CN102568853A - Super-capacitor electrode based on vertical oriented graphene and manufacturing method thereof - Google Patents
Super-capacitor electrode based on vertical oriented graphene and manufacturing method thereof Download PDFInfo
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- CN102568853A CN102568853A CN2012100513484A CN201210051348A CN102568853A CN 102568853 A CN102568853 A CN 102568853A CN 2012100513484 A CN2012100513484 A CN 2012100513484A CN 201210051348 A CN201210051348 A CN 201210051348A CN 102568853 A CN102568853 A CN 102568853A
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Abstract
The invention discloses a super-capacitor electrode based on vertical oriented graphene and a manufacturing method thereof. The electrode comprises a current collector and a graphene nanosheet, wherein the graphene nanosheet is vertical to the surface of the current collector; each graphene nanosheet comprises 1-10 layers of graphene. In the manufacturing process, the current collector is heated to 600-1000 DEG C; a carbon element contained gas is adopted as a precursor gas to generate a plasma; the current collector is placed in the plasma; a vertical oriented graphene nanosheet directly grows on the surface of the current collector by using a plasma reinforced chemical vapor deposition method, and after the vertical oriented graphene nanosheet grows for 5 minutes to 8 hours, the obtained current collector with the vertical oriented graphene nanosheet grown on the surface is the super-capacitor electrode. The super-capacitor electrode with the vertical oriented graphene as active material can be made in one step so that the use of adhesives and agglomeration of graphene are avoided, the benefit of material infiltration and ionic diffusion is achieved and the potential in effective energy storage area of the graphene and the property of the super-capacitor is improved.
Description
Technical field
The present invention relates to the energy storage material technical field, relate in particular to a kind of electrode of super capacitor based on vertical orientated Graphene and preparation method thereof.
Background technology
Energy storage is the important step in using energy source and the sustainable development process, and the development of energy storage technology is the key factor that promotes the new forms of energy large-scale development.Ultracapacitor (Supercapacitors) is a kind of electrochemical energy storage device between traditional capacitor and secondary cell.Proper ultracapacitor is a double electric layer capacitor; Its operation principle is the interfacial electric double layer theoretical (Electrochemical double-layer capacitance) that roentgen Helmholtz (H. Helmholtz) proposed in 1853, promptly produces electrostatic capacitance through the Process of Charge Separation on active material and the electrolyte interface and carries out energy storage.The tradition double electric layers supercapacitor is general to adopt the porous carbon structure that has than bigger serface as the energy storage active material, as: active carbon (～1200 m
2/ g), carbon black (80～230 m
2/ g), carbon fiber (～1630 m
2/ g), Graphite cloth (～630 m
2/ g), carbon gel (～650 m
2/ g) etc., thereby make active material with the unit contact interface of electrolyte on can store more ion and realize a farad level electric capacity.Simultaneously; Because the static energy storage principle of double electric layers supercapacitor; Can realize charging rate in theory than high 1～2 one magnitude of battery; Power density is 5～20 times of battery, and the cycle charge-discharge number of times is 100～200 times of battery, embodies the potentiality of high-power quick charge and long circulation life.Therefore, develop the high-performance ultracapacitor that has high capacitance, high power density and high-energy-density concurrently, will effectively promote China's new forms of energy large-scale development, potential application comprises wind-powered electricity generation photovoltaic industry, intelligent grid construction and new-energy automobile industry etc.
The key that the ultracapacitor performance improves is the breakthrough of energy storage active material.Graphene (graphene) be by carbon atom according to
Sp 2The hexangle type that hybridized orbit is formed is the two dimensional crystal structure of honeycomb lattice, and thickness is merely the monolayer carbon atomic diameter.Because its unique two-dimensional structure and excellent crystal quality, Graphene has huge specific area (2630 m
2g
-1), simultaneously at conductivity (electron mobility 20000 cm
2V
-1s
-1), thermal conductivity (conductive coefficient 5300 Wm
-1k
-1), Mechanics of Machinery intensity (strength degree 42 Nm
-1) etc. the aspect all show very excellent characteristic.Extra large nurse of Univ Manchester UK in 2004 (Geim A.) and Nuo Woxiaoluofu people such as (Novoselov K.) first Graphene is separated from graphite (
Novoselov KS, Geim AK, et al. Science, 2004; 306:666-669).Based on excellent properties and the huge applications potentiality that this novel nano-material showed, obtained Nobel Prize in physics in 2010 in double harness.Huge specific area (2675 m that Graphene had
2/ g, the highest in all material with carbon elements at present), make it have the potentiality of carrying out high-efficiency energy-storage as the electrode of super capacitor active material.Research shows that Graphene can be realized the energy density of 53.1 Wh/kg when keeping high power density (9838 W/kg) and high charge speed (less than 2 min) in ion electrolyte, reach the level of metal-hydrogen nickel battery basically; 80
oHighest energy density under the C working temperature can reach 136 Wh/kg (
Liu, C. G., et al. Nano Lett. 2010,10,4863-4868).In theory, if the huge specific area of Graphene is made full use of, can realize～electric capacity of 550 F/g.
The Graphene electrode of super capacitor that extensively adopts is at present realized through following steps: at first prepare graphene oxide through the Hummer method; Obtain Graphene through electronation or thermal reduction then, at last through binding agent with Graphene be bonded at collection liquid surface obtain electrode (
Eda, G., et al. Nat. Nanotechnol. 2008,3,270-274).Number of patent application is the multiple preparation method who discloses grapheme material in the patent documents such as 201110093737.9,201110048734.3,201110060953.3.But all be parallel to collection liquid surface through Graphene in the electrode of these methods making; Very easily again reunite owing to the effect of Van der Waals force; Be unfavorable for infiltration and the ions diffusion migration of material in electrolyte, hindered making full use of the huge specific area of Graphene.To this problem, the solution that present a kind of quilt is extensively attempted be through add between graphene layer nanometric spacer (like CNT and spherical nano-sized carbon/metallic particles etc.) suppress between the multi-layer graphene reunion (
Fan, Z. J., et al. Adv. Mater. 2010,22,3723-3728,
Zhang, L. L., et al. ACS Nano 2010,4,7030-7036).The method has obtained certain effect in laboratory scale research, be difficult for promoting but generally technology is comparatively complicated.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, a kind of electrode of super capacitor based on vertical orientated Graphene and preparation method thereof is provided.
Electrode of super capacitor based on vertical orientated Graphene is made up of collector and graphene nanometer sheet, and graphene nanometer sheet is perpendicular to collection liquid surface, and every graphene nanometer sheet is all by being made up of 1～10 layer graphene.
Said current collector material is gold, silver, copper, aluminium, iron, stainless steel, nickel or carbon.
Said graphene nanometer sheet thickness is 1～20 nanometer, highly is 0.05～100 micron, and width is 0.01～5 micron, and adjacent graphene nanometer sheet spacing is 0.01～5 micron.
Manufacture method based on the electrode of super capacitor of vertical orientated Graphene is: heating collector to 600～1000
oC; Produce plasma with carbon elements gas as precursor gas; Collector is placed in the plasma, through the plasma enhanced chemical vapor deposition method, at the vertical orientated graphene nanometer sheet of collection liquid surface direct growth; After growing 5 minutes～8 hours, the gained surface is long to have the collector of vertical orientated graphene nanometer sheet to be electrode of super capacitor.
Said plasma is microwave plasma, radio-frequency inductance coupling plasma, radio frequency capacitance coupling plasma, hyperfrequency plasma, electron beam plasma or normal pressure normal glow discharge plasma.
Said carbon elements gas is the mist of one or more and argon gas, nitrogen, helium or hydrogen in methane, ethane, acetylene, ethene, carbon monoxide, carbon dioxide or the carbon tetrafluoride.
The beneficial effect that the present invention compared with prior art has:
1) there is not the multi-layer graphene agglomeration in the vertical orientated graphene nanometer sheet as electrode active material; To help ion from electrolyte to the transfer of surface of active material diffusion and ion in surface of active material; And then help improving ion in the electrolyte, and finally help the raising of ultracapacitor charging rate at the absorption and the desorption rate of electrolyte/active material contact surface;
2) vertical orientated structure helps the infiltration of Graphene active material in electrolyte (particularly organic electrolyte), can utilize the better advantage of Graphene wetability in organic electrolyte to a greater extent.Because organic electrolyte is compared aqueous solution electrolysis liquid and had bigger voltage window, therefore the ultracapacitor based on vertical orientated Graphene and organic electrolyte has the potentiality that realize high-energy-density;
3) realize the direct growth of vertical orientated Graphene through the plasma enhanced chemical vapor deposition method at collection liquid surface; Avoided the use of binding agent in the traditional electrode manufacturing process; Reduced the negative effect of binding agent, will effectively reduce internal resistance, improved power density energy storage characteristic.
Description of drawings
Fig. 1 is the structural representation based on the electrode of super capacitor of vertical orientated Graphene;
Fig. 2 is the electrode of super capacitor sem photograph that the embodiment of the invention 1 is made;
Fig. 3 is the transmission electron microscope picture of vertical orientated Graphene active material in the electrode of super capacitor made of the embodiment of the invention 1;
Fig. 4 is the electrode of super capacitor sem photograph that the embodiment of the invention 2 is made;
Fig. 5 is the electrode of super capacitor sem photograph that the embodiment of the invention 3 is made;
Fig. 6 is the cyclic voltammogram of electrode of super capacitor in 6M KOH aqueous solution electrolysis liquid that the embodiment of the invention 1 is made;
Fig. 7 is the cyclic voltammogram of electrode of super capacitor in 1 M TEABF4/AN organic electrolyte that the embodiment of the invention 1 is made.
Embodiment
As shown in Figure 1, to form by collector 1 and graphene nanometer sheet 2 based on the electrode of super capacitor of vertical orientated Graphene, graphene nanometer sheet is perpendicular to collection liquid surface, and every graphene nanometer sheet is all by being made up of 1～10 layer graphene.
Said current collector material is gold, silver, copper, aluminium, iron, stainless steel, nickel (containing nickel foam) or carbon.
Said graphene nanometer sheet thickness is 1～20 nanometer, highly is 0.05～100 micron, and width is 0.01～5 micron, and adjacent graphene nanometer sheet spacing is 0.01～5 micron.
Manufacture method based on the electrode of super capacitor of vertical orientated Graphene is: heating collector to 600～1000
oC; Produce plasma with carbon elements gas as precursor gas; Collector is placed in the plasma, through the plasma enhanced chemical vapor deposition method, at the vertical orientated graphene nanometer sheet of collection liquid surface direct growth; After growing 5 minutes～24 hours, the gained surface is long to have the collector of vertical orientated graphene nanometer sheet to be electrode of super capacitor.
Said plasma is microwave plasma, radio-frequency inductance coupling plasma, radio frequency capacitance coupling plasma, hyperfrequency plasma, electron beam plasma or normal pressure normal glow discharge plasma.
Said carbon elements gas is the mist of one or more and argon gas, nitrogen, helium or hydrogen in methane, ethane, acetylene, ethene, carbon monoxide, carbon dioxide or the carbon tetrafluoride.
Embodiment 1: be collector with the stainless steel substrates, adopt normal pressure normal glow discharge plasma enhanced vapor deposition technology, making with vertical orientated Graphene is the electrode of super capacitor of active material.
In quartz ampoule, quartz ampoule is placed in the heating furnace with the needle placement of 0.025 millimeter stainless steel substrates and tapering 1:10.Needle point is perpendicular to the stainless steel substrates surface, and the distance of needle point and stainless steel substrates is 7 millimeters.Stainless steel substrates ground connection, needle point connect high pressure negative electricity power supply.Feed hydrogen and argon gas mist (total flow: 2000 ml/min in the quartz ampoule; Volume ratio: 1:1), and stainless steel substrates is heated to 700 through heating furnace
oC.Keeping 700
oUnder the prerequisite of C heating, close hydrogen and argon gas mist, feed argon gas, methane and steam mist simultaneously.Mist total flow 1500 ml/min, argon gas and methane volume ratio are 10:1, mist relative humidity is 38.5%.Open high pressure negative electricity power supply, the adjustment service voltage is 4.6 kilovolts, between collector and needle point, forms gas discharge normal pressure normal glow plasma.Continuous discharge is powered-down after 30 minutes, closes heating furnace, closes argon gas, methane and steam mist simultaneously, feeds hydrogen and argon gas mist (total flow: 2000 ml/min simultaneously; Volume ratio: 1:1), cooling naturally.When temperature is lower than 50
oDuring C, close hydrogen and argon gas mist, take out sample, promptly obtaining with the stainless steel substrates is collector, is the electrode of super capacitor of active material with vertical orientated Graphene.Fig. 2 is the electrode of super capacitor sem photograph that the embodiment of the invention 1 is made.Shown in Figure 3 is the transmission electron microscope picture of vertical orientated Graphene active material in the electrode made of the embodiment of the invention 1.Graphene nanometer sheet directly prepares through plasma enhanced chemical vapor deposition method perpendicular to collection liquid surface, does not add binding agent, and resulting graphene nanometer sheet is made up of 1～10 layer graphene.
Embodiment 2: be collector with the nickel foam, adopt normal pressure normal glow discharge plasma enhanced vapor deposition technology, making with vertical orientated Graphene is the electrode of super capacitor of active material.
In quartz ampoule, quartz ampoule is placed in the heating furnace with the needle placement of nickel foam and tapering 1:10.Needle point is perpendicular to the stainless steel substrates surface, and the distance of needle point and stainless steel substrates is 7 millimeters.Nickel foam ground connection, needle point connect high pressure negative electricity power supply.Feed hydrogen and argon gas mist (total flow: 2000 ml/min in the quartz ampoule; Volume ratio: 1:1), and stainless steel substrates is heated to 1000 through heating furnace
oC.Keeping 1000
oUnder the prerequisite of C heating, close hydrogen and argon gas mist, feed argon gas, acetylene and steam mist simultaneously.Mist total flow 1500 ml/min, argon gas and acetylene volume ratio are 10:1, mist relative humidity is 38.5%.Open high pressure negative electricity power supply, the adjustment service voltage is 4.6 kilovolts, between collector and needle point, forms gas discharge normal pressure normal glow plasma.Continuous discharge is powered-down after 5 minutes, closes heating furnace, closes argon gas, acetylene and steam mist simultaneously, feeds hydrogen and argon gas mist (total flow: 2000 ml/min simultaneously; Volume ratio: 1:1), cooling naturally.When temperature is lower than 50
oDuring C, close hydrogen and argon gas mist, take out sample, promptly obtaining with the nickel foam is collector, is the electrode of super capacitor of active material with vertical orientated Graphene.Fig. 4 is the electrode of super capacitor sem photograph that the embodiment of the invention 2 is made.
Embodiment 3: be collector with the copper sheet, adopt microwave plasma to strengthen gas phase deposition technology, making with vertical orientated Graphene is the electrode of super capacitor of active material.
Copper sheet is placed in the microwave plasma reactor.Plasma reactor is taken out low pressure to 100 handkerchief.Open microwave plasma reactor and input power is adjusted into 600 watts, copper sheet is heated to 600
oC.Feed mist (total flow 200 ml/min of methane and hydrogen after 10 minutes; Volume ratio: 10:1), and the microwave plasma input power is adjusted into 800 watts.Continue to close the microwave plasma power supply after 20 minutes, close methane and hydrogen simultaneously, feed hydrogen and argon gas mist (total flow: 200 ml/min simultaneously; Volume ratio: 1:1), cooling naturally.When temperature is lower than 50
oDuring C, close hydrogen and argon gas mist, take out sample, promptly obtaining with the copper sheet is collector, is the electrode of super capacitor of active material with vertical orientated Graphene.Fig. 5 is the electrode of super capacitor sem photograph that the embodiment of the invention 3 is made.
Embodiment 4: be collector with the stainless steel substrates, adopt radio-frequency inductance coupling plasma plasma enhanced vapor deposition technology, making with vertical orientated Graphene is the electrode of super capacitor of active material.
Stainless steel substrates is placed in the radio-frequency inductance coupling plasma reactor (frequency 13.56 megahertzes).Plasma reactor is taken out low pressure to 5 handkerchief.Copper sheet is heated to 700
oC opens the radio-frequency inductance coupling plasma reactor and input power is adjusted into 900 watts.Feed mist (total flow 20 ml/min of methane and argon gas after 20 minutes; Volume ratio: 9:1), and maintenance radio-frequency inductance coupling plasma reactor input power is 900 watts.Continue to close the microwave plasma power supply after 3 hours, close methane and argon gas simultaneously, feed hydrogen and argon gas mist (total flow: 20 ml/min simultaneously; Volume ratio: 1:1), cooling naturally.When temperature is lower than 50
oDuring C, close hydrogen and argon gas mist, take out sample, promptly obtaining with the stainless steel substrates is collector, is the electrode of super capacitor of active material with vertical orientated Graphene.
Press embodiment 1 and make two symmetry electrodes, be assembled into small-sized button cell formula ultracapacitor and carry out electrochemical property test.The small-sized button cell formula ultracapacitor that is assembled adopts 6M KOH aqueous solution electrolysis liquid and 1 M TEABF4/AN organic electrolyte respectively, carries out cyclic voltammetric and testing impedance.Like Fig. 6 and shown in Figure 7, to sweep to 1000 mV/s under the speed at 10 mV/s, cyclic voltammogram basically all presents good rectangular shape, has proved outstanding electric double layer capacitance characteristic.Sweep under the speed identical; The electric capacity of prepared ultracapacitor in 6 M KOH aqueous solution electrolysis liquid is 91.9%～104.8% with capacitance ratio in 1 M TEABF4/AN organic electrolyte; Organic electrolyte electric capacity result on the low side when this result is different from the horizontal Graphene of employing or traditional active carbon as active material; The vertical orientated structure that has confirmed Graphene helps the Graphene active material at electrolyte, the particularly infiltration in the organic electrolyte.Owing in organic electrolyte, can realize bigger voltage window, so this result will help the raising of ultracapacitor energy density.In addition; Testing impedance shows; Adopt the break frequency of electrode in 6M KOH aqueous solution electrolysis liquid and 1 M TEABF4/AN organic electrolyte that the embodiment of the invention makes respectively up to 259 hertz with 3174 hertz; Confirmed ion good diffusion and chimeric in active material, this will help the raising that ultracapacitor discharges and recharges speed and power density.
The above embodiment of the present invention only be for explain that the present invention does for example, but not be to execution mode of the present invention or implement the qualification of material.In fact, this method may be implemented in multiple anti-600
oThe current collector material of the above high temperature of C; The plasma occurring mode comprises microwave plasma, radio-frequency inductance coupling plasma, radio frequency capacitance coupling plasma, hyperfrequency plasma, electron beam plasma, normal pressure normal glow discharge plasma etc.; The carbon elements precursor gas also comprises mist of one or more and argon gas, nitrogen, helium or hydrogen in methane, ethane, acetylene, ethene, carbon monoxide, carbon dioxide or the carbon tetrafluoride etc., can't give exhaustive at this.Allly belong to conspicuous variation or the change that technical scheme of the present invention is amplified, and the conversion of current collector material, carbon elements precursor gas or plasma occurring mode, still be in the row of protection scope of the present invention.
Claims (6)
1. electrode of super capacitor based on vertical orientated Graphene; It is characterized in that: this electrode is made up of collector (1) and graphene nanometer sheet (2); Graphene nanometer sheet is perpendicular to collection liquid surface, and every graphene nanometer sheet is all by being made up of 1～10 layer graphene.
2. a kind of electrode of super capacitor based on vertical orientated Graphene according to claim 1 is characterized in that: said current collector material is gold, silver, copper, aluminium, iron, stainless steel, nickel or carbon.
3. a kind of electrode of super capacitor according to claim 1 based on vertical orientated Graphene; It is characterized in that: said graphene nanometer sheet thickness is 1～20 nanometer; Highly be 0.05～100 micron, width is 0.01～5 micron, and adjacent graphene nanometer sheet spacing is 0.01～5 micron.
4. the manufacture method of the electrode of super capacitor based on vertical orientated Graphene as claimed in claim 1 is characterized in that: heating collector to 600～1000
oC; Produce plasma with carbon elements gas as precursor gas; Collector is placed in the plasma, through the plasma enhanced chemical vapor deposition method, at the vertical orientated graphene nanometer sheet of collection liquid surface direct growth; After growing 5 minutes～8 hours, the gained surface is long to have the collector of vertical orientated graphene nanometer sheet to be electrode of super capacitor.
5. the manufacture method of a kind of electrode of super capacitor based on vertical orientated Graphene according to claim 4, it is characterized in that: said plasma is microwave plasma, radio-frequency inductance coupling plasma, radio frequency capacitance coupling plasma, hyperfrequency plasma, electron beam plasma or normal pressure normal glow discharge plasma.
6. the manufacture method of a kind of electrode of super capacitor based on vertical orientated Graphene according to claim 4 is characterized in that: said carbon elements gas is the mist of one or more and argon gas, nitrogen, helium or hydrogen in methane, ethane, acetylene, ethene, carbon monoxide, carbon dioxide or the carbon tetrafluoride.
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| CN103864061A (en) * | 2012-12-13 | 2014-06-18 | 财团法人工业技术研究院 | Apparatus and method for forming graphene sheet |
| CN103924209A (en) * | 2014-04-30 | 2014-07-16 | 中国科学院重庆绿色智能技术研究院 | Method for directly and conformally covering graphene on surface of needle point |
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