CN103985556A - Electrochemical energy storage apparatus and manufacturing method thereof - Google Patents
Electrochemical energy storage apparatus and manufacturing method thereof Download PDFInfo
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- CN103985556A CN103985556A CN201310051143.0A CN201310051143A CN103985556A CN 103985556 A CN103985556 A CN 103985556A CN 201310051143 A CN201310051143 A CN 201310051143A CN 103985556 A CN103985556 A CN 103985556A
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- energy storage
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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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Abstract
The invention discloses an electrochemical energy storage apparatus and a manufacturing method thereof. The electrochemical energy storage apparatus comprises at least two electrochemical capacitors arranged to be laminated. Each electrochemical capacitor comprises a pair of electrodes, and a diaphragm and an electrolyte which are disposed between the pair of electrodes.
Description
Field
The disclosure relates to electrochemical field.
Background
Electrochemical capacitor (electrochemical capacitors, ECs), also claims ultracapacitor (supercapacitors), is a kind of electrochemical energy storing device of novel environment friendly.Its operation principle is to carry out stored charge by forming electric double layer between electrode and electrolyte interface, savings energy.Electrochemical capacitor has the plurality of advantages such as the speed of discharging and recharging is fast, power density is high, long service life, high-efficiency environment friendly, therefore in real life, is widely used.For example, it can be for each side fields such as battery backup system, uninterrupted power supply, hybrid vehicles (HEV).Electrochemical capacitor comprises electrode, collector, barrier film, the large part of electrolyte four, and that outer enclosure structure mainly contains is button-shaped, takeup type and stacked three kinds.The electrochemical capacitor of current industrial preparation mainly be take organic system as main, adopts absorbent charcoal material as electrode material, and electrolyte is selected organic electrolyte, and charging/discharging voltage can reach 2.7V.Although the voltage of organic system electrochemical capacitor has improved much compared with the voltage of water system electrochemical capacitor (1V), energy density increases substantially, yet still in the application of some high voltage systems, has its limitation.
General introduction
The disclosure provides electrochemical energy storage device on the one hand, and it comprises the electrochemical capacitor of at least two stacked settings, and described electrochemical capacitor comprises pair of electrodes and the barrier film between described pair of electrodes and electrolyte.
The disclosure provides the method for manufacturing electrochemical energy storage device on the other hand, and it comprises 1) at least two electrochemical capacitors are provided; And 2) by the stacked series connection of described electrochemical capacitor.
Brief Description Of Drawings
Fig. 1 is the structural representation of the electrochemical energy storage device of the disclosure one embodiment.
Fig. 2 is the constant current charge-discharge curve of the electrochemical energy storage device of preparation in embodiment 1 of the present disclosure.
Fig. 3 is the cyclic voltammetry curve of the electrochemical energy storage device of preparation in embodiment 1 of the present disclosure.
Fig. 4 is the electrochemical impedance curve of the electrochemical energy storage device of preparation in embodiment 1 of the present disclosure.
Fig. 5 is the constant current charge-discharge curve of the electrochemical energy storage device of preparation in embodiment 2 of the present disclosure.
Describe in detail
In the following description, comprise that some concrete details is to provide comprehensive understanding to each disclosed embodiment.Yet those skilled in the relevant art will appreciate that, do not adopt one or more these concrete details, and adopt in the situation of other method, parts, material etc., can realize embodiment.
Unless requirement in addition in the disclosure, in whole specification and claims thereafter, word " comprises " and " comprising " should be interpreted as meaning open, that include formula, " includes but not limited to ".
" embodiment " mentioned in whole specification or " embodiment " or " in another embodiment " or " in certain embodiments " mean to comprise and relevant concrete reference feature, structure or feature described in this embodiment at least one embodiment.Therefore phrase " in one embodiment " or " in embodiments " or " in another embodiment " or " in certain embodiments " that, in whole specification, diverse location occurs needn't all refer to same embodiment.In addition concrete key element, structure or feature combination in one or more embodiments in any suitable manner.
definition
Therefore, non-separately have contrary explanation, otherwise in specification and claims, following term used has the following meaning:
In the disclosure, term " binding agent " means and can, the bond material of film forming of active electrode material, be generally macromolecular material.
In the disclosure, term " solvent " means the liquid that can dissolve solid, liquid or gas solute.
In the disclosure, term " collector " means structure or the part that collects electric current, and its function is mainly that the electric current of cell active materials generation is collected to form larger electric current and externally exported.
In the disclosure, term " conducting resinl " mean solidify or dry after there is the adhesive of certain electric conductivity.
Embodiment
The disclosure provides electrochemical energy storage device on the one hand, and it comprises the electrochemical capacitor of at least two stacked settings, and described electrochemical capacitor comprises pair of electrodes and the barrier film between described pair of electrodes and electrolyte.
In certain embodiments, described electrode is membrane electrode.
In certain embodiments, electrode material comprises electrode active material and binding agent.
In certain embodiments, the mass content of described electrode active material accounts for the 50%-100% of whole electrode material.
The illustrative examples that can be used in electrode active material of the present disclosure includes but not limited to the positive pole powder material containing elemental lithium of porous activated carbon, Graphene, modified graphene material, active carbon and graphene composite material, carbonaceous mesophase spherules, native graphite, modified graphite, coated graphite, carbon nano-fiber, carbon nano-tube, coke, silica flour, silicon line, lithium ion battery use, powder body material containing elemental lithium that lithium ion battery is used and composition thereof.
The illustrative examples that can be used in binding agent of the present disclosure includes but not limited to the high molecular polymers such as polytetrafluoroethylene, polymethylacrylic acid, polymethyl methacrylate, Kynoar, butadiene-styrene rubber, carboxymethyl cellulose and mixture, POLYPROPYLENE GLYCOL, polyamide, poly-aramid fiber.
In certain embodiments, described electrode material also comprises conductive black, acetylene black, Ketjen black, graphite, Graphene, carbon nano-fiber, conductive fiber, wire or its mixture.
In certain embodiments, the mass ratio of described electrode active material and described binding agent is 90:10.
In certain embodiments, the mass ratio of described electrode active material, described conductive black and described binding agent is 85:5:10.
In certain embodiments, electrode active material, conductive black and binding agent are compressed on and on collector, prepare membrane electrode.In certain embodiments, after electrode active material, conductive black and binding agent being dispersed in solution, spin-coating film is prepared membrane electrode on collector.
The illustrative examples that can be used in collector of the present disclosure includes but not limited to the sticking conductive polymer film of Copper Foil, aluminium foil and tool.
In certain embodiments, collector can coated with conductive glue to improve conductive capability.
The illustrative examples that can be used in barrier film of the present disclosure includes but not limited to the Non-woven fabrics film that cellulose material porous septum, porous polypropylene film, nonwoven fabrics and electrodeless material are filled.
In certain embodiments, described electrolyte is organic electrolyte.
The electrolytical illustrative examples can be used in organic electrolyte of the present disclosure includes but not limited to organic quaternary ammonium salt and lithium salts.
In certain embodiments, the electrolyte in described organic electrolyte is selected from tetraethyl boron fluoric acid ammonium salt, lithium hexafluoro phosphate, LiBF4 and LiBOB.
The illustrative examples that can be used in the solvent in organic electrolyte of the present disclosure includes but not limited to acetonitrile, propylene carbonate, vinyl carbonate, dimethyl carbonate, diethyl carbonate, ethylene glycol, glycerine or its mixture.
In certain embodiments, the area of described electrode is 0.1cm
2to 2000cm
2.
In certain embodiments, the electrochemical capacitor of described stacked setting comprises at least one double-face electrode.
In certain embodiments, the encapsulating structure of described electrochemical energy storage device is button, takeup type or stacked.
In certain embodiments, the collector edge coating of the enclosure of described encapsulating structure and described electrode has insulating material.
The illustrative examples that can be used in insulating material of the present disclosure includes but not limited to as high molecular polymers such as water-base cement, polypropylene, polyethylene, Kynoar, polytetrafluoroethylene, POLYPROPYLENE GLYCOL, poly-methyl acrylate, polyamide, poly-aramid fibers.
In certain embodiments, before forming coat, insulating material is the form that solution, emulsion, powder etc. can form mobile or adhesion layer.
In certain embodiments, the electrochemical energy storage device that electrochemical energy storage device is electric double layer.
In certain embodiments, electrochemical energy storage device comprises the electrochemical capacitor of two stacked settings, and described in each, electrochemical capacitor comprises pair of electrodes and the barrier film between described pair of electrodes and electrolyte.
Comprising that with electrochemical energy storage device in the relevant embodiment of the electrochemical capacitor of two stacked settings, the both sides of electrochemical energy storage device are single-side electrode, centre is double-face electrode, is provided with barrier film and electrolyte between electrode.
The structural design that electrochemical energy storage device of the present disclosure is connected by inner laminated, not only the voltage of monolithic capacitor has been brought up to 5.4V, and there is good chemical property, and keeping the high-power while, the energy density of whole device is also improved and (can reaches 19.3Whkg
cell -1), be 4 times of common absorbent charcoal based monomer electrochemical capacitor energy density.And the method for this internal series-connection can reduce the packaging cost of device greatly, there is very important market using value.
The disclosure provides the method for manufacturing electrochemical energy storage device on the other hand, and it comprises 1) at least two electrochemical capacitors are provided; And 2) by the stacked series connection of described electrochemical capacitor.
In certain embodiments, the method for manufacturing electrochemical energy storage device comprises 1) two electrochemical capacitors are provided; And 2) by the stacked series connection of described electrochemical capacitor.
In the embodiment relevant with two electrochemical capacitors are provided, the both sides of electrochemical energy storage device are single-side electrode, and centre is double-face electrode, is provided with barrier film and electrolyte between electrode.
Below by specific embodiment, the invention relating in the disclosure is specifically described, these embodiment, only for these inventions are further detailed, can not be interpreted as the restriction to its protection range.
Embodiment
Embodiment 1
1) preparation of electrode slice
(No. 1, specific area is 3100m to the absorbent charcoal material that Pulan, Tianjin nanosecond science and technology Co., Ltd is produced
2g
-1) and polytetrafluoroethylene PTFE according to the mass ratio of 90:10, mix (adding a small amount of ethanol), be rolled into the film that thickness is about 100 μ m, be cut into afterwards the disk that diameter is 13mm, vacuumize 12h under 120 ° of C, is cooled to room temperature and weighs.Get two electrode slices that quality equates (being about 3mg), 180 ° of C are hot-pressed onto one side to be had on the aluminium foil of conducting resinl coating (diameter is 16mm); Separately get two electrode slices that equate with front electrode slice quality, respectively symmetrical being hot-pressed onto on the positive and negative of double spread aluminium foil.The aluminium foil edge of four electrode slices all carries out surface-coated with the coatings CMC hydrosol.Vacuumize 6h under 180 ° of C, is transferred to (moisture: <1ppm in glove box afterwards afterwards; Oxygen: <10ppm).
2) preparation of high-voltage electrochemical capacitor
In glove box, by the placement that faces up of a single-side electrode sheet, place afterwards a barrier film thereon, then continue to place double-face electrode sheet in the above, then put another barrier film, finally place another single-side electrode sheet, electrode surface is down.The center alignment of four electrodes, drips 1M Et
4nBF
4/ AN organic electrolyte, is packaged in the button cell shell that scribbles coatings and obtains electrochemical capacitor according to the method for packing of button cell afterwards.The high-voltage electrochemical capacitor of preparing in this example is at 0-5.4V, 1Ag
-1test condition under, electrode is 190Fg than electric capacity
-1, the energy density of device integral body reaches 19.3Wh kg
cell -1(pressing 40% of electrode material energy density calculates).At 10Ag
-1high current charge-discharge test condition under, electrode is 161Fg than electric capacity
-1, the energy density of device integral body is 16.3Whkg
cell -1, power density is 2kWkg
cell -1.Simultaneously at 1Ag
-1test condition under, the capacity after 5000 charge and discharge cycles still remains on 84% left and right.
Embodiment 2
1) preparation of electrode slice
(No. 2, specific area is 2300m to the absorbent charcoal material that Pulan, Tianjin nanosecond science and technology Co., Ltd is produced
2g
-1), conductive black and polytetrafluoroethylene PTFE mix (adding a small amount of ethanol) according to the mass ratio of 85:5:10, be rolled into the film that thickness is about 100 μ m, be cut into afterwards the disk that diameter is 13mm, vacuumize 12h under 120 ° of C, is cooled to room temperature and weighs.Get two electrode slices that quality equates (being about 4mg), 180 ° of C are hot-pressed onto one side to be had on the aluminium foil of conducting resinl coating (diameter is 16mm); Separately get two electrode slices that equate with front electrode slice quality, respectively symmetrical being hot-pressed onto on the positive and negative of double spread aluminium foil.The aluminium foil edge of four electrode slices all carries out surface-coated with coatings PVDF/NMP solution.Vacuumize 6h under 180 ° of C, is transferred to (moisture: <1ppm in glove box afterwards afterwards; Oxygen: <10ppm).
2) preparation of high-voltage electrochemical capacitor
In glove box, by the placement that faces up of a single-side electrode sheet, place afterwards a barrier film thereon, then continue to place double-face electrode sheet in the above, then put another barrier film, finally place another single-side electrode sheet, electrode surface is down.The center alignment of four electrodes, drips 1M Et
4nBF
4/ PC organic electrolyte, is packaged in the button cell shell that scribbles coatings and obtains electrochemical capacitor according to the method for packing of button cell afterwards.The high-voltage electrochemical capacitor of preparing in this example is at 0-5.4V, 1Ag
-1test condition under, electrode is 135Fg than electric capacity
-1, the energy density of device integral body reaches 13.7Whkg
cell -1(pressing 40% of electrode material energy density calculates).
The restriction that this invention technical scheme is formed is described and the description of its embodiment be should not be understood as to the above-mentioned generality to the invention relating in the disclosure.Those skilled in the art are according to the disclosure, can be under the prerequisite of the invention inscape without prejudice to related, to above-mentioned general description or/and the public technology feature in embodiment (comprising embodiment) increases, reduces or combines, formation belongs to other technical scheme of described invention.
Claims (14)
1. electrochemical energy storage device, it comprises the electrochemical capacitor of at least two stacked settings, described electrochemical capacitor comprises pair of electrodes and the barrier film between described pair of electrodes and electrolyte.
2. electrochemical energy storage device as claimed in claim 1, wherein said electrode is membrane electrode.
3. electrochemical energy storage device as claimed in claim 1 or 2, wherein electrode material comprises electrode active material and binding agent, preferred electrode active material is porous activated carbon, Graphene, modified graphene material, active carbon and graphene composite material, carbonaceous mesophase spherules, native graphite, modified graphite, coated graphite, carbon nano-fiber, carbon nano-tube, coke, silica flour, silicon line, the positive pole powder material containing elemental lithium that lithium ion battery is used, the powder body material containing elemental lithium that lithium ion battery is used or its mixture and preferred binding agent are polytetrafluoroethylene, polymethylacrylic acid, polymethyl methacrylate, Kynoar, butadiene-styrene rubber, carboxymethyl cellulose and composition thereof, POLYPROPYLENE GLYCOL, polyamide, poly-aramid fiber or its mixture.
4. electrochemical energy storage device as claimed in claim 3, wherein said electrode material also comprises conductive black, acetylene black, Ketjen black, graphite, Graphene, carbon nano-fiber, conductive fiber, wire or its mixture.
5. the electrochemical energy storage device as described in arbitrary claim in claim 1 to 4, wherein said barrier film is selected from the Non-woven fabrics film that cellulose material porous septum, porous polypropylene film, nonwoven fabrics, electrodeless material are filled.
6. the electrochemical energy storage device as described in arbitrary claim in claim 1 to 5, wherein said electrolyte is organic electrolyte.
7. electrochemical energy storage device as claimed in claim 6, the electrolyte in wherein said organic electrolyte is organic quaternary ammonium salt or lithium salts, is preferably tetraethyl boron fluoric acid ammonium salt, lithium hexafluoro phosphate, LiBF4 and LiBOB.
8. the electrochemical energy storage device as described in claim 6 or 7, the solvent in wherein said organic electrolyte is selected from acetonitrile, propylene carbonate, vinyl carbonate, dimethyl carbonate, diethyl carbonate, ethylene glycol, glycerine or its mixture.
9. the electrochemical energy storage device as described in arbitrary claim in claim 1 to 8, the area of wherein said electrode is 0.1cm
2to 2000cm
2.
10. the electrochemical energy storage device as described in arbitrary claim in claim 1 to 9, the electrochemical capacitor of wherein said stacked setting comprises at least one double-face electrode.
11. electrochemical energy storage devices as described in arbitrary claim in claim 1 to 10, the encapsulating structure of wherein said electrochemical energy storage device is button, takeup type or stacked.
12. electrochemical energy storage devices as claimed in claim 11, the collector edge coating of the enclosure of wherein said encapsulating structure and described electrode has insulating material, and preferred insulating material is water-base cement, polypropylene, polyethylene, Kynoar, polytetrafluoroethylene, POLYPROPYLENE GLYCOL, poly-methyl acrylate, polyamide, poly-aramid fiber or its mixture.
13. electrochemical energy storage devices as described in arbitrary claim in claim 1 to 12, its electrochemical energy storage device that is electric double layer.
14. manufacture the method for electrochemical energy storage device, and it comprises
1) provide at least two electrochemical capacitors; And
2) by the stacked series connection of described electrochemical capacitor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201310051143.0A CN103985556A (en) | 2013-02-08 | 2013-02-08 | Electrochemical energy storage apparatus and manufacturing method thereof |
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|---|---|---|---|
| CN201310051143.0A CN103985556A (en) | 2013-02-08 | 2013-02-08 | Electrochemical energy storage apparatus and manufacturing method thereof |
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Cited By (2)
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|---|---|---|---|---|
| CN108147937A (en) * | 2017-12-21 | 2018-06-12 | 常州大学 | A kind of preparation method of quaternary ammonium salt |
| CN111599610A (en) * | 2020-06-01 | 2020-08-28 | 安徽普和电子有限公司 | Preparation method of wide-temperature-area electrolyte for super capacitor |
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| CN1345075A (en) * | 2001-11-02 | 2002-04-17 | 中国科学院上海冶金研究所 | Manufacture of high-voltage electrochemical capacitor |
| CN101304104A (en) * | 2007-05-11 | 2008-11-12 | Tdk株式会社 | Electrochemical device and manufacturing method thereof |
| CN101853738A (en) * | 2010-04-06 | 2010-10-06 | 珠海清华科技园创业投资有限公司 | Super capacitor for instruments |
| CN102176372A (en) * | 2010-12-08 | 2011-09-07 | 广东四会互感器厂有限公司 | Cylindrical dry type high-voltage capacitor core |
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2013
- 2013-02-08 CN CN201310051143.0A patent/CN103985556A/en active Pending
Patent Citations (4)
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| CN1345075A (en) * | 2001-11-02 | 2002-04-17 | 中国科学院上海冶金研究所 | Manufacture of high-voltage electrochemical capacitor |
| CN101304104A (en) * | 2007-05-11 | 2008-11-12 | Tdk株式会社 | Electrochemical device and manufacturing method thereof |
| CN101853738A (en) * | 2010-04-06 | 2010-10-06 | 珠海清华科技园创业投资有限公司 | Super capacitor for instruments |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108147937A (en) * | 2017-12-21 | 2018-06-12 | 常州大学 | A kind of preparation method of quaternary ammonium salt |
| CN111599610A (en) * | 2020-06-01 | 2020-08-28 | 安徽普和电子有限公司 | Preparation method of wide-temperature-area electrolyte for super capacitor |
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Application publication date: 20140813 |
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