CN101127276B - Organic electrolyte system mixing electrochemical capacitor and its making method - Google Patents
Organic electrolyte system mixing electrochemical capacitor and its making method Download PDFInfo
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- CN101127276B CN101127276B CN2006101094232A CN200610109423A CN101127276B CN 101127276 B CN101127276 B CN 101127276B CN 2006101094232 A CN2006101094232 A CN 2006101094232A CN 200610109423 A CN200610109423 A CN 200610109423A CN 101127276 B CN101127276 B CN 101127276B
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/13—Energy storage using capacitors
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Abstract
The utility model relates to a new electrochemical capacitor, which is characterized in that: ion insertion materials are used in the anode of the capacitor as anode active materials; a porous carbon electrode with larger specific surface area is used in the cathode of the capacitor; organic electrolyte solution is adopted as the electrolyte; an electronic insulating membrane is arranged between the anode and the cathode electrode for the ion passing through. The utility model has the advantages of high energy and power density, better application prospect, and is widely used in the electric energy storage in the fields as the electronic industries, transportation, electric power, and mining and metallurgy.
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 one type of 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 at present is that like 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, 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 like 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 following:
The positive pole of capacitor (1) uses the ion insert material as active material, like lithium ion insert material LiCoO
2Deng; The negative pole of capacitor (2) uses the porous carbon materials electrode of bigger serface, like absorbent charcoal material; With organic solution as electrolyte; Having between the both positive and negative polarity can be through the electronic isolation barrier film (3) of ion.
Anodal (1) preparation process is following: 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, roll-in as the positive pole of capacitor.Its intermediate ion insert material should have following structural formula: M1
xM2
yA
zWherein M can be Li, Mg, Al, Cr or their combination for embedding element, and 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 kinds: common deposited method, vapour deposition process, sol-gal process, mixed-sintering method, codeposition sintering process etc.
Negative pole (2) preparation process is following: 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, roll-in as the negative pole of capacitor.Wherein porous carbon materials be following one or more: activated carbon powder, NACF, active carbon cloth, activated carbon felt, CNT, 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, like 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 fiber 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 energy utilization efficiency is high, 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
Lift the preparation method of three embodiment brief description electrochemical capacitors of the present invention below.
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 thick, through dry, roll-forming, as positive pole.
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 thick, through dry, roll-forming, 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 that a slice is anodal are 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 accomplished, and after arrangement, puts into capacitor casing, and with bolted, seal adjustment pole position.Filling electrolyte adds seal valve, can use after activated and the 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 (5)
1. organic electrolyte system mixing electrochemical capacitor, the positive pole (1) that it is characterized in that capacitor is ion insert material Li
0.96Mg
0.04FePO
4As active material, the negative pole of capacitor (2) is the porous carbon materials electrode of bigger serface, has between the both positive and negative polarity to soak full organic electrolyte solution as electrolyte in the barrier film (3) through the electronic isolation barrier film (3) of ion.
2. electrochemical capacitor according to claim 1 is characterized in that the insert material preparation method has following several kinds: common deposited method, vapour deposition process, sol-gal process, mixed-sintering method, codeposition sintering process.
3. electrochemical capacitor according to claim 1 is characterized in that porous carbon materials electrode (2) is is main active substances with following one or more: activated carbon powder, NACF, active carbon cloth, activated carbon felt, CNT, carbon aerogels, active vitrescence charcoal, nano-pore vitrescence charcoal, porous graphite, graphite fibre, porous hard carbon.
4. electrochemical capacitor according to claim 1, 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.
5. electrochemical capacitor according to claim 1 is characterized in that electronic isolation barrier film (3) is: polyoxyethylene, polypropylene, nylon, polyethene microporous membrane, asbestos paper, polyethylene, glass fiber, or their composite material.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2006101094232A CN101127276B (en) | 2006-08-15 | 2006-08-15 | Organic electrolyte system mixing electrochemical capacitor and its making method |
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| CN2006101094232A CN101127276B (en) | 2006-08-15 | 2006-08-15 | Organic electrolyte system mixing electrochemical capacitor and its making method |
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| CN101127276A CN101127276A (en) | 2008-02-20 |
| CN101127276B true CN101127276B (en) | 2012-03-28 |
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Families Citing this family (5)
| 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 |
| 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 |
| CN106253738B (en) * | 2016-08-12 | 2019-04-05 | 王海清 | A kind of High Density Charge electric field generator |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1674178A (en) * | 2005-02-04 | 2005-09-28 | 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 |
| CN1717758A (en) * | 2003-05-09 | 2006-01-04 | Tdk株式会社 | Electrochemical capacitor |
| CN1734689A (en) * | 2004-08-13 | 2006-02-15 | 中国人民解放军63971部队 | Composite oxide electrochemical capacitor and preparation method thereof |
| EP1655798A1 (en) * | 2004-11-08 | 2006-05-10 | Elexcel Corporation Ltd. | Positive electrode for lithium cell |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1717758A (en) * | 2003-05-09 | 2006-01-04 | Tdk株式会社 | Electrochemical capacitor |
| CN1734689A (en) * | 2004-08-13 | 2006-02-15 | 中国人民解放军63971部队 | Composite oxide electrochemical capacitor and preparation method thereof |
| EP1655798A1 (en) * | 2004-11-08 | 2006-05-10 | Elexcel Corporation Ltd. | Positive electrode for lithium cell |
| CN1674178A (en) * | 2005-02-04 | 2005-09-28 | 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 |
Non-Patent Citations (1)
| Title |
|---|
| CN 1717758 A,全文. |
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