CN106252100A - The pretreatment unit of electrode for super capacitor active material and preprocess method thereof - Google Patents
The pretreatment unit of electrode for super capacitor active material and preprocess method thereof Download PDFInfo
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- CN106252100A CN106252100A CN201610393357.XA CN201610393357A CN106252100A CN 106252100 A CN106252100 A CN 106252100A CN 201610393357 A CN201610393357 A CN 201610393357A CN 106252100 A CN106252100 A CN 106252100A
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- 239000003990 capacitor Substances 0.000 title claims abstract description 37
- 239000011149 active material Substances 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 19
- 230000032683 aging Effects 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims description 96
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 38
- 239000002002 slurry Substances 0.000 claims description 29
- -1 polyethylene Polymers 0.000 claims description 24
- 239000003792 electrolyte Substances 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 20
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000007772 electrode material Substances 0.000 claims description 18
- 230000004888 barrier function Effects 0.000 claims description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 8
- JKJWYKGYGWOAHT-UHFFFAOYSA-N bis(prop-2-enyl) carbonate Chemical compound C=CCOC(=O)OCC=C JKJWYKGYGWOAHT-UHFFFAOYSA-N 0.000 claims description 7
- 238000005859 coupling reaction Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000004964 aerogel Substances 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical group CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 claims description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 238000010586 diagram Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims 1
- 229920002472 Starch Polymers 0.000 claims 1
- 239000002131 composite material Substances 0.000 claims 1
- 239000000835 fiber Substances 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229920001155 polypropylene Polymers 0.000 claims 1
- 235000019698 starch Nutrition 0.000 claims 1
- 239000008107 starch Substances 0.000 claims 1
- 239000000178 monomer Substances 0.000 abstract description 49
- 125000000524 functional group Chemical group 0.000 abstract description 8
- 238000004146 energy storage Methods 0.000 abstract 1
- 230000005611 electricity Effects 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000003466 welding Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- 230000004044 response Effects 0.000 description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 4
- 239000004327 boric acid Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000005213 imbibition Methods 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- DOARWPHSJVUWFT-UHFFFAOYSA-N lanthanum nickel Chemical compound [Ni].[La] DOARWPHSJVUWFT-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- LPLLVINFLBSFRP-UHFFFAOYSA-N 2-methylamino-1-phenylpropan-1-one Chemical compound CNC(C)C(=O)C1=CC=CC=C1 LPLLVINFLBSFRP-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 240000003023 Cosmos bipinnatus Species 0.000 description 1
- 235000005956 Cosmos caudatus Nutrition 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003738 black carbon Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 238000012536 packaging technology Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical group CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
Abstract
The present invention relates to pretreatment unit and the preprocess method thereof of a kind of electrode for super capacitor active material, belong to technical field of new energy storage.Described pretreatment unit includes reacting pile, vacuum pump, charge-discharge test instrument, water bath with thermostatic control, topping-up pump and agitator；Described preprocess method can effectively solve that existing electrode for super capacitor surface of active material functional group content is high, battery core aerogenesis is serious so that the problem such as monomer capacity is low, internal resistance is big and cycle life is poor after aging, thus obtain a kind of low surface functional group content, after aging or high-temperature load, monomer does not play drum, high power capacity, low internal resistance and the electrode for super capacitor active material having extended cycle life.
Description
Technical field
The present invention relates to the pretreatment unit of electrode for super capacitor active material and use this device to carry out electrode active
The method of property pretreatment.
Background technology
Commercial electrode for super capacitor surface of active material is generally enriched with more active function groups, especially with chemistry
Electrode active material prepared by activation method.If the electrode active material containing more active function groups being prepared as electrode go forward side by side
One step is assembled into ultracapacitor monomer, as long as the monomer assembled is through aging or high-temperature load test, electrode active material table
The active function groups in face will produce irreversible reaction with electrolyte, generates various mixed gases and causes the active material on electrode
There is rapid degradation in layer, so that ultracapacitor monomer has shown as the most afterwards, drum is serious, capacity reduces, internal resistance increases and the longevity
The Multiple Failure Modes such as life minimizing.
After aging or high-temperature load are tested, the failure modes such as drum, in recent years state can occur for ultracapacitor monomer
Inside and outside priority reports a series of solution.As Chinese patent CN102543481 B reports a kind of to entering the battery core before shell
The technique that energising aging techniques assembles ultracapacitor monomer in advance.The monomer packaging technology provided according to this patent, first exists
At 100-150 DEG C, the battery core of winding is vacuum dried 8-72 hour；Then by the battery core of vacuum impregnation organic electrolyte 50
It is energized 10 hours with 2.7V constant voltage at DEG C；Again the battery core after aging for energising is placed in circular aluminum hull, finally seals.But should
Technical scheme is in energising ageing process, and active function groups more on electrode can generate with electrolyte generation irreversible reaction
Various mixed gases discharge from electrolyte, although monomer can be extended the time of drum has occurred during follow-up test,
But owing to electrode deteriorates in ageing process, still result in monomer cycle life not enough.Kiyoshi Horita etc. exist
[J] .Carbon, 1996,34 (2), the apparent condition by modifying carbon black is proposed, by the functional group of black carbon surface in 217 222
Being changed into hydrophilic by hydrophobicity, the carbon black containing hydrophilic functional group is prone to stir into slurry in water, but either dredges
Water functional group or hydrophilic functional groups, all can cause with electrolyte generation irreversible reaction in ultracapacitor ageing process
Monomer plays the Multiple Failure Modes such as drum.
Summary of the invention
Occur monomer to rise after aging or high-temperature load are tested for ultracapacitor in above-mentioned prior art and rouse serious, appearance
The Multiple Failure Modes such as amount reduction, internal resistance increase and life-span minimizing, applicant proposed by simulating the aging of ultracapacitor
Technique autonomous Design pretreatment unit, is placed in the reaction pile of pretreatment unit logical by electrode for super capacitor active material
Electro-active, remove the technical scheme of the too much active function groups on electrode active material surface to greatest extent.
A first aspect of the present invention provides a kind of electrode for super capacitor active material pretreatment unit, described device
Including reaction pile, vacuum pump, charge-discharge test instrument, water bath with thermostatic control, topping-up pump and agitator, wherein, the outside of reaction pile
For insulating barrier, the internal barrier film by centre is divided into positive pole zone and negative regions, and plus plate current-collecting body is just being positioned at reaction pile
In territory, polar region, negative current collector is positioned in the negative regions of reaction pile, the positive pole zone in reaction pile and negative regions
Respectively being furnished with an agitator, there are two interfaces at the top of reaction pile, are connected with topping-up pump and vacuum pump respectively；Described reaction electricity
Heap plus plate current-collecting body is connected with the positive terminal of charge-discharge test instrument through insulating barrier through lead-out wire, reacts pile negative pole currect collecting
Body is connected with the negative terminal of charge-discharge test instrument through insulating barrier through lead-out wire；Described reaction pile is placed in water bath with thermostatic control
In.
In some embodiments, the volume of described reaction pile is 10L, and top can freely be opened, in order to reaction
The positive pole zone of pile and negative regions add electrode for super capacitor active material；It is positioned at reaction pile positive pole zone
The electrode active material in this region and ultracapacitor electrolyte can be stirred into uniform slurry by agitator, are positioned at reaction
The electrode active material in this region and ultracapacitor electrolyte can be stirred into uniformly by the agitator of pile negative regions
Slurry；After reacting the sealing of pile top, with vacuum pump, reaction pile can be evacuated to vacuum≤-0.098Mpa；
Described topping-up pump can be to reaction pile quantification fluid injection；Described water bath with thermostatic control controllable temperature scope is 5 DEG C-100 DEG C, temperature control essence
Degree is for ± 0.1 DEG C.
A second aspect of the present invention provides a kind of method of electrode for super capacitor active material pretreatment, described side
Method uses aforementioned pretreatment unit, and it comprises the following steps:
1) electrode for super capacitor active material is separately added in positive pole zone and the negative regions of reaction pile, close
Envelope reaction pile, bets into super electrolyte for capacitor at vacuum≤-0.098Mpa, controls electrode active material and electrolysis
It is the slurry of 10wt%-50wt% that liquid forms range of solid content；
2) temperature of regulating thermostatic water-bath is to 60 DEG C-80 DEG C, with the anode collection of charge-discharge test instrument coupled reaction pile
Body and negative current collector, first by reaction pile constant-current charge to 2.5V-3.0V, then to reaction pile constant voltage under 2.5V-3.0V
Charge more than 8 hours, after charging complete, reaction pile is discharged to below 0.1V, completes the aging of slurry；
3) slurry after aging is taken out from from reaction pile, dilute with the solvent that maybe can mix identical with bath composition
Release slurry, be washed out and drying is to pretreatment electrode active material.
In some embodiments, described electrode active material is selected from activated carbon, Graphene, NACF, charcoal gas
Gel or CNT.
In some embodiments, described plus plate current-collecting body or described negative current collector are selected from aluminum, copper, silver, Jin Huo
Wire netting that platinum is made or metallic plate.
In some embodiments, described reaction pile barrier film, selected from cellulosic separator, polyethylene diagrams or poly-third
Alkene barrier film.
In some embodiments, described ultracapacitor electrolyte is molten selected from the acetonitrile of tetraethyl ammonium Tetrafluoroboric acid
Liquid, the carbonic allyl ester solution of tetraethyl ammonium Tetrafluoroboric acid, the acetonitrile solution of triethyl methyl ammonium Tetrafluoroboric acid, triethyl methyl
The carbonic allyl ester solution of ammonium Tetrafluoroboric acid, the SP2 type high-voltage electrolyte of SK group of Korea S and the DLC3702 type of company of Xin Zhou nation
One in high-voltage electrolyte；The concentration of electrolyte choosing is can be 0.7M-2.5M.In some embodiments, electrolyte is dense
Degree is 1M.
In some embodiments, dilute electrode active material slurry or clean new electrode active material solvent selected from second
Nitrile, Allyl carbonate, chloroform, carbon tetrachloride, benzene, normal propyl alcohol, isopropanol, acrylonitrile, ethyl acetate, dichloroethanes, ethanol, second
One or more in ether or Carbon bisulfide.
The water used in embodiments of the present invention is deionized water.
" room temperature " of the present invention represents the temperature of 20-30 DEG C.
The definition "or" that the present invention uses represents alternative, if appropriate, can they be combined, namely
Saying, term "or" includes each listed independent alternative and combinations thereof.Such as, " solvent is selected from acetonitrile, carbonic acid
Propylene, chloroform, carbon tetrachloride, benzene, normal propyl alcohol, isopropanol, acrylonitrile, ethyl acetate, dichloroethanes, ethanol, ether or two
Nitric sulfid." represent solvent can be acetonitrile, Allyl carbonate, chloroform, carbon tetrachloride, benzene, normal propyl alcohol, isopropanol, acrylonitrile,
One or more among ethyl acetate, dichloroethanes, ethanol, ether, Carbon bisulfide.
The most in contrast, otherwise, all scopes that the present invention quotes include end value.Such as, " 60-80
Water-bath at DEG C " represent that bath temperature T is in the range of 60 DEG C≤T≤80 DEG C.
Technical scheme can effectively solve existing electrode for super capacitor surface of active material functional group
Content is high, after aging, battery core aerogenesis is serious so that the problem such as monomer capacity is low, internal resistance is big and cycle life is poor, thus obtains one
Kind of low surface functional group content, after aging or high-temperature load, monomer does not play drum, high power capacity, low internal resistance and surpassing of having extended cycle life
Level capacitor electrode active material.
Accompanying drawing explanation
Fig. 1 is the structural representation of the pretreatment unit of electrode for super capacitor active material.
In Fig. 1,1 is reaction pile；2 is vacuum pump；3 is charge-discharge test instrument；4 is water bath with thermostatic control；5 is topping-up pump；6 are
Agitator；7 is reaction pile plus plate current-collecting body；8 is reaction pile negative current collector；9 is barrier film；10 is cushion block.
Detailed description of the invention
The following stated is the preferred embodiment of the present invention, and what the present invention was protected is not limited to the following side of being preferable to carry out
Formula.It should be pointed out that, for a person skilled in the art these innovation and creation conceive on the basis of, the some deformation made and
Improve, broadly fall into protection scope of the present invention.Raw material used in embodiment all can be by being either commercially available.
Embodiment 1
Weigh 1000 grams of activated carbon for super capacitors to be separately added in positive pole zone and the negative regions of reaction pile, close
Envelope reaction pile, is evacuated to-0.098MPa with vacuum pump by reaction pile；In reaction pile, 2000 grams are injected with topping-up pump
1M tetraethyl ammonium Tetrafluoroboric acid solution in acetonitrile, respectively with positive pole zone and the negative pole district of blender stirring reaction pile
Territory, making activated carbon for super capacitors and the 1M tetraethyl ammonium Tetrafluoroboric acid solution in acetonitrile form solid content is 33.3wt%
Slurry；The temperature of regulating thermostatic water-bath is to 60 DEG C, after question response stack temperature reaches to stablize, connects anti-with charge-discharge test instrument
Answer plus plate current-collecting body and the negative current collector of pile, first by 2.7V more electric to reaction under 2.7V for reaction pile constant-current charge
Heap constant-voltage charge 10 hours, is discharged to 0V by reaction pile after charging complete；Slurry after aging is taken from from reaction pile
Go out, with 2000 grams of dilution in acetonitrile slurries, filter, obtain pretreatment activated carbon for super capacitors；By pretreatment ultracapacitor
Clean 3 times with 3000 grams of acetonitriles with activated carbon, dry at 120 DEG C.
Pre-Treatment of Activated for dry gained material is obtained successively after slurrying, coating, roll-in the electrode that thickness is 200 μm.
Electrode is cut into wide 35mm, positive pole length 570mm, negative pole length 525mm.Use the super capacitor that NKK company of Japan produces
Device special TF4035 type barrier film is wound into battery core together with the both positive and negative polarity cut.Take 60 battery cores and be placed in 1M tetraethyl ammonium tetrafluoro
In boric acid solution in acetonitrile, vacuum impregnation is to saturated imbibition state, loads in shell by the battery core impregnated, and sealing obtains Φ
22*45 welding needle type ultracapacitor monomer.Taking 30 monomers to be energized 1000 hours with 2.7V constant voltage at 60 DEG C, observing monomer is
No generation drum, the capacity of test unit and internal resistance.Remaining monomer all first with 5A constant-current charge to 2.7V, then with 5A constant-current discharge
To 1.35V, and circulate 100,000 times by this discharge and recharge condition, observe whether monomer has occurred drum, the capacity of test unit and direct current
Internal resistance.Test result is shown in Table 1.
Embodiment 2
Weigh 1000 grams of Graphenes to be separately added in positive pole zone and the negative regions of reaction pile, seal reaction pile,
With vacuum pump, reaction pile is evacuated to-0.098MPa；In reaction pile, 1500 grams of 1M tetraethyl ammoniums are injected with topping-up pump
Tetrafluoroboric acid solution in Allyl carbonate, respectively with positive pole zone and the negative regions of blender stirring reaction pile, makes
It is the slurry of 40wt% that Graphene and the 1M tetraethyl ammonium Tetrafluoroboric acid solution in Allyl carbonate forms solid content；Regulation perseverance
The temperature of tepidarium is to 70 DEG C, after question response stack temperature reaches to stablize, with the positive pole of charge-discharge test instrument coupled reaction pile
Collector and negative current collector, first by reaction pile constant-current charge to 2.5V, then to reaction pile constant-voltage charge 10 under 2.5V
Hour, after charging complete, reaction pile is discharged to 0V；Slurry after aging is taken out, with 3000 grams of carbon from from reaction pile
Acid propylene ester diluted slurry, filters, obtains pretreating graphite alkene；Pretreating graphite alkene is cleaned 3 by 2000 grams of Allyl carbonaties
Secondary, dry at 180 DEG C.
Prepared by electrode, monomer assembles and test event is with embodiment 1, and test result is shown in Table 1.
Embodiment 3
Weigh 1000 grams of NACFs to be separately added in positive pole zone and the negative regions of reaction pile, seal reaction electricity
Heap, is evacuated to-0.098MPa with vacuum pump by reaction pile；In reaction pile, 3000 grams of 1M triethyl groups are injected with topping-up pump
Ammonium methyl Tetrafluoroboric acid solution in Allyl carbonate, respectively with positive pole zone and the negative pole district of blender stirring reaction pile
Territory, makes NACF and 1M triethyl methyl ammonium Tetrafluoroboric acid form solid content at the solution in Allyl carbonate to be
The slurry of 25wt%；The temperature of regulating thermostatic water-bath, to 70 DEG C, after question response stack temperature reaches to stablize, uses charge-discharge test instrument
The plus plate current-collecting body of coupled reaction pile and negative current collector, first by 2.5V more right under 2.5V for reaction pile constant-current charge
Reaction pile constant-voltage charge 10 hours, is discharged to 0V by reaction pile after charging complete；By the slurry after aging from from reaction electricity
Heap takes out, with 2000 grams of ethanol dilution slurries, filters, obtain Pre-Treatment of Activated Carbon fibe；Pre-Treatment of Activated Carbon fibe is used
2500 grams of ethanol purge 3 times, dry at 150 DEG C.
Prepared by electrode, monomer assembles and test event is with embodiment 1, and test result is shown in Table 1.
Embodiment 4
Weigh 1000 grams of charcoal-aero gels to be separately added in positive pole zone and the negative regions of reaction pile, seal reaction electricity
Heap, is evacuated to-0.098MPa with vacuum pump by reaction pile；In reaction pile, 1200 grams of 1M triethyl groups are injected with topping-up pump
Ammonium methyl Tetrafluoroboric acid solution in acetonitrile, respectively with positive pole zone and the negative regions of blender stirring reaction pile, makes
It is the slurry of 45.5wt% that charcoal-aero gel and the 1M triethyl methyl ammonium Tetrafluoroboric acid solution in acetonitrile forms solid content；Regulation
The temperature of water bath with thermostatic control is to 60 DEG C, after question response stack temperature reaches to stablize, with charge-discharge test instrument coupled reaction pile just
Pole collector and negative current collector, first by reaction pile constant-current charge to 2.7V, then to reaction pile constant-voltage charge under 2.7V
10 hours, after charging complete, reaction pile is discharged to 0V；Slurry after aging is taken out, with 3500 grams from from reaction pile
Diluted ethyl acetate slurry, filters, obtains pretreatment charcoal-aero gel；Pretreatment charcoal-aero gel is cleaned by 2500 grams of ethyl acetate
3 times, dry at 100 DEG C.
Prepared by electrode, monomer assembles and test event is with embodiment 1, and test result is shown in Table 1.
Embodiment 5
Weigh 1000 grams of CNTs to be separately added in positive pole zone and the negative regions of reaction pile, seal reaction electricity
Heap, is evacuated to-0.098MPa with vacuum pump by reaction pile；In reaction pile, 4000 Ke Xin cosmos nations are injected public with topping-up pump
The DLC3702 type high-voltage electrolyte of department, respectively with positive pole zone and the negative regions of blender stirring reaction pile, makes carbon nanometer
It is the slurry of 20wt% that the DLC3702 type high-voltage electrolyte of Guan Yuxin Zhou Bang company forms solid content；The temperature of regulating thermostatic water-bath
Degree is to 60 DEG C, after question response stack temperature reaches to stablize, with the plus plate current-collecting body of charge-discharge test instrument coupled reaction pile with negative
Pole collector, first by reaction pile constant-current charge to 3V, then to reacting pile constant-voltage charge 10 hours, after charging complete under 3V
Reaction pile is discharged to 0V；Slurry after aging is taken out from from reaction pile, with 2000 grams of benzene diluted slurries, filters,
Obtain pretreatment CNT；Pretreatment CNT is cleaned 3 times with 2600 grams of benzene, dries at 200 DEG C.
Prepared by electrode, monomer assembles and test event is with embodiment 1, and test result is shown in Table 1.
Embodiment 6
Weigh 1000 grams of activated carbon for super capacitors to be separately added in positive pole zone and the negative regions of reaction pile, close
Envelope reaction pile, is evacuated to-0.098MPa with vacuum pump by reaction pile；In reaction pile, 3400 grams are injected with topping-up pump
The SP2 type high-voltage electrolyte of SK group of Korea S, respectively with positive pole zone and the negative regions of blender stirring reaction pile, makes to surpass
Level capacitor activated carbon is the slurry of 22.7wt% with the SP2 type high-voltage electrolyte formation solid content of SK group of Korea S；Regulation
The temperature of water bath with thermostatic control is to 60 DEG C, after question response stack temperature reaches to stablize, with charge-discharge test instrument coupled reaction pile just
Pole collector and negative current collector, first by reaction pile constant-current charge to 2.85V, then fill reaction pile constant voltage under 2.85V
Electricity 10 hours, is discharged to 0V by reaction pile after charging complete；Slurry after aging is taken out, with 2600 from from reaction pile
Gram ether diluted slurry, filters, obtains pretreatment activated carbon for super capacitors；Pretreatment activated carbon for super capacitors is used
3000 grams of ether clean 3 times, dry at 140 DEG C.
Prepared by electrode, monomer assembles and test event is with embodiment 1, and test result is shown in Table 1.
Comparative example 1
Commercial activated carbon for super capacitors is obtained the electrode that thickness is 200 μm successively after slurrying, coating, roll-in.
Electrode is cut into wide 35mm, positive pole length 570mm, negative pole length 525mm.Use the super capacitor that NKK company of Japan produces
Device special TF4035 type barrier film is wound into battery core together with the both positive and negative polarity cut.Take 60 battery cores and be placed in 1M tetraethyl ammonium tetrafluoro
In boric acid solution in acetonitrile, vacuum impregnation is to saturated imbibition state, loads in shell by the battery core impregnated, and sealing obtains Φ
22*45 welding needle type ultracapacitor monomer.Taking 30 monomers to be energized 1000 hours with 2.7V constant voltage at 60 DEG C, observing monomer is
No generation drum, the capacity of test unit and internal resistance.Remaining monomer all first with 5A constant-current charge to 2.7V, then with 5A constant-current discharge
To 1.35V, and circulate 100,000 times by this discharge and recharge condition, observe whether monomer has occurred drum, the capacity of test unit and direct current
Internal resistance.Test result is shown in Table 1.
Comparative example 2
Commercial activated carbon for super capacitors is obtained the electrode that thickness is 200 μm successively after slurrying, coating, roll-in.
Electrode is cut into wide 35mm, positive pole length 570mm, negative pole length 525mm.Use the super capacitor that NKK company of Japan produces
Device special TF4035 type barrier film is wound into battery core together with the both positive and negative polarity cut.Take 60 battery cores and be placed in 1M tetraethyl ammonium tetrafluoro
In boric acid solution in acetonitrile, vacuum impregnation is to saturated imbibition state, in the battery core loading shell that will impregnate, with interior survey equipped with
The cover plate vacuum seal of lanthanum-nickel alloy, obtains Φ 22*45 welding needle type ultracapacitor monomer.Take 30 monomers at 60 DEG C with
2.7V constant voltage is energized 1000 hours, observes whether monomer has occurred drum, the capacity of test unit and internal resistance.Remaining monomer all first with
5A constant-current charge is to 2.7V, then with 5A constant-current discharge to 1.35V, and circulates 100,000 times by this discharge and recharge condition, observes monomer and is
No generation drum, the capacity of test unit and DC internal resistance.Test result is shown in Table 1.
Comparative example 3
Commercial activated carbon for super capacitors is obtained the electrode that thickness is 200 μm successively after slurrying, coating, roll-in.
Electrode is cut into wide 35mm, positive pole length 570mm, negative pole length 525mm.Use the super capacitor that NKK company of Japan produces
Device special TF4035 type barrier film is wound into battery core together with the both positive and negative polarity cut.Take 60 battery cores and be placed in 1M tetraethyl ammonium tetrafluoro
In boric acid solution in acetonitrile, vacuum impregnation is to saturated imbibition state, and the battery core of electrolyte above-mentioned to vacuum impregnation is at 50 DEG C
It is energized 10 hours with 2.7V constant voltage, finally the battery core after aging for energising is loaded in shell, sealing, obtain Φ 22*45 welding needle type and surpass
Level capacitor monomer.The part taking gained monomer is energized 1000 hours with 2.7V constant voltage at 60 DEG C, observes whether monomer is sent out
Drum, the capacity of test unit and internal resistance are given birth to.Remaining monomer all first with 5A constant-current charge to 2.7V, then with 5A constant-current discharge extremely
1.35V, and circulate 100,000 times by this discharge and recharge condition, observe whether monomer has occurred drum, in the capacity of test unit and direct current
Resistance.Test result is shown in Table 1.
Table 1 super capacitor electric core and monomer test result
According to the result of embodiment 1-6, with the ultracapacitor electricity consumption of the pretreatment unit pretreatment of autonomous Design
Electrode prepared by pole active material, is assembled into Φ 22*45 welding needle type ultracapacitor monomer, through high-temperature load 1000 hours or follow
After ring 100,000 times, drum, monomer capacity all not having occurred is more than 100F, and DC internal resistance is less than 12.5m Ω.Directly by super capacitor
Electrode assembling prepared by device activated carbon becomes Φ 22*45 welding needle type ultracapacitor monomer, by comparative example 1 gained monomer through high temperature
After load 1000 hours or circulation 100,000 times, drum occurring substantially to rise, capacity is less than 90F, and DC internal resistance is more than 22m Ω；By comparative example
Still it is notable to there is substantially to rise drum, capacity attenuation and internal resistance increase effect for 1000 hours through high-temperature load in 2 gained monomers, monomer warp
Occur slight rising to rouse after circulating 100,000 times, show that the lanthanum-nickel alloy in cover plate has and absorb the part produced by electrochemical action
The ability of mixed gas；Owing to the battery core of comparative example 3 experienced before being assembled into Φ 22*45 welding needle type ultracapacitor monomer
Energising in 10 hours is aging, rouses although assembled monomer only occurs slight after high-temperature load 1000 hours or circulation 100,000 times,
But monomer capacity is the most on the low side, and DC internal resistance is the most relatively large.
Claims (9)
1. an electrode for super capacitor active material pretreatment unit, described device includes reacting pile, vacuum pump, charge and discharge
Electric tester, water bath with thermostatic control, topping-up pump and agitator, it is characterised in that the outside of reaction pile is insulating barrier, reaction pile
The internal barrier film by centre is divided into positive pole zone and negative regions, and plus plate current-collecting body is positioned in the positive pole zone of reaction pile,
Negative current collector is positioned in the negative regions of reaction pile, and positive pole zone and negative regions in reaction pile are respectively furnished with one
Agitator, there are two interfaces at the top of reaction pile, are connected with topping-up pump and vacuum pump respectively；Described reaction pile anode collection
Body is connected with the positive terminal of charge-discharge test instrument through insulating barrier through lead-out wire, and reaction pile negative current collector is through lead-out wire
Negative terminal through insulating barrier with charge-discharge test instrument is connected；Described reaction pile is placed in water bath with thermostatic control.
Electrode active material pretreatment unit the most according to claim 1, it is characterised in that the volume of reaction pile is
10L, top can freely be opened.
Electrode active material pretreatment unit the most according to claim 1, it is characterised in that described plus plate current-collecting body or
Described negative current collector is selected from wire netting or the metallic plate that aluminum, copper, silver, gold or platinum are made.
Electrode active material pretreatment unit the most according to claim 1, it is characterised in that described barrier film is selected from fiber
Element barrier film, polyethylene diagrams or polypropylene diaphragm.
5. the preprocess method of an electrode for super capacitor active material, it is characterised in that use as claimed in claim 1
Device, comprise the following steps:
1) electrode for super capacitor active material is separately added in positive pole zone and the negative regions of reaction pile, seals anti-
Answer pile, bet into super electrolyte for capacitor at vacuum≤-0.098Mpa, control electrode active material and electrolyte shape
Becoming range of solid content is the slurry of 10wt%-50wt%；
2) temperature of regulating thermostatic water-bath is to 60 DEG C-80 DEG C, with the plus plate current-collecting body of charge-discharge test instrument coupled reaction pile and
Negative current collector, first by reaction pile constant-current charge to 2.5V-3.0V, then to reaction pile constant-voltage charge 8 under 2.5V-3.0V
More than hour, after charging complete, reaction pile is discharged to below 0.1V, completes the aging of slurry；
3) slurry after aging is taken out from from reaction pile, starch with the solvent dilution that maybe can mix identical with bath composition
Material, is washed out and drying is to pretreatment electrode active material.
Method the most according to claim 5, it is characterised in that described electrode active material selected from activated carbon, Graphene,
NACF, charcoal-aero gel or CNT.
Method the most according to claim 5, it is characterised in that described ultracapacitor electrolyte is selected from tetraethyl ammonium
The acetonitrile solution of Tetrafluoroboric acid, the carbonic allyl ester solution of tetraethyl ammonium Tetrafluoroboric acid, the second of triethyl methyl ammonium Tetrafluoroboric acid
Nitrile solution or the carbonic allyl ester solution of triethyl methyl ammonium Tetrafluoroboric acid.
Method the most according to claim 7, it is characterised in that the concentration of described ultracapacitor electrolyte choosing is
0.7M-2.5M。
Method the most according to claim 5, it is characterised in that described solvent selected from acetonitrile, Allyl carbonate, chloroform,
In carbon tetrachloride, benzene, normal propyl alcohol, isopropanol, acrylonitrile, ethyl acetate, dichloroethanes, ethanol, ether or Carbon bisulfide one
Plant or multiple.
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| CN101465417A (en) * | 2007-12-19 | 2009-06-24 | 中国科学院金属研究所 | Electrochemical treatment method for improving vanadium cell electrode material activity |
| CN101777667A (en) * | 2005-07-22 | 2010-07-14 | 株式会社Lg化学 | Pre-treatment method of electrode active material |
| JP2014086382A (en) * | 2012-10-26 | 2014-05-12 | Kaneka Corp | Method for manufacturing nonaqueous electrolyte secondary battery, and battery manufactured by the method |
| CN104303357A (en) * | 2012-05-18 | 2015-01-21 | 丰田自动车株式会社 | Method for producing non-aqueous secondary battery |
| CN104401992A (en) * | 2014-10-22 | 2015-03-11 | 深圳市贝特瑞新能源材料股份有限公司 | Method for preparing activated carbon for super capacitor with fruit shells as raw material and application of activated carbon |
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2016
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101777667A (en) * | 2005-07-22 | 2010-07-14 | 株式会社Lg化学 | Pre-treatment method of electrode active material |
| CN101465417A (en) * | 2007-12-19 | 2009-06-24 | 中国科学院金属研究所 | Electrochemical treatment method for improving vanadium cell electrode material activity |
| CN104303357A (en) * | 2012-05-18 | 2015-01-21 | 丰田自动车株式会社 | Method for producing non-aqueous secondary battery |
| JP2014086382A (en) * | 2012-10-26 | 2014-05-12 | Kaneka Corp | Method for manufacturing nonaqueous electrolyte secondary battery, and battery manufactured by the method |
| CN104401992A (en) * | 2014-10-22 | 2015-03-11 | 深圳市贝特瑞新能源材料股份有限公司 | Method for preparing activated carbon for super capacitor with fruit shells as raw material and application of activated carbon |
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