CN101127276A - Organic electrolyte system mixed electrochemical capacitor and preparation method thereof - Google Patents
Organic electrolyte system mixed electrochemical capacitor and preparation method thereof Download PDFInfo
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- CN101127276A CN101127276A CNA2006101094232A CN200610109423A CN101127276A CN 101127276 A CN101127276 A CN 101127276A CN A2006101094232 A CNA2006101094232 A CN A2006101094232A CN 200610109423 A CN200610109423 A CN 200610109423A CN 101127276 A CN101127276 A CN 101127276A
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- 239000003990 capacitor Substances 0.000 title claims abstract description 56
- 239000005486 organic electrolyte Substances 0.000 title claims abstract description 8
- 238000002360 preparation method Methods 0.000 title claims description 21
- 239000000463 material Substances 0.000 claims abstract description 20
- 239000003792 electrolyte Substances 0.000 claims abstract description 7
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- 239000003610 charcoal Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 230000004888 barrier function Effects 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 7
- 239000011149 active material Substances 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- -1 polyoxyethylene Polymers 0.000 claims description 6
- 239000005030 aluminium foil Substances 0.000 claims description 5
- 239000007767 bonding agent Substances 0.000 claims description 5
- 239000006258 conductive agent Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 238000002955 isolation Methods 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000004966 Carbon aerogel Substances 0.000 claims description 2
- 239000004677 Nylon Substances 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 159000000013 aluminium salts Chemical class 0.000 claims description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 239000010425 asbestos Substances 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 238000005137 deposition process Methods 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- 229910021385 hard carbon Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910003002 lithium salt Inorganic materials 0.000 claims description 2
- 159000000002 lithium salts Chemical class 0.000 claims description 2
- 159000000003 magnesium salts Chemical class 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000012982 microporous membrane Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229920001778 nylon Polymers 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000000123 paper Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 229910052895 riebeckite Inorganic materials 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 239000013543 active substance Substances 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 150000002500 ions Chemical class 0.000 abstract description 7
- 238000004146 energy storage Methods 0.000 abstract description 2
- 238000005272 metallurgy Methods 0.000 abstract description 2
- 238000005065 mining Methods 0.000 abstract description 2
- 238000009413 insulation Methods 0.000 abstract 1
- 239000007774 positive electrode material Substances 0.000 abstract 1
- 239000002250 absorbent Substances 0.000 description 4
- 230000002745 absorbent Effects 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000007790 scraping Methods 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910002640 NiOOH Inorganic materials 0.000 description 1
- 229910018502 Ni—H Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
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- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
A novel electrochemical capacitor is characterized in that an ion embedding material is used as a positive electrode active material for a positive electrode of the capacitor. The negative electrode uses a porous carbon material electrode with large specific surface area, an organic electrolyte solution is used as an electrolyte, and an electronic insulation diaphragm capable of passing ions is arranged between the positive electrode and the negative electrode. The electrochemical capacitor has higher energy density and power density and better application prospect, and can be widely applied to electric energy storage in the fields of electronic industry, transportation, electric power, mining and metallurgy and the like.
Description
Technical field
The present invention relates to hybrid electrochemical capacitor of a kind of organic electrolyte system and preparation method thereof, belong to electronics, power domain, can be widely used in the electrical power storage in fields such as electronics industry, communications and transportation, electric power, mining and metallurgy.
Background technology
Electrochemical capacitor is a kind of novel energy-storing device, utilizes electric double layer ionic adsorption/desorption principle or accelerated surface faraday reaction (pseudo-capacitance) accumulate principle storage power.Compare with traditional capacitor, electrochemical capacitor has high capacitance, LF-response and low equivalent series resistance preferably, thereby in the deficiency that has remedied traditional capacitor aspect electronic circuit and the micro appliance, be used to provide needed big electric capacity in the electronic circuit, become class novel electronic components and parts, in electronics industry, be widely used, and part has replaced electrolytic capacitor.In recent years, along with the miniaturization of electronics, electric equipment and the continuous development of electric automobile industry, electrochemical capacitor power supply and impulse power electrical source has in support caused people's attention day by day, and various countries begin to support the research and development of electrochemical capacitor in succession.Electrochemical capacitor also has broad application prospects in military field, can be used as the startup power supply of tank, rocket extract car etc., improve the cryogenic property of these military vehicles, and the high-specific-power electrochemical capacitor also will be one of first-selected power supply of weapons such as high power laser weapon, magnetic artillery.
Compare with battery, electrochemical capacitor has longer cycle life, safety, advantage such as memoryless, the more important thing is that electrochemical capacitor has the performance that the not available high power of battery discharges and recharges continuously, therefore, electrochemical capacitor is a kind of energy storage device that has development potentiality.
The electrochemical capacitor that technology is comparatively ripe is that as patent ZL99208460.1, CN1229517A etc., its both positive and negative polarity is formed by porous activated carbon with the double electric layer capacitor of porous activated carbon as electrode material at present, and specific energy and specific power are all lower.Because the charcoal material surface micropore that exists electrolyte to be difficult to arrive, can't make full use of the surface of active carbon, simultaneously, the specific surface of absorbent charcoal material can not unrestrictedly improve, and therefore, it is little to utilize the high-ratio surface material to obtain the leeway of big specific capacity.In addition, absorbent charcoal material itself has higher contact resistance, has influenced the raising of the power-performance of double electric layer capacitor.Comparatively speaking, pseudo-capacitance is accurate faraday's process, and specific energy is relevant with the electrochemically reactive of electrode material, can increase substantially the capacity characteristic of material, thereby increases substantially the specific capacity of capacitor.
Material with higher pseudo capacitance, studying more is RuO
2Deng precious metal material,, use RuO as CN1345074A
2Constitute electrochemical capacitor with absorbent charcoal composite material, specific capacity is higher, simultaneously very high power-performance is arranged also, but its fancy price has limited its commercialization and further used.Patent such as CN1369886A are also arranged, use MnO
2Constituting electrochemical capacitor and CN1277444A and CN2574196Y etc. with active carbon uses NiOOH material and active carbon to constitute hybrid super capacitor, make the cost of electrochemical capacitor that reduction to a certain degree arranged, but because these capacitors are all water solution system, monomer voltage is low, thereby the potentiality that performance improves are little.
Summary of the invention
The object of the present invention is to provide a kind of organic electrolyte system mixing electrochemical capacitor and preparation method thereof,, and this capacitor is had than ickel-cadmium cell, the better power characteristic of Ni-H cell with the energy density of raising electrochemical capacitor.
Technical scheme of the present invention is as follows:
The positive pole of capacitor (1) uses the ion insert material as active material, as lithium ion insert material LiCoO
2Deng; The negative pole of capacitor (2) uses the porous carbon materials electrode of bigger serface, as absorbent charcoal material; With organic solution as electrolyte; Having between the both positive and negative polarity can be by the electronic isolation barrier film (3) of ion.
Anodal (1) preparation process is as follows: with the ion insert material is active material, adds conductive agent, and furnishing slurries such as bonding agent are coated on the plus plate current-collecting bodies such as aluminium foil (4), after drying, the roll-in as the positive pole of capacitor.Its intermediate ion insert material should have following structural formula: M1
xM2
yA
zWherein M is for embedding element, can be Li, Mg, Al, Cr or their combination, M2 is host's element, can be Mn, Ni, Co, Fe, V, Mg, Al, Cr, Ti, Mo or their combination, A is O, P, S, N, Cl, F, B or their combination, and x, y can not be zero simultaneously, and z can not be zero.Ion insert material preparation method has following several: common deposited method, vapour deposition process, sol-gal process, mixed-sintering method, codeposition sintering process etc.
Negative pole (2) preparation process is as follows: be active material with the porous carbon materials, add conductive agent, furnishing slurries such as bonding agent are coated on the negative current collectors such as aluminium foil (5), after drying, the roll-in as the negative pole of capacitor.Wherein porous carbon materials be following one or more: activated carbon powder, activated carbon fiber, active carbon cloth, activated carbon felt, carbon nano-tube, carbon aerogels, active vitrescence charcoal, nano-pore vitrescence charcoal, porous graphite, graphite fibre, porous hard carbon etc.
Capacitor electrolyte is an organic electrolyte, and electrolytic salt is one of ammonium salt, lithium salts, magnesium salts, aluminium salt, chromic salts or their mixture, as LiPF
6Be dissolved in the EC/DMC mixed solvent, form 1M LiPF6-EC/DMC (50v%).
The electronic isolation barrier film (3) of capacitor is: polyoxyethylene, polypropylene, nylon, polyethene microporous membrane, asbestos paper, polyethylene, glass fibre or their composite material etc.
The electrochemical capacitor of the present invention's preparation, the life-span is long, price is low, has high energy density and power density, and the energy utilization efficiency height can be widely used in industries such as electric power, traffic, electronics.
Description of drawings
Fig. 1 is the structure chart of electrochemical capacitor of the present invention.
1 positive pole, 2 negative poles, 3 barrier films, 4 plus plate current-collecting bodies, 5 negative current collectors, 6 anodal electric current exits, 7 cathodal current exits, 8 capacitor monomers
Fig. 2 is the typical charging and discharging curve of electrochemical capacitor of the present invention.
Embodiment
Below for the preparation method of three embodiment brief description electrochemical capacitors of the present invention.
Embodiment 1
The preparation of anode of electrochemical capacitor
Prepare Li with sol-gel process
0.96Mg
0.04FePO
4, 700 ℃ of sintering are 24 hours under nitrogen protection, obtain embedding lithium type active material, and the carbon black that adds 5% mass ratio is as conductive agent, and the PVdF that adds 7% mass ratio is as bonding agent, with N-methyl pyrrolidone furnishing slurry.With slurry-scraping method with the even blade coating of above-mentioned slurry on the aluminium foil of 20 micron thickness, drying, roll-forming are as positive pole.
Embodiment 2
The preparation of electrochemical capacitor negative pole
Get active carbon as negative active core-shell material, the conductive carbon black that adds 15% mass ratio is as conductive agent, and the PVdF that adds 7% mass ratio is as bonding agent, with N-methyl pyrrolidone furnishing slurry.With slurry-scraping method with the even blade coating of above-mentioned slurry on the aluminium foil of 20 micron thickness, drying, roll-forming are as negative pole.
The preparation of electrochemical capacitor
Get the positive pole of above embodiment 1 and the negative pole of embodiment 2 and be cut into suitable pole piece, on lug, weld conducting strip, materials such as the good bolt of cloth, barrier film on mounting clip, the conducting strip of a slice positive pole is enclosed within on the bolt of one side, barrier film is folded on one side, pave tension, be enclosed within on the bolt, barrier film is separated two electrodes at the conducting strip of another side with a slice negative pole.Continue to put with positive pole.To form the electrode group with upper type.The pole plate assembling is finished, and puts into capacitor casing after arrangement, adjusts the pole position, with bolted, seals.Filling electrolyte adds seal valve, can use after the activated and sorting.Reach with the electrochemical capacitor voltage of present embodiment preparation and can be charged to 3.0V, specific energy can reach more than the 8Wh/kg, and specific power can reach more than 2～3kW/kg, and performance is higher than common charcoal/charcoal electrochemical capacitor far away.
Claims (6)
1. organic electrolyte system mixing electrochemical capacitor and preparation method thereof, it is characterized in that: the positive pole of capacitor (1) is that the ion insert material is as active material, the negative pole of capacitor (2) is the porous carbon materials electrode of bigger serface, have between the both positive and negative polarity and can soak full organic electrolyte solution as electrolyte in the barrier film (3) by the electronic isolation barrier film (3) of ion; Anodal (1) preparation process is as follows: with the ion insert material is active material, adds conductive agent, bonding agent furnishing slurry, be coated on the plus plate current-collecting bodies such as aluminium foil (4), after drying, the roll-in as the positive pole of capacitor.
2. electrochemical capacitor according to claim 1 and preparation method thereof is characterized in that the ion insert material has following structural formula: M1
xM2
yA
zWherein M is for embedding element, can be Li, Mg, Al, Cr or their combination, M2 is host's element, can be Mn, Ni, Co, Fe, V, Mg, Al, Cr, Ti, Mo or their combination, A is O, P, S, N, Cl, F, B or their combination, and x, y can not be zero simultaneously, and z can not be zero.
3. electrochemical capacitor according to claim 1 and preparation method thereof, it is following several to it is characterized in that the insert material preparation method has: common deposited method, vapour deposition process, sol-gal process, mixed-sintering method, codeposition sintering process.
4. electrochemical capacitor according to claim 1 and preparation method thereof is characterized in that porous carbon materials electrode (2) is is main active substances with following one or more: activated carbon powder, activated carbon fiber, active carbon cloth, activated carbon felt, carbon nano-tube, carbon aerogels, active vitrescence charcoal, nano-pore vitrescence charcoal, porous graphite, graphite fibre, porous hard carbon.
5. electrochemical capacitor according to claim 1 and preparation method thereof, the solvent that it is characterized in that electrolyte is an organic solvent, electrolytic salt is one of ammonium salt, lithium salts, magnesium salts, aluminium salt, chromic salts or their mixture.
6. electrochemical capacitor according to claim 1 and preparation method thereof is characterized in that electronic isolation barrier film (3) is: polyoxyethylene, polypropylene, nylon, polyethene microporous membrane, asbestos paper, polyethylene, glass fibre, or their composite material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006101094232A CN101127276B (en) | 2006-08-15 | 2006-08-15 | Organic electrolyte system mixing electrochemical capacitor and its making method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006101094232A CN101127276B (en) | 2006-08-15 | 2006-08-15 | Organic electrolyte system mixing electrochemical capacitor and its making method |
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| Publication Number | Publication Date |
|---|---|
| CN101127276A true CN101127276A (en) | 2008-02-20 |
| CN101127276B CN101127276B (en) | 2012-03-28 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006101094232A Expired - Fee Related CN101127276B (en) | 2006-08-15 | 2006-08-15 | Organic electrolyte system mixing electrochemical capacitor and its making method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101847764A (en) * | 2010-02-26 | 2010-09-29 | 上海奥威科技开发有限公司 | High-specific-energy/high-specific-power type super battery |
| CN101847516A (en) * | 2010-02-26 | 2010-09-29 | 上海奥威科技开发有限公司 | Capacitor battery of high-specific-energy organic system |
| CN101847513A (en) * | 2010-02-26 | 2010-09-29 | 上海奥威科技开发有限公司 | Preparation process of long-lived negative pole piece and capacitor battery using negative pole piece |
| CN101409154B (en) * | 2008-09-24 | 2011-05-04 | 上海奥威科技开发有限公司 | Organic mixed super capacitor |
| CN106253738A (en) * | 2016-08-12 | 2016-12-21 | 王海清 | A kind of High Density Charge electric field generator |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004335889A (en) * | 2003-05-09 | 2004-11-25 | Tdk Corp | Electrochemical capacitor |
| CN1734689B (en) * | 2004-08-13 | 2010-09-08 | 中国人民解放军63971部队 | Electrochemical capacitor with composite oxide electrode and preparation method thereof |
| JP4819342B2 (en) * | 2004-11-08 | 2011-11-24 | エレクセル株式会社 | Positive electrode for lithium battery and lithium battery using the same |
| CN100492562C (en) * | 2005-02-04 | 2009-05-27 | 中国科学院成都有机化学有限公司 | Composite oxide electrode material and producing method thereof, and mixed super capacitor |
-
2006
- 2006-08-15 CN CN2006101094232A patent/CN101127276B/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101409154B (en) * | 2008-09-24 | 2011-05-04 | 上海奥威科技开发有限公司 | Organic mixed super capacitor |
| CN101847764A (en) * | 2010-02-26 | 2010-09-29 | 上海奥威科技开发有限公司 | High-specific-energy/high-specific-power type super battery |
| CN101847516A (en) * | 2010-02-26 | 2010-09-29 | 上海奥威科技开发有限公司 | Capacitor battery of high-specific-energy organic system |
| CN101847513A (en) * | 2010-02-26 | 2010-09-29 | 上海奥威科技开发有限公司 | Preparation process of long-lived negative pole piece and capacitor battery using negative pole piece |
| CN101847513B (en) * | 2010-02-26 | 2013-08-07 | 上海奥威科技开发有限公司 | Preparation process of long-lived negative pole piece and capacitor battery using negative pole piece |
| CN106253738A (en) * | 2016-08-12 | 2016-12-21 | 王海清 | A kind of High Density Charge electric field generator |
| CN106253738B (en) * | 2016-08-12 | 2019-04-05 | 王海清 | A kind of High Density Charge electric field generator |
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| CN101127276B (en) | 2012-03-28 |
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