CN101819884B - Method for preparing porous carbon thin film material used for supercapacitor electrode - Google Patents
Method for preparing porous carbon thin film material used for supercapacitor electrode Download PDFInfo
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- CN101819884B CN101819884B CN 200910021718 CN200910021718A CN101819884B CN 101819884 B CN101819884 B CN 101819884B CN 200910021718 CN200910021718 CN 200910021718 CN 200910021718 A CN200910021718 A CN 200910021718A CN 101819884 B CN101819884 B CN 101819884B
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Abstract
The invention discloses a method for preparing a porous carbon thin film material used for a supercapacitor electrode. The method comprises the following steps of: placing a substrate at a deposition position in a container at the deposition temperature of between 750 and 800 DEG C; pumping air out of the container by using a vacuum pump so that the container reaches high vacuum, namely a vacuum state of 1<-7> to 10<-8> Pa; introducing an inert protective gas into the container and controlling the flow rate of the inert protective gas to be 70 to 80 mL/s by using a mass flow meter; introducing a reducing gas into the container and controlling the flow rate of the reducing gas to be 70 to 80 mL/s by using the mass flow meter; introducing a mixed gas of hydrocarbons into the container and controlling the flow rate of the mixed gas to be 50 to 80 mL/s by using the mass flow meter; heating the container; keeping the temperature when the container is heated to 900 to 1,000 DEG C for 1 to 2 hours; and depositing porous carbon on the substrate through a reduction reaction of the mixed gas of the hydrocarbons so that the porous carbon thin film material is obtained.
Description
Technical field
The present invention relates to a kind of preparation method who is used for the porous carbon thin film material of electrode of super capacitor.
Background technology
Ultracapacitor owing to be with a wide range of applications with enormous and latent market become the international energy hot research fields.Ultracapacitor mainly is divided into electric double layer type ultracapacitor and oxidation-reduction type ultracapacitor.Mainly by the surface area decision of material, its theoretical capacity is directly proportional with the specific area of electrode material the specific capacity of electric double layer type ultracapacitor.Mainly be to do electrode material through employing active carbon or CNT at present, its specific capacity is approximately 50～150F/g.For with pure active carbon or the CNT ultracapacitor as electrode, because the material with carbon element specific area is lower, its low specific volume problem has become its bottleneck as electrode material for super capacitor of restriction.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method who is used for the porous carbon thin film material of electrode of super capacitor.
The present invention realizes that like this its preparation process is:
(1) at first under 750-800 ℃ of depositing temperature the deposition position place in container put into substrate;
(2) with vacuum pump the air in the container is extracted out, made to reach high vacuum in the container, promptly 10
-7～10
-8The vacuum state of Pa;
(3) in container, feed inert protective gas, using the flow of mass flowmenter control inert protective gas is 70～80mL/s;
(4) in container, feed reducing gas, using mass flowmenter control gaseous flow is 70～80mL/s;
(5) in container, feed the hydro carbons mist then, using mass flowmenter control gaseous flow is 50～80mL/s;
(6) with container heating, be incubated when being heated to 900～1000 ℃, time remaining 1～2 hour, the reduction reaction of hydrocarbon mixture gas makes and deposits porous carbon in the substrate, promptly gets porous carbon thin film material.
Usefulness of the present invention is: preparation method of the present invention prepares porous carbon thin film material; Its chemical vapor deposition processes carries out under the high-temperature low-pressure condition; Temperature high deposition can improve the crystalline perfection of porous carbon crystal significantly, and deposition process can be carried out on large size substrate or many substrates; Low-pressure chemical vapor deposition causes the diffusion coefficient of reacting gas to improve about three one magnitude; Thereby improved the diffusivity of reacting gas and product; The long and is that porous carbon depositing of thin film speed has been improved more than the one magnitude, and the probability that film gauge uniformity is good, the gas phase forming core causes particle contamination is little, film is comparatively fine and close.
In addition; Maximum benefit is that this kind porous carbon thin film material can directly make electrode; Need not add additives such as graphite, water and binding agent, improve the conductance of electrode, improve the specific area of material with carbon element simultaneously yet; Capacitor output specific capacity obviously improves, and this method has the effect of highly significant on the specific volume that improves carbon electrode.
Embodiment
Embodiment 1:
(1) at first under 750 ℃ depositing temperature in quartz ampoule the deposition position place put into stainless (steel) wire;
(2) utilize vacuum pump that the air in the quartz ampoule is extracted out, make to reach high vacuum in the quartz ampoule, promptly 10
-7～10
-8The vacuum state of Pa;
(3) in quartz ampoule, feed nitrogen, use the flow of mass flowmenter control nitrogen to be 70mL/s;
(4) in quartz ampoule, feed hydrogen, use the flow of mass flowmenter control hydrogen to be 75mL/s;
(5) flow that uses mass flowmenter control methane gas then mixes these three kinds of hydrocarbon gas as 70mL/s as the flow of 52mL/s, the ethylene gas flow as 60mL/s, propane gas, and the hydro carbons mist is fed in the quartz ampoule;
(6) to quartz ampoule heating and under 950 ℃ temperature, be incubated, time remaining 1 hour, the reduction reaction of hydrocarbon mixture gas makes and deposits porous carbon on the stainless (steel) wire, promptly gets porous carbon thin film material.
Embodiment 2:
(1) at first under 780 ℃ depositing temperature in quartz ampoule the deposition position place put into nickel screen;
(2) utilize vacuum pump that the air in the quartz ampoule is extracted out, make to reach high vacuum in the quartz ampoule, promptly (10
-710
-8The vacuum state of Pa;
(3) in quartz ampoule, feed nitrogen, use the flow of mass flowmenter control nitrogen to be 75mL/s;
(4) in quartz ampoule, feed hydrogen, use the flow of mass flowmenter control hydrogen to be 70mL/s;
(5) flow that uses mass flowmenter control methane gas then mixes three kinds of hydrocarbon gas as 70mL/s as the flow of 55mL/s, the ethylene gas flow as 65mL/s, propane gas, and the hydro carbons mist is fed in the quartz ampoule;
(6) to quartz ampoule heating and under 950 ℃ temperature, be incubated, time remaining 1.5 hours, the reduction reaction of hydrocarbon mixture gas makes and deposits porous carbon on the nickel screen, promptly gets porous carbon thin film material.
Embodiment 3:
(1) at first under 750 ℃ depositing temperature in quartz ampoule the deposition position place put into stainless (steel) wire;
(2) utilize vacuum pump that the air in the quartz ampoule is extracted out, make to reach high vacuum in the quartz ampoule, promptly 10
-7～10
-8The vacuum state of Pa;
(3) in quartz ampoule, feed argon gas, use the flow of mass flowmenter control argon gas to be 70mL/s;
(4) in quartz ampoule, feed hydrogen, use the flow of mass flowmenter control hydrogen to be 75mL/s;
(5) flow that uses mass flowmenter control methane gas then mixes three kinds of hydrocarbon gas as 70mL/s as the flow of 52mL/s, the ethylene gas flow as 60mL/s, propane gas, then the hydro carbons mist is fed in the quartz ampoule;
(6) to quartz ampoule heating and under 950 ℃ temperature, be incubated, time remaining 2 hours, the reduction reaction of hydrocarbon mixture gas makes and deposits porous carbon on the stainless (steel) wire, promptly gets porous carbon thin film material.
Embodiment 4:
(1) at first under 780 ℃ depositing temperature in quartz ampoule the deposition position place put into nickel screen;
(2) utilize vacuum pump that the air in the quartz ampoule is extracted out, make to reach high vacuum in the quartz ampoule, promptly 10
-7～10
-8The vacuum state of Pa;
(3) in quartz ampoule, feed argon gas, use the flow of mass flowmenter control argon gas to be 75mL/s;
(4) in quartz ampoule, feed hydrogen, use the flow of mass flowmenter control hydrogen to be 70mL/s;
(5) flow that uses mass flowmenter control methane gas then mixes three kinds of hydrocarbon gas as 70mL/s as the flow of 55mL/s, the ethylene gas flow as 65mL/s, propane gas, then the hydro carbons mist is fed in the quartz ampoule;
(6) to quartz ampoule heating and under 950 ℃ of temperature, be incubated, time remaining 1 hour, the reduction reaction of hydrocarbon mixture gas makes and deposits porous carbon on the nickel screen, promptly gets porous carbon thin film material.
Embodiment 5:
(1) at first under 790 ℃ depositing temperature in quartz ampoule the deposition position place put into stainless (steel) wire;
(2) utilize vacuum pump that the air in the quartz ampoule is extracted out, make to reach high vacuum in the quartz ampoule, promptly 10
-7～10
-8The vacuum state of Pa;
(3) in quartz ampoule, feed nitrogen, use the flow of mass flowmenter control nitrogen to be 76mL/s;
(4) in quartz ampoule, feed hydrogen, use the flow of mass flowmenter control hydrogen to be 75mL/s;
(5) flow that uses mass flowmenter control methane gas then mixes these four kinds of hydrocarbon gas as 70mL/s as the gas flow of 55mL/s, the ethane flow as 75mL/s, propane gas as the flow of 65mL/s, propylene gas, then the hydro carbons mist is fed in the quartz ampoule;
(6) to container heating and under 970 ℃ of temperature, be incubated, time remaining 1.5 hours, the reduction reaction of hydrocarbon mixture gas makes and deposits porous carbon on the stainless steel substrates, promptly gets porous carbon thin film material.
Embodiment 6:
(1) at first under 800 ℃ depositing temperature in quartz ampoule the deposition position place put into stainless (steel) wire;
(2) utilize vacuum pump that the air in the quartz ampoule is extracted out, make to reach high vacuum in the quartz ampoule, promptly 10
-7～10
-8The vacuum state of Pa;
(3) in quartz ampoule, feed nitrogen, use the flow of mass flowmenter control nitrogen to be 80mL/s;
(4) in quartz ampoule, feed hydrogen, use the flow of mass flowmenter control hydrogen to be 80mL/s;
(5) flow that uses mass flowmenter control methane gas then mixes these four kinds of hydrocarbon gas as 65mL/s as the gas flow of 55mL/s, the ethane flow as 75mL/s, propane gas as the flow of 70mL/s, propylene gas, then the hydro carbons mist is fed in the quartz ampoule;
(6) to container heating and under 950 ℃ of temperature, be incubated, time remaining 2 hours, the reduction reaction of hydrocarbon mixture gas makes and deposits porous carbon on the stainless steel substrates, promptly gets porous carbon thin film material.
Embodiment 7:
(1) at first under 790 ℃ depositing temperature in quartz ampoule the deposition position place put into stainless (steel) wire;
(2) utilize vacuum pump that the air in the quartz ampoule is extracted out, make to reach high vacuum in the quartz ampoule, promptly 10
-7～10
-8The vacuum state of Pa;
(3) in quartz ampoule, feed argon gas, use the flow of mass flowmenter control argon gas to be 76mL/s;
(4) in quartz ampoule, feed hydrogen, use the flow of mass flowmenter control hydrogen to be 75mL/s;
(5) flow that uses mass flowmenter control methane gas then mixes these four kinds of hydrocarbon gas as 70mL/s as the gas flow of 55mL/s, the ethane flow as 75mL/s, propane gas as the flow of 65mL/s, propylene gas, then the hydro carbons mist is fed in the quartz ampoule;
(6) to container heating and under 970 ℃ of temperature, be incubated, time remaining 1 hour, the reduction reaction of hydrocarbon mixture gas makes and deposits porous carbon on the stainless steel substrates, promptly gets porous carbon thin film material.
Embodiment 8:
(1) at first under 800 ℃ depositing temperature in quartz ampoule the deposition position place put into stainless (steel) wire;
(2) utilize vacuum pump that the air in the quartz ampoule is extracted out, make to reach high vacuum in the quartz ampoule, promptly 10
-7～10
-8The vacuum state of Pa;
(3) in quartz ampoule, feed argon gas, use the flow of mass flowmenter control argon gas to be 80mL/s;
(4) in quartz ampoule, feed hydrogen, use the flow of mass flowmenter control hydrogen to be 80mL/s;
(5) flow that uses mass flowmenter control methane gas then mixes these four kinds of hydrocarbon gas as 65mL/s as the gas flow of 55mL/s, the ethane flow as 75mL/s, propane gas as the flow of 70mL/s, propylene gas, then the hydro carbons mist is fed in the quartz ampoule;
(6) to container heating and under 950 ℃ temperature, be incubated, time remaining 1.5 hours, the reduction reaction of hydrocarbon mixture gas makes and deposits porous carbon on the stainless steel substrates, promptly gets porous carbon thin film material.
Claims (7)
1. the preparation method who is used for the porous carbon thin film material of electrode of super capacitor adopts chemical vapour deposition technique, through the reduction reaction of cracking source hydrocarbon gas, in substrate, deposits porous carbon thin film material, the steps include:
(1) at first under 750～800 ℃ of depositing temperatures the deposition position place in container put into substrate;
(2) with vacuum pump the air in the container is extracted out, made to reach high vacuum in the container, promptly 10
-7～10
-8The vacuum state of Pa;
(3) in container, feed inert protective gas, using the flow of mass flowmenter control inert protective gas is 70～80mL/s;
(4) in container, feed reducing gas, using mass flowmenter control gaseous flow is 70～80mL/s;
(5) in container, feed the hydro carbons mist then, with mass flowmenter control gaseous flow, the flow that makes methane gas respectively is that the flow of 52mL/s, ethylene gas is that the flow of 60mL/s, propane gas is 70mL/s; Perhaps the flow of methane gas is that the flow of 55mL/s, ethylene gas is that the flow of 65mL/s, propane gas is 70mL/s; Perhaps the flow of methane gas is that the flow of 65mL/s, propylene gas is that the gas flow of 55mL/s, ethane is that the flow of 75mL/s, propane gas is 70mL/s; Perhaps the flow of methane gas is that the flow of 70mL/s, propylene gas is that the gas flow of 55mL/s, ethane is that the flow of 75mL/s, propane gas is 65mL/s;
(6) with container heating, be incubated when being heated to 900～1000 ℃, time remaining 1～2 hour, the reduction reaction of hydrocarbon mixture gas makes and deposits porous carbon in the substrate, promptly gets porous carbon thin film material.
2. the preparation method who is used for the porous carbon thin film material of electrode of super capacitor according to claim 1 is characterized in that: described substrate is a stainless (steel) wire, or stainless steel substrates, or nickel screen, or the nickel sheet.
3. the preparation method who is used for the porous carbon thin film material of electrode of super capacitor according to claim 1 is characterized in that: described vacuum pump is the system that oil sealing mechanical pump and composite molecular pump are formed.
4. the preparation method who is used for the porous carbon thin film material of electrode of super capacitor according to claim 1 is characterized in that: described container is the high purity quartz pipe.
5. the preparation method who is used for the porous carbon thin film material of electrode of super capacitor according to claim 1 is characterized in that: described inert protective gas is a nitrogen, or argon gas.
6. preparation method who is used for the finished electrode of ultracapacitor; The substrate that it is characterized in that depositing porous carbon thin film material as claimed in claim 1 is as collector; Platinum filament is as lead; Lead and collector adopt the spot welding mode to weld, then on the oil pressure tablet press machine with the pole piece compacting, obtain finished electrode.
7. ultracapacitor; The electrodes use symmetry constructional device that it is characterized in that ultracapacitor; Both positive and negative polarity is finished electrode as claimed in claim 6, and electrode diaphragm is a kind of in microporous polypropylene membrane and the polyvinyl alcohol film, and electrolyte is the potassium hydroxide alkali lye of 2mol or 6mol.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200910021718 CN101819884B (en) | 2009-03-14 | 2009-03-14 | Method for preparing porous carbon thin film material used for supercapacitor electrode |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910021718 CN101819884B (en) | 2009-03-14 | 2009-03-14 | Method for preparing porous carbon thin film material used for supercapacitor electrode |
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| Publication Number | Publication Date |
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| CN101819884A CN101819884A (en) | 2010-09-01 |
| CN101819884B true CN101819884B (en) | 2012-11-07 |
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| CN102664106B (en) * | 2012-05-24 | 2014-07-16 | 山西迪诺科技有限公司 | Composite electrode material |
| CN108369870A (en) * | 2016-06-06 | 2018-08-03 | 住友电气工业株式会社 | For the porous carbon materials of electrical double layer capacitor electrodes, its manufacturing method and electrical double layer capacitor electrodes |
| CN106622248B (en) * | 2016-11-21 | 2019-09-27 | 清华大学 | A kind of porous nickel and the compound of carbon and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101290837A (en) * | 2008-06-11 | 2008-10-22 | 天津大学 | Preparing method of porous carbon electrode of super capacitor with high magnified charge-discharge performance |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101290837A (en) * | 2008-06-11 | 2008-10-22 | 天津大学 | Preparing method of porous carbon electrode of super capacitor with high magnified charge-discharge performance |
Non-Patent Citations (5)
| Title |
|---|
| Alan M. Cassell et al.Large Scale CVD Synthesis of Single-Walled Carbon Nanotubes.《J. Phys. Chem. B》.1999,第103卷6484-6492. * |
| JP特开2007-179932A 2007.07.12 |
| 李燕等.低压化学气相沉积法制备单壁碳纳米管.《功能材料》.2003,第34卷(第5期),538,539,542. * |
| 李茂刚等.碳纳米管薄膜电极的制备及电容吸附性能.《功能材料与器件学报》.2007,第13卷(第1期),35-38. * |
| 王茂章.由不同碳源合成及制备纳米碳管的进展.《新型炭材料》.2003,第18卷(第4期),250-264. * |
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