CN102509627A - Method for preparing carbon particulate supercapacitor electrode in situ by adopting foamed nickel - Google Patents
Method for preparing carbon particulate supercapacitor electrode in situ by adopting foamed nickel Download PDFInfo
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- CN102509627A CN102509627A CN2011103706342A CN201110370634A CN102509627A CN 102509627 A CN102509627 A CN 102509627A CN 2011103706342 A CN2011103706342 A CN 2011103706342A CN 201110370634 A CN201110370634 A CN 201110370634A CN 102509627 A CN102509627 A CN 102509627A
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- foamed nickel
- carbon particulate
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- situ
- carbon
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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
Abstract
The invention discloses a method for preparing carbon particulate supercapacitor electrode in situ by adopting foamed nickel. The foamed nickel serves as a conductive framework of the capacitor electrode; Ni(NO3)2 or Fe(NO3)3 services as an activator; the foamed nickel is soaked in the aqueous solution of the Ni(NO3)2 or the Fe(NO3)3 for 3 hours, and the concentration of the aqueous solution of the Ni(NO3)2 or the Fe(NO3)3 is 1mol/L to saturation; after being dried, the foamed nickel is placed in a hot wire and radio-frequency plasma composite chemical vapor deposition system, and then is vacuumized; a foamed nickel substrate is heated to 500 DEG C under the condition of adding N2, is deoxidized by adding high-purity H2 for 60 minutes; and lastly, a chemical vapor deposition reaction is carried out by adding CH4, the volume ratio of the CH4 and the H2 is 1:1 to 6:1, the current passing through the hot wire is 20A to 40A, the radio frequency power is 100W to 300W, the reaction time is 30 minutes to 60 minutes, and the carbon particulate electrode generated in situ on the foamed nickel framework is obtained. In the method, the carbon particulate electrode is generated in situ on the foamed nickel framework directly, the contact area of the carbon particulate supercapacitor and the foamed nickel is larger, and the adhesion effect is better, slurry combination in the prior art is not required, and the production cost is further lowered.
Description
Technical field
The present invention relates to a kind of method of nickel foam in-situ preparing carbon particulate electrode material for super capacitor.
Background technology
Ultracapacitor is a kind of device of the novel store electrical energy between traditional capacitor and battery.It has energy density and the specific capacity more much higher than traditional capacitor, has the power density more much bigger than battery simultaneously again.Ultracapacitor generally has following characteristics: (1) has high energy density and power density; (2) have the big electric current of abrupt release, the charging interval is short, charge efficiency is high advantage; (3) has the advantage that has extended cycle life; (4) serviceability temperature wide ranges, cryogenic property is superior.(5) has the advantage that leakage current is little, the self discharge time is long; (6) environmentally safe is the ultracapacitor of electrode material with the material with carbon element especially, can be used as real green energy resource.
Material with carbon element is a kind of electrode material for super capacitor commonly used, and the material with carbon element that can be used for electrode of super capacitor mainly comprises: activated carbon, carbon fiber, vitreous carbon, graphite, carbon black, carbon aerogels, CNT etc.
The activated carbon specific area is big, chemical stability good, and cheap, is to use maximum carbon electrode materials, and its application technology in ultracapacitor is also the most ripe.Nickel foam be a kind of porosity at the typical froth metal more than 90%, as the afflux material of electrode matrix, have and carry electrode active material and the dual-use function that compiles electrochemical reaction current.All kinds of batteries that nickel foam is widely used in, in the capacitor as the electrodes conduct matrix.
At present; The preparation method of ultra electrode capacitor electrode mixes material with carbon element with conductive agent and binding agent; Be coated in again on the conducting base after closing slurry, the ratio of material with carbon element and binding agent, closing the technology of slurry and being coated with sizing process all has bigger influence to the performance of electrode material.
Summary of the invention
The purpose of this invention is to provide a kind of method that adopts heated filament and radio frequency plasma composite chemical gas phase deposition technology at nickel foam growth in situ carbon particulate electrode of super capacitor; Simplified the ultracapacitor preparation technology based on material with carbon element, prepared carbon particulate electrode of super capacitor has higher capacitance.
The present invention adopts heated filament and radio frequency plasma composite chemical gas phase deposition technology, is carbon source with CH4, at nickel foam substrate growth growth in situ carbon particulate, as electrode material for super capacitor.
The method of a kind of nickel foam in-situ preparing carbon particulate electrode of super capacitor provided by the invention is a conducting matrix grain with the nickel foam, with Ni (NO
3)
2Or Fe (NO
3)
3As catalyst, adopt heated filament and radio frequency plasma composite chemical gas-phase deposition, hydrogen is as reducing gas, CH
4As carbon source, preparation carbon particulate electrode of super capacitor.
Said Ni (NO
3)
2The concentration range of the aqueous solution is 1mol/L～saturated.
Said Fe (NO
3)
3The concentration range of the aqueous solution is 1mol/L～saturated.
Said CH
4: H
2Volume ratio is 1～6: 1, and reaction temperature is 500 ℃.
The heating current of said heated filament is 20～40A.
The radio-frequency power of said radio frequency plasma is 100～300W.
Said heated filament and radio frequency plasma composite chemical vapour deposition time are 30～60min.
The method of a kind of nickel foam in-situ preparing carbon particulate electrode of super capacitor provided by the invention specifically comprises the steps:
1. the processing of nickel foam substrate
Nickel foam is cut into small pieces; Ultrasonic cleaning 20min in 0.01mol/L NaOH removes surface and oil contaminant, after washed with de-ionized water; Ultrasonic cleaning 20min again in rare HCl; To remove the oxide on surface,, subsequent use after the vacuumize with ultrasonic cleaning 20min in ethanolic solution again after washed with de-ionized water to the neutrality.
With nickel foam at 1mol/L～saturated Ni (NO
3)
2Or Fe (NO
3)
3Soak 4h in the solution, then 80 ℃ of following vacuumizes.
2. the growth in situ of carbon particulate electrode of super capacitor
Nickel foam after the drying is put into heated filament and radio frequency plasma composite chemical gas-phase deposition system, take out back of the body end vacuum to 10 earlier
-3Pa, closure molecule pump afterwards feeds high pure nitrogen, under blanket of nitrogen, substrate is heated to 500 ℃, feeds high-purity hydrogen afterwards and reduces Ni (NO
3)
2Or Fe (NO
3)
3, the recovery time is 60min.
Under the underlayer temperature of 500 ℃ of maintenances, feed CH subsequently
4Gas, volume ratio are CH
4: H
2=1～6: 1, reaction pressure is 28Pa, opens heater supply, and voltage is 40V, and electric current is 20～40A, opens radio-frequency power supply again, and power setting is 100～300W, finishes reaction behind 30～60min, closes H
2And CH
4The back is at N
2Be cooled to normal temperature in the atmosphere, obtain the surface and be black, the carbon particulate electrode material of growth in situ on the nickel foam skeleton.
3. the carbon particulate electrode material being placed on concentration is to soak 3h in 10% the PTFE aqueous solution, obtains the carbon particulate electrode of super capacitor with the twin rollers compacting behind the vacuumize 10h.Go out two Φ 1.6mm electrode slices again, put into the button cell shell, add 1mol/L Na
2SO4 solution impregnation 3h processes the button ultracapacitor after sealing.
In the said step 1, adopt saturated Ni (NO
3)
2Solution soaking foam nickel has part Ni (NO
3)
2By the absorption of the skeleton of nickel foam, after hydrogen heat is handled, Ni (NO
3)
2Be decomposed into Ni particle, with CH with higher catalytic activity
4The carbon active group that high temperature heated filament and plasma environment decompose down reacts, and generates carbon particulate.
Beneficial effect of the present invention:
This method need not adorned activated carbon particles and mix with conductive agent and binding agent; Be coated on the conducting base again after closing slurry; This method carbon particulate and nickel foam are not through adhesive bond; But directly with the carbon particulate growth in situ on the nickel foam skeleton, the contact area between carbon particulate and the nickel foam is bigger, bond effect is better.Reduced and closed the slurry step in the traditional handicraft, further reduced production costs.
Description of drawings
Fig. 1 is the SEM photo of the carbon particulate electrode of super capacitor of nickel foam growth in situ of the present invention.
Embodiment
Embodiment 1,
The nickel foam that cleaning is good is put into saturated Ni (NO
3)
2Soak 4h in the solution, then at 80 ℃ of following vacuumize 3h.
Dried nickel foam is put into heated filament and radio frequency plasma composite chemical gas-phase deposition system; Take out back of the body end vacuum earlier to 10-3Pa; The closure molecule pump feeds high pure nitrogen afterwards, under blanket of nitrogen, substrate is heated to 500 ℃; Feed high-purity hydrogen again behind the heating 30min and reduce, the recovery time is 60min.
Under the underlayer temperature of 500 ℃ of maintenances, feed CH subsequently
4Gas, gas volume is than being CH
4: H
2=2: 1, reaction pressure is 28Pa, opens heater supply, and voltage is 40V, and electric current is 28A, opens radio-frequency power supply again, and power setting is 150W, finishes reaction behind the 45min, closes H
2And CH
4The back is at N
2Be cooled to normal temperature in the atmosphere, obtain the surface and be the carbon particulate electrode of super capacitor of black.
Again the carbon particulate electrode of super capacitor being put into concentration is that 10% the PTFE aqueous solution soaks 3h, is pressed into electrode with twin rollers behind the vacuumize 10h.Go out two Φ 1.6mm electrode slices again, put into the button cell shell, add 1mol/LNa2SO4 solution impregnation 3h, process the button ultracapacitor after sealing.Adopt battery test system to carry out the constant current charge-discharge test.The specific capacity of carbon particulate electrode is 64F/g.
Embodiment 2.
Identical with step with embodiment 1 other condition, nickel foam is at 1mol/L Ni (NO
3)
2Soak 4h in the solution, be used as electrode base sheet after the drying.Adopt same heated filament and radio frequency plasma composite chemical gas-phase deposition again, the carbon particulate electrode specific capacity that makes is 38F/g.
Embodiment 3.
Identical with embodiment 1 other condition with step, change CH
4And H
2Volume ratio is CH
4: H
2=1: 1, the specific capacity of the carbon particulate electrode of preparation is 56F/g.
Embodiment 4
Identical with embodiment 1 other condition with step, change CH
4And H
2Volume ratio is CH
4: H
2=6: 1, the specific capacity of the carbon particulate electrode of preparation is 20F/g.
Embodiment 5.
Identical with step with embodiment 1 other condition, nickel foam is at 1mol/LFe (NO
3)
3Soak 4h in the solution, be used as electrode base sheet after the drying.Adopt same heated filament and radio frequency plasma composite chemical gas-phase deposition again, the carbon particulate electrode specific capacity that makes is 32F/g.
Embodiment 6.
Identical with step with embodiment 1 other condition, nickel foam is at saturated Fe (NO
3)
3Soak 4h in the solution, be used as electrode base sheet after the drying.Adopt same heated filament and radio frequency plasma composite chemical gas-phase deposition again, the carbon particulate electrode specific capacity that makes is 58F/g.
Embodiment 7.
Identical with step with embodiment 1 other condition, radio-frequency power is set to 100W, and the carbon particulate electrode specific capacity that makes is 10F/g.
Embodiment 8.
Identical with step with embodiment 1 other condition, radio-frequency power is set to 300W, and the carbon particulate electrode specific capacity that makes is 40F/g.
Embodiment 9.
Identical with step with embodiment 1 other condition, the heated filament heating current is set to 40A, and the carbon particulate electrode specific capacity that makes is 60F/g.
Embodiment 10.
Identical with step with embodiment 1 other condition, the heated filament heating current is set to 20A, and the carbon particulate electrode specific capacity that makes is 20F/g.
Embodiment 11.
Identical with step with embodiment 1 other condition, the reaction time of heated filament and plasma activated chemical vapour deposition is 30min, and the carbon particulate electrode specific capacity that makes is 40F/g.
Embodiment 12.
Identical with step with embodiment 1 other condition, the reaction time of heated filament and plasma activated chemical vapour deposition is 60min, and the carbon particulate electrode specific capacity that makes is 50F/g.
Claims (7)
1. the method for a nickel foam in-situ preparing carbon particulate electrode of super capacitor is characterized in that: be conducting matrix grain with the nickel foam, with Ni (NO
3)
2Or Fe (NO
3)
3As catalyst, adopt heated filament and radio frequency plasma composite chemical gas-phase deposition, hydrogen is as reducing gas, CH
4As carbon source, preparation carbon particulate electrode of super capacitor.
2. method according to claim 1 is characterized in that: said Ni (NO
3)
2The concentration range of the aqueous solution is 1mol/L～saturated.
3. method according to claim 1 is characterized in that: said Fe (NO
3)
3The concentration range of the aqueous solution is 1mol/L～saturated.
4. method according to claim 1 is characterized in that: said CH
4: H
2Volume ratio is 1～6: 1, and reaction temperature is 500 ℃.
5. method according to claim 1 is characterized in that: the heating current of said heated filament is 20～40A.
6. method according to claim 1 is characterized in that: the radio-frequency power of said radio frequency plasma is 100～300W.
7. method according to claim 1 is characterized in that: said heated filament and radio frequency plasma composite chemical vapour deposition time are 30～60min.
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|---|---|---|---|
| CN2011103706342A CN102509627A (en) | 2011-11-18 | 2011-11-18 | Method for preparing carbon particulate supercapacitor electrode in situ by adopting foamed nickel |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103706342A CN102509627A (en) | 2011-11-18 | 2011-11-18 | Method for preparing carbon particulate supercapacitor electrode in situ by adopting foamed nickel |
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|---|---|
| CN102509627A true CN102509627A (en) | 2012-06-20 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105448542A (en) * | 2015-12-04 | 2016-03-30 | 大连理工常州研究院有限公司 | Method for preparing porous carbon film by plasma enhanced chemical vapor deposition method |
| CN114744224A (en) * | 2022-04-21 | 2022-07-12 | 浙江理工大学 | Preparation and application of nitrogen-doped carbon nanotube-loaded nickel-cobalt composite nanowire |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1903793A (en) * | 2005-07-26 | 2007-01-31 | 中国科学院物理研究所 | Carbon silicon composite material, its preparation method and use |
| CN101591775A (en) * | 2009-06-18 | 2009-12-02 | 天津理工大学 | Be applicable to the thin film deposition system device of diamond heat-sink membrane |
| CN101661840A (en) * | 2009-07-23 | 2010-03-03 | 武汉大学 | Preparation method of super capacitor |
-
2011
- 2011-11-18 CN CN2011103706342A patent/CN102509627A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1903793A (en) * | 2005-07-26 | 2007-01-31 | 中国科学院物理研究所 | Carbon silicon composite material, its preparation method and use |
| CN101591775A (en) * | 2009-06-18 | 2009-12-02 | 天津理工大学 | Be applicable to the thin film deposition system device of diamond heat-sink membrane |
| CN101661840A (en) * | 2009-07-23 | 2010-03-03 | 武汉大学 | Preparation method of super capacitor |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105448542A (en) * | 2015-12-04 | 2016-03-30 | 大连理工常州研究院有限公司 | Method for preparing porous carbon film by plasma enhanced chemical vapor deposition method |
| CN114744224A (en) * | 2022-04-21 | 2022-07-12 | 浙江理工大学 | Preparation and application of nitrogen-doped carbon nanotube-loaded nickel-cobalt composite nanowire |
| CN114744224B (en) * | 2022-04-21 | 2023-11-21 | 浙江理工大学 | Preparation and application of nitrogen-doped carbon nanotube-loaded nickel-cobalt composite nanowire |
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Application publication date: 20120620 |