CN103325571A - Current collector of super-capacitor battery and prepare method of surficial carbon film of same - Google Patents
Current collector of super-capacitor battery and prepare method of surficial carbon film of same Download PDFInfo
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- CN103325571A CN103325571A CN2012100780447A CN201210078044A CN103325571A CN 103325571 A CN103325571 A CN 103325571A CN 2012100780447 A CN2012100780447 A CN 2012100780447A CN 201210078044 A CN201210078044 A CN 201210078044A CN 103325571 A CN103325571 A CN 103325571A
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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 invention relates to a current collector of a super-capacitor battery and a method of depositing a carbon film on the surface of the same. The method comprises a step of ultrasonic cleaning of the current collector, a step of ion cleaning of the current collector and a step of depositing the carbon film with the thickness of 0.2 micrometer to 0.6 micrometer on the surface of the current collector by adopting the technology of using radio frequency plasma for enhancing chemical vapor deposition. The current collector of the super-capacitor battery and the method of depositing carbon film on the surface of the same prolong the service life of the current collector, and further improve service performance of the super-capacitor battery.
Description
Technical field
The present invention relates to super capacitance cell, relate in particular to the super capacitance cell collector and in the method for super capacitance cell collection liquid surface depositing carbon film.
Background technology
Super capacitance cell is a kind of novel energy device that occurs in recent years, different from conventional electric capacity, its capacity can reach farad even thousand farads of levels, it is a kind of a kind of novel energy device between battery and electric capacity, have the large and high two-fold advantage of power of battery density of conventional capacitive energy density concurrently, its energy density is far above conventional electric capacity, and power density is far above common batteries.Super capacitance cell has the advantages such as volume is little, capacity is large, charging rate is fast, discharge power is high, the life-span is long, working temperature is wide.Because its unique advantage that has makes super capacitance cell have wide application prospects in fields such as mobile communication, industry, electric automobile, Aero-Space and science and techniques of defence.
Super capacitance cell is comprised of electrode, electrolyte, collector and barrier film four parts.In the super capacitance cell preparation flow, its core technology is the preparation of electrode material and electrode, and electrode material mainly contains material with carbon element, metal oxide materials and conducting polymer materials.Usually, electrode preparation method is directly it to be coated in collection liquid surface after electrode material, conductive agent, binding agent are prepared into water/absolute ethyl alcohol slurry, or slurry is dried and after roll forming machine is pressed into the certain thickness electrode slice, it is being overlayed at collection liquid surface, again through behind cutting, the riveted joint lead-in wire, according to the order assembling super capacitance cell core of positive pole, barrier film, negative pole, barrier film.
High internal resistance is the main cause that the restriction super capacitance cell discharges and recharges power, and high internal resistance can't be satisfied super capacitance cell to the instructions for use of high-energy-density, high power density, and the super capacitance cell life-span is reduced.Contact resistance is one of super capacitance cell internal resistance main source between electrode coat and the collector.In addition, preparing at present the collector that the super capacitance cell both positive and negative polarity generally uses is nickel, and the super capacitance cell operating voltage of this structure is less than normal.For improving the super capacitance cell operating voltage, notification number is that the Chinese invention patent application of CN1348596A discloses a kind of sized nickel hydroxide/carbon super capacitance cell preparation method, in this patent application, with nickel as current collector material, for improving the electric capacity operating voltage, in coatings such as negative current collector electroplate, gold, although the method has significantly improved the super capacitance cell operating voltage, but improved its preparation cost at collection liquid surface plating precious metal element, limited its commercial applications.US Patent No. 6804108 discloses a kind of electrode preparation method, and its electrode is comprised of two-layer, and ground floor is the conductive layer of being combined with collector, and the second layer is the electrode material that contains active material.The method has certain effect for reducing the super capacitance cell internal resistance, but still collector is arranged with coat thickness is large, bond strength is low, be difficult to the effectively problem of assurance useful life.
Problem for prior art exists is necessary the super capacitance cell collection liquid surface is carried out modification in fact.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of collection liquid surface carbon film preparation method, to improve the serviceability of collector.
In order to solve the problems of the technologies described above, collection liquid surface carbon film preparation method provided by the invention comprises:
S100, Ultrasonic Cleaning collector step;
S200, Ion Cleaning collector step; And
S300, adopting radio frequency plasma to strengthen chemical vapour deposition (CVD) (RF-PECVD) technique is 0.2～0.6um carbon film step at the collection liquid surface deposit thickness.
Above-mentioned method wherein, in step S100, comprises step:
S110 carries out Ultrasonic Cleaning through cleaning agent, running water, acetone and deionized water successively with collector; And
S120 will dry in baking oven and be installed on the runing rest of chemical vapour deposition (CVD) vacuum chamber through the collector behind the Ultrasonic Cleaning.
Above-mentioned method wherein, among the step S110, comprises step:
S111 adopts the running water Ultrasonic Cleaning 10～15min that is added with cleaning agent, removes the collection liquid surface greasy dirt;
S112 is with the residual cleaning agent of running water flushing collection liquid surface that flows;
S113 adopts respectively Ultrasonic Cleaning 10～15min of acetone and deionized water successively, removes the residual spot of collection liquid surface.
Above-mentioned method wherein, in step S200, comprises step:
S210 is evacuated to 2～5 * 10 to described chemical vapour deposition (CVD) vacuum chamber
-1Then Pa passes into Ar gas to vacuum chamber;
S220 opens runing rest and radio-frequency power supply when vacuum chamber pressure is 2～5Pa, a large amount of argon ions that produce when radio-frequency power is 100～300W bombard, clean 10～15min to collection liquid surface.
Above-mentioned method wherein, among the described step S300, comprises step:
S310 is 2～5 * 10 at vacuum chamber pressure
-1In vacuum chamber, pass into Ar gas and CH during Pa
4
S320 opens radio-frequency power supply when vacuum chamber pressure is 3～15Pa, and at radio-frequency power 150～300W, the collector Dc bias is-1500V～-200V deposit 20～60min.
Above-mentioned method, wherein, in step S310, the Ar throughput that passes into is 20～50sccm mark condition milliliter per minute (standard-state cubic centimeter per minute is called for short sccm), the CH4 flow is 4～25sccm.
Above-mentioned method, wherein, in the S320 step, the collector temperature is not higher than 80 ℃.
Above-mentioned method, wherein, described collector is the super capacitance cell collectors such as nickel foil, nickel foam, punching nickel, aluminium foil, Copper Foil or stainless steel foil.
The present invention further provides a kind of super capacitance cell collector that adopts said method to make, described collection liquid surface deposits the carbon film of 0.2～0.6 μ m.
Beneficial functional of the present invention is, the cleaning of collector comprises Ultrasonic Cleaning and Ion Cleaning, has increased surface activity, has improved adhesion between carbon film and the collector body surface, and then has improved the serviceability of super capacitance cell.
Describe the present invention below in conjunction with the drawings and specific embodiments, but not as a limitation of the invention.
Description of drawings
Fig. 1 is the method flow diagram of collection liquid surface depositing carbon film of the present invention;
Fig. 2 is the detail flowchart of the Ultrasonic Cleaning among Fig. 1;
Fig. 3 is the detail flowchart of the Ultrasonic Cleaning among Fig. 2;
Fig. 4 is the detail flowchart of the Ion Cleaning among Fig. 1;
Fig. 5 is the detail flowchart of the depositing operation among Fig. 1;
Fig. 6 is the carbon film stereoscan photograph of embodiment method preparation.
Wherein, Reference numeral
S100～S320 step
Embodiment
Below in conjunction with the drawings and specific embodiments technical solution of the present invention being described in detail, further understanding purpose of the present invention, scheme and effect, but is not the restriction as claims protection range of the present invention.
Consult Fig. 1 to Fig. 5, as shown in the figure, the method for collection liquid surface depositing carbon film provided by the invention may further comprise the steps:
S100, Ultrasonic Cleaning collector step;
S200, Ion Cleaning collector step; And
S300, adopting radio frequency plasma to strengthen chemical vapour deposition (CVD) (RF-PECVD) technique is 0.2～0.6um carbon film step at the collection liquid surface deposit thickness.
Particularly, in described step S100, comprise step: S110, carry out Ultrasonic Cleaning through cleaning agent, running water, acetone and deionized water successively with collector; S120 will dry in baking oven and be installed on the runing rest of chemical vapour deposition (CVD) vacuum chamber through the collector behind the Ultrasonic Cleaning.In described step S110, comprise again step: S111, adopt the running water Ultrasonic Cleaning 10～15min that is added with cleaning agent, remove the collection liquid surface greasy dirt; S112 is with the residual cleaning agent of running water flushing collection liquid surface that flows; S113 adopts respectively Ultrasonic Cleaning 10～15min of acetone and deionized water successively, removes the residual spot of collection liquid surface.
In described step S200, comprise again step: S210, described chemical vapour deposition (CVD) vacuum chamber is evacuated to 2～5 * 10
-1Then Pa passes into Ar gas to vacuum chamber; S220 opens runing rest and radio-frequency power supply when vacuum chamber pressure is 2～5Pa, a large amount of argon ions that produce when radio-frequency power is 100～300W bombard, clean 10～15min to collection liquid surface.
Among the described step S300, comprising again step: S310, is 2～5 * 10 at vacuum chamber pressure
-1In vacuum chamber, pass into Ar gas and CH during Pa
4S320 opens radio-frequency power supply when vacuum chamber pressure is 3～15Pa, and at radio-frequency power 150～300W, the collector Dc bias is-1500V～-200V deposit 20～60min.Preferably, in step S310, the Ar throughput that passes into is 20～50sccm, and the CH4 flow is 4～25sccm.And in the S320 step, the collector temperature is not higher than 80 ℃.
Can find out from top description, the cleaning of collector comprises Ultrasonic Cleaning and Ion Cleaning among the present invention, in Ultrasonic Cleaning, at first adopt cleaning agent to remove surface and oil contaminant, adopt again the agent of running water flushing collection liquid surface residual cleaning, then use the residual spot of acetone Ultrasonic Cleaning, in baking oven, dry after adopting at last the deionized water Ultrasonic Cleaning.Adopt Ar Ions Bombardment, cleaning before the depositing carbon film, increase collection liquid surface active, improve adhesion between carbon film and the collector.
The carbon film that makes by the inventive method has higher useful life, thereby can improve preferably the serviceability of collector.Below in conjunction with specific embodiment method of the present invention is described in detail.
Embodiment 1
The employing nickel foam is current collector material, at first adopt the running water Ultrasonic Cleaning 10～15min that is added with cleaning agent, the nickel surface greasy dirt defoams, cleaning agent with the running water flushing nickel foam remained on surface that flows, then adopt successively respectively Ultrasonic Cleaning 10～15min of acetone and deionized water, the spot that the nickel surface that defoams is residual with being installed on the RF-PECVD vacuum chamber runing rest after the nickel foam oven dry, then is evacuated to 2～5 * 10 at last
-1Pa passes into Ar gas to vacuum chamber again, opens runing rest and radio-frequency power supply when vacuum chamber pressure is 2～5Pa, and a large amount of argon ions that produce when radio-frequency power is 100～300W bombard, clean 10～15min to the nickel foam surface.
After cleaning is finished, adopt RF-PECVD equipment to prepare the carbon film that thickness is 0.2～0.6 μ m, sedimentary condition is as follows: be 2～5 * 10 at vacuum chamber pressure
-1In vacuum chamber, pass into Ar gas and CH during Pa
4, the Ar throughput is 20～50sccm, CH
4Flow is 4～25sccm, opens radio-frequency power supply when vacuum chamber pressure is 3～15Pa, at radio-frequency power 150～300W, the collector Dc bias is-200～-1500V deposit 20～60min, make the carbon film that thickness is 0.2～0.6 μ m.Fig. 6 is carbon film ESEM (SEM) photo of nickel foam surface preparation, carbon film Local Cracking after nickel foam is suppressed through roll forming machine.
Embodiment 2
The employing aluminium foil is current collector material, cleaning is cleaned aluminium foil among the employing embodiment 1, when being 2 * 10-1Pa, vacuum chamber pressure in vacuum chamber, passes into Ar gas and CH4, the Ar flow is 40sccm, the CH4 flow is 20sccm, opens radio-frequency power supply when the vacuum chamber pressure is 13Pa, is 300W at radio-frequency power, the collector Dc bias is-1200V deposit 30min, makes the carbon film that thickness is 0.4 μ m.
The present invention compared with prior art has the following advantages:
(1) the preparation carbon film has advantages of that take CH4 as raw material preparation cost is low;
(2) adopt collector temperature low (less than 80 ℃) in RF-PECVD (radio frequency plasma increase chemical vapour deposition technique) the depositing carbon film process, overcome carbon film and the collector thermal coefficient of expansion does not mate the residual stress problems that causes, alleviate the problem because the carbon film that stress causes comes off, prolonged modification collector useful life.
And by the collector that adopts method of the present invention to make, its collection liquid surface deposits the carbon film layer that thickness is 0.2～0.6 μ m, thereby can improve well the useful life of collector, and then improves well the serviceability of super capacitance cell.
Certainly; the present invention also can have other various embodiments; in the situation that do not deviate from spirit of the present invention and essence thereof; those of ordinary skill in the art work as can make according to the present invention various corresponding changes and distortion, but these corresponding changes and distortion all should belong to the protection range of the appended claim of the present invention.
Claims (9)
1. a collection liquid surface carbon film preparation method is characterized in that, comprising:
S100, Ultrasonic Cleaning collector step;
S200, Ion Cleaning collector step; And
S300, adopting radio frequency plasma to strengthen chemical vapor deposition method is 0.2～0.6 μ m carbon film step at the collection liquid surface deposit thickness.
2. method according to claim 1 is characterized in that, in described step S100, comprises step:
S110 carries out Ultrasonic Cleaning through cleaning agent, running water, acetone and deionized water successively with collector; And
S120 will dry in baking oven and be installed on the runing rest of chemical vapour deposition (CVD) vacuum chamber through the collector behind the Ultrasonic Cleaning.
3. method according to claim 2 is characterized in that, among the step S110, comprises step:
S111 adopts the running water Ultrasonic Cleaning 10～15min that is added with cleaning agent, removes the collection liquid surface greasy dirt;
S112 is with the residual cleaning agent of running water flushing collection liquid surface that flows;
S113 adopts respectively Ultrasonic Cleaning 10～15min of acetone and deionized water successively, removes the residual spot of collection liquid surface.
4. method according to claim 2 is characterized in that, in step S200, comprises step:
S210 is evacuated to 2～5 * 10 to described chemical vapour deposition (CVD) vacuum chamber
-1Then Pa passes into Ar gas to vacuum chamber;
S220 opens runing rest and radio-frequency power supply when vacuum chamber pressure is 2～5Pa, a large amount of argon ions that produce when radio-frequency power is 100～300W bombard, clean 10～15min to collection liquid surface.
5. method according to claim 1 is characterized in that, among the described step S300, comprises step:
S310 is 2～5 * 10 at vacuum chamber pressure
-1In vacuum chamber, pass into Ar gas and CH during Pa
4
S320 opens radio-frequency power supply when vacuum chamber pressure is 3～15Pa, and at radio-frequency power 150～300W, vacuum chamber matrix Dc bias is-1500V～-200V deposit 20～60min.
6. method according to claim 5 is characterized in that, in step S310, the Ar throughput that passes into is 20～50sccm, CH
4Flow is 4～25sccm.
7. method according to claim 5 is characterized in that, in the S320 step, the temperature of collector is not higher than 80 ℃.
8. method according to claim 1 is characterized in that, described collector is nickel foil, nickel foam, punching nickel, aluminium foil, Copper Foil or stainless steel wave super capacitance cell collector.
9. a super capacitance cell collector that adopts the described method of claim 1-7 any one to make is characterized in that, collection liquid surface deposits the carbon film of 0.2～0.6 μ m.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2012100780447A CN103325571A (en) | 2012-03-22 | 2012-03-22 | Current collector of super-capacitor battery and prepare method of surficial carbon film of same |
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| CN2012100780447A CN103325571A (en) | 2012-03-22 | 2012-03-22 | Current collector of super-capacitor battery and prepare method of surficial carbon film of same |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105336912A (en) * | 2015-09-14 | 2016-02-17 | 哈尔滨工业大学 | Method for enhancing lithium ion battery current collector and active material adhesion |
| CN105405684A (en) * | 2015-12-21 | 2016-03-16 | 哈尔滨工业大学 | Method for improving Al collector electrode via plasma treatment |
| CN103971952B (en) * | 2014-04-16 | 2016-08-24 | 山东精工电子科技有限公司 | A kind of preparation method of carbon film |
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| CN101448740A (en) * | 2006-05-22 | 2009-06-03 | 株式会社丰田中央研究所 | Amorphous carbon film, method for forming amorphous carbon film, electroconductive member comprising amorphous carbon film, and separator for fuel battery |
| CN102354610A (en) * | 2011-08-23 | 2012-02-15 | 吉林大学 | Method for preparing combined electrode material of graphite/cobalt hydroxide super capacitor |
| CN102354609A (en) * | 2011-08-23 | 2012-02-15 | 吉林大学 | Method for preparing graphene-nickel hydroxide composite electrode material for super capacitor |
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2012
- 2012-03-22 CN CN2012100780447A patent/CN103325571A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101448740A (en) * | 2006-05-22 | 2009-06-03 | 株式会社丰田中央研究所 | Amorphous carbon film, method for forming amorphous carbon film, electroconductive member comprising amorphous carbon film, and separator for fuel battery |
| CN102354610A (en) * | 2011-08-23 | 2012-02-15 | 吉林大学 | Method for preparing combined electrode material of graphite/cobalt hydroxide super capacitor |
| CN102354609A (en) * | 2011-08-23 | 2012-02-15 | 吉林大学 | Method for preparing graphene-nickel hydroxide composite electrode material for super capacitor |
Non-Patent Citations (1)
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| 张艳: "rf PECVD法在不锈钢表面沉积类金刚石碳膜的性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, no. 12, 15 December 2006 (2006-12-15), pages 0200 - 237 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103971952B (en) * | 2014-04-16 | 2016-08-24 | 山东精工电子科技有限公司 | A kind of preparation method of carbon film |
| CN105336912A (en) * | 2015-09-14 | 2016-02-17 | 哈尔滨工业大学 | Method for enhancing lithium ion battery current collector and active material adhesion |
| CN105405684A (en) * | 2015-12-21 | 2016-03-16 | 哈尔滨工业大学 | Method for improving Al collector electrode via plasma treatment |
| CN105405684B (en) * | 2015-12-21 | 2017-09-26 | 哈尔滨工业大学 | A kind of method that plasma treatment improves Al colelctor electrodes |
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Application publication date: 20130925 |