CN104319117B - A kind of preparation method of 3D bowl-shape mixing nanostructured Graphene electrode material for super capacitor - Google Patents
A kind of preparation method of 3D bowl-shape mixing nanostructured Graphene electrode material for super capacitor Download PDFInfo
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Abstract
A kind of preparation method of 3D bowl-shape mixing nanostructured Graphene electrode material for super capacitor, the present invention relates to the preparation method of Graphene electrode material for super capacitor.The invention solves the problems that in existing graphene preparation method, the too high change that may cause graphene-structured property of temperature and the formation of Graphene fold, hinder the transmission of electric charge, make electric charge bury in oblivion probability to increase, also charge-conduction and the effective area of storage is led to substantially reduce, and the area of two dimensional surface substrate is certain, limit the Graphene quantity that can deposit, make the problem that the effective ratio area of electrode material cannot continue to improve.Method：Base material is placed in plasma enhanced chemical vapor deposition vacuum equipment, is passed through argon, adjust pressure and simultaneously heat up, then base material is made annealing treatment, then be passed through carbon-source gas and deposited, be finally cooled to room temperature.The present invention is used for a kind of preparation of 3D bowl-shape mixing nanostructured Graphene electrode material for super capacitor.
Description
Technical field
The present invention relates to the preparation method of Graphene electrode material for super capacitor.
Background technology
Ultracapacitor is a kind of new type of energy storage device, has the features such as high power, high efficiency, life-span length, environmental friendliness,
It develops and applies and have good prospect in multiple fields such as national defence, consumer electronics and auto industrys.Compared to traditional fuel
Battery and secondary cell, ultracapacitor has higher power density, therefore in the automotive industry, by it with fuel cell simultaneously
Connection is as the dynamical system of electric automobile.Simultaneously as the service life cycle of relatively low cost and overlength, ultracapacitor exists
It is widely used in consumption electronic product.Although the energy density of ultracapacitor is far above traditional electrochemical capacitor,
But it is less than fuel cell and secondary cell, this problem seriously constrains the application of ultracapacitor.Therefore, develop high-performance electric
Pole material, to improve its energy density, is one of emphasis of present research.In recent years, Graphene becomes and prepares super capacitor electrode
The active material of pole, this makes Graphene and its composite have much unique property mainly due to two dimension conjugation graphite-structure
Can, including excellent electric property, mechanical property and optical property etc., also give its huge specific surface area so as to improve
Super capacitor energy density aspect has potential value.
However, in conventional graphite alkene preparation method, temperature is too high may cause graphene-structured property change and
The formation of Graphene fold, the number of plies of most importantly uncontrollable Graphene, easily stack.The Graphene of a large amount of stackings is not
Only hinder the transmission of electric charge, make electric charge bury in oblivion probability and increase, also lead to charge-conduction and the effective area of storage to substantially reduce.
Meanwhile, the area of two dimensional surface substrate is certain, limits the Graphene quantity that can deposit, and makes the effective ratio table of electrode material
Area cannot continue to improve.The Graphene quantity of deposition to be improved is necessary for increasing the area of its substrate, is unfavorable for highly integrated
Spend the application in micro-nano electronic device.
Content of the invention
The invention solves the problems that in existing graphene preparation method, the too high change that may cause graphene-structured property of temperature
Change the formation with Graphene fold, hinder the transmission of electric charge, make electric charge bury in oblivion probability and increase, also lead to charge-conduction and storage
Effective area substantially reduce, and the area of two dimensional surface substrate is certain, limits the Graphene quantity that can deposit, makes electricity
The effective ratio area of pole material cannot continue the problem improving, and provides a kind of 3D bowl-shape mixing nanostructured Graphene super
The preparation method of capacitor electrode material.
A kind of preparation method of 3D bowl-shape mixing nanostructured Graphene electrode material for super capacitor, specifically according to
Lower step is carried out：
First, base material is placed in plasma enhanced chemical vapor deposition vacuum equipment, being evacuated to pressure is 5Pa
Hereinafter, with gas flow as 65sccm～95sccm is passed through argon, adjusts vacuum pumping rate by PECVD
In deposition vacuum device, pressure is controlled to 100Pa～300Pa, and in pressure under 100Pa～300Pa and argon gas atmosphere, to rise
Warm speed is that temperature is heated up most 700 DEG C～900 DEG C by 30 DEG C/min；
2nd, temperature be 700 DEG C～900 DEG C, pressure be under 100Pa～300Pa and argon gas atmosphere, base material to be carried out
Annealing, annealing time is 15min～60min；
3rd, it is passed through carbon-source gas, the gas flow adjusting carbon-source gas is 5sccm～35sccm, the gas flow of argon
For 65sccm～95sccm, and adjust vacuum pumping rate pressure in plasma enhanced chemical vapor deposition vacuum equipment is controlled
For 200Pa～1000Pa, then depositing system radio-frequency power supply frequency be 13.56MHz, radio-frequency power be 150W～250W, pressure
Strong is 200Pa～1000Pa and temperature is deposited under conditions of 700 DEG C～900 DEG C, and sedimentation time is 20min～60min；
Described carbon-source gas are 100sccm with the total gas couette of argon；
4th, after deposition terminates, close radio-frequency power supply and heating power supply, stop being passed through carbon-source gas, continue with gas flow
It is passed through argon for 65sccm～95sccm, and adjust vacuum pumping rate by plasma enhanced chemical vapor deposition vacuum equipment
Pressure is controlled to 100Pa～300Pa, cold for 700 DEG C～900 DEG C from temperature under pressure is for 100Pa～300Pa and argon gas atmosphere
But to room temperature, that is, obtain 3D bowl-shape mixing nanostructured Graphene electrode material for super capacitor.
The invention has the beneficial effects as follows：1st, the base material that the present invention selects is Pt/Ti/SiO2/ Si multilamellar mixed substrates
By annealing, material, by adding Ti between traditional Pt/Si substrate, can achieve that planar substrates are changed into three-dimensional bowl structure.
This is relatively low mainly due to the fusing point of Pt, in 700 DEG C～900 DEG C annealing processes, atom agglomeration can occur.Meanwhile,
Solid solubility in Ti for the Pt is relatively low, and Ti wettability of the surface poor it is impossible to dissolving each other or sprawling completely.Therefore when Pt layer is very thin
When (150nm～200nm), by optimizing annealing temperature and time, in annealing process, Pt layer can occur atom in Ti layer surface
Reunite and form bowl-shape three-dimensional porous structure.This bowl-shape three-dimensional porous structure base material is conducive to improving vertical-growth
The distribution density of Graphene, can improve the specific surface area of electrode material further.Meanwhile, Ti has good electric conductivity, has
It is beneficial to prepare high performance graphene-based ultracapacitor.
2nd, the present invention utilizes plasma enhanced chemical vapor deposition method, and on substrate, growth in situ goes out few layer and vertically gives birth to
Long Graphene, this orthotropic Graphene has the incomparable advantage of other porous carbon materials：The vertically stone of growth
Black alkene can provide 50 μ F/cm3～70 μ F/cm3Edge plane (basal plane be about 3 μ F/cm3)；The edge participating in electric charge storage is put down
The reallocation of electric charge storage with directly contact, can be reduced in face, thus increase storage capacity burying in oblivion probability with reducing electric charge；Open
Structure so that many effect of holes of material is greatly lowered, reduce ion drag force；Graphene not only conducts electricity very well in itself, and permissible
In the material surface growth that electric conductivity is excellent, reduce electron drag；The three dimensional structure that vertical-growth is formed increases effectively
Add the effective ratio area of grapheme material, overcome the shortcoming optimization of the Graphene electrodes material of conventional two-dimensional structure stacking
The approach of electric charge transmission, increased charge-conduction and the effective area of storage, and then lifts the electrochemistry of ultracapacitor
Can, and can be directly by the use of 3D bowl-shape mixing nanostructured Graphene as the electrode material of ultracapacitor.
3rd, the present invention one step completes the preparation of mixing nanostructured Graphene electrodes material bowl-shape to 3D, and method is simple, high
Effect, low cost, it is easy to industrialized production, the Graphene quality preparing is high, in micro-nano electronic device, solaode electricity
The fields such as pole, optical-electrical converter, transparent conductive film have a good application prospect.
The present invention is used for a kind of preparation method of 3D bowl-shape mixing nanostructured Graphene electrode material for super capacitor.
Brief description
Fig. 1 is the scanning electricity of the 3D bowl-shape mixing nanostructured Graphene electrode material for super capacitor of embodiment one preparation
Mirror picture；
Fig. 2 is the Raman light of the 3D bowl-shape mixing nanostructured Graphene electrode material for super capacitor of embodiment one preparation
Spectrum；1 is D peak, and 2 is G peak, and 3 is 2D peak；
Fig. 3 is the transmission electricity of the 3D bowl-shape mixing nanostructured Graphene electrode material for super capacitor of embodiment one preparation
Mirror picture；
Fig. 4 is the electrochemistry survey directly as electrode material for the 3D bowl-shape mixing nanostructured Graphene of embodiment one preparation
Test result, 1 is to sweep fast 50mV/s；2 is to sweep fast 20mV/s；3 is to sweep fast 10mV/s；4 is to sweep fast 5mV/s；5 is to sweep fast 2mV/s.
Specific embodiment
Technical solution of the present invention is not limited to the specific embodiment of act set forth below, also include each specific embodiment it
Between combination in any.
Specific embodiment one：A kind of 3D described in present embodiment bowl-shape mixing nanostructured Graphene ultracapacitor
The preparation method of electrode material, specifically follows the steps below：
First, base material is placed in plasma enhanced chemical vapor deposition vacuum equipment, being evacuated to pressure is 5Pa
Hereinafter, with gas flow as 65sccm～95sccm is passed through argon, adjusts vacuum pumping rate by PECVD
In deposition vacuum device, pressure is controlled to 100Pa～300Pa, and in pressure under 100Pa～300Pa and argon gas atmosphere, to rise
Warm speed is that temperature is heated up most 700 DEG C～900 DEG C by 30 DEG C/min；
2nd, temperature be 700 DEG C～900 DEG C, pressure be under 100Pa～300Pa and argon gas atmosphere, base material to be carried out
Annealing, annealing time is 15min～60min；
3rd, it is passed through carbon-source gas, the gas flow adjusting carbon-source gas is 5sccm～35sccm, the gas flow of argon
For 65sccm～95sccm, and adjust vacuum pumping rate pressure in plasma enhanced chemical vapor deposition vacuum equipment is controlled
For 200Pa～1000Pa, then depositing system radio-frequency power supply frequency be 13.56MHz, radio-frequency power be 150W～250W, pressure
Strong is 200Pa～1000Pa and temperature is deposited under conditions of 700 DEG C～900 DEG C, and sedimentation time is 20min～60min；
Described carbon-source gas are 100sccm with the total gas couette of argon；
4th, after deposition terminates, close radio-frequency power supply and heating power supply, stop being passed through carbon-source gas, continue with gas flow
It is passed through argon for 65sccm～95sccm, and adjust vacuum pumping rate by plasma enhanced chemical vapor deposition vacuum equipment
Pressure is controlled to 100Pa～300Pa, cold for 700 DEG C～900 DEG C from temperature under pressure is for 100Pa～300Pa and argon gas atmosphere
But to room temperature, that is, obtain 3D bowl-shape mixing nanostructured Graphene electrode material for super capacitor.
Present embodiment step 2 forms it into three-dimensional porous structure.
Present embodiment step 3 deposited graphite alkene in substrate, makes carbon-source gas, argon in the presence of radio-frequency power supply
Ionization, is decomposed into plasma, by chemical reaction, finally deposited graphite alkene in substrate.
The beneficial effect of present embodiment is：1st, the base material that present embodiment is selected is Pt/Ti/SiO2/ Si multilamellar
By annealing, mixed substrates material, by adding Ti between traditional Pt/Si substrate, can achieve that planar substrates are changed into three-dimensional bowl
Shape structure.This is relatively low mainly due to the fusing point of Pt, atom can be occurred to reunite existing in 700 DEG C～900 DEG C annealing processes
As.Meanwhile, solid solubility in Ti for the Pt is relatively low, and Ti wettability of the surface poor it is impossible to dissolving each other or sprawling completely.Therefore when
During Pt layer very thin (150nm～200nm), by optimizing annealing temperature and time, in annealing process, Pt layer can be in Ti layer surface
Atom is occurred to reunite and form bowl-shape three-dimensional porous structure.This bowl-shape three-dimensional porous structure base material is conducive to improving
The distribution density of vertical-growth Graphene, can improve the specific surface area of electrode material further.Meanwhile, Ti has good leading
Electrically, be conducive to preparing high performance graphene-based ultracapacitor.
2nd, present embodiment utilizes plasma enhanced chemical vapor deposition method, and on substrate, growth in situ goes out few layer and hangs down
The Graphene of straight growth, this orthotropic Graphene has the incomparable advantage of other porous carbon materials：Vertically grow
Graphene 50 μ F/cm can be provided3～70 μ F/cm3Edge plane (basal plane be about 3 μ F/cm3)；Participate in the side of electric charge storage
Edge plane with directly contact, can reduce the reallocation of electric charge storage, thus increase storage capacity burying in oblivion probability with reducing electric charge；Open
The structure of putting property makes many effect of holes of material be greatly lowered, and reduces ion drag force；Graphene not only conducts electricity very well in itself, and
Electron drag can be reduced in the excellent material surface growth of electric conductivity；The three dimensional structure that vertical-growth is formed is effective
Increased the effective ratio area of grapheme material, the shortcoming overcoming the Graphene electrodes material of conventional two-dimensional structure stacking
Optimize the approach of electric charge transmission, increased charge-conduction and the effective area of storage, and then lift the electrification of ultracapacitor
Learn performance, and can be directly by the use of 3D bowl-shape mixing nanostructured Graphene as the electrode material of ultracapacitor.
3rd, present embodiment one step completes the preparation of mixing nanostructured Graphene electrodes material bowl-shape to 3D, method letter
Single, efficiently, low cost, it is easy to industrialized production, the Graphene quality preparing is high, in micro-nano electronic device, solar energy
The fields such as battery electrode, optical-electrical converter, transparent conductive film have a good application prospect.
Specific embodiment two：Present embodiment from unlike specific embodiment one：Substrate material described in step one
Expect for Pt/Ti/SiO2/ Si multilamellar mixed substrates material.Other identical with specific embodiment one.
Base material described in this specific embodiment can use as the collector of ultracapacitor.
Specific embodiment three：Unlike one of present embodiment and specific embodiment one or two：Described Pt layer
Thickness is 150nm～200nm；Described Ti thickness degree is 20nm；Described SiO2Thickness degree is 300nm.Other with concrete reality
Apply mode one or two identical.
Specific embodiment four：Unlike one of present embodiment and specific embodiment one to three：Institute in step 3
The carbon-source gas stated are methane.Other identical with specific embodiment one to three.
Specific embodiment five：Unlike one of present embodiment and specific embodiment one to four：In step one
Pressure is under 100Pa～300Pa and argon gas atmosphere, temperature is heated up most 800 DEG C with heating rate for 30 DEG C/min.Other with
Specific embodiment one to four is identical.
Specific embodiment six：Unlike one of present embodiment and specific embodiment one to five：In step 2
Temperature is 700 DEG C～900 DEG C, pressure is under 100Pa～300Pa and argon gas atmosphere, base material to be made annealing treatment, annealing
Time is 60min.Other identical with specific embodiment one to five.
Specific embodiment seven：Unlike one of present embodiment and specific embodiment one to six：Adjust in step 3
The gas flow of section carbon-source gas is 10sccm, the gas flow of argon is 90sccm.Other and specific embodiment one to six
Identical.
Specific embodiment eight：Unlike one of present embodiment and specific embodiment one to seven：Adjust in step 3
Pressure in plasma enhanced chemical vapor deposition vacuum equipment is controlled to 600Pa by section vacuum pumping rate, then in deposition system
System radio-frequency power supply frequency is 13.56MHz, radio-frequency power is 200W, pressure is 600Pa and temperature is sunk under the conditions of 800 DEG C
Long-pending, sedimentation time is 60min.Other identical with specific embodiment one to seven.
Verify beneficial effects of the present invention using following examples：
Embodiment one：
A kind of preparation side of the bowl-shape mixing nanostructured Graphene electrode material for super capacitor of the 3D described in the present embodiment
Method, specifically follows the steps below：
First, base material is placed in plasma enhanced chemical vapor deposition vacuum equipment, being evacuated to pressure is 5Pa
Hereinafter, argon is passed through for 90sccm with gas flow, adjusts vacuum pumping rate by plasma enhanced chemical vapor deposition vacuum
In device, pressure is controlled to 200Pa, and in pressure under 200Pa and argon gas atmosphere, with heating rate for 30 DEG C/min by temperature
Heat up most 800 DEG C；
2nd, temperature be 800 DEG C, pressure be under 200Pa and argon gas atmosphere, base material to be made annealing treatment, during annealing
Between be 60min；
3rd, it is passed through carbon-source gas, the gas flow adjusting carbon-source gas is 10sccm, the gas flow of argon is
90sccm, and adjust vacuum pumping rate and pressure in plasma enhanced chemical vapor deposition vacuum equipment is controlled to 600Pa, so
Afterwards depositing system radio-frequency power supply frequency be 13.56MHz, radio-frequency power be 200W, pressure be 600Pa and temperature be 800 DEG C
Under the conditions of deposited, sedimentation time be 60min；
Described carbon-source gas are 100sccm with the total gas couette of argon；
4th, after deposition terminates, close radio-frequency power supply and heating power supply, stop being passed through carbon-source gas, continue with gas flow
It is passed through argon for 90sccm, and adjusts vacuum pumping rate and pressure in plasma enhanced chemical vapor deposition vacuum equipment is controlled
For 200Pa, under pressure is for 200Pa and argon gas atmosphere, it is cooled to room temperature from temperature for 800 DEG C, that is, obtain 3D bowl-shape mixing nanometer
Structure graphite alkene electrode material for super capacitor.
Base material described in step one is Pt/Ti/SiO2/ Si multilamellar mixed substrates material；
Described Pt thickness degree is 150nm；Described Ti thickness degree is 20nm；Described SiO2Thickness degree is 300nm；
Carbon-source gas described in step 3 are methane.
Fig. 1 is the scanning electricity of the 3D bowl-shape mixing nanostructured Graphene electrode material for super capacitor of embodiment one preparation
Mirror picture；Can be seen that from scanning electron microscopic picture, substrate surface has the bowl-shape hole of uniformly dense distribution in a large number, diameter is about
800nm, forms cellular loose and porous structure.The graphene uniform vertical-growth of sheet is in bowl-shape hole surface, common structure
Become three dimensional structure.
Fig. 2 is the Raman light of the 3D bowl-shape mixing nanostructured Graphene electrode material for super capacitor of embodiment one preparation
Spectrum, optical maser wavelength is 532nm；By D in Raman spectrum, the position at G, 2D peak and relative peak intensity ratio are it may be said that bright obtain
The carbon nanomaterial quality obtaining is good, and defect is less, and is few layer graphene.
Fig. 3 is the transmission electricity of the 3D bowl-shape mixing nanostructured Graphene electrode material for super capacitor of embodiment one preparation
Mirror picture；As seen from the figure, in 100nm, Graphene is in bleach shape to graphene film size, and the number of plies between 3～5 layers, belongs to
In few layer graphene, illustrate that the Graphene quality that PECVD prepares is higher, specific surface area big it is adaptable to ultracapacitor
Electrode material.
Fig. 4 is the electrochemistry survey directly as electrode material for the 3D bowl-shape mixing nanostructured Graphene of embodiment one preparation
Test result, 1 is to sweep fast 50mV/s；2 is to sweep fast 20mV/s；3 is to sweep fast 10mV/s；4 is to sweep fast 5mV/s；5 is to sweep fast 2mV/s；Profit
It is respectively than electric capacity when sweep speed is 50mV/s, 20mV/s, 10mV/s, 5mV/s and 2mV/s with electrochemical workstation test
703μF/cm2、755μF/cm2、810μF/cm2、882μF/cm2With 1052 μ F/cm2.Use two dimensional surface material compared to tradition
The Graphene electrode of super capacitor of substrate preparation, it improves about 70% (using the preparation of two dimensional surface material substrate than electric capacity
Graphene electrodes material ratio electric capacity a maximum of about of 600 μ F/cm2).
As known from the above, embodiment is passed through to carry out heat treatment from multilamellar hybrid radix and to it, so that planar substrates is formed
Three-dimensional porous structure, improves the distribution density of Graphene, and then increases the specific surface area of material.Meanwhile, using plasma
The technology of body chemical vapor phase growing, the few layer graphene of original position vertical-growth in the substrate of three-dimensional porous structure, due to plasma
The introducing of body, not only makes that reaction is temperature required to decrease, and is simultaneously also beneficial to Graphene original position vertical-growth in substrate, no
Easily there is stacking phenomenon.The 3D bowl-shape mixing nanostructured Graphene electrodes material being obtained using the method, with having of electrolyte
Effect contact area is big, and ion drag force is little, is conducive to transmission and the storage of electric charge, and electric charge is buried in oblivion probability and reduced, and makes the energy storage of material
Ability improves.
Embodiment two：
A kind of preparation side of the bowl-shape mixing nanostructured Graphene electrode material for super capacitor of the 3D described in the present embodiment
Method, specifically follows the steps below：
First, base material is placed in plasma enhanced chemical vapor deposition vacuum equipment, being evacuated to pressure is 5Pa
Hereinafter, argon is passed through for 90sccm with gas flow, adjusts vacuum pumping rate by plasma enhanced chemical vapor deposition vacuum
In device, pressure is controlled to 200Pa, and in pressure under 200Pa and argon gas atmosphere, with heating rate for 30 DEG C/min by temperature
Heat up most 800 DEG C；
Described base material is Pt/Ti/SiO2/ Si multilamellar mixed substrates material；
Described Pt thickness degree is 150nm；Described Ti thickness degree is 20nm；Described SiO2Thickness degree is 300nm；
2nd, temperature be 800 DEG C, pressure be under 200Pa and argon gas atmosphere, base material to be made annealing treatment, during annealing
Between be 15min；
3rd, it is passed through carbon-source gas, the gas flow adjusting carbon-source gas is 10sccm, the gas flow of argon is
90sccm, and adjust vacuum pumping rate and pressure in plasma enhanced chemical vapor deposition vacuum equipment is controlled to 600Pa, so
Afterwards depositing system radio-frequency power supply frequency be 13.56MHz, radio-frequency power be 200W, pressure be 600Pa and temperature be 800 DEG C
Under the conditions of deposited, sedimentation time be 60min；
Described carbon-source gas are methane is 100sccm with the total gas couette of argon；
4th, after deposition terminates, close radio-frequency power supply and heating power supply, stop being passed through carbon-source gas, continue with gas flow
It is passed through argon for 90sccm, and adjusts vacuum pumping rate and pressure in plasma enhanced chemical vapor deposition vacuum equipment is controlled
For 200Pa, under pressure is for 200Pa and argon gas atmosphere, it is cooled to room temperature from temperature for 800 DEG C, that is, obtain 3D bowl-shape mixing nanometer
Structure graphite alkene electrode material for super capacitor.
The 3D bowl-shape mixing nanostructured Graphene of embodiment two preparation is tied directly as the electro-chemical test of electrode material
Really, compare electric capacity when sweep speed is for 50mV/s, 20mV/s, 10mV/s, 5mV/s and 2mV/s using electrochemical workstation test
It is respectively 337 μ F/cm2、425μF/cm2、561μF/cm2、642μF/cm2With 779 μ F/cm2.
Embodiment three：
A kind of preparation side of the bowl-shape mixing nanostructured Graphene electrode material for super capacitor of the 3D described in the present embodiment
Method, specifically follows the steps below：
First, base material is placed in plasma enhanced chemical vapor deposition vacuum equipment, being evacuated to pressure is 5Pa
Hereinafter, argon is passed through for 90sccm with gas flow, adjusts vacuum pumping rate by plasma enhanced chemical vapor deposition vacuum
In device, pressure is controlled to 200Pa, and in pressure under 200Pa and argon gas atmosphere, with heating rate for 30 DEG C/min by temperature
Heat up most 800 DEG C；
Described base material is Pt/Ti/SiO2/ Si multilamellar mixed substrates material；
Described Pt thickness degree is 150nm；Described Ti thickness degree is 20nm；Described SiO2Thickness degree is 300nm；
2nd, temperature be 800 DEG C, pressure be under 200Pa and argon gas atmosphere, base material to be made annealing treatment, during annealing
Between be 30min；
3rd, it is passed through carbon-source gas, the gas flow adjusting carbon-source gas is 10sccm, the gas flow of argon is
90sccm, and adjust vacuum pumping rate and pressure in plasma enhanced chemical vapor deposition vacuum equipment is controlled to 600Pa, so
Afterwards depositing system radio-frequency power supply frequency be 13.56MHz, radio-frequency power be 200W, pressure be 600Pa and temperature be 800 DEG C
Under the conditions of deposited, sedimentation time be 60min；
Described carbon-source gas are methane is 100sccm with the total gas couette of argon；
4th, after deposition terminates, close radio-frequency power supply and heating power supply, stop being passed through carbon-source gas, continue with gas flow
It is passed through argon for 90sccm, and adjusts vacuum pumping rate and pressure in plasma enhanced chemical vapor deposition vacuum equipment is controlled
For 200Pa, under pressure is for 200Pa and argon gas atmosphere, it is cooled to room temperature from temperature for 800 DEG C, that is, obtain 3D bowl-shape mixing nanometer
Structure graphite alkene electrode material for super capacitor.
The 3D bowl-shape mixing nanostructured Graphene of embodiment three preparation is tied directly as the electro-chemical test of electrode material
Really, compare electric capacity when sweep speed is for 50mV/s, 20mV/s, 10mV/s, 5mV/s and 2mV/s using electrochemical workstation test
It is respectively 358 μ F/cm2、502μF/cm2、671μF/cm2、792μF/cm2With 913 μ F/cm2.
Example IV：
A kind of preparation side of the bowl-shape mixing nanostructured Graphene electrode material for super capacitor of the 3D described in the present embodiment
Method, specifically follows the steps below：
First, base material is placed in plasma enhanced chemical vapor deposition vacuum equipment, being evacuated to pressure is 5Pa
Hereinafter, argon is passed through for 90sccm with gas flow, adjusts vacuum pumping rate by plasma enhanced chemical vapor deposition vacuum
In device, pressure is controlled to 200Pa, and in pressure under 200Pa and argon gas atmosphere, with heating rate for 30 DEG C/min by temperature
Heat up most 800 DEG C；
Described base material is Pt/Ti/SiO2/ Si multilamellar mixed substrates material；
Described Pt thickness degree is 150nm；Described Ti thickness degree is 20nm；Described SiO2Thickness degree is 300nm；
2nd, temperature be 800 DEG C, pressure be under 200Pa and argon gas atmosphere, base material to be made annealing treatment, during annealing
Between be 60min；
3rd, it is passed through carbon-source gas, the gas flow adjusting carbon-source gas is 20sccm, the gas flow of argon is
80sccm, and adjust vacuum pumping rate and pressure in plasma enhanced chemical vapor deposition vacuum equipment is controlled to 600Pa, so
Afterwards depositing system radio-frequency power supply frequency be 13.56MHz, radio-frequency power be 200W, pressure be 600Pa and temperature be 800 DEG C
Under the conditions of deposited, sedimentation time be 60min；
Described carbon-source gas are methane is 100sccm with the total gas couette of argon；
4th, after deposition terminates, close radio-frequency power supply and heating power supply, stop being passed through carbon-source gas, continue with gas flow
It is passed through argon for 90sccm, and adjusts vacuum pumping rate and pressure in plasma enhanced chemical vapor deposition vacuum equipment is controlled
For 200Pa, under pressure is for 200Pa and argon gas atmosphere, it is cooled to room temperature from temperature for 800 DEG C, that is, obtain 3D bowl-shape mixing nanometer
Structure graphite alkene electrode material for super capacitor.
The 3D bowl-shape mixing nanostructured Graphene of example IV preparation is tied directly as the electro-chemical test of electrode material
Really, compare electric capacity when sweep speed is for 50mV/s, 20mV/s, 10mV/s, 5mV/s and 2mV/s using electrochemical workstation test
It is respectively 377 μ F/cm2、512μF/cm2、642μF/cm2、709μF/cm2With 788 μ F/cm2.
Embodiment five：
A kind of preparation side of the bowl-shape mixing nanostructured Graphene electrode material for super capacitor of the 3D described in the present embodiment
Method, specifically follows the steps below：
First, base material is placed in plasma enhanced chemical vapor deposition vacuum equipment, being evacuated to pressure is 5Pa
Hereinafter, argon is passed through for 90sccm with gas flow, adjusts vacuum pumping rate by plasma enhanced chemical vapor deposition vacuum
In device, pressure is controlled to 200Pa, and in pressure under 200Pa and argon gas atmosphere, with heating rate for 30 DEG C/min by temperature
Heat up most 800 DEG C；
Described base material is Pt/Ti/SiO2/ Si multilamellar mixed substrates material；
Described Pt thickness degree is 150nm；Described Ti thickness degree is 20nm；Described SiO2Thickness degree is 300nm；
2nd, temperature be 800 DEG C, pressure be under 200Pa and argon gas atmosphere, base material to be made annealing treatment, during annealing
Between be 60min；
3rd, it is passed through carbon-source gas, the gas flow adjusting carbon-source gas is 30sccm, the gas flow of argon is
70sccm, and adjust vacuum pumping rate and pressure in plasma enhanced chemical vapor deposition vacuum equipment is controlled to 600Pa, so
Afterwards depositing system radio-frequency power supply frequency be 13.56MHz, radio-frequency power be 200W, pressure be 600Pa and temperature be 800 DEG C
Under the conditions of deposited, sedimentation time be 60min；
Described carbon-source gas are methane is 100sccm with the total gas couette of argon；
4th, after deposition terminates, close radio-frequency power supply and heating power supply, stop being passed through carbon-source gas, continue with gas flow
It is passed through argon for 90sccm, and adjusts vacuum pumping rate and pressure in plasma enhanced chemical vapor deposition vacuum equipment is controlled
For 200Pa, under pressure is for 200Pa and argon gas atmosphere, it is cooled to room temperature from temperature for 800 DEG C, that is, obtain 3D bowl-shape mixing nanometer
Structure graphite alkene electrode material for super capacitor.
The 3D bowl-shape mixing nanostructured Graphene of embodiment five preparation is tied directly as the electro-chemical test of electrode material
Really, compare electric capacity when sweep speed is for 50mV/s, 20mV/s, 10mV/s, 5mV/s and 2mV/s using electrochemical workstation test
It is respectively 321 μ F/cm2、489μF/cm2、576μF/cm2、654μF/cm2With 703 μ F/cm2.
Claims (6)
1. a kind of preparation method of 3D bowl-shape mixing nanostructured Graphene electrode material for super capacitor is it is characterised in that one kind
The preparation method of 3D bowl-shape mixing nanostructured Graphene electrode material for super capacitor follows the steps below：
First, base material is placed in plasma enhanced chemical vapor deposition vacuum equipment, be evacuated to pressure be 5Pa with
Under, with gas flow as 65sccm～95sccm is passed through argon, adjust vacuum pumping rate and PECVD sinks
In long-pending vacuum equipment, pressure is controlled to 100Pa～300Pa, and in pressure under 100Pa～300Pa and argon gas atmosphere, to heat up
Speed is that temperature is heated up most 700 DEG C～900 DEG C by 30 DEG C/min；
Base material described in step one is Pt/Ti/SiO2/ Si multilamellar mixed substrates material；Described Pt thickness degree is 150nm
～200nm；Described Ti thickness degree is 20nm；Described SiO2Thickness degree is 300nm；
2nd, temperature be 700 DEG C～900 DEG C, pressure be under 100Pa～300Pa and argon gas atmosphere, base material to be annealed
Process, annealing time is 15min～60min；
3rd, it is passed through carbon-source gas, the gas flow adjusting carbon-source gas is 5sccm～35sccm, the gas flow of argon is
65sccm～95sccm, and adjust vacuum pumping rate pressure in plasma enhanced chemical vapor deposition vacuum equipment is controlled to
200Pa～1000Pa, then depositing system radio-frequency power supply frequency be 13.56MHz, radio-frequency power be 150W～250W, pressure
It is to be deposited under conditions of 200Pa～1000Pa and temperature are 700 DEG C～900 DEG C, sedimentation time is 20min～60min；
Described carbon-source gas are 100sccm with the total gas couette of argon；
4th, after deposition terminates, close radio-frequency power supply and heating power supply, stop being passed through carbon-source gas, continuation with gas flow is
65sccm～95sccm is passed through argon, and adjust vacuum pumping rate will in plasma enhanced chemical vapor deposition vacuum equipment press
It is controlled to by force 100Pa～300Pa, be 700 DEG C～900 DEG C from temperature under pressure is for 100Pa～300Pa and argon gas atmosphere and cool down
To room temperature, that is, obtain 3D bowl-shape mixing nanostructured Graphene electrode material for super capacitor.
2. the preparation of a kind of 3D according to claim 1 bowl-shape mixing nanostructured Graphene electrode material for super capacitor
Method is it is characterised in that the carbon-source gas described in step 3 are methane.
3. the preparation of a kind of 3D according to claim 1 bowl-shape mixing nanostructured Graphene electrode material for super capacitor
Method it is characterised in that in pressure under 100Pa～300Pa and argon gas atmosphere in step one, with heating rate for 30 DEG C/min
Temperature is heated up most 800 DEG C.
4. the preparation of a kind of 3D according to claim 1 bowl-shape mixing nanostructured Graphene electrode material for super capacitor
Method it is characterised in that in step 2 temperature be 700 DEG C～900 DEG C, pressure be under 100Pa～300Pa and argon gas atmosphere right
Base material is made annealing treatment, and annealing time is 60min.
5. the preparation of a kind of 3D according to claim 1 bowl-shape mixing nanostructured Graphene electrode material for super capacitor
Method it is characterised in that in step 3 adjust carbon-source gas gas flow be 10sccm, argon gas flow be 90sccm.
6. the preparation of a kind of 3D according to claim 1 bowl-shape mixing nanostructured Graphene electrode material for super capacitor
Method is it is characterised in that adjust vacuum pumping rate by pressure in plasma enhanced chemical vapor deposition vacuum equipment in step 3
Be controlled to 600Pa, then depositing system radio-frequency power supply frequency be 13.56MHz, radio-frequency power be 200W, pressure be 600Pa and
Temperature is deposited under the conditions of being 800 DEG C, and sedimentation time is 60min.
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| CN105336505A (en) * | 2015-12-02 | 2016-02-17 | 哈尔滨工业大学 | Preparing method for nitrogen-doping graphene electrode material |
| CN105551831B (en) * | 2016-01-11 | 2017-11-10 | 上海交通大学 | A kind of preparation method and application of bowl-shape nitrogen-doped carbon hollow-particle |
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