carbon nano-tube has huge specific area, good electrical conductivity and excellent chemical stability, therefore carbon nano-tube is used to prepare the focus that double electric layer capacitor becomes a research, but the specific capacity of carbon nano-tube ultra-capacitor is lower.Tied " based on the double electric layer capacitor of carbon nano-tube " delivered on the Song Dengzai " University Of Nanchang's journal (industry science version) " (2002 as Zhang Jianyu, Ceng Xiaoshu, Cai, 24 the 3rd phases of volume, the 13-15 page or leaf), adopt carbon nano-tube as the both positive and negative polarity active material, prepared double electric layer capacitor based on carbon nano-tube; Zhang Bin etc. " preparation of double electric layer capacitor carbon nano-tube solid pole plate " delivered on " electronic letters, vol " is (2000 for another example, 28 the 8th phases of volume, the 13-15 page or leaf), adopt carbon nano-tube as the both positive and negative polarity active material, prepared the double electric layer capacitor based on carbon nano-tube, its specific energy is all lower.
The positive and negative electrode material difference that mixes the type ultra-capacitor, the mechanism difference of two electrode store charges." the Hybrid electrochemical capacitors basedon polyaniline and activated carbon electrodes " that on " Journal of Power Sources ", delivers as Jong Hyeok Park etc. (2002,111 volumes, the 185-190 page or leaf), with polyaniline as positive electrode active materials, active carbon as negative active core-shell material, the 6mol/L KOH aqueous solution is as electrolyte, and Celgard3501 is as barrier film.But the contact resistance between activated carbon granule is bigger, especially activated carbon granule hour, contact resistance between activated carbon granule can be very big, this makes the active carbon conductivity not as the carbon nano-tube height, be unfavorable for improving the specific power of ultra-capacitor, and the electrochemical stability of active carbon is also good not as carbon nano-tube, especially when applying high operating voltage, side reaction takes place in active carbon easily, generate accessory substances such as carbon dioxide, this is all very unfavorable for the operating voltage, specific energy and the cyclical stability that improve ultra-capacitor.And the diameter of carbon nano-tube is nano level, this makes carbon nano-tube have very high specific surface in bigger space, the length of carbon nano-tube can reach micron or longer, have very big draw ratio, this makes carbon nano-tube have very high conductivity, and this helps improving the specific power of ultra-capacitor, and carbon nano-tube has more stable structure, the electrochemical stability of carbon nano-tube is better than active carbon, when applying high operating voltage, is not easy to take place side reaction.These are all very favourable for the specific energy and the cyclical stability that improve ultra-capacitor.But up to the present, polyaniline also of no use mixes the type ultra-capacitor as positive electrode active materials, carbon nano-tube as what negative material was assembled into.
Summary of the invention
The purpose of this invention is to provide a kind of polyaniline/carbon nano tube hybrid type ultra-capacitor, can give full play to the potentiality of positive and negative electrode material, form to coordinate and complementation, thereby can further improve the technical indicators such as specific energy, specific power of ultra-capacitor.
Technical scheme of the present invention is as follows: a kind of polyaniline/carbon nano tube hybrid type ultra-capacitor, its structure contains anodal electric current collection body, positive pole, electrolyte and barrier film, negative pole and cathodal current collection body successively, it is characterized in that: the described anodal composite material that adopts polyaniline or polyaniline and material with carbon element to form is made, described material with carbon element is one or more in carbon nano-tube, active carbon, carbon fiber or the acetylene black, and wherein the mass percentage content of material with carbon element is less than 30%; The composite material that described negative pole adopts carbon nano-tube or carbon nano-tube and active carbon, carbon fiber or acetylene black to form is made, and wherein the mass percentage content of active carbon, carbon fiber or acetylene black is less than 30%.
In order to satisfy people's different demands to ultra-capacitor under different condition, make the ultra-capacitor performance have more excellent properties, used positive electrode is 0.1～5 with the quality of negative material than scope among the present invention, it optimizes quality is 0.2～2 than scope.
Electrolyte described in the present invention adopts LiPF
6(lithium hexafluoro phosphate), LiBF
4(LiBF4), LiClO
4(lithium perchlorate), LiCF
3SO
3(three fluosulfonic acid lithiums), (C
2H
5)
4NPF
6(tetraethylammonium hexafluorophosphate), (C
2H
5)
4NBF
4(tetraethylammonium tetrafluoroborate), (C
2H
5)
4NClO
4(perchloric acid tetraethyl ammonium), (C
2H
5)
4NCF
3SO
3(three fluosulfonic acid tetraethyl ammoniums), (C
4H
9)
4NPF
6(hexafluorophosphate), (C
4H
9)
4NBF
4(tetrabutyl ammonium tetrafluoroborate), (C
4H
9)
4NClO
4(TBAP), (C
4H
9)
4NCF
3SO
3(three fluosulfonic acid TBuAs) or their mixture are electrolyte, and adopting propene carbonate, ethylene carbonate, butylene, acetonitrile or their mixed liquor is solvent.
The present invention compared with prior art, have the following advantages and the high-lighting effect: it is the positive electrode active materials of the composite material of main component as ultra-capacitor that the present invention adopts with polyaniline or with the polyaniline, with carbon nano-tube or with the carbon nano-tube is the negative active core-shell material of the composite material of main component as ultra-capacitor, the characteristics of electrode material itself have been made full use of, just can give full play to, the potentiality of negative electrode material, form and coordinate and complementation, has height ratio capacity thereby form, high-energy-density, high stability and long circulation life mix the type ultra-capacitor, not only the performance that improves ultra-capacitor had significant high-lighting effect, and its composition is versatile and flexible, can satisfy people's different demands to capacitor under different condition.Compare with the carbon nano-tube ultra-capacitor, still compare with the polyaniline ultra-capacitor, polyaniline/carbon nano tube hybrid type ultra-capacitor all has higher specific energy and specific power.Shown in embodiment 1, comparative example 1 and 2, to compare with the carbon nano-tube ultra-capacitor, the specific energy of polyaniline/carbon nano tube hybrid type ultra-capacitor has improved 135%, and average specific power has improved 7%; Compare with the polyaniline ultra-capacitor, the specific energy of polyaniline/carbon nano tube hybrid type ultra-capacitor has improved 30%, and average specific power has improved 100%.Compare with the metal oxide containing precious metals ultra-capacitor, this novel type ultra-capacitor that mixes has lower-cost advantage.In a word, polyaniline/carbon nano tube hybrid type ultra-capacitor is that a kind of cost is low, the novel ultra-capacitor of excellent performance.
Description of drawings
Fig. 1 is the structural representation of polyaniline/carbon nano tube hybrid type ultra-capacitor.
Fig. 2 is the charging and discharging curve of polyaniline/carbon nano tube hybrid type ultra-capacitor.
Fig. 3 is the charging and discharging curve of polyaniline ultra-capacitor.
Fig. 4 is the charging and discharging curve of carbon nano-tube ultra-capacitor.
Fig. 5 is the specific energy and the specific power figure of polyaniline/carbon nano tube hybrid type ultra-capacitor, polyaniline ultra-capacitor and carbon nano-tube ultra-capacitor.
Embodiment
The manufacturing process of polyaniline provided by the present invention/carbon nano tube hybrid type ultra-capacitor adopts method conventional in the prior art, and this method generally comprises 5 steps, and first step is anodal electric current collection body of preparation and cathodal current collection body; Second step is that preparation is anodal, i.e. polyaniline electrode; The 3rd step is preparation negative pole, i.e. carbon nanotube electrode; The 4th step is preparation electrolyte and barrier film; The 5th step is with anodal electric current collection body/positive pole/electrolyte and barrier film/negative pole/cathodal current collection body, is assembled into by Fig. 1 to mix the type ultra-capacitor.
Polyaniline positive electrode active materials of the present invention, can adopt the polyaniline one pack system, also can be to be main active constituent with polyaniline, add composite material or composite material that its mass percent is formed less than 30% material with carbon element, described material with carbon element is one or more in carbon nano-tube, active carbon, carbon fiber or the acetylene black.Positive electrode active materials can also adopt the copolymer of aniline and pyrroles, thiophene, methylthiophene, or the blend of polyaniline and polypyrrole, polythiophene, poly-methylthiophene, in above-mentioned copolymer or blend, can also add carbon nano-tube, active carbon, carbon fiber or acetylene black.
Negative active core-shell material described in the present invention can adopt a kind of material of pure nano-carbon tube, and also can adopt with the carbon nano-tube is key component, adds the composite material that its weight ratio is formed less than 30% active carbon, carbon fiber or acetylene black.
In order to satisfy people's different demands to ultra-capacitor under different condition, make ultra-capacitor have more excellent properties, used positive electrode is 0.1～5 with the quality of negative material than scope among the present invention, it optimizes quality is 0.2～2 than scope.Concrete mass ratio can be determined the mass ratio of positive electrode and negative material according to the consistent principle of capacity of the capacity and the negative material of positive electrode.
Described carbon nanometer tube negative pole can be a carbon nano-tube of utilizing method preparations such as laser bombardment method, chemical vapor deposition method, electric glow discharge method, direct-current arc electric discharge, gas combustion method, catalyst high temperature pyrolytic cracking (HTP), and by method processed carbon nanotubes such as chemistry or physics.It also can be the mixture of carbon nano-tube and active carbon, carbon fiber, acetylene black.
Below in conjunction with embodiment the present invention is described more completely, yet the present invention can implement, and not will be understood that the present invention only limits to each embodiment provided here by many different modes.And the purpose that these embodiments are provided is to make the present invention openly thoroughly fully, fully passes on thought of the present invention to the those skilled in the art.
Embodiment 1:
Polyaniline and carbon nano tube compound material (wherein containing 10% carbon nano-tube) are mixed with acetylene black, drip the acetone soln of PVDF-HFP, and be applied on the nickel foam, after the compacting, vacuumize promptly gets polyaniline electrode.Wherein: polyaniline and carbon nano tube compound material/acetylene black/PVDF-HFP=0.85/0.1/0.05 (mass ratio).
Carbon nano-tube and acetylene black are mixed, drip the acetone soln of PVDF-HFP (vinylidene fluoride-hexafluoropropylene copolymer), and be applied on the nickel foam, after the compacting, vacuumize promptly gets carbon nanotube electrode.Wherein: carbon nano-tube/acetylene black/PVDF-HFP=0.85/0.1/0.05 (mass ratio).
Respectively as positive and negative electrode, is positive and negative electrode electric current collection body with the nickel foam, with 1mol/L LiPF with above-mentioned polyaniline electrode and carbon nanotube electrode
6The EC/DEC of (lithium hexafluoro phosphate) (ethylene carbonate/butylene=1 volume ratio) solution is as electrolyte, make barrier film with the Celgard2300 microporous barrier, in being full of the atmosphere of argon gas, anodal electric current collection body/polyaniline electrode/electrolyte and barrier film/carbon nanotube electrode/cathodal current collection body are assembled into polyaniline/carbon nano tube hybrid type ultra-capacitor.Capacitor produced specific energy can reach 6.8Wh/kg.
Embodiment 2:
Polyaniline and acetylene black are mixed, drip the acetone soln of PVDF-HFP, and be applied on the nickel foam, after the compacting, vacuumize promptly gets polyaniline electrode.Wherein: polyaniline/acetylene black/PVDF-HFP=0.85/0.1/0.05 (mass ratio), wherein polyaniline 8.5mg.
Carbon nano-tube and acetylene black are mixed, drip the acetone soln of PVDF-HFP, and be applied on the nickel foam, after the compacting, vacuumize promptly gets carbon nanotube electrode.Wherein: carbon nano-tube/acetylene black/PVDF-HFP=0.85/0.1/0.05 (mass ratio), wherein carbon nano-tube 17mg.
Respectively as positive and negative electrode, is positive and negative electrode electric current collection body with the nickel foam, with 1mol/L LiPF with above-mentioned polyaniline electrode and carbon nanotube electrode
6EC/DEC (ethylene carbonate/butylene=1 volume ratio) solution is as electrolyte, make barrier film with the Celgard2300 microporous barrier, in being full of the atmosphere of argon gas, anodal electric current collection body/polyaniline positive pole/electrolyte and barrier film/carbon nanometer tube negative pole/cathodal current collection body are assembled into polyaniline/carbon nano tube hybrid type ultra-capacitor.Capacitor produced specific energy is 6.5Wh/kg.
Embodiment 3:
Polyaniline and acetylene black are mixed, drip the acetone soln of PVDF-HFP, and be applied on the nickel foam, after the compacting, vacuumize promptly gets polyaniline electrode.Wherein: polyaniline/acetylene black/PVDF-HFP=0.85/0.1/0.05 (mass ratio), wherein polyaniline 8.5mg.
Carbon nano-tube, active carbon and acetylene black are mixed, drip the acetone soln of PVDF-HFP, and be applied on the nickel foam, after the compacting, vacuumize promptly gets carbon nanotube electrode.Wherein: carbon nano-tube/active carbon/acetylene black/PVDF-HFP=0.75/0.1/0.1/0.05 (mass ratio), wherein carbon nano-tube and active carbon are 25.5mg.
Respectively as positive and negative electrode, is positive and negative electrode electric current collection body with the nickel foam, with 1mol/L LiPF with above-mentioned polyaniline electrode and carbon nanotube electrode
6EC/DEC (ethylene carbonate/butylene=1 volume ratio) solution is as electrolyte, make barrier film with the Celgard2300 microporous barrier, in being full of the atmosphere of argon gas, anodal electric current collection body/polyaniline positive pole/electrolyte and barrier film/carbon nanometer tube negative pole/cathodal current collection body are assembled into polyaniline/carbon nano tube hybrid type ultra-capacitor.Capacitor produced specific energy is 6.6Wh/kg.
Embodiment 4:
Polyaniline, carbon fiber and acetylene black are mixed, drip the acetone soln of PVDF-HFP, and be applied on the nickel foam, after the compacting, vacuumize promptly gets polyaniline electrode.Wherein: polyaniline/carbon fiber/acetylene black/PVDF-HFP=0.80/0.05/0.1/0.05 (mass ratio), wherein polyaniline 8.0mg.
Carbon nano-tube and acetylene black are mixed, drip the acetone soln of PVDF-HFP, and be applied on the nickel foam, after the compacting, vacuumize promptly gets carbon nanotube electrode.Wherein: carbon nano-tube/carbon fiber/acetylene black/PVDF-HFP=0.80/0.05/0.1/0.05 (mass ratio), wherein carbon nano-tube 32mg.
Respectively as positive and negative electrode, is positive and negative electrode electric current collection body with the nickel foam, with 1mol/L LiPF with above-mentioned polyaniline electrode and carbon nanotube electrode
6EC/DEC (ethylene carbonate/butylene=1 volume ratio) solution is as electrolyte, make barrier film with the Celgard2300 microporous barrier, in being full of the atmosphere of argon gas, anodal electric current collection body/polyaniline positive pole/electrolyte and barrier film/carbon nanometer tube negative pole/cathodal current collection body are assembled into polyaniline/carbon nano tube hybrid type ultra-capacitor.Capacitor produced specific energy is 6.1Wh/kg.
Embodiment 5:
Polyaniline and acetylene black are mixed, drip the acetone soln of PVDF-HFP, and be applied on the nickel foam, after the compacting, vacuumize promptly gets polyaniline electrode.Wherein: polyaniline/acetylene black/PVDF-HFP=0.85/0.1/0.05 (mass ratio), wherein polyaniline 1mg.
Carbon nano-tube and acetylene black are mixed, drip the acetone soln of PVDF-HFP, and be applied on the nickel foam, after the compacting, vacuumize promptly gets carbon nanotube electrode.Wherein: carbon nano-tube/acetylene black/PVDF-HFP=0.85/0.1/0.05 (mass ratio), wherein carbon nano-tube 10mg.
Respectively as positive and negative electrode, is positive and negative electrode electric current collection body with the nickel foam, with 1mol/L LiPF with above-mentioned polyaniline electrode and carbon nanotube electrode
6EC/DEC (ethylene carbonate/butylene=1 volume ratio) solution is as electrolyte, make barrier film with the Celgard2300 microporous barrier, in being full of the atmosphere of argon gas, anodal electric current collection body/polyaniline positive pole/electrolyte and barrier film/carbon nanometer tube negative pole/cathodal current collection body are assembled into polyaniline/carbon nano tube hybrid type ultra-capacitor.Capacitor produced specific energy is 2.8Wh/kg.
Embodiment 6:
Polyaniline, active carbon and acetylene black are mixed, drip the acetone soln of PVDF-HFP, and be applied on the nickel foam, after the compacting, vacuumize promptly gets polyaniline electrode.Wherein: polyaniline/active carbon/acetylene black/PVDF-HFP=0.80/0.05/0.1/0.05 (mass ratio), wherein polyaniline 16mg.
Carbon nano-tube and acetylene black are mixed, drip the acetone soln of PVDF-HFP, and be applied on the nickel foam, after the compacting, vacuumize promptly gets carbon nanotube electrode.Wherein: carbon nano-tube/acetylene black/PVDF-HFP=0.85/0.1/0.05 (mass ratio), wherein carbon nano-tube 8.5mg.
Respectively as positive and negative electrode, is positive and negative electrode electric current collection body with the nickel foam, with 1mol/L LiPF with above-mentioned polyaniline electrode and carbon nanotube electrode
6EC/DEC (ethylene carbonate/butylene=1 volume ratio) solution is as electrolyte, make barrier film with the Celgard2300 microporous barrier, in being full of the atmosphere of argon gas, anodal electric current collection body/polyaniline positive pole/electrolyte and barrier film/carbon nanometer tube negative pole/cathodal current collection body are assembled into polyaniline/carbon nano tube hybrid type ultra-capacitor.Capacitor produced specific energy is 5.5Wh/kg.
Embodiment 7:
Polyaniline and acetylene black are mixed, drip the acetone soln of PVDF-HFP, and be applied on the nickel foam, after the compacting, vacuumize promptly gets polyaniline electrode.Wherein: polyaniline/acetylene black/PVDF-HFP=0.85/0.1/0.05 (mass ratio), wherein polyaniline 25.5mg.
Carbon nano-tube and acetylene black are mixed, drip the acetone soln of PVDF-HFP, and be applied on the nickel foam, after the compacting, vacuumize promptly gets carbon nanotube electrode.Wherein: carbon nano-tube/acetylene black/PVDF-HFP=0.85/0.1/0.05 (mass ratio), wherein carbon nano-tube 8.5mg.
Respectively as positive and negative electrode, is positive and negative electrode electric current collection body with the nickel foam, with 1mol/L LiPF with above-mentioned polyaniline electrode and carbon nanotube electrode
6EC/DEC (ethylene carbonate/butylene=1 volume ratio) solution is as electrolyte, make barrier film with the Celgard2300 microporous barrier, in being full of the atmosphere of argon gas, anodal electric current collection body/polyaniline positive pole/electrolyte and barrier film/carbon nanometer tube negative pole/cathodal current collection body are assembled into polyaniline/carbon nano tube hybrid type ultra-capacitor.Capacitor produced specific energy is 3.6Wh/kg.
Embodiment 8:
Polyaniline and acetylene black are mixed, drip the acetone soln of PVDF-HFP, and be applied on the nickel foam, after the compacting, vacuumize promptly gets polyaniline electrode.Wherein: polyaniline/acetylene black/PVDF-HFP=0.85/0.1/0.05 (mass ratio), wherein polyaniline 34mg.
Carbon nano-tube and acetylene black are mixed, drip the acetone soln of PVDF-HFP, and be applied on the nickel foam, after the compacting, vacuumize promptly gets carbon nanotube electrode.Wherein: carbon nano-tube/acetylene black/PVDF-HFP=0.85/0.1/0.05 (mass ratio), wherein carbon nano-tube 8.5mg.
Respectively as positive and negative electrode, is positive and negative electrode electric current collection body with the nickel foam, with 1mol/L LiPF with above-mentioned polyaniline electrode and carbon nanotube electrode
6EC/DEC (ethylene carbonate/butylene=1 volume ratio) solution is as electrolyte, make barrier film with the Celgard2300 microporous barrier, in being full of the atmosphere of argon gas, anodal electric current collection body/polyaniline positive pole/electrolyte and barrier film/carbon nanometer tube negative pole/cathodal current collection body are assembled into polyaniline/carbon nano tube hybrid type ultra-capacitor.Capacitor produced specific energy is 3.3Wh/kg.
Embodiment 9:
Polyaniline and acetylene black are mixed, drip the acetone soln of PVDF-HFP, and be applied on the nickel foam, after the compacting, vacuumize promptly gets polyaniline electrode.Wherein: polyaniline/acetylene black/PVDF-HFP=0.85/0.1/0.05 (mass ratio), wherein polyaniline 42.5mg.
Carbon nano-tube and acetylene black are mixed, drip the acetone soln of PVDF-HFP, and be applied on the nickel foam, after the compacting, vacuumize promptly gets carbon nanotube electrode.Wherein: carbon nano-tube/acetylene black/PVDF-HFP=0.85/0.1/0.05 (mass ratio), wherein carbon nano-tube 8.5mg.
Respectively as positive and negative electrode, is positive and negative electrode electric current collection body with the nickel foam, with 1mol/L LiPF with above-mentioned polyaniline electrode and carbon nanotube electrode
6EC/DEC (ethylene carbonate/butylene=1 volume ratio) solution is as electrolyte, make barrier film with the Celgard2300 microporous barrier, in being full of the atmosphere of argon gas, anodal electric current collection body/polyaniline positive pole/electrolyte and barrier film/carbon nanometer tube negative pole/cathodal current collection body are assembled into polyaniline/carbon nano tube hybrid type ultra-capacitor.Capacitor produced specific energy is 2.8Wh/kg.
Embodiment 10:
Polyaniline and acetylene black are mixed, drip the acetone soln of PVDF-HFP, and be applied on the nickel foam, after the compacting, vacuumize promptly gets polyaniline electrode.Wherein: polyaniline/acetylene black/PVDF-HFP=0.73/0.27/0.1 (mass ratio), wherein polyaniline 7.3mg.
Carbon nano-tube and acetylene black are mixed, drip the acetone soln of PVDF-HFP, and be applied on the nickel foam, after the compacting, vacuumize promptly gets carbon nanotube electrode.Wherein: carbon nano-tube/acetylene black/PVDF-HFP=0.73/0.27/0.1 (mass ratio), wherein carbon nano-tube 7.3mg.
With above-mentioned polyaniline electrode as positive and negative electrode, with the nickel foam is positive and negative electrode electric current collection body, with 1mol/L tetraethylammonium tetrafluoroborate EC/DEC (ethylene carbonate/butylene=1 volume ratio) solution as electrolyte, make barrier film with the Celgard2300 microporous barrier, in being full of the atmosphere of argon gas, be assembled into the polyaniline ultra-capacitor according to the level of anodal electric current collection body/polyaniline positive pole/electrolyte and barrier film/polyaniline negative pole/cathodal current collection body.Capacitor produced specific energy is 6.3Wh/kg.
Embodiment 11:
Polyaniline and acetylene black are mixed, drip the acetone soln of PVDF-HFP, and be applied on the nickel foam, after the compacting, vacuumize promptly gets polyaniline electrode.Wherein: polyaniline/acetylene black/PVDF-HFP=0.95/0.05 (mass ratio), wherein polyaniline 9.5mg.
Carbon nano-tube and acetylene black are mixed, drip the acetone soln of PVDF-HFP, and be applied on the nickel foam, after the compacting, vacuumize promptly gets carbon nanotube electrode.Wherein: carbon nano-tube/acetylene black/PVDF-HFP=0.95/0.05 (mass ratio), wherein carbon nano-tube 9.5mg.
With above-mentioned polyaniline electrode as positive and negative electrode, with the nickel foam is positive and negative electrode electric current collection body, with the acetonitrile solution of 1mol/L tetraethylammonium tetrafluoroborate as electrolyte, make barrier film with the Celgard2300 microporous barrier, in being full of the atmosphere of argon gas, be assembled into the polyaniline ultra-capacitor according to the level of anodal electric current collection body/polyaniline positive pole/electrolyte and barrier film/polyaniline negative pole/cathodal current collection body.Capacitor produced specific energy can reach 6Wh/kg.
The comparative example 1:
Polyaniline and carbon nano tube compound material (wherein containing 10% carbon nano-tube) are mixed with acetylene black, drip the acetone soln of PVDF-HFP, and be applied on the nickel foam, after the compacting, vacuumize promptly gets polyaniline electrode.Wherein: polyaniline and carbon nano tube compound material/acetylene black/PVDF-HFP=0.85/0.1/0.05 (mass ratio).
As positive and negative electrode, is positive and negative electrode electric current collection body with the nickel foam, with 1mol/L LiPF with above-mentioned polyaniline electrode
6EC/DEC (ethylene carbonate/butylene=1 volume ratio) solution is as electrolyte, make barrier film with the Celgard2300 microporous barrier, in being full of the atmosphere of argon gas, be assembled into the polyaniline ultra-capacitor according to the level of anodal electric current collection body/polyaniline electrode/electrolyte and barrier film/polyaniline electrode/cathodal current collection body.Capacitor produced specific energy can reach 5.2Wh/kg.
From Fig. 2,3 and 5 as can be seen, under the discharging condition of constant current 17.6A/kg, the specific energy of polyaniline ultra-capacitor is 5.24Wh/kg, and average specific power is 90W/kg, and the specific energy of polyaniline/carbon nano tube hybrid type ultra-capacitor is 6.83Wh/kg, average specific power is 180W/kg, compare with the polyaniline ultra-capacitor, the specific energy of polyaniline/carbon nano tube hybrid type ultra-capacitor has improved 30%, and average specific power has improved 100%.
The comparative example 2:
Carbon nano-tube and acetylene black are mixed, drip the acetone soln of PVDF-HFP, and be applied on the nickel foam, after the compacting, vacuumize promptly gets carbon nanotube electrode.Wherein: carbon nano-tube/acetylene black/PVDF-HFP=0.85/0.1/0.05 (mass ratio).
As positive and negative electrode, is positive and negative electrode electric current collection body with the nickel foam, with 1mol/L LiPF with above-mentioned carbon nanotube electrode
6EC/DEC (ethylene carbonate/butylene=1 volume ratio) solution is as electrolyte, make barrier film with the Celgard2300 microporous barrier, in being full of the atmosphere of argon gas, be assembled into the carbon nano-tube ultra-capacitor according to anodal electric current collection body/carbon nano-tube positive pole/electrolyte and barrier film/carbon nanometer tube negative pole/cathodal current collection body level.Capacitor produced specific energy can reach 3.2Wh/kg.
From Fig. 2,4 and 5 as can be seen, under the discharging condition of constant current 118A/kg, the specific energy of carbon nano-tube ultra-capacitor is 1.7Wh/kg, and average specific power is 980kW/kg, and the specific energy of polyaniline/carbon nano tube hybrid type ultra-capacitor is 4Wh/kg, average specific power is 1050W/kg, compare with the carbon nano-tube ultra-capacitor, the specific energy of polyaniline/carbon nano tube hybrid type ultra-capacitor has improved 135%, and average specific power has improved 7%.
Claims (4)
1. polyaniline/carbon nano tube hybrid type ultra-capacitor, its structure contains anodal electric current collection body, positive pole, electrolyte and barrier film, negative pole and cathodal current collection body successively, it is characterized in that: the described anodal composite material that adopts polyaniline or polyaniline and material with carbon element to form is made, described material with carbon element is one or more in carbon nano-tube, active carbon, carbon fiber or the acetylene black, and wherein the mass percentage content of material with carbon element is less than 30%; The composite material that described negative pole adopts carbon nano-tube or carbon nano-tube and active carbon, carbon fiber or acetylene black to form is made, and wherein the mass percentage content of active carbon, carbon fiber or acetylene black is less than 30%.
2. according to the described ultra-capacitor of claim 1, it is characterized in that: the mass ratio of used positive electrode and negative material is 0.1～5.
3. according to according to the described ultra-capacitor of claim 2, it is characterized in that: the mass ratio of used positive electrode and negative material is 0.2～2.
4. according to the described ultra-capacitor of claim 1, it is characterized in that: described electrolyte adopts LiPF
6, LiBF
4, LiClO
4, LiCF
3SO
3, (C
2H
5)
4NPF
6, (C
2H
5)
4NBF
4, (C
2H
5)
4NClO
4, (C
2H
5)
4NCF
3SO
3, (C
4H
9)
4NPF
6, (C
4H
9)
4NBF
4, (C
4H
9)
4NClO
4, (C
4H
9)
4NCF
3SO
3Or their mixture is electrolyte, and adopting propene carbonate, ethylene carbonate, butylene, acetonitrile or their mixed liquor is solvent.
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