CN103646789A - Preparation method of graphene-platinum supercapacitor composite electrode materials - Google Patents
Preparation method of graphene-platinum supercapacitor composite electrode materials Download PDFInfo
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Abstract
The invention relates to preparation methods for composite electrode materials, particularly to a preparation method of graphene-platinum supercapacitor composite electrode materials. The preparation method of the graphene-platinum supercapacitor composite electrode materials aims at solving the problems that the preparation temperature is relatively high in graphene prepared through an existing CVD (chemical vapor deposition) method and graphene of centimeter magnitude cannot serve as electrode materials to be applied to a supercapacitor. The preparation method of the graphene-platinum supercapacitor composite electrode materials comprises placing substrate materials into a plasma enhanced chemical vapor deposition vacuum unit, introducing argon, performing heat preservation at a temperature of 700 DEG C to 900 DEG C; introducing carbon source gas for deposition, stopping introducing the carbon source gas after the deposition is finished, and finally performing cooling to a temperature below 100 DEG C to obtain the graphene-platinum supercapacitor composite electrode materials. According to the preparation method of the graphene-platinum supercapacitor composite electrode materials, the preparation temperature is low, the specific volume is high, the electronic resistance is reduced, and the prepared graphene-platinum supercapacitor composite electrode materials can serve as graphene-platinum supercapacitor composite electrode materials to be applied to the supercapacitor.
Description
Technical field
The present invention relates to the preparation method of combination electrode material.
Background technology
Along with the arrival of information age, people have had higher requirement to energy storage device.Ultracapacitor has the incomparable advantage of current widely used lithium battery: power density is high, and charge-discharge velocity is fast, and cycle life reaches more than ten thousand times, and operating temperature range is wide etc.Therefore, ultracapacitor is widely used in industries such as automobile, consumption electronic products at present.How to improve 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 electricity and mechanical performance, corrosion resistance, chemistry and high-temperature stability, is one of desirable electrode material of ultracapacitor.Use Graphene to manufacture ultracapacitor, the problem such as can well solve that other material with carbon element specific surfaces are little, poorly conductive, specific capacity are little is all higher than the energy storage density of at present all ultracapacitors.
At present, the preparation method of Graphene has a lot, as tape stripping method, SiC decomposition method, graphite oxide reducing process and chemical gaseous phase depositing process etc.Wherein, although the Graphene quality that tape stripping method obtains is high, output is extremely low, efficiency is low, randomness is large, only can be applicable to laboratory research and use.SiC epitaxial growth method efficiency is low, and controllability is poor, and cost Graphene higher and that prepare is difficult to shift.Owing to there is strong oxidizing process in chemical stripping method, causes the Graphene defect prepared extremely many, second-rate and size is less (micron dimension).Chemical gaseous phase depositing process has the advantages such as easy operation, Graphene quality simple, that prepare are high, size large (centimetre magnitude) and gets most of the attention, and is usually used in preparing big size graphene transistor and transparent conductive film etc.
Yet, utilize at present CVD method to prepare Graphene, its preparation temperature is higher, and 1000 ℃ of left and right, the Graphene of centimetre magnitude can not be applied in ultracapacitor as electrode material, has limited greatly the practical application of grapheme material at microelectronic component.For this reason, be necessary to further investigate in this regard, the breakthrough of this direction to Graphene the application on electrode material for super capacitor and suitability for industrialized production significant.
In sum, Graphene prepared by existing CVD method exists preparation temperature higher, and 1000 ℃ of left and right, and the Graphene existing in the graphene-based ultracapacitor prepared of physics and chemical method is of poor quality, fault of construction many and (be less than 50 μ F/cm than electric capacity is low
2), therefore the Graphene of centimetre magnitude can not be applied to the problem in ultracapacitor as electrode material.
Summary of the invention
The present invention will solve Graphene prepared by existing CVD method and exist preparation temperature higher, the Graphene of centimetre magnitude can not be applied to the problem in ultracapacitor as electrode material, and a kind of preparation method of Graphene-platinum composite electrode material for super capacitor is provided.
A preparation method for Graphene-platinum composite electrode material for super capacitor, specifically carries out according to following steps:
One, base material is placed in to plasma enhanced chemical vapor deposition vacuum plant, being evacuated to pressure is below 5Pa, the gas flow of take passes into argon gas as 10sccm～50sccm, regulate vacuum pumping rate that pressure in plasma enhanced chemical vapor deposition vacuum plant is controlled as 100Pa～300Pa, and be in 30min, temperature to be heated up to most 700 ℃～900 ℃ under 100Pa～300Pa and argon gas atmosphere at pressure, and be to be incubated 10min～60min at 700 ℃～900 ℃ in temperature;
Two, pass into carbon-source gas, regulating the gas flow ratio of carbon-source gas and argon gas is (5～35): 80, and regulate vacuum pumping rate that pressure in plasma enhanced chemical vapor deposition vacuum plant is controlled as 200Pa～700Pa, then in depositing system radio-frequency power supply frequency, be 13.56MHz, radio-frequency power is 150W～250W, pressure is that 200Pa～700Pa and temperature are to deposit under 700 ℃～900 ℃ conditions, sedimentation time is 40min～80min, after deposition finishes, close radio-frequency power supply and heating power supply, stop passing into carbon-source gas, continuation be take gas flow and is passed into argon gas as 20sccm～60sccm, and regulate vacuum pumping rate that pressure in plasma enhanced chemical vapor deposition vacuum plant is controlled as 50Pa～200Pa, at pressure, be under 50Pa～200Pa and argon gas atmosphere, from temperature, to be 700 ℃～900 ℃ to be cooled to below 100 ℃, obtain Graphene-platinum composite electrode material for super capacitor.
The invention has the beneficial effects as follows: 1, the present invention utilizes plasma enhanced chemical vapor deposition method, on backing material, deposit few layer graphene, substrate platinum film not only has excellent electric conductivity, can directly as collector body, use, and formed unique three-dimensional structure has increased specific area effectively in chemical vapor deposition processes.
2, the present invention has introduced the humidification of plasma, has not only avoided utilizing high temperature to carry out pyrolysis carbon-source gas, and has greatly improved the decomposition efficiency of carbon-source gas.Base material preannealing before deposition is processed the unique three-dimensional structure forming has increased specific area effectively.At substrate surface, not only can there is not stacking phenomenon in the direct vertical-growth of Graphene of preparing by plasma vapor deposition processes, and fine with surface conjunction.Vertically the edge plane of the Graphene of growth participation charge storage can directly contact, and reduces the reallocation of charge storage, thereby increase storage capacity and reduce electric charge, buries in oblivion probability; Open structure greatly reduces the porous effect of material, reduces ion drag force; Graphene not only itself conducts electricity very well, and can reduce electron drag in the material surface growth of electric conductivity excellence, and specific volume can reach 600 μ F/cm
2above.
3, method of the present invention is simple, preparation temperature low (700 ℃～900 ℃), efficiently, low-cost, be convenient to suitability for industrialized production, the Graphene quality preparing is good, in fields such as micro-nano electronic device, electrode of solar battery, optical-electrical converter, transparent conductive films, has a good application prospect.
The present invention is for a kind of preparation method of Graphene-platinum composite electrode material for super capacitor.
Accompanying drawing explanation
Fig. 1 be in embodiment mono-platinum/silicon chip before not depositing Graphene and deposition after photo; A is platinum/silicon chip photo before not depositing Graphene; B is photo after platinum/silicon chip deposition Graphene;
Fig. 2 is the ESEM picture of platinum/silicon chip vertical-growth Graphene in embodiment mono-;
Fig. 3 is the Raman spectrum of platinum/silicon chip vertical-growth Graphene in embodiment mono-;
Fig. 4 is the transmission electron microscope picture of platinum/silicon chip vertical-growth Graphene in embodiment mono-;
Fig. 5 be the platinum/silicon chip of vertical-growth Graphene in embodiment mono-directly as the Electrochemical results of electrode material, in figure, be the different cyclic voltammograms of sweeping under speed; 1 for sweeping fast 2mV/s; 2 for sweeping fast 5mV/s; 3 for sweeping fast 10mV/s; 4 for sweeping fast 20mV/s; 5 for sweeping fast 50mV/s.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the combination in any between each embodiment.
Embodiment 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 to plasma enhanced chemical vapor deposition vacuum plant, being evacuated to pressure is below 5Pa, the gas flow of take passes into argon gas as 10sccm～50sccm, regulate vacuum pumping rate that pressure in plasma enhanced chemical vapor deposition vacuum plant is controlled as 100Pa～300Pa, and be in 30min, temperature to be heated up to most 700 ℃～900 ℃ under 100Pa～300Pa and argon gas atmosphere at pressure, and be to be incubated 10min～60min at 700 ℃～900 ℃ in temperature;
Two, pass into carbon-source gas, regulating the gas flow ratio of carbon-source gas and argon gas is (5～35): 80, and regulate vacuum pumping rate that pressure in plasma enhanced chemical vapor deposition vacuum plant is controlled as 200Pa～700Pa, then in depositing system radio-frequency power supply frequency, be 13.56MHz, radio-frequency power is 150W～250W, pressure is that 200Pa～700Pa and temperature are to deposit under 700 ℃～900 ℃ conditions, sedimentation time is 40min～80min, after deposition finishes, close radio-frequency power supply and heating power supply, stop passing into carbon-source gas, continuation be take gas flow and is passed into argon gas as 20sccm～60sccm, and regulate vacuum pumping rate that pressure in plasma enhanced chemical vapor deposition vacuum plant is controlled as 50Pa～200Pa, at pressure, be under 50Pa～200Pa and argon gas atmosphere, from temperature, to be 700 ℃～900 ℃ to be cooled to below 100 ℃, obtain Graphene-platinum composite electrode material for super capacitor.
Present embodiment is utilized plasma enhanced chemical vapor deposition method, by action of plasma, can efficiently decompose carbon-source gas (as CH
4deng) form and to there is in a large number highly active carbon-based group, these high-activity carbon groups, by chemical reaction, finally deposit the orthotropic few layer graphene of petal-shaped in substrate.Owing to introducing action of plasma, not only avoided utilizing high temperature to carry out pyrolysis carbon-source gas, and greatly improved the decomposition efficiency of carbon-source gas.In platinum/silicon base that selection can directly be used as collector body, deposit orthotropic few layer graphene, it not only has excellent electric conductivity, and unique three-dimensional structure that preannealing processing forms before deposition has increased specific area effectively.At substrate surface, not only can there is not stacking phenomenon in the direct vertical-growth of Graphene of preparing by plasma vapor deposition processes, and fine with surface conjunction.Vertically the edge plane of the Graphene of growth participation charge storage can directly contact, and reduces the reallocation of charge storage, thereby increase storage capacity and reduce electric charge, buries in oblivion probability; Open structure greatly reduces the porous effect of material, reduces ion drag force; Graphene not only itself conducts electricity very well, and can, in the material surface growth of electric conductivity excellence, reduce electron drag.Present embodiment is simple, and efficient, low cost, is convenient to suitability for industrialized production, and the Graphene quality preparing is high, in fields such as micro-nano electronic device, electrode of solar battery, optical-electrical converter, transparent conductive films, has a good application prospect.
The beneficial effect of present embodiment is: 1, present embodiment is utilized plasma enhanced chemical vapor deposition method, on backing material, deposit few layer graphene, substrate platinum film not only has excellent electric conductivity, can directly as collector body, use, and formed unique three-dimensional structure has increased specific area effectively in chemical vapor deposition processes.
2, present embodiment has been introduced the humidification of plasma, has not only avoided utilizing high temperature to carry out pyrolysis carbon-source gas, and has greatly improved the decomposition efficiency of carbon-source gas.Base material preannealing before deposition is processed the unique three-dimensional structure forming has increased specific area effectively.At substrate surface, not only can there is not stacking phenomenon in the direct vertical-growth of Graphene of preparing by plasma vapor deposition processes, and fine with surface conjunction.Vertically the edge plane of the Graphene of growth participation charge storage can directly contact, and reduces the reallocation of charge storage, thereby increase storage capacity and reduce electric charge, buries in oblivion probability; Open structure greatly reduces the porous effect of material, reduces ion drag force; Graphene not only itself conducts electricity very well, and can reduce electron drag in the material surface growth of electric conductivity excellence, and specific volume is greater than 381.67 μ F/cm
2.
3, the method for present embodiment is simple, preparation temperature low (700 ℃～900 ℃), efficiently, low-cost, be convenient to suitability for industrialized production, the Graphene quality preparing is good, in fields such as micro-nano electronic device, electrode of solar battery, optical-electrical converter, transparent conductive films, has a good application prospect.
Embodiment two: present embodiment is different from embodiment one: the basis material described in step 1 is platinum/silicon chip substrate material, in wherein said platinum/silicon substrate material, platinum layer thickness is 100nm～500nm.Other is identical with embodiment one.
The collector body that platinum/silicon chip substrate material described in this embodiment can be used as ultracapacitor is simultaneously used.
Embodiment three: present embodiment is different from one of embodiment one or two: the basis material described in step 1 is platinum/silicon chip substrate material, in wherein said platinum/silicon substrate material, platinum layer thickness is 200nm.Other is identical with embodiment one or two.
The collector body that platinum/silicon chip substrate material described in this embodiment can be used as ultracapacitor is simultaneously used.
Embodiment four: present embodiment is different from one of embodiment one to three: the carbon-source gas described in step 1 is methane.Other is identical with embodiment one to three.
Embodiment five: present embodiment is different from one of embodiment one to four: in step 1 and be to be incubated 30min at 700 ℃～900 ℃ in temperature.Other is identical with embodiment one to four.
Embodiment six: present embodiment is different from one of embodiment one to five: then in 30min, temperature is heated up to most 850 ℃ in step 1.Other is identical with embodiment one to five.
Embodiment seven: present embodiment is different from one of embodiment one to six: the gas flow ratio that regulates carbon-source gas and argon gas in step 2 is 20:80.Other is identical with embodiment one to six.
Embodiment eight: present embodiment is different from one of embodiment one to seven: pass into carbon-source gas in step 2, regulating the gas flow ratio of carbon-source gas and argon gas is (5～35): 80, and regulate vacuum pumping rate that pressure in plasma enhanced chemical vapor deposition vacuum plant is controlled as 300Pa.Other is identical with embodiment one to seven.
Embodiment nine: present embodiment is different from one of embodiment one to eight: in step 2, radio-frequency power is 200W.Other is identical with embodiment one to eight.
Embodiment ten: present embodiment is different from one of embodiment one to nine: in step 2, sedimentation time is 60min.Other is identical with embodiment one to nine.
Adopt following examples to verify beneficial effect of the present invention:
Embodiment mono-:
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 to plasma enhanced chemical vapor deposition vacuum plant, being evacuated to pressure is below 5Pa, the gas flow of take passes into argon gas as 20sccm, regulate vacuum pumping rate that pressure in plasma enhanced chemical vapor deposition vacuum plant is controlled as 200Pa, and be in 30min, temperature to be heated up to most 850 ℃ under 200Pa and argon gas atmosphere at pressure, and be to be incubated 30min at 850 ℃ in temperature;
Described basis material is platinum/silicon chip substrate material, and in platinum/silicon substrate material, platinum layer thickness is 200nm.
Two, pass into CH
4, regulate CH
4flow be that the flow of 20sccm and argon gas is 80sccm, and regulate vacuum pumping rate that pressure in plasma enhanced chemical vapor deposition vacuum plant is controlled as 300Pa, then in depositing system radio-frequency power supply frequency, be 13.56MHz, radio-frequency power is 200W, pressure is that 300Pa and temperature are to deposit under 850 ℃ of conditions, sedimentation time is 60min, after deposition finishes, close radio-frequency power supply and heating power supply, stop passing into carbon-source gas, continuation be take gas flow and is passed into argon gas as 40sccm, and regulate vacuum pumping rate that pressure in plasma enhanced chemical vapor deposition vacuum plant is controlled as 100Pa, at pressure, be under 100Pa and argon gas atmosphere, from temperature, to be 850 ℃ to be cooled to below 100 ℃, obtain Graphene-platinum composite electrode material for super capacitor.
In embodiment mono-platinum/silicon chip before not depositing Graphene and after deposition photo as shown in Figure 1, a is platinum/silicon chip photo before not depositing Graphene, b is photo after platinum/silicon chip deposition; Deposit as shown in Figure 1 platinum/silicon chip after Graphene and darken dimmedly, illustrated that material with carbon element is at surface deposition.
In embodiment mono-, the ESEM picture of platinum/silicon chip vertical-growth Graphene as shown in Figure 2; Have as shown in Figure 2 orthotropic Graphene to generate, the size of monolithic Graphene is in 100nm left and right.
In embodiment mono-, as shown in Figure 3, optical maser wavelength is 532nm to the Raman spectrum of platinum/silicon chip vertical-growth Graphene; D in Raman spectrum as shown in Figure 3, G, the strong ratio in the position at 2D peak and relative peak, can illustrate that the Graphene number of plies of acquisition is few and quality good.
In embodiment mono-, the transmission electron microscope picture of platinum/silicon chip vertical-growth Graphene as shown in Figure 4; The number of plies of Graphene seldom, and is vertical-growth as shown in Figure 4.
Platinum/the silicon chip of the vertical-growth Graphene of embodiment mono-preparation is directly as the Electrochemical results of electrode material, in figure, for different, sweeps cyclic voltammogram under speed as shown in Figure 5.When being 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), sweep speed is respectively 381.67 μ F/cm than electric capacity as shown in Figure 5
2, 433.33 μ F/cm
2, 460 μ F/cm
2, 508.33 μ F/cm
2with 633.33 μ F/cm
2.
Embodiment bis-:
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 to plasma enhanced chemical vapor deposition vacuum plant, being evacuated to pressure is below 5Pa, the gas flow of take passes into argon gas as 20sccm, regulate vacuum pumping rate that pressure in plasma enhanced chemical vapor deposition vacuum plant is controlled as 200Pa, and be in 30min, temperature to be heated up to most 850 ℃ under 200Pa and argon gas atmosphere at pressure, and be to be incubated 30min at 850 ℃ in temperature;
Described basis material is platinum/silicon chip substrate material, and in platinum/silicon substrate material, platinum layer thickness is 200nm.
Two, pass into CH
4, regulate CH
4flow be that the flow of 10sccm and argon gas is 80sccm, and regulate vacuum pumping rate that pressure in plasma enhanced chemical vapor deposition vacuum plant is controlled as 300Pa, then in depositing system radio-frequency power supply frequency, be 13.56MHz, radio-frequency power is 200W, pressure is that 300Pa and temperature are to deposit under 850 ℃ of conditions, sedimentation time is 60min, after deposition finishes, close radio-frequency power supply and heating power supply, stop passing into carbon-source gas, continuation be take gas flow and is passed into argon gas as 40sccm, and regulate vacuum pumping rate that pressure in plasma enhanced chemical vapor deposition vacuum plant is controlled as 100Pa, at pressure, be under 100Pa and argon gas atmosphere, from temperature, to be 850 ℃ to be cooled to below 100 ℃, obtain Graphene-platinum composite electrode material for super capacitor.
Platinum/the silicon chip of the vertical-growth Graphene of embodiment bis-preparation directly utilizes electrochemical workstation test as electrode material, show that Electrochemical results is respectively 173.33 μ F/cm than electric capacity when sweep speed is 50mV/s, 20mV/s, 10mV/s, 5mV/s and 2mV/s
2, 155 μ F/cm
2, 158.33 μ F/cm
2, 171.67 μ F/cm
2with 238.75 μ F/cm
2.
Embodiment tri-:
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 to plasma enhanced chemical vapor deposition vacuum plant, being evacuated to pressure is below 5Pa, the gas flow of take passes into argon gas as 20sccm, regulate vacuum pumping rate that pressure in plasma enhanced chemical vapor deposition vacuum plant is controlled as 200Pa, and be in 30min, temperature to be heated up to most 850 ℃ under 200Pa and argon gas atmosphere at pressure, and be to be incubated 30min at 850 ℃ in temperature;
Described basis material is platinum/silicon chip substrate material, and in platinum/silicon substrate material, platinum layer thickness is 200nm.
Two, pass into CH
4, regulate CH
4flow be that the flow of 30sccm and argon gas is 80sccm, and regulate vacuum pumping rate that pressure in plasma enhanced chemical vapor deposition vacuum plant is controlled as 300Pa, then in depositing system radio-frequency power supply frequency, be 13.56MHz, radio-frequency power is 200W, pressure is that 300Pa and temperature are to deposit under 850 ℃ of conditions, sedimentation time is 60min, after deposition finishes, close radio-frequency power supply and heating power supply, stop passing into carbon-source gas, continuation be take gas flow and is passed into argon gas as 40sccm, and regulate vacuum pumping rate that pressure in plasma enhanced chemical vapor deposition vacuum plant is controlled as 100Pa, at pressure, be under 100Pa and argon gas atmosphere, from temperature, to be 850 ℃ to be cooled to below 100 ℃, obtain Graphene-platinum composite electrode material for super capacitor.
In embodiment tri-, the platinum/silicon chip of the vertical-growth Graphene of preparation directly utilizes electrochemical workstation test as electrode material, show that Electrochemical results is respectively 330 μ F/cm than electric capacity when sweep speed is 50mV/s, 20mV/s, 10mV/s, 5mV/s and 2mV/s
2, 370.83 μ F/cm
2, 391.67 μ F/cm
2, 425 μ F/cm
2with 487.5 μ F/cm
2.
Embodiment tetra-:
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 to plasma enhanced chemical vapor deposition vacuum plant, being evacuated to pressure is below 5Pa, the gas flow of take passes into argon gas as 20sccm, regulate vacuum pumping rate that pressure in plasma enhanced chemical vapor deposition vacuum plant is controlled as 200Pa, and be in 30min, temperature to be heated up to most 850 ℃ under 200Pa and argon gas atmosphere at pressure, and be to be incubated 30min at 850 ℃ in temperature;
Described basis material is platinum/silicon chip substrate material, and in platinum/silicon substrate material, platinum layer thickness is 200nm.
Two, pass into CH
4, regulate CH
4flow be that the flow of 20sccm and argon gas is 80sccm, and regulate vacuum pumping rate that pressure in plasma enhanced chemical vapor deposition vacuum plant is controlled as 500Pa, then in depositing system radio-frequency power supply frequency, be 13.56MHz, radio-frequency power is 200W, pressure is that 500Pa and temperature are to deposit under 850 ℃ of conditions, sedimentation time is 60min, after deposition finishes, close radio-frequency power supply and heating power supply, stop passing into carbon-source gas, continuation be take gas flow and is passed into argon gas as 40sccm, and regulate vacuum pumping rate that pressure in plasma enhanced chemical vapor deposition vacuum plant is controlled as 100Pa, at pressure, be under 100Pa and argon gas atmosphere, from temperature, to be 850 ℃ to be cooled to below 100 ℃, obtain Graphene-platinum composite electrode material for super capacitor.
In embodiment tetra-, the platinum/silicon chip of the vertical-growth Graphene of preparation directly utilizes electrochemical workstation test as electrode material, show that Electrochemical results is respectively 133.17 μ F/cm than electric capacity when sweep speed is 50mV/s, 20mV/s, 10mV/s, 5mV/s and 2mV/s
2, 147.08 μ F/cm
2, 171.66 μ F/cm
2, 225 μ F/cm
2with 420.83 μ F/cm
2.
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 to plasma enhanced chemical vapor deposition vacuum plant, being evacuated to pressure is below 5Pa, the gas flow of take passes into argon gas as 20sccm, regulate vacuum pumping rate that pressure in plasma enhanced chemical vapor deposition vacuum plant is controlled as 200Pa, and be in 30min, temperature to be heated up to most 850 ℃ under 200Pa and argon gas atmosphere at pressure, and be to be incubated 30min at 850 ℃ in temperature;
Described basis material is platinum/silicon chip substrate material, and in platinum/silicon substrate material, platinum layer thickness is 200nm.
Two, pass into CH
4, regulate CH
4flow be that the flow of 20sccm and argon gas is 80sccm, and regulate vacuum pumping rate that pressure in plasma enhanced chemical vapor deposition vacuum plant is controlled as 700Pa, then in depositing system radio-frequency power supply frequency, be 13.56MHz, radio-frequency power is 200W, pressure is that 700Pa and temperature are to deposit under 850 ℃ of conditions, sedimentation time is 60min, after deposition finishes, close radio-frequency power supply and heating power supply, stop passing into carbon-source gas, continuation be take gas flow and is passed into argon gas as 40sccm, and regulate vacuum pumping rate that pressure in plasma enhanced chemical vapor deposition vacuum plant is controlled as 100Pa, at pressure, be under 100Pa and argon gas atmosphere, from temperature, to be 850 ℃ to be cooled to below 100 ℃, obtain Graphene-platinum composite electrode material for super capacitor.
In embodiment five, the platinum/silicon chip of the vertical-growth Graphene of preparation directly utilizes electrochemical workstation test as electrode material, show that Electrochemical results is respectively 91.33 μ F/cm than electric capacity when sweep speed is 50mV/s, 20mV/s, 10mV/s, 5mV/s and 2mV/s
2, 102.08 μ F/cm
2, 125 μ F/cm
2, 203.33 μ F/cm
2with 347.92 μ F/cm
2.
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 to plasma enhanced chemical vapor deposition vacuum plant, being evacuated to pressure is below 5Pa, the gas flow of take passes into argon gas as 20sccm, regulate vacuum pumping rate that pressure in plasma enhanced chemical vapor deposition vacuum plant is controlled as 200Pa, and be in 30min, temperature to be heated up to most 850 ℃ under 200Pa and argon gas atmosphere at pressure, and be to be incubated 30min at 850 ℃ in temperature;
Described basis material is platinum/silicon chip substrate material, and in platinum/silicon substrate material, platinum layer thickness is 200nm.
Two, pass into CH
4, regulate CH
4flow be that the flow of 20sccm and argon gas is 80sccm, and regulate vacuum pumping rate that pressure in plasma enhanced chemical vapor deposition vacuum plant is controlled as 300Pa, then in depositing system radio-frequency power supply frequency, be 13.56MHz, radio-frequency power is 200W, pressure is that 300Pa and temperature are to deposit under 850 ℃ of conditions, sedimentation time is 30min, after deposition finishes, close radio-frequency power supply and heating power supply, stop passing into carbon-source gas, continuation be take gas flow and is passed into argon gas as 40sccm, and regulate vacuum pumping rate that pressure in plasma enhanced chemical vapor deposition vacuum plant is controlled as 100Pa, at pressure, be under 100Pa and argon gas atmosphere, from temperature, to be 850 ℃ to be cooled to below 100 ℃, obtain Graphene-platinum composite electrode material for super capacitor.
In embodiment six, the platinum/silicon chip of the vertical-growth Graphene of preparation directly utilizes electrochemical workstation test as electrode material, show that Electrochemical results is respectively 142.33 μ F/cm than electric capacity when sweep speed is 50mV/s, 20mV/s, 10mV/s, 5mV/s and 2mV/s
2, 177.68 μ F/cm
2, 205 μ F/cm
2, 223.15 μ F/cm
2with 297.12 μ F/cm
2.
Claims (10)
1. a preparation method for Graphene-platinum composite electrode material for super capacitor, is characterized in that a kind of preparation method of Graphene-platinum composite electrode material for super capacitor carries out according to following steps:
One, base material is placed in to plasma enhanced chemical vapor deposition vacuum plant, being evacuated to pressure is below 5Pa, the gas flow of take passes into argon gas as 10sccm～50sccm, regulate vacuum pumping rate that pressure in plasma enhanced chemical vapor deposition vacuum plant is controlled as 100Pa～300Pa, and be in 30min, temperature to be heated up to most 700 ℃～900 ℃ under 100Pa～300Pa and argon gas atmosphere at pressure, and be to be incubated 10min～60min at 700 ℃～900 ℃ in temperature;
Two, pass into carbon-source gas, regulating the gas flow ratio of carbon-source gas and argon gas is (5～35): 80, and regulate vacuum pumping rate that pressure in plasma enhanced chemical vapor deposition vacuum plant is controlled as 200Pa～700Pa, then in depositing system radio-frequency power supply frequency, be 13.56MHz, radio-frequency power is 150W～250W, pressure is that 200Pa～700Pa and temperature are to deposit under 700 ℃～900 ℃ conditions, sedimentation time is 40min～80min, after deposition finishes, close radio-frequency power supply and heating power supply, stop passing into carbon-source gas, continuation be take gas flow and is passed into argon gas as 20sccm～60sccm, and regulate vacuum pumping rate that pressure in plasma enhanced chemical vapor deposition vacuum plant is controlled as 50Pa～200Pa, at pressure, be under 50Pa～200Pa and argon gas atmosphere, from temperature, to be 700 ℃～900 ℃ to be cooled to below 100 ℃, obtain Graphene-platinum composite electrode material for super capacitor.
2. the preparation method of a kind of Graphene-platinum composite electrode material for super capacitor according to claim 1, it is characterized in that the basis material described in step 1 is platinum/silicon chip substrate material, in wherein said platinum/silicon substrate material, platinum layer thickness is 100nm～500nm.
3. the preparation method of a kind of Graphene-platinum composite electrode material for super capacitor according to claim 1, is characterized in that the basis material described in step 1 is platinum/silicon chip substrate material, and in wherein said platinum/silicon substrate material, platinum layer thickness is 200nm.
4. the preparation method of a kind of Graphene-platinum composite electrode material for super capacitor according to claim 1, is characterized in that the carbon-source gas described in step 1 is methane.
5. the preparation method of a kind of Graphene-platinum composite electrode material for super capacitor according to claim 1, is characterized in that in step 1 and in temperature being to be incubated 30min at 700 ℃～900 ℃.
6. the preparation method of a kind of Graphene-platinum composite electrode material for super capacitor according to claim 1, is characterized in that in 30min, temperature being heated up to most 850 ℃ in step 1.
7. the preparation method of a kind of Graphene-platinum composite electrode material for super capacitor according to claim 1, is characterized in that in step 2, regulating the flow-rate ratio of carbon-source gas and argon gas is 20:80.
8. the preparation method of a kind of Graphene-platinum composite electrode material for super capacitor according to claim 1, it is characterized in that passing in step 2 carbon-source gas, regulating the flow-rate ratio of carbon-source gas and argon gas is (5～35): 80, and regulating vacuum pumping rate and keeping pressure is 300Pa.
9. the preparation method of a kind of Graphene-platinum composite electrode material for super capacitor according to claim 1, is characterized in that in step 2, radio-frequency power is 200W.
10. the preparation method of a kind of Graphene-platinum composite electrode material for super capacitor according to claim 1, is characterized in that in step 2, sedimentation time is 60min.
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