CN101217073A - A mixed type polymer super capacitor - Google Patents
A mixed type polymer super capacitor Download PDFInfo
- Publication number
- CN101217073A CN101217073A CNA2007100946723A CN200710094672A CN101217073A CN 101217073 A CN101217073 A CN 101217073A CN A2007100946723 A CNA2007100946723 A CN A2007100946723A CN 200710094672 A CN200710094672 A CN 200710094672A CN 101217073 A CN101217073 A CN 101217073A
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- CN
- China
- Prior art keywords
- super capacitor
- polymer
- dielectric film
- kynoar
- flake
- Prior art date
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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 a hybrid polymer super capacitor, including an anode flake, a cathode flake and a polymer electrolyte membrane which is arranged between the anode flake and the cathode flake, the material components of the anode flake include graphite, conductive carbon black and kynoar, the material components of the cathode flake include activated carbon or mesoporous carbon or nano carbon tube or carbon aerogel, conductive carbon black and kynoar, and the invention is characterized in that: the components of the anode flake also include lithium ion embedded compound. The invention uses the polymer electrolyte membrane to solve the problem of liquid leakage and uses the hybrid structure to greatly improve the capacity of the super capacitor, so the invention can be well applied in the occasions which need high power and high energy.
Description
Technical field
The present invention relates to a kind of capacitor, particularly disclose a kind of mixed type polymer super capacitor, belong to the capacitor technology field.
Background technology
Ultracapacitor is a kind of model electrochemical energy storage device between traditional capacitor and battery, and it compares traditional capacitor higher static capacity, can reach thousand farads to ten thousand farads levels; Comparing battery has the higher power density and the cycle life of overlength, so it combines the advantage of traditional capacitor and battery, is a kind of chemical power source that has a extensive future.It has the specific capacity height, power is big, the life-span is long, the warm limit for width of working, characteristics such as non-maintaining.Ultracapacitor mainly is to utilize the formed electric double layer of electrode/electrolyte interface separation of charge, or realizes the storage of electric charge and energy by electrode surface faraday's " pseudo-capacitance " that redox reaction produced fast.At present, in order to improve the energy density of ultracapacitor, the general structural design that adopts mixed type, it is the unpolarized electrode (as nickel hydroxide) of the utmost point employing battery of ultracapacitor, another utmost point adopts the polarizing electrode (as active carbon) of double electric layer capacitor, and this hybrid super capacitor energy density can reach 12～15Wh/Kg.
Ultracapacitor divides by electrolyte can be divided into water system electrolyte, organic bath, three kinds of ultracapacitors of polymer dielectric.Water system electrolyte ultracapacitor is owing to be subjected to the restriction of the decomposition voltage of water, and its operating voltage makes that its energy density is lower about 1V; Though and organic bath ultracapacitor operating voltage can reach more than the 4V, there is the problem of electrolyte leakage; Polymer dielectric ultracapacitor not only operating voltage is higher, and safety, nothing leaks, and is convenient to ultracapacitor and develops towards miniature, ultrathin, special-shaped direction.The polymer dielectric of use on ultracapacitor has two kinds of solid polymer electrolyte and gel polymer electrolytes, and the solid polymer electrolyte room-temperature conductivity is low, poor practicability is so what generally be applied in ultracapacitor is gel-type polymer electrolyte.
Summary of the invention
The objective of the invention is ultracapacitor pole piece material structure: positive plate and negative plate material are different, disclose a kind of mixed type polymer super capacitor, make advantages such as product of the present invention has high power, high-energy, has extended cycle life, non-environmental-pollution, high security.
The present invention combines the advantage separately of hybrid super capacitor and polymer super capacitor, improved the energy density of ultracapacitor on the one hand, solved safety problems such as electrolytic solution for super capacitor leakage, inflatable on the other hand, made it can be applied in industries such as vehicle manufacturing industry, power industry, power supply industry, communications industry, military aerospace industry better.
The present invention is achieved in that a kind of mixed type polymer super capacitor, comprise positive plate, negative plate and the polymer dielectric film between positive and negative plate, the material component of described positive plate comprises graphite, conductive black and Kynoar, the material component of described negative plate comprises active carbon or mesoporous charcoal or nano carbon tube or charcoal-aero gel, conductive black and Kynoar, it is characterized in that: the positive plate component comprises that also lithium ion embeds compound, and described lithium ion embeds compound at LiCoO
2, LiMn
2O
4, LiNiO
2, LiFePO
4, LiNi
0.8Co
0.2O
2Or LiNi
1/3Co
1/3Mn
1/3O
2In choose one or more, also can adopt in the resulting material of doping that above-mentioned embedding compound is carried out metallic element one or more, doping elements is: one or more among Li, Co, Ni, Mn, Fe, Cu, Al, Mg and the Zn; Described polymer dielectric film adopts the dielectric film of the gel-type polymer that contains lithium salts, and it is polyacrylonitrile or polyoxyethylene or Kynoar, lithium salts and plasticizer that this polymer dielectric film is made used slurry component.
Among the present invention, the making step of positive plate is: take by weighing LiMn according to certain mass ratio
2O
4Or other lithium ion embeds after compound, graphite powder, conductive black, PVDF (Kynoar), NMP (1-Methyl-2-Pyrrolidone) mix, be stirred to paste, be coated on then on the aluminium foil, through vacuum drying (120～130 ℃), roll after, be cut into certain size.The making step of negative plate is: take by weighing after active carbon or other raw material of wood-charcoal material, conductive black, PVDF (Kynoar), NMP (1-Methyl-2-Pyrrolidone) mix according to certain mass ratio, be stirred to paste, be coated on the Copper Foil then, through vacuum drying (120～130 ℃), roll after, be cut into certain size.
Among the present invention, the making step of polymer dielectric film is (is example with the polyoxyethylene film): at first with polymer (PEO) and lithium salts (LiClO
4) to be dissolved in 40～50 ℃ mass ratio respectively be in 1: 1 the mixed solution of EC-PC, treat after the dissolving fully two kinds of solution to be mixed, stir into uniform colloid at 70～80 ℃, be poured on then between two glass plates and form thin layer, under reduced pressure remove organic solvent in 120 ℃ of heating under the situation again, just can obtain pliable and tough solid film, be cut into the size of regulation then.
Among the present invention, the assembling of ultracapacitor is to adopt overlapped way, promptly carry out lamination according to the such mode of positive plate/polymer dielectric film/negative plate, the anodal utmost point group of the electric core that will fold is welded on the aluminum lug then, negative pole utmost point group is welded on the nickel system lug, and the aluminum plastic film of the electric core after welding being put into forming seals.
The lithium salts that gel polymer electrolyte of the present invention uses is at LiClO
4, LiBF
4, LiPF
6, LiCF
3SO
3Or LiN (CF
3SO
2)
2In choose a kind ofly, the concentration of lithium salts is 0.5～2.0mol/L.
Among the present invention, the plasticizer that polymer dielectric uses is one or both the combination among EC (ethylene carbonate), PC (propene carbonate), EMC (ethyl-methyl carbonic ester), DMC (dimethyl carbonate) and the GBL (gamma-butyrolacton), its combining form at mass ratio at PC: EC=1: 1～2, EMC: EC=1: 1～2 or DMC: EC=1: choose a kind of in 1～2.
The invention has the beneficial effects as follows: on the one hand owing to use the supercapacitor structures of mixed type, the unpolarized electrode lithium ion embedding compound of battery is combined with the carbon structure materials such as polarizing electrode active carbon that can form electric double layer, significantly improved the energy density of ultracapacitor, use the gel-type polyelectrolyte membranes on the other hand, can make arbitrary shape and size, eliminate problems such as ultracapacitor leakage, inflatable, made ultracapacitor safer.Therefore, the ultracapacitor of this high-energy, high power, high safety can satisfy the more applications occasion, have the stronger market competitiveness.
Embodiment
The invention will be further described below in conjunction with embodiment.
Mixed type polymer super capacitor of the present invention comprises positive plate, negative plate and the dielectric film between positive and negative plate.
Embodiment 1:
The preparation of polymer dielectric film (is example with the polyoxyethylene film): according to mass ratio PEO: (EC+PC)=(annotate: EC+PC mixed liquor mass ratio 1: 1) taken by weighing required consumption, then take by weighing PEO be dissolved in 40～50 ℃ the mixed solution of EC-PC at 1: 9.6; Press mass ratio LiClO then
4: (EC+PC)=(annotate: EC+PC mixed liquor mass ratio 1: 1) taken by weighing required consumption, then with take by weighing LiClO at 1: 9.6
4Be dissolved in 40～50 ℃ the mixed solution of EC-PC; Treat two kinds of mixed liquors dissolve fully after with its mixing, stir into uniform colloid at 70～80 ℃, be poured on then between two glass plates and form thin layer, under reduced pressure remove organic solvent in 120 ℃ of heating under the situation again, just can obtain pliable and tough solid film, be cut into the size of regulation then.
Embodiment 2:
Positive plate is made: with LiMn
2O
4, graphite powder, conductive black, PVDF be 80: 10: 5 by mass ratio: 5 mix, with NMP furnishing slurry, be coated on then on the aluminium foil of 16 μ, drying, roll, cut-parts are made into positive plate.Negative plate is made: is to mix at 80: 15: 5 active carbon, conductive black, PVDF by mass ratio, with NMP furnishing slurry, be coated on then on the Copper Foil of 10 μ, drying, roll, cut-parts are made into negative plate.Adopt embodiment 1 prepared polymer dielectric film, carry out lamination according to the mode that positive plate/polymer dielectric film/negative plate is such, the anodal utmost point group of the electric core that will fold is welded on the aluminum lug then, negative pole utmost point group is welded on the nickel system lug, the aluminum plastic film of electric core after welding being put into forming seals, and is assembled into the polymerization ultracapacitor.Capacitor carries out performance test after changing into, specific energy reaches 40Wh/Kg (based on both positive and negative polarity active material calculation of total), and after 2000 circulations, capability retention shows superior cycle performance more than 97%.
Embodiment 3: positive plate is made: with LiCoO
2, graphite powder, conductive black, PVDF be 75: 15: 7 by mass ratio: 3 mix, with NMP furnishing slurry, be coated on then on the aluminium foil of 16 μ, drying, roll, cut-parts are made into positive plate.Negative plate is made: is to mix at 75: 20: 5 active carbon, conductive black, PVDF by mass ratio, with NMP furnishing slurry, be coated on then on the Copper Foil of 10 μ, drying, roll, cut-parts are made into negative plate.Adopt the polymer dielectric film of embodiment 1 made, carry out lamination according to the mode that positive plate/polymer dielectric film/negative plate is such, the anodal utmost point group of the electric core that will fold is welded on the aluminum lug then, negative pole utmost point group is welded on the nickel system lug, the aluminum plastic film of electric core after welding being put into forming seals, and is assembled into the polymerization ultracapacitor.Capacitor carries out performance test after changing into, specific energy reaches 43Wh/Kg (based on both positive and negative polarity active material calculation of total), and after 2000 circulations, capability retention shows better cycle performance more than 95%.
Embodiment 4: positive plate is made: with LiNiO
2, graphite powder, conductive black, PVDF be 85: 7: 4 by mass ratio: 4 mix, with NMP furnishing slurry, be coated on then on the aluminium foil of 16 μ, drying, roll, cut-parts are made into positive plate.Negative plate is made: is to mix at 85: 10: 5 active carbon, conductive black, PVDF by mass ratio, with NMP furnishing slurry, be coated on then on the Copper Foil of 10 μ, drying, roll, cut-parts are made into negative plate.Adopt the polymer dielectric film of embodiment 1 made, carry out lamination according to the mode that positive plate/polymer dielectric film/negative plate is such, the anodal utmost point group of the electric core that will fold is welded on the aluminum lug then, negative pole utmost point group is welded on the nickel system lug, the aluminum plastic film of electric core after welding being put into forming seals, and is assembled into the polymerization ultracapacitor.Capacitor carries out performance test after changing into, specific energy reaches 47Wh/Kg (based on both positive and negative polarity active material calculation of total), and after 2000 circulations, capability retention is more than 92%.
Claims (3)
1. mixed type polymer super capacitor, comprise positive plate, negative plate and the polymer dielectric film between positive and negative plate, the material component of described positive plate comprises graphite, conductive black and Kynoar, the material component of described negative plate comprises active carbon or mesoporous charcoal or nano carbon tube or charcoal-aero gel, conductive black and Kynoar, it is characterized in that: the positive plate component comprises that also lithium ion embeds compound, and described lithium ion embeds compound at LiCoO
2, LiMn
2O
4, LiNiO
2, LiFePO
4, LiNi
0.8Co
0.2O
2Or LiNi
1/3Co
1/3Mn
1/3O
2In choose one or more, or in the resulting material of doping that above-mentioned embedding compound is carried out metallic element one or more, doping elements is: one or more among Li, Co, Ni, Mn, Fe, Cu, Al, Mg and the Zn; Described polymer dielectric film adopts the dielectric film of the gel-type polymer that contains lithium salts, and it is polyacrylonitrile or polyoxyethylene or Kynoar, lithium salts and plasticizer that this polymer dielectric film is made used slurry component.
2. a kind of mixed type polymer super capacitor according to claim 1 is characterized in that: the lithium salts that described gel polymer electrolyte uses is at LiClO
4, LiBF
4, LiPF
6, LiCF
3SO
3Or LiN (CF
3SO
2)
2In choose a kind ofly, the concentration of lithium salts is 0.5～2.0mol/L.
3. a kind of mixed type polymer super capacitor according to claim 1, it is characterized in that: the plasticizer that described gel polymer electrolyte uses is one or both the combination in ethylene carbonate, propene carbonate, ethyl-methyl carbonic ester, dimethyl carbonate and the gamma-butyrolacton, and its combining form mass ratio is at propene carbonate: ethylene carbonate=1: 1～2, ethyl-methyl carbonic ester: ethylene carbonate=1: 1～2 or dimethyl carbonate: choose a kind of in ethylene carbonate=1: 1～2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100946723A CN101217073A (en) | 2007-12-28 | 2007-12-28 | A mixed type polymer super capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100946723A CN101217073A (en) | 2007-12-28 | 2007-12-28 | A mixed type polymer super capacitor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101217073A true CN101217073A (en) | 2008-07-09 |
Family
ID=39623481
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|---|---|---|---|
| CNA2007100946723A Pending CN101217073A (en) | 2007-12-28 | 2007-12-28 | A mixed type polymer super capacitor |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102509617A (en) * | 2011-11-30 | 2012-06-20 | 江苏富朗特新能源有限公司 | Organic super capacitor with low internal resistance |
| CN101719422B (en) * | 2010-01-08 | 2012-08-29 | 西北工业大学 | Anode material for lithium ion capacitor or battery and preparation method thereof |
| CN103474250A (en) * | 2012-06-08 | 2013-12-25 | 海洋王照明科技股份有限公司 | Super capacitor and manufacturing method thereof |
| CN103545117A (en) * | 2013-10-30 | 2014-01-29 | 中国第一汽车股份有限公司 | Composite material for supercapacitor and preparation method thereof |
| CN103545113A (en) * | 2013-10-30 | 2014-01-29 | 中国第一汽车股份有限公司 | Lithium-ion mixture super capacitor |
| CN103560019A (en) * | 2013-10-30 | 2014-02-05 | 中国第一汽车股份有限公司 | Zinc icon mixed super capacitor |
| WO2014081793A1 (en) * | 2012-11-21 | 2014-05-30 | Ut-Battelle, Llc | Nitrogen-sulfur-carbon nanocomposites and their application as cathode materials in lithium-sulfur batteries |
-
2007
- 2007-12-28 CN CNA2007100946723A patent/CN101217073A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101719422B (en) * | 2010-01-08 | 2012-08-29 | 西北工业大学 | Anode material for lithium ion capacitor or battery and preparation method thereof |
| CN102509617A (en) * | 2011-11-30 | 2012-06-20 | 江苏富朗特新能源有限公司 | Organic super capacitor with low internal resistance |
| CN103474250A (en) * | 2012-06-08 | 2013-12-25 | 海洋王照明科技股份有限公司 | Super capacitor and manufacturing method thereof |
| US9455439B2 (en) | 2012-11-21 | 2016-09-27 | Ut-Battelle, Llc | Nitrogen—sulfur—carbon nanocomposites and their application as cathode materials in lithium—sulfur batteries |
| US11251433B2 (en) | 2012-11-21 | 2022-02-15 | Ut-Battelle, Llc | Nitrogen-sulfur-carbon nanocomposites and their application as cathode materials in lithium-sulfur batteries |
| US10044039B2 (en) | 2012-11-21 | 2018-08-07 | Ut-Batelle, Llc | Nitrogen-sulfur-carbon nanocomposites and their application as cathode materials in lithium-sulfur batteries |
| WO2014081793A1 (en) * | 2012-11-21 | 2014-05-30 | Ut-Battelle, Llc | Nitrogen-sulfur-carbon nanocomposites and their application as cathode materials in lithium-sulfur batteries |
| CN103545117A (en) * | 2013-10-30 | 2014-01-29 | 中国第一汽车股份有限公司 | Composite material for supercapacitor and preparation method thereof |
| CN103545113B (en) * | 2013-10-30 | 2016-05-11 | 中国第一汽车股份有限公司 | A kind of lithium ion hybrid super capacitor |
| CN103545117B (en) * | 2013-10-30 | 2016-08-17 | 中国第一汽车股份有限公司 | A kind of composite for ultracapacitor and preparation method thereof |
| CN103560019B (en) * | 2013-10-30 | 2016-05-04 | 中国第一汽车股份有限公司 | A kind of zinc ion hybrid super capacitor |
| CN103560019A (en) * | 2013-10-30 | 2014-02-05 | 中国第一汽车股份有限公司 | Zinc icon mixed super capacitor |
| CN103545113A (en) * | 2013-10-30 | 2014-01-29 | 中国第一汽车股份有限公司 | Lithium-ion mixture super capacitor |
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Open date: 20080709 |