CN103646789B - A kind of preparation method of Graphene-platinum composite electrode material for super capacitor - Google Patents
A kind of preparation method of Graphene-platinum composite electrode material for super capacitor Download PDFInfo
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 86
- 239000007772 electrode material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 239000003990 capacitor Substances 0.000 title claims abstract description 35
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 100
- 239000007789 gas Substances 0.000 claims abstract description 73
- 239000000463 material Substances 0.000 claims abstract description 52
- 229910052786 argon Inorganic materials 0.000 claims abstract description 50
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims abstract description 41
- 238000000151 deposition Methods 0.000 claims abstract description 27
- 230000008021 deposition Effects 0.000 claims abstract description 16
- 229910052710 silicon Inorganic materials 0.000 claims description 41
- 239000010703 silicon Substances 0.000 claims description 41
- 238000005086 pumping Methods 0.000 claims description 29
- 239000000758 substrate Substances 0.000 claims description 27
- 238000009413 insulation Methods 0.000 claims description 11
- 238000004062 sedimentation Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 9
- 230000001105 regulatory effect Effects 0.000 claims description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 57
- 229910021389 graphene Inorganic materials 0.000 abstract description 51
- 238000000034 method Methods 0.000 abstract description 18
- 238000005229 chemical vapour deposition Methods 0.000 abstract description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 39
- 238000003860 storage Methods 0.000 description 9
- 229910002804 graphite Inorganic materials 0.000 description 8
- 239000010439 graphite Substances 0.000 description 8
- -1 graphite alkene Chemical class 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000010408 sweeping Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000001237 Raman spectrum Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 238000005019 vapor deposition process Methods 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007792 gaseous phase Substances 0.000 description 2
- 241000931526 Acer campestre Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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Abstract
A kind of preparation method of Graphene-platinum composite electrode material for super capacitor, the preparation method that the present invention relates to combination electrode material. The invention solves the problems that Graphene prepared by existing CVD method exists preparation temperature higher, the Graphene of centimetres can not be applied to the problem in ultracapacitor as electrode material. Method: base material is placed in plasma enhanced chemical vapor deposition vacuum equipment, pass into argon, and temperature be at 700 DEG C～900 DEG C be incubated, pass into carbon-source gas again to be deposited, after deposition terminates, stop passing into carbon-source gas, be finally cooled to less than 100 DEG C, namely obtain Graphene-platinum composite electrode material for super capacitor. The preparation method preparation temperature of a kind of Graphene of the present invention-platinum composite electrode material for super capacitor is low, and specific volume is high, reduces electron drag, can be applied to ultracapacitor as electrode material. The present invention is for the preparation method of a kind of Graphene-platinum composite electrode material for super capacitor.
Description
Technical field
The preparation method that the present invention relates to combination electrode material.
Background technology
Along with the arrival of information age, energy storage device has been had higher requirement by people. Ultracapacitor has the advantage that current widely used lithium battery is incomparable: power density is high, and charge-discharge velocity is fast, and cycle life reaches more than ten thousand times, operating temperature range width etc. Therefore, ultracapacitor is widely used in the industry such as automobile, consumption electronic products at present. How improving the energy density of ultracapacitor, the exploitation of high performance electrode material is one of key technology. At present, carbon nanomaterial, owing to having the many advantages such as good electrical and mechanical performance, corrosion resistance, chemistry and high-temperature stability, is one of desirable electrode material of ultracapacitor. Graphene is used to manufacture ultracapacitor, it is possible to well to solve the problems such as other material with carbon element specific surfaces are little, poorly conductive, specific capacity are little, all higher than the energy storage density of current all of ultracapacitor.
At present, the preparation method of Graphene has a lot, such as adhesive tape stripping method, SiC decomposition method, graphite oxide reducing process and chemical gaseous phase depositing process etc. Wherein, although the Graphene quality that adhesive tape stripping method obtains is high, but yield is extremely low, efficiency is low, randomness is big, only can be suitably used for laboratory research and uses. SiC epitaxial growth method efficiency is low, and controllability is poor, and Graphene that is relatively costly and that prepare is difficult to shift. Chemical stripping method, owing to there is Strong oxdiative process, causes that the Graphene defect prepared is extremely many, second-rate and smaller (micron dimension). Chemical gaseous phase depositing process has the advantage such as easy operation, high, the size big (centimetres) of Graphene quality simple, that prepare and gets most of the attention, and is usually used in preparing big size graphene transistor and transparent conductive film etc.
But, prepare Graphene currently with CVD method, its preparation temperature is higher, and at about 1000 DEG C, the Graphene of centimetres can not be applied in ultracapacitor as electrode material, significantly limit the grapheme material practical application at microelectronic component. For this reason, it is necessary to further investigate in this regard, breaking through Graphene application on electrode material for super capacitor and industrialized production of the direction is significant.
In sum, it is higher to there is preparation temperature in Graphene prepared by existing CVD method, at about 1000 DEG C, and the Graphene existed in the graphene-based ultracapacitor prepared of physics and chemical method is of poor quality, fault of construction is many and lower than electric capacity (less than 50 μ F/cm2), therefore the Graphene of centimetres can not be applied to the problem in ultracapacitor as electrode material.
Summary of the invention
The invention solves the problems that Graphene prepared by existing CVD method exists preparation temperature higher, the Graphene of centimetres can not be applied to the problem in ultracapacitor as electrode material, and the preparation method that a kind of Graphene-platinum composite electrode material for super capacitor is provided.
The preparation method of a kind of Graphene-platinum composite electrode material for super capacitor, specifically carries out according to following steps:
One, base material is placed in plasma enhanced chemical vapor deposition vacuum equipment, being evacuated to pressure is below 5Pa, argon is passed into for 10sccm～50sccm with gas flow, regulate vacuum pumping rate to be controlled by pressure in plasma enhanced chemical vapor deposition vacuum equipment as 100Pa～300Pa, and pressure be under 100Pa～300Pa and argon gas atmosphere in 30min by temperature most 700 DEG C～900 DEG C, and temperature be at 700 DEG C～900 DEG C insulation 10min～60min;
Two, pass into carbon-source gas, the gas flow ratio regulating carbon-source gas and argon is (5～35): 80, and regulate vacuum pumping rate pressure in plasma enhanced chemical vapor deposition vacuum equipment is controlled as 200Pa～700Pa, then it is 13.56MHz in depositing system radio-frequency power supply frequency, radio-frequency power is 150W～250W, pressure is 200Pa～700Pa and temperature is be deposited under 700 DEG C～900 DEG C conditions, sedimentation time is 40min～80min, after deposition terminates, close radio-frequency power supply and heating power supply, stop passing into carbon-source gas, continue to pass into argon with gas flow for 20sccm～60sccm, and regulate vacuum pumping rate pressure in plasma enhanced chemical vapor deposition vacuum equipment is controlled as 50Pa～200Pa, it is be 700 DEG C～900 DEG C from temperature under 50Pa～200Pa and argon gas atmosphere to be cooled to less than 100 DEG C at pressure, namely Graphene-platinum composite electrode material for super capacitor is obtained.
The invention has the beneficial effects as follows: 1, the present invention utilizes plasma enhanced chemical vapor deposition method, backing material deposits few layer graphene, substrate platinum film not only has the electric conductivity of excellence, collector body can be directly used as use, and the unique three-dimensional structure formed in chemical vapor deposition processes effectively increases specific surface area.
2, invention introduces the potentiation of plasma, not only avoid and utilize high temperature to carry out pyrolysis carbon-source gas, and drastically increase the decomposition efficiency of carbon-source gas. The unique three-dimensional structure that base material pre-anneal treatment before deposition is formed effectively increases specific surface area. At substrate surface, not only will not there is stacking phenomenon in the direct vertical-growth of Graphene prepared by plasma vapor deposition processes, and fine with surface combination.The Graphene vertically grown participates in the edge plane of electric charge storage and can directly contact, and reduces the reallocation of electric charge storage, buries in oblivion probability thus increasing storage capacity with reducing electric charge; Open structure makes many effect of holes of material be greatly lowered, and reduces ion drag force; Graphene not only itself conducts electricity very well, and can grow at the material surface that electric conductivity is excellent, reduces electron drag, and specific volume is up to 600 μ F/cm2Above.
3, the method for the present invention is simple, preparation temperature low (700 DEG C～900 DEG C), efficiently, low cost, it is easy to industrialized production, the Graphene quality prepared is good, has a good application prospect in fields such as micro-nano electronic device, electrode of solar battery, optical-electrical converter, transparent conductive films.
The present invention is for the preparation method of a kind of Graphene-platinum composite electrode material for super capacitor.
Accompanying drawing explanation
Fig. 1 be in embodiment one platinum/silicon chip before non-deposited graphite alkene and deposition after photo; A is platinum/silicon chip photo before non-deposited graphite alkene; B is photo after platinum/silicon chip deposited graphite alkene;
Fig. 2 is the scanning electron microscopic picture of platinum in embodiment one/silicon chip vertical-growth Graphene;
Fig. 3 is the Raman spectrum of platinum in embodiment one/silicon chip vertical-growth Graphene;
Fig. 4 is the transmission electron microscope picture of platinum in embodiment one/silicon chip vertical-growth Graphene;
Fig. 5 is that in embodiment one, the platinum/silicon chip of vertical-growth Graphene, directly as the Electrochemical results of electrode material, sweeps the cyclic voltammogram under speed for difference in figure; 1 for sweeping speed 2mV/s; 2 for sweeping speed 5mV/s; 3 for sweeping speed 10mV/s; 4 for sweeping speed 20mV/s; 5 for sweeping speed 50mV/s.
Detailed description of the invention
Technical solution of the present invention is not limited to the detailed description of the invention of act set forth below, also includes the combination in any between each detailed description of the invention.
Detailed description of the invention one: the preparation method of a kind of Graphene-platinum composite electrode material for super capacitor described in present embodiment, specifically carries out according to following steps:
One, base material is placed in plasma enhanced chemical vapor deposition vacuum equipment, being evacuated to pressure is below 5Pa, argon is passed into for 10sccm～50sccm with gas flow, regulate vacuum pumping rate to be controlled by pressure in plasma enhanced chemical vapor deposition vacuum equipment as 100Pa～300Pa, and pressure be under 100Pa～300Pa and argon gas atmosphere in 30min by temperature most 700 DEG C～900 DEG C, and temperature be at 700 DEG C～900 DEG C insulation 10min～60min;
Two, pass into carbon-source gas, the gas flow ratio regulating carbon-source gas and argon is (5～35): 80, and regulate vacuum pumping rate pressure in plasma enhanced chemical vapor deposition vacuum equipment is controlled as 200Pa～700Pa, then it is 13.56MHz in depositing system radio-frequency power supply frequency, radio-frequency power is 150W～250W, pressure is 200Pa～700Pa and temperature is be deposited under 700 DEG C～900 DEG C conditions, sedimentation time is 40min～80min, after deposition terminates, close radio-frequency power supply and heating power supply, stop passing into carbon-source gas, continue to pass into argon with gas flow for 20sccm～60sccm, and regulate vacuum pumping rate pressure in plasma enhanced chemical vapor deposition vacuum equipment is controlled as 50Pa～200Pa, it is be 700 DEG C～900 DEG C from temperature under 50Pa～200Pa and argon gas atmosphere to be cooled to less than 100 DEG C at pressure, namely Graphene-platinum composite electrode material for super capacitor is obtained.
Present embodiment utilizes plasma enhanced chemical vapor deposition method, by action of plasma can efficient-decomposition carbon-source gas (such as CH4Deng) formed there is highly active carbon-based group in a large number, these high-activity carbon groups pass through chemical reaction, finally deposit the orthotropic few layer graphene of petal-shaped in substrate.Owing to introducing action of plasma, not only avoid and utilize high temperature to carry out pyrolysis carbon-source gas, and drastically increase the decomposition efficiency of carbon-source gas. Selection can be directly used as the orthotropic few layer graphene of platinum/deposited on silicon substrates that collector body uses, and it not only has the electric conductivity of excellence, and the unique three-dimensional structure that pre-anneal treatment is formed before deposition effectively increases specific surface area. At substrate surface, not only will not there is stacking phenomenon in the direct vertical-growth of Graphene prepared by plasma vapor deposition processes, and fine with surface combination. The Graphene vertically grown participates in the edge plane of electric charge storage and can directly contact, and reduces the reallocation of electric charge storage, buries in oblivion probability thus increasing storage capacity with reducing electric charge; Open structure makes many effect of holes of material be greatly lowered, and reduces ion drag force; Graphene not only itself conducts electricity very well, and can grow at the material surface that electric conductivity is excellent, reduces electron drag. Present embodiment is simple, and efficiently, low cost, it is simple to industrialized production, the Graphene quality prepared is high, has a good application prospect in fields such as micro-nano electronic device, electrode of solar battery, optical-electrical converter, transparent conductive films.
Present embodiment provides the benefit that: 1, present embodiment utilizes plasma enhanced chemical vapor deposition method, backing material deposits few layer graphene, substrate platinum film not only has the electric conductivity of excellence, collector body can be directly used as use, and the unique three-dimensional structure formed in chemical vapor deposition processes effectively increases specific surface area.
2, present embodiment introduces the potentiation of plasma, not only avoid and utilizes high temperature to carry out pyrolysis carbon-source gas, and drastically increases the decomposition efficiency of carbon-source gas. The unique three-dimensional structure that base material pre-anneal treatment before deposition is formed effectively increases specific surface area. At substrate surface, not only will not there is stacking phenomenon in the direct vertical-growth of Graphene prepared by plasma vapor deposition processes, and fine with surface combination. The Graphene vertically grown participates in the edge plane of electric charge storage and can directly contact, and reduces the reallocation of electric charge storage, buries in oblivion probability thus increasing storage capacity with reducing electric charge; Open structure makes many effect of holes of material be greatly lowered, and reduces ion drag force; Graphene not only itself conducts electricity very well, and can grow at the material surface that electric conductivity is excellent, reduces electron drag, and specific volume is more than 381.67 μ F/cm2。
3, the method for present embodiment is simple, preparation temperature low (700 DEG C～900 DEG C), efficiently, low cost, it is easy to industrialized production, the Graphene quality prepared is good, has a good application prospect in fields such as micro-nano electronic device, electrode of solar battery, optical-electrical converter, transparent conductive films.
Detailed description of the invention two: present embodiment and detailed description of the invention one the difference is that: the base material described in step one is platinum/silicon chip substrate material, and in wherein said platinum/silicon chip substrate material, platinum layer thickness is 100nm～500nm. Other is identical with detailed description of the invention one.
Platinum described in this detailed description of the invention/silicon chip substrate material uses at the same time as the collector body of ultracapacitor.
Detailed description of the invention three: one of present embodiment and detailed description of the invention one or two the difference is that: the base material described in step one is platinum/silicon chip substrate material, and in wherein said platinum/silicon chip substrate material, platinum layer thickness is 200nm.Other is identical with detailed description of the invention one or two.
Platinum described in this detailed description of the invention/silicon chip substrate material uses at the same time as the collector body of ultracapacitor.
Detailed description of the invention four: one of present embodiment and detailed description of the invention one to three the difference is that: the carbon-source gas described in step one is methane. Other is identical with detailed description of the invention one to three.
Detailed description of the invention five: one of present embodiment and detailed description of the invention one to four the difference is that: in step one and in temperature be insulation 30min at 700 DEG C～900 DEG C. Other is identical with detailed description of the invention one to four.
Detailed description of the invention six: one of present embodiment and detailed description of the invention one to five the difference is that: in step one then in 30min by temperature most 850 DEG C. Other is identical with detailed description of the invention one to five.
Detailed description of the invention seven: one of present embodiment and detailed description of the invention one to six the difference is that: the gas flow ratio regulating carbon-source gas and argon in step 2 is 20:80. Other is identical with detailed description of the invention one to six.
Detailed description of the invention eight: one of present embodiment and detailed description of the invention one to seven the difference is that: step 2 passes into carbon-source gas, the gas flow ratio regulating carbon-source gas and argon be (5～35): 80, and regulates vacuum pumping rate and control pressure in plasma enhanced chemical vapor deposition vacuum equipment to be 300Pa. Other is identical with detailed description of the invention one to seven.
Detailed description of the invention nine: one of present embodiment and detailed description of the invention one to eight the difference is that: in step 2, radio-frequency power is 200W. Other is identical with detailed description of the invention one to eight.
Detailed description of the invention ten: one of present embodiment and detailed description of the invention one to nine the difference is that: in step 2, sedimentation time is 60min. Other is identical with detailed description of the invention one to nine.
Adopt following example checking beneficial effects of the present invention:
Embodiment one:
The preparation method of a kind of Graphene-platinum composite electrode material for super capacitor described in the present embodiment, specifically carries out according to following steps:
One, base material is placed in plasma enhanced chemical vapor deposition vacuum equipment, being evacuated to pressure is below 5Pa, argon is passed into for 20sccm with gas flow, regulate vacuum pumping rate to be controlled by pressure in plasma enhanced chemical vapor deposition vacuum equipment as 200Pa, and pressure be under 200Pa and argon gas atmosphere in 30min by temperature most 850 DEG C, and temperature be at 850 DEG C insulation 30min;
Described base material is platinum/silicon chip substrate material, and in platinum/silicon chip substrate material, platinum layer thickness is 200nm.
Two, CH is passed into4, regulate CH4The flow that flow is 20sccm and argon be 80sccm, and regulate vacuum pumping rate pressure in plasma enhanced chemical vapor deposition vacuum equipment is controlled as 300Pa, then it is 13.56MHz in depositing system radio-frequency power supply frequency, radio-frequency power is 200W, pressure is 300Pa and temperature is be deposited under 850 DEG C of conditions, sedimentation time is 60min, after deposition terminates, close radio-frequency power supply and heating power supply, stop passing into carbon-source gas, continue to pass into argon with gas flow for 40sccm, and regulate vacuum pumping rate pressure in plasma enhanced chemical vapor deposition vacuum equipment is controlled as 100Pa, it is be 850 DEG C from temperature under 100Pa and argon gas atmosphere to be cooled to less than 100 DEG C at pressure, namely Graphene-platinum composite electrode material for super capacitor is obtained.
In embodiment one, before non-deposited graphite alkene and after deposition, photo is as it is shown in figure 1, a is platinum/silicon chip photo before non-deposited graphite alkene to platinum/silicon chip, and b is photo after platinum/silicon chip deposition; Platinum/silicon chip after deposited graphite alkene darkens dimmed as shown in Figure 1, has illustrated that material with carbon element deposits on surface.
In embodiment one, the scanning electron microscopic picture of platinum/silicon chip vertical-growth Graphene is as shown in Figure 2; Having orthotropic Graphene to generate as shown in Figure 2, the size of monolithic graphite alkene is at about 100nm.
In embodiment one, the Raman spectrum of platinum/silicon chip vertical-growth Graphene is as it is shown on figure 3, optical maser wavelength is 532nm; The strong ratio in position and relative peak at D, G, 2D peak in Raman spectrum as shown in Figure 3, it is possible to illustrate that the Graphene number of plies obtained is few and quality good.
In embodiment one, the transmission electron microscope picture of platinum/silicon chip vertical-growth Graphene is as shown in Figure 4; The number of plies of Graphene is little as shown in Figure 4, and is vertical-growth.
Platinum/the silicon chip of the vertical-growth Graphene of embodiment one preparation, directly as the Electrochemical results of electrode material, sweeps the cyclic voltammogram under speed as shown in Figure 5 for difference in figure. As shown in Figure 5 when sweep speed is 50mV/s (in Fig. 5 5), 20mV/s (in Fig. 5 4), 10mV/s (in Fig. 5 3), 5mV/s (in Fig. 5 2) and 2mV/s (in Fig. 5 1) than electric capacity respectively 381.67 μ F/cm2、433.33μF/cm2、460μF/cm2、508.33μF/cm2With 633.33 μ F/cm2。
Embodiment two:
The preparation method of a kind of Graphene-platinum composite electrode material for super capacitor described in the present embodiment, specifically carries out according to following steps:
One, base material is placed in plasma enhanced chemical vapor deposition vacuum equipment, being evacuated to pressure is below 5Pa, argon is passed into for 20sccm with gas flow, regulate vacuum pumping rate to be controlled by pressure in plasma enhanced chemical vapor deposition vacuum equipment as 200Pa, and pressure be under 200Pa and argon gas atmosphere in 30min by temperature most 850 DEG C, and temperature be at 850 DEG C insulation 30min;
Described base material is platinum/silicon chip substrate material, and in platinum/silicon chip substrate material, platinum layer thickness is 200nm.
Two, CH is passed into4, regulate CH4The flow that flow is 10sccm and argon be 80sccm, and regulate vacuum pumping rate pressure in plasma enhanced chemical vapor deposition vacuum equipment is controlled as 300Pa, then it is 13.56MHz in depositing system radio-frequency power supply frequency, radio-frequency power is 200W, pressure is 300Pa and temperature is be deposited under 850 DEG C of conditions, sedimentation time is 60min, after deposition terminates, close radio-frequency power supply and heating power supply, stop passing into carbon-source gas, continue to pass into argon with gas flow for 40sccm, and regulate vacuum pumping rate pressure in plasma enhanced chemical vapor deposition vacuum equipment is controlled as 100Pa, it is be 850 DEG C from temperature under 100Pa and argon gas atmosphere to be cooled to less than 100 DEG C at pressure, namely Graphene-platinum composite electrode material for super capacitor is obtained.
Platinum/the silicon chip of vertical-growth Graphene of embodiment two preparation utilizes electrochemical workstation to test directly as electrode material, draw Electrochemical results when sweep speed is 50mV/s, 20mV/s, 10mV/s, 5mV/s and 2mV/s than electric capacity respectively 173.33 μ F/cm2、155μF/cm2、158.33μF/cm2、171.67μF/cm2With 238.75 μ F/cm2。
Embodiment three:
The preparation method of a kind of Graphene-platinum composite electrode material for super capacitor described in the present embodiment, specifically carries out according to following steps:
One, base material is placed in plasma enhanced chemical vapor deposition vacuum equipment, being evacuated to pressure is below 5Pa, argon is passed into for 20sccm with gas flow, regulate vacuum pumping rate to be controlled by pressure in plasma enhanced chemical vapor deposition vacuum equipment as 200Pa, and pressure be under 200Pa and argon gas atmosphere in 30min by temperature most 850 DEG C, and temperature be at 850 DEG C insulation 30min;
Described base material is platinum/silicon chip substrate material, and in platinum/silicon chip substrate material, platinum layer thickness is 200nm.
Two, CH is passed into4, regulate CH4The flow that flow is 30sccm and argon be 80sccm, and regulate vacuum pumping rate pressure in plasma enhanced chemical vapor deposition vacuum equipment is controlled as 300Pa, then it is 13.56MHz in depositing system radio-frequency power supply frequency, radio-frequency power is 200W, pressure is 300Pa and temperature is be deposited under 850 DEG C of conditions, sedimentation time is 60min, after deposition terminates, close radio-frequency power supply and heating power supply, stop passing into carbon-source gas, continue to pass into argon with gas flow for 40sccm, and regulate vacuum pumping rate pressure in plasma enhanced chemical vapor deposition vacuum equipment is controlled as 100Pa, it is be 850 DEG C from temperature under 100Pa and argon gas atmosphere to be cooled to less than 100 DEG C at pressure, namely Graphene-platinum composite electrode material for super capacitor is obtained.
In embodiment three, the platinum/silicon chip of vertical-growth Graphene of preparation utilizes electrochemical workstation to test directly as electrode material, draw Electrochemical results when sweep speed is 50mV/s, 20mV/s, 10mV/s, 5mV/s and 2mV/s than electric capacity respectively 330 μ F/cm2、370.83μF/cm2、391.67μF/cm2、425μF/cm2With 487.5 μ F/cm2。
Embodiment four:
The preparation method of a kind of Graphene-platinum composite electrode material for super capacitor described in the present embodiment, specifically carries out according to following steps:
One, base material is placed in plasma enhanced chemical vapor deposition vacuum equipment, being evacuated to pressure is below 5Pa, argon is passed into for 20sccm with gas flow, regulate vacuum pumping rate to be controlled by pressure in plasma enhanced chemical vapor deposition vacuum equipment as 200Pa, and pressure be under 200Pa and argon gas atmosphere in 30min by temperature most 850 DEG C, and temperature be at 850 DEG C insulation 30min;
Described base material is platinum/silicon chip substrate material, and in platinum/silicon chip substrate material, platinum layer thickness is 200nm.
Two, CH is passed into4, regulate CH4The flow that flow is 20sccm and argon be 80sccm, and regulate vacuum pumping rate pressure in plasma enhanced chemical vapor deposition vacuum equipment is controlled as 500Pa, then it is 13.56MHz in depositing system radio-frequency power supply frequency, radio-frequency power is 200W, pressure is 500Pa and temperature is be deposited under 850 DEG C of conditions, sedimentation time is 60min, after deposition terminates, close radio-frequency power supply and heating power supply, stop passing into carbon-source gas, continue to pass into argon with gas flow for 40sccm, and regulate vacuum pumping rate pressure in plasma enhanced chemical vapor deposition vacuum equipment is controlled as 100Pa, it is be 850 DEG C from temperature under 100Pa and argon gas atmosphere to be cooled to less than 100 DEG C at pressure, namely Graphene-platinum composite electrode material for super capacitor is obtained.
In embodiment four, the platinum/silicon chip of vertical-growth Graphene of preparation utilizes electrochemical workstation to test directly as electrode material, draw Electrochemical results when sweep speed is 50mV/s, 20mV/s, 10mV/s, 5mV/s and 2mV/s than electric capacity respectively 133.17 μ F/cm2、147.08μF/cm2、171.66μF/cm2、225μF/cm2With 420.83 μ F/cm2。
Embodiment five:
The preparation method of a kind of Graphene-platinum composite electrode material for super capacitor described in the present embodiment, specifically carries out according to following steps:
One, base material is placed in plasma enhanced chemical vapor deposition vacuum equipment, being evacuated to pressure is below 5Pa, argon is passed into for 20sccm with gas flow, regulate vacuum pumping rate to be controlled by pressure in plasma enhanced chemical vapor deposition vacuum equipment as 200Pa, and pressure be under 200Pa and argon gas atmosphere in 30min by temperature most 850 DEG C, and temperature be at 850 DEG C insulation 30min;
Described base material is platinum/silicon chip substrate material, and in platinum/silicon chip substrate material, platinum layer thickness is 200nm.
Two, CH is passed into4, regulate CH4The flow that flow is 20sccm and argon be 80sccm, and regulate vacuum pumping rate pressure in plasma enhanced chemical vapor deposition vacuum equipment is controlled as 700Pa, then it is 13.56MHz in depositing system radio-frequency power supply frequency, radio-frequency power is 200W, pressure is 700Pa and temperature is be deposited under 850 DEG C of conditions, sedimentation time is 60min, after deposition terminates, close radio-frequency power supply and heating power supply, stop passing into carbon-source gas, continue to pass into argon with gas flow for 40sccm, and regulate vacuum pumping rate pressure in plasma enhanced chemical vapor deposition vacuum equipment is controlled as 100Pa, it is be 850 DEG C from temperature under 100Pa and argon gas atmosphere to be cooled to less than 100 DEG C at pressure, namely Graphene-platinum composite electrode material for super capacitor is obtained.
In embodiment five, the platinum/silicon chip of vertical-growth Graphene of preparation utilizes electrochemical workstation to test directly as electrode material, draw Electrochemical results when sweep speed is 50mV/s, 20mV/s, 10mV/s, 5mV/s and 2mV/s than electric capacity respectively 91.33 μ F/cm2、102.08μF/cm2、125μF/cm2、203.33μF/cm2With 347.92 μ F/cm2。
Embodiment six:
The preparation method of a kind of Graphene-platinum composite electrode material for super capacitor described in the present embodiment, specifically carries out according to following steps:
One, base material is placed in plasma enhanced chemical vapor deposition vacuum equipment, being evacuated to pressure is below 5Pa, argon is passed into for 20sccm with gas flow, regulate vacuum pumping rate to be controlled by pressure in plasma enhanced chemical vapor deposition vacuum equipment as 200Pa, and pressure be under 200Pa and argon gas atmosphere in 30min by temperature most 850 DEG C, and temperature be at 850 DEG C insulation 30min;
Described base material is platinum/silicon chip substrate material, and in platinum/silicon chip substrate material, platinum layer thickness is 200nm.
Two, CH is passed into4, regulate CH4The flow that flow is 20sccm and argon be 80sccm, and regulate vacuum pumping rate pressure in plasma enhanced chemical vapor deposition vacuum equipment is controlled as 300Pa, then it is 13.56MHz in depositing system radio-frequency power supply frequency, radio-frequency power is 200W, pressure is 300Pa and temperature is be deposited under 850 DEG C of conditions, sedimentation time is 30min, after deposition terminates, close radio-frequency power supply and heating power supply, stop passing into carbon-source gas, continue to pass into argon with gas flow for 40sccm, and regulate vacuum pumping rate pressure in plasma enhanced chemical vapor deposition vacuum equipment is controlled as 100Pa, it is be 850 DEG C from temperature under 100Pa and argon gas atmosphere to be cooled to less than 100 DEG C at pressure, namely Graphene-platinum composite electrode material for super capacitor is obtained.
In embodiment six, the platinum/silicon chip of vertical-growth Graphene of preparation utilizes electrochemical workstation to test directly as electrode material, draw Electrochemical results when sweep speed is 50mV/s, 20mV/s, 10mV/s, 5mV/s and 2mV/s than electric capacity respectively 142.33 μ F/cm2、177.68μF/cm2、205μF/cm2、223.15μF/cm2With 297.12 μ F/cm2。
Claims (8)
1. the preparation method of Graphene-platinum composite electrode material for super capacitor, it is characterised in that the preparation method of a kind of Graphene-platinum composite electrode material for super capacitor carries out according to following steps:
One, base material is placed in plasma enhanced chemical vapor deposition vacuum equipment, being evacuated to pressure is below 5Pa, argon is passed into for 10sccm～50sccm with gas flow, regulate vacuum pumping rate to be controlled by pressure in plasma enhanced chemical vapor deposition vacuum equipment as 100Pa～300Pa, and pressure be under 100Pa～300Pa and argon gas atmosphere in 30min by temperature most 700 DEG C～900 DEG C, and temperature be at 700 DEG C～900 DEG C insulation 10min～60min;
Two, pass into carbon-source gas, the gas flow ratio regulating carbon-source gas and argon is (5～35): 80, and regulate vacuum pumping rate pressure in plasma enhanced chemical vapor deposition vacuum equipment is controlled as 200Pa～700Pa, then it is 13.56MHz in depositing system radio-frequency power supply frequency, radio-frequency power is 150W～250W, pressure is 200Pa～700Pa and temperature is be deposited under 700 DEG C～900 DEG C conditions, sedimentation time is 40min～80min, after deposition terminates, close radio-frequency power supply and heating power supply, stop passing into carbon-source gas, continue to pass into argon with gas flow for 20sccm～60sccm, and regulate vacuum pumping rate pressure in plasma enhanced chemical vapor deposition vacuum equipment is controlled as 50Pa～200Pa, it is be 700 DEG C～900 DEG C from temperature under 50Pa～200Pa and argon gas atmosphere to be cooled to less than 100 DEG C at pressure, namely Graphene-platinum composite electrode material for super capacitor is obtained,
Base material described in step one is platinum/silicon chip substrate material, and in wherein said platinum/silicon chip substrate material, platinum layer thickness is 100nm～500nm.
2. the preparation method of a kind of Graphene-platinum composite electrode material for super capacitor according to claim 1, it is characterised in that the carbon-source gas described in step one is methane.
3. the preparation method of a kind of Graphene-platinum composite electrode material for super capacitor according to claim 1, it is characterised in that in step one and temperature be at 700 DEG C～900 DEG C insulation 30min.
4. the preparation method of a kind of Graphene-platinum composite electrode material for super capacitor according to claim 1, it is characterised in that by temperature most 850 DEG C in 30min in step one.
5. the preparation method of a kind of Graphene-platinum composite electrode material for super capacitor according to claim 1, it is characterised in that the flow-rate ratio regulating carbon-source gas and argon in step 2 is 20:80.
6. the preparation method of a kind of Graphene-platinum composite electrode material for super capacitor according to claim 1, it is characterized in that step 2 passes into carbon-source gas, the flow-rate ratio regulating carbon-source gas and argon be (5～35): 80, adjustment vacuum pumping rate to keep pressure be 300Pa.
7. the preparation method of a kind of Graphene-platinum composite electrode material for super capacitor according to claim 1, it is characterised in that in step 2, radio-frequency power is 200W.
8. the preparation method of a kind of Graphene-platinum composite electrode material for super capacitor according to claim 1, it is characterised in that in step 2, sedimentation time is 60min.
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| CN104319117B (en) * | 2014-10-27 | 2017-03-01 | 哈尔滨工业大学 | A kind of preparation method of 3D bowl-shape mixing nanostructured Graphene electrode material for super capacitor |
| CN104269283B (en) * | 2014-10-27 | 2017-03-22 | 哈尔滨工业大学 | Preparation method of high-specific-capacitance graphene supercapacitor electrode material |
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