CN103440995A - Electrode material for super capacitor and preparing method thereof - Google Patents
Electrode material for super capacitor and preparing method thereof Download PDFInfo
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Abstract
The invention provides an electrode material for a super capacitor. The electrode material is of a unique structure, wherein 2 to 7 layers of graphene with the BET specific surface area over 300m2/g serves as a conductive agent and is mixed with activated carbon and binder, so that a layered graphene conductive agent is evenly distributed among activated carbon particles in a penetrating mode. According to the structure, on one hand, the contact area of the graphene and the activated carbon particles is increased and the electron transport efficiency is improved; on the other hand, contact gaps among the activated carbon particles are adjusted, the storage of electrolyte ions is facilitated, and the continuous supply of the ions is achieved. Therefore, compared with activated carbon base electrode materials of mixed acetylene black, a carbon nano tube and a graphite conductive agent, the electrode material for the super capacitor has the advantages that the properties of specific capacitance, power density, energy density, rate capability, cycling stability and the like are greatly improved.
Description
Technical field
The invention belongs to the ultracapacitor technical field, be specifically related to a kind of electrode material for ultracapacitor.
Background technology
Ultracapacitor because its power density is high, the characteristics such as fast, the non-maintaining environmental protection of long service life, charging rate have application prospect preferably in fields such as national defence, space flight and aviation, auto industry, consumer electronics, communications, but its low energy densities has restricted its extensive use at present.
Active carbon is one of electrode material that ultracapacitor is commonly used, the advantages such as it has abundant raw material, cheap, electrochemical stability is high, technology maturation.But the character such as the specific area of active carbon, pore-size distribution, microstructure, surface functional group and conductance greatly affect the performance of absorbent charcoal based ultracapacitor.Wherein, the conductivity of absorbent charcoal material is one of key factor affected the ultracapacitor performance.On the one hand, the conductivity of absorbent charcoal material affects the constant current charge-discharge performance of ultracapacitor, thereby the energy density of ultracapacitor is had to material impact; On the other hand, the conductivity of absorbent charcoal material also directly affects the equivalent series resistance of ultracapacitor, and then affects the power-performance of ultracapacitor.In addition, the high rate performance quality of ultracapacitor is also closely related with the conductivity of active carbon electrode material.Therefore, the conductivity of improving absorbent charcoal material is to improve the row of absorbent charcoal based super capacitor performance and one of effective method.And can effectively improve the conductivity of active carbon electrode material by adding conductive agent.
Can effectively improve the conductivity of active carbon electrode material by adding conductive agent.At present, conductive agent commonly used has acetylene black (Zhang H, Zhang W, et al.SolidState Ionics.2008; 79 (33): 946-950), carbon nano-tube (Taberna PL, Chevallier G, Simon P, et al.Mater Res Bull.006; 413): 478-484), blocky graphite (Michael M, Prabaharan S.J Power Sources.2004; 136 (2): 250-256), and the morphosis of different conductive agents is also different to the Conductivity of active carbon electrode material.The acetylene black of nano-scale is easily reunited during as conductive agent, causes its electronics and ion transportation ability greatly to reduce, and therefore, the performance of ultracapacitor also reduces greatly.The size of blocky graphite is in micron dimension, and its internal resistance is lower, but during using blocky graphite as conductive agent, after the graphite of block structure mixes with activated carbon particles, conductivity is confined to the EDGE CONTACT part of the two, causes effectively bringing into play the electric action of graphite.The fibrous carbon nanotube is during as conductive agent, and the netted passage of its formation is conducive to the electronics transportation, but can't improve hole between activated carbon granule and the reservoir electrolyte ion.
Summary of the invention
Technical purpose of the present invention is to provide a kind of absorbent charcoal based electrode material for ultracapacitor, and this electrode material has height ratio capacity, high-specific-power, high-energy-density, good high rate performance and long cycle performance,
The present invention realizes that the technical scheme that above-mentioned technical purpose adopts is: a kind of electrode material for ultracapacitor, by active carbon, sheet Graphene and binding agent, formed, and wherein, the number of plies of sheet Graphene is 2 layers～7 layers, the BET specific area is at 300m
2more than/g; As shown in Figure 1, the sheet graphene uniform is interspersed between activated carbon granule; And the mass ratio of sheet Graphene and activated carbon is 1:19～1:1.
As preferably, the number of plies of sheet Graphene is 3 layers～5 layers.
As preferably, the BET specific area of sheet Graphene is at 350m
2/ g～1000m
2/ g.
Described binding agent, for boning active carbon and conductive agent, makes it fixed-type, and its kind is not limit, and comprises polytetrafluoroethylene (PTFE), Kynoar (PVDF), polyvinyl alcohol (PVA), sodium carboxymethylcellulose (CMC) etc.Binder content is not limit, and preferably accounts for 5%～10% of activated carbon quality.
The preparation method of described Graphene does not limit, and comprises the chemical stripping method, take graphite oxide as precursor, uses the means such as electronation, solvothermal, thermal expansion reduction to obtain Graphene; Synthetic method, by organic precursor synthesizing graphite alkene, or the solvent heat synthesizing graphite alkene etc.; The catalytic growth method, comprise the silicon carbide epitaxial growth Graphene, vapour deposition Graphene etc.
Consider the problems such as the complexity of operation and elapsed time; in the present invention, preferably adopt the method for microwave thermal reduction to make required Graphene; be specially: adopt Hummer ' s chemical method to prepare graphite oxide; this graphite oxide is scattered in deionized water and forms dispersion liquid; obtain graphite oxide after Freeze Drying Technique is processed, then this graphite oxide is put into to microwave oven, adopt microwave thermal reduction (Zhu Y; Murali S, et al.Carbon.2010; 48 (7): 2118-22) technology makes it peel off that to be reduced to graphite rare.In addition, the defect sturcture of utilizing this microwave thermal reducing process to make the graphite oxide microwave peel off the Graphene that reduces and form compares SP
2carbon atom can be stored more multi-charge, makes the material surface CHARGE DISTRIBUTION inhomogeneous, thereby produces CHARGE DISTRIBUTION electric capacity, and defect sturcture distributed capacitance more at most is larger.This defect sturcture also makes surface functionality increase, and the Graphene surface is strengthened with the suction-operated of electrolyte ion, and while finally forming electric double layer, its fixed-layer capacitance increases.Thereby the defect sturcture that this microwave is peeled off Graphene also contributes to raising to compare capacitive property.
It is method commonly used in this area that described Hummer ' s chemical method prepares graphite oxide, that is: native graphite, sodium nitrate, the concentrated sulfuric acid are mixed and to be placed in the ice-water bath mechanical agitation even, then add the potassium permanganate stirring reaction, to after the dilution of the product of gained, add hydrogen peroxide to remove excessive potassium permanganate again, finally with after hydrochloric acid and deionization washing, obtaining graphite oxide.
The present invention also provides a kind of preparation method of the electrode material for above-mentioned ultracapacitor, adopt traditional cladding process that active carbon, sheet Graphene and binding agent evenly are blended in solvent and form slurry, then this slurry evenly is coated in to substrate material surface, drying is processed rear compression molding, obtains electrode material.
In above-mentioned preparation method, described solvent includes but not limited to ethanol, propyl alcohol, the tert-butyl alcohol, 1-METHYLPYRROLIDONE.
In above-mentioned preparation method, described basis material is not limit, and comprises porous material, such as porous foam nickel, aluminum foil material, titanium material etc.
In sum, to select the number of plies be that 2 layers～7 layers, BET specific area are at 300m in the present invention
2graphene more than/g, as conductive agent, forms the electrode material with new structure after mixing with activated carbon granule, characteristics are as follows:
(1) Graphene is sheet, have advantages of that thinner thickness, area are larger, when with after active carbon mixes, just because of this architectural feature of Graphene, can " flexibly and comfortably " " intert " between activated carbon granule, form a kind of electrode material structure of uniqueness.In this electrode material structure, graphene uniform " interts " between activated carbon granule, can increase on the one hand the contact area of Graphene and activated carbon granule, for the electronics transportation provides the passage of " spaciousness ", thereby has improved the electronics conevying efficiency; Can adjust the contact gap between activated carbon granule on the other hand, be conducive to the storage of electrolyte ion, realize lasting ion supply, thereby effectively prevent " the hungry effect " of electrolyte ion.
(2) inventor finds, although Graphene has high conductivity, increase the conductivity that Graphene contributes to improve electrode material in activated carbon, but the performance of electrode material not is simple linear increment relation with Graphene content, but when the mass ratio of sheet Graphene and activated carbon is chosen as 1:20～1:1, electrode material is realized high-performance, and when the mass ratio of sheet Graphene and activated carbon is chosen as 1:15～1:7, the performance of electrode material further improves.
(3) experiment confirms, with acetylene black, carbon nano-tube, graphite etc., for the absorbent charcoal based electrode material of conductive agent, compare, the performances such as ratio electric capacity, power density, energy density, high rate performance, cyclical stability of the absorbent charcoal based electrode material that Graphene is conductive agent are take in the present invention to be had and greatly improves and improve.
The accompanying drawing explanation
Fig. 1 is that the structural representation of the absorbent charcoal based electrode material that Graphene is conductive agent is take in the present invention;
(a) figure in Fig. 2 is the graphite oxide aqueous dispersions outside drawing in the embodiment of the present invention 1;
(b) figure in Fig. 2 is the oxidation graphite solid outside drawing in the embodiment of the present invention 1;
(c) figure in Fig. 2 is the graphene powder outside drawing in the embodiment of the present invention 1;
(a) figure in Fig. 3 is the scanning electron microscope (SEM) photograph of Graphene in the embodiment of the present invention 1;
(b) figure in Fig. 3 is the transmission electron microscope picture of Graphene in the embodiment of the present invention 1;
(c) figure in Fig. 3 be the embodiment of the present invention 1 step (1) with (2) in graphite, graphite oxide, the XRD diffraction pattern of Graphene;
(d) figure in Fig. 3 is the C1s swarming figure in the graphite oxide x-ray photoelectron energy spectrogram in the embodiment of the present invention 1 step (1);
(e) figure in Fig. 3 be the embodiment of the present invention 1 step (1) with (2) in graphite oxide and the x-ray photoelectron power spectrum of Graphene always scheme;
(f) figure in Fig. 3 be the embodiment of the present invention 1 step (1) with (2) in graphite, graphite oxide, the Raman figure of Graphene;
(a) figure in Fig. 4 is the cyclic voltammetry curve figure of ultracapacitor of the absorbent charcoal based electrode slice assembling of different Graphene content in embodiment 1～12;
(b) figure in Fig. 4 is the constant-current discharge time diagram of ultracapacitor of the absorbent charcoal based electrode slice assembling of different Graphene content in embodiment 1～12;
(a)～(e) in Fig. 5 figure does not add the scanning electron microscope (SEM) photograph that adds the absorbent charcoal based electrode material of Graphene, acetylene black, carbon nano-tube, graphite agent in the active carbon electrode material of conductive agent and above-described embodiment 1 and comparative example 1～3;
(f) figure in Fig. 5 is the XRD diffraction schematic diagram of Graphene in above-described embodiment 1 and comparative example 1～3, acetylene black, carbon nano-tube, graphite;
(g) figure in Fig. 5 is active carbon isothermal adsorption curve chart;
(h) figure in Fig. 5 is the isothermal adsorption curve chart of the Graphene in embodiment 1;
(a) figure in Fig. 6 is the cyclic voltammetry curve figure of the ultracapacitor that adopts the electrode material in embodiment 1 and comparative example 1～3 to make;
(b) figure in Fig. 6 is that the ultracapacitor that adopts the electrode material in embodiment 1 to make is swept the cyclic voltammetry curve figure under speed in difference;
(c) figure in Fig. 6 is the constant current charge-discharge curve chart of the ultracapacitor that adopts the electrode material in embodiment 1 and comparative example 1～3 to make;
(d) figure in Fig. 6 be the ultracapacitor that adopts the electrode material in embodiment 1 and comparative example 1～3 to make the electrochemical AC impedance spectrogram;
(a) figure in Fig. 7 is the high rate performance comparison diagram of the ultracapacitor that adopts the electrode material in embodiment 1 and comparative example 1～3 to make;
(b) figure in Fig. 7 is the cyclical stability comparison diagram of the ultracapacitor that adopts the electrode material in embodiment 1 and comparative example 1～3 to make;
(c) figure in Fig. 7 is that the power density of the ultracapacitor that adopts the electrode material in embodiment 1 and comparative example 1～3 to make is relatively schemed;
(d) figure in Fig. 7 is the energy density comparison diagram of the ultracapacitor that adopts the electrode material in embodiment 1 and comparative example 1～3 to make;
(e) figure in Fig. 7 is the equivalent series resistance comparison diagram of the ultracapacitor that adopts the electrode material in embodiment 1 and comparative example 1～3 to make;
(f) figure in Fig. 7 be the ultracapacitor that adopts the electrode material in embodiment 1 and comparative example 1～3 to make 10mV/s sweep under speed than electric capacity comparison diagram.
Embodiment
Further illustrate the present invention below in conjunction with accompanying drawing and embodiment.It should be understood that these embodiment, only for the present invention is described, limit the scope of the invention and be not used in.
Embodiment 1:
In the present embodiment, for the electrode material of ultracapacitor, active carbon, sheet Graphene and binding agent Kynoar (PTFE), consist of, wherein, the number of plies of sheet Graphene is 2 layers～7 layers, and the BET specific area is at 300m
2more than/g; As shown in Figure 1, the sheet Graphene is interspersed between activated carbon granule; And the mass ratio of Graphene and activated carbon is that 1:9(take Graphene and quality of activated carbon and be benchmark, the Graphene quality accounts for 10%), the binding agent quality account for Graphene and activated carbon quality and 5%.
The preparation method of above-mentioned electrode material is as follows:
(1) adopt the synthetic graphite oxide of Hummer ' s chemical method
The concentrated sulfuric acid of the native graphite of 4g (10000 order), 3g sodium nitrate, 135mL98% is evenly mixed and is placed in 0 ℃ of ice-water bath mechanical agitation 5 hours; Then, slowly add 24g potassium permanganate, under room temperature, stirring reaction is 7 days, the viscous fluid of gained is transferred in the beaker that fills the 200mL deionized water and is diluted, stirring at room 2 hours; Then, the hydrogen peroxide of 12mL30wt% is joined in this dilution to stirring at room 2 hours; Finally, successively with after 5% hydrochloric acid and deionized water centrifuge washing, obtaining graphite oxide.
(2) the microwave thermal reduction prepares Graphene
Graphite oxide is scattered in deionized water and obtains the graphite oxide water dispersion solution, by obtaining oxidation graphite solid after freeze drying; Take out the oxidation graphite solid of about 10mg and put into the microwave oven Microwave Treatment 10～15 minutes, microwave reduction is peeled off and is obtained Graphene.
In Fig. 2, (a) (b) is (c) the Graphene black powder that obtains oxidation graphite solid and obtain after the microwave thermal reduction after the graphite oxide aqueous dispersions that makes in above-mentioned steps (2), freeze drying successively.
Fig. 3 (a) is the scanning electron microscope (SEM) photograph of the above-mentioned Graphene made.Therefrom can find out, microwave is peeled off the Graphene surface made a lot of folds.
Fig. 3 (b) is the transmission electron microscope picture of the above-mentioned Graphene made.Therefrom can find out, microwave is peeled off the Graphene made and is laminar structured, and its number of plies is about 2～7 layers, belongs to few layer graphene.
Fig. 3 (c) be above-mentioned steps (1) with (2) in graphite, graphite oxide, the XRD diffraction pattern of Graphene.Therefrom can find out, native graphite (10000 order) is after strong oxidation, and diffraction maximum (002) moves to left to 10 ° of left and right, illustrate that graphite oxide generates, and after the microwave thermal processing, diffraction maximum (002) is shifted to the right to again 25 ° of left and right, illustrates that Graphene generates.
Fig. 3 (d) and the x-ray photoelectron energy spectrogram that is (e) Graphene that makes after the graphite oxide that makes in above-mentioned steps (2) and microwave are peeled off.Therefrom can find out, after oxidation, C/O becomes 12:1 than by 3:1, illustrates that microwave reduction is comparatively abundant.
Fig. 3 (f) be above-mentioned steps (1) with (2) in graphite, graphite oxide, the Raman figure of Graphene.As can be seen from the figure, the D/G peak ratio of Graphene is 1.30, higher than graphite oxide (D/G=1.25) and native graphite (D/G=0.80), illustrate that the defect sturcture of the Graphene obtained after the microwave thermal reduction is more, and the space charge effect produced by defect sturcture is conducive to contribute electric capacity.
(3) prepare absorbent charcoal based electrode material
The Graphene that above-mentioned steps is made, active carbon, and binding agent PTFE is blended in appropriate ethanol, ultrasonic emulsification becomes the stickiness slurry, wherein, the mass ratio of Graphene and active carbon is 1:9, the PTFE quality account for Graphene and quality of activated carbon and 5%; Then, this stickiness slurry evenly is coated on the nickel foam that diameter is 12mm, in 120 ℃ of vacuumizes 18 hours, and, in the 20MPa lower sheeting, obtains absorbent charcoal based electrode slice.
In embodiment 2～10, electrode material for ultracapacitor is basic identical with the electrode material of embodiment 1 respectively, unique different be that the mass ratio of Graphene and activated carbon is followed successively by 9:1,8:2,7:3,6:4,5:5,4:6,3:7,2:8,1.5:8.5,0.5:9.5,0:10, take Graphene and quality of activated carbon and be benchmark, the Graphene quality accounts for 90%, 80%, 70%, 60%, 50%, 40%, 30%, 20%, 15%, 5%, 0% successively.
In the preparation method of above-mentioned electrode material and embodiment 1, the preparation method of electrode material is basic identical, unique different be that the mass ratio of Graphene and active carbon is followed successively by 9:1,8:2,7:3,6:4,5:5,4:6,3:7,2:8,1.5:8.5,0.5:9.5,0:10 in step (3).
Respectively the absorbent charcoal based electrode slice made in above-described embodiment 1～12 is assembled into to the button ultracapacitor, wherein, electrolyte is 6M KOH aqueous electrolyte, and barrier film adopts all-glass paper.
Adopt the chemical property of the above-mentioned button ultracapacitor of cyclic voltammetry, by the test certain voltage, sweep speed and descend this super capacitor electric current to judge its chemical property with the change curve of voltage.In mensuration, setting voltage is swept speed for 10mV/s, 20mV/s, 50mV/s, 100mV/s, 200mV/s; Aqueous electrolyte window voltage scope is from-1.0V to 0V; It is 5mV that the electrochemical AC impedance test applies sinusoidal bias voltage; The test frequency scope is that 100mHz is to 100KHz; Constant current charge-discharge density is 0.1A/g, 0.15A/g, 0.5A/g, 0.75A/g, 1.0A/g, 1.5A/g, 2.0A/g, and charging voltage is 1.0V.Fig. 4 (a) is the cyclic voltammetry curve figure of ultracapacitor of the absorbent charcoal based electrode slice assembling of above-mentioned different Graphene content.Fig. 4 (b) is the constant-current discharge time diagram of ultracapacitor of the absorbent charcoal based electrode slice assembling of above-mentioned different Graphene content.As can be seen from the figure, when the mass ratio of Graphene and active carbon be 1:19～1:1(, take Graphene and quality of activated carbon and be benchmark, the Graphene quality accounts for 5%～50%) time, prepared ultracapacitor obtains higher ratio electric capacity; When the mass ratio of Graphene and active carbon, during higher than 5:5, the ratio electric capacity of prepared ultracapacitor reduces on the contrary; When the mass ratio of Graphene and active carbon be 1:9(, take Graphene and quality of activated carbon and be benchmark, the Graphene quality accounts for 10%) time, prepared ultracapacitor than electric capacity the best.
The comparative example 1:
The present embodiment is the comparative example of above-described embodiment 1.
In the present embodiment, for the electrode material of ultracapacitor, by active carbon, acetylene black and binding agent PTFE, formed.Wherein, the mass ratio of acetylene black and activated carbon be 1:9(, take acetylene black and active carbonaceous amount and be benchmark, the acetylene black quality accounts for 10%), the binding agent quality account for acetylene black and activated carbon quality and 5%.
In the preparation method of above-mentioned electrode material and embodiment 1, the preparation method of electrode material is basic identical, unique different be in step (3), replace Graphene by acetylene black, with active carbon and binding agent PTFE, be blended in appropriate ethanol.
The comparative example 2:
The present embodiment is the comparative example of above-described embodiment 1.
In the present embodiment, for the electrode material of ultracapacitor, by active carbon, carbon nano-tube and binding agent PTFE, formed.Wherein, the mass ratio of carbon nano-tube and activated carbon be 1:9(, take carbon nano-tube and active carbonaceous amount and be benchmark, the acetylene black quality accounts for 10%), the binding agent quality account for carbon nano-tube and activated carbon quality and 5%.
In the preparation method of above-mentioned electrode material and embodiment 1, the preparation method of electrode material is basic identical, unique different be in step (3), replace Graphene by carbon nano-tube, with active carbon and binding agent PTFE, be blended in appropriate ethanol.
The comparative example 3:
The present embodiment is the comparative example of above-described embodiment 1.
In the present embodiment, for the electrode material of ultracapacitor, by active carbon, graphite and binding agent PTFE, formed.Wherein, the mass ratio of graphite and activated carbon be 1:9(, take graphite and active carbonaceous amount and be benchmark, the graphite quality accounts for 10%), the binding agent quality account for graphite and activated carbon quality and 5%.
In the preparation method of above-mentioned electrode material and embodiment 1, the preparation method of electrode material is basic identical, unique different be in step (3), replace Graphene with graphite, with active carbon and binding agent PTFE, be blended in appropriate ethanol.
Respectively the absorbent charcoal based electrode slice made in above-mentioned comparative example 1～3 is assembled into to the button ultracapacitor, wherein, electrolyte is 6M KOH aqueous electrolyte, and barrier film adopts all-glass paper.
(a)～(e) in Fig. 5 figure does not add the scanning electron microscope (SEM) photograph that adds the absorbent charcoal based electrode material of Graphene, acetylene black, carbon nano-tube, graphite agent in the active carbon electrode material of conductive agent and above-described embodiment 1 and comparative example 1～3.From Fig. 5 (a), can find out, activated carbon granule is micron-scale, and particle size distribution is inhomogeneous.From Fig. 5 b) can find out, the sheet Graphene closely is interspersed between activated carbon granule, illustrates that Graphene has improved the hole between activated carbon granule, and this stores for electric transmission and electrolyte the condition that provides good.And the Graphene of sheet and the contact area of granular activated carbon are larger, thereby have improved activated carbon granule and connect nucleophobic ability.In Fig. 5 (c), the acetylene black of nano-scale is inhomogeneous is dispersed between activated carbon granule and reunites, and has greatly reduced the electronics conevying efficiency.Fig. 5 (d) although in fibrous carbon nano-tube formed effective conductive network, it can't improve the hole between activated carbon granule, thereby the lasting supply of unwarrantable electrolyte ion.Fig. 5 (e) is although block graphite has good crystallinity (as Fig. 5 (f) XRD diffraction schematic diagram), its conductivity be confined to the graphite particle orientation and with the contact area of activated carbon granule.
Fig. 5 (g) is the isothermal adsorption curve chart of active carbon.Fig. 5 (h) is the isothermal adsorption curve chart of the Graphene in embodiment 1.From Fig. 5 (g) and 5(h) can be by following Brunauer-Emmett-Teller(BET) specific area of formula (1) calculated activity carbon and Graphene.
Wherein, in formula (1), P is the equalizing pressure of adsorbed gas, P
obe the saturated vapour pressure of synthermal lower adsorbed gas, V is the volume of adsorbate, V
mthe volume of absorbate while being the monolayer saturated adsorption, C is constant (relevant with heat of adsorption).
Calculate, the specific area of activated carbon is 1968m
2/ g, the specific area of Graphene is only 370m
2/ g, so microwave is while peeling off Graphene as conductive agent, the electric double layer capacitance of its contribution can not be ignored.Thereby, in case of the present invention, microwave is peeled off the effect that Graphene not only serves as conductive agent, and contribution part electric double layer capacitance.
The chemical property of the ultracapacitor that adopts the electrode material in cyclic voltammetry above-described embodiment 1 and comparative example 1～3 to make.In mensuration, setting voltage is swept speed for 10mV/s, 20mV/s, 50mV/s, 100mV/s, 200mV/s; Aqueous electrolyte window voltage scope is from-1.0V to 0V; It is 5mV that the electrochemical AC impedance test applies sinusoidal bias voltage; The test frequency scope is that 100m Hz is to 100KHz; Constant current charge-discharge density is 0.1A/g, 0.15A/g, 0.5A/g, 0.75A/g, 1.0A/g, 1.5A/g, 2.0A/g, and charging voltage is 1.0V.
Fig. 6 (a) is the cyclic voltammetry curve figure of the ultracapacitor that adopts the electrode material in above-described embodiment 1 and comparative example 1～3 to make; Fig. 6 (b) is that the ultracapacitor that adopts the electrode material in above-described embodiment 1 to make is swept the cyclic voltammetry curve figure under speed in difference; Fig. 6 (c) is the constant current charge-discharge curve chart of the ultracapacitor that adopts the electrode material in above-described embodiment 1 and comparative example 1～3 to make; Fig. 6 (d) be the ultracapacitor that adopts the electrode material in above-described embodiment 1 and comparative example 1～3 to make the electrochemical AC impedance spectrogram.Fig. 6 (a) all is tending towards rectangle with the cyclic voltammetry curve in Fig. 6 (b), illustrates that the electric capacity of each ultracapacitor derives from the electric double layer capacitance of electrode and electrolyte interface and do not have fake capacitance to produce.From Fig. 6 (a) and Fig. 6 (c), can find out, compare and add acetylene black, carbon nano-tube, graphite agent, the absorbent charcoal based electrode material that adds the graphene conductive agent has larger ratio electric capacity.By following formula (2), calculate, add the specific capacity of the absorbent charcoal based ultracapacitor of graphene conductive additive to reach 295F/g when current density is 100mA/g, improved 95%, 55% and 40% than the specific capacity of the absorbent charcoal based ultracapacitor that adds graphite, acetylene black, carbon nanotube conducting agent respectively.
Wherein, in formula, C is than electric capacity, I
consbe constant current, m is the quality of single electrode material, and dV/dt is the slope obtained by the matching of constant-current discharge curve linear.
And, from Fig. 6 (d), can find out, add the equivalent series resistance minimum of the absorbent charcoal based electrode material of graphene conductive agent, illustrate that the graphene conductive agent has effectively improved the particle contact between activated carbon granule.
Fig. 7 (a) is the high rate performance comparison diagram of the ultracapacitor that adopts the electrode material in above-described embodiment 1 and comparative example 1～3 to make; Fig. 7 (b) is the cyclical stability comparison diagram of the ultracapacitor that adopts the electrode material in above-described embodiment 1 and comparative example 1～3 to make; Fig. 7 (c) is the power-performance comparison diagram of the ultracapacitor that adopts the electrode material in above-described embodiment 1 and comparative example 1～3 to make; Fig. 7 (d) is the energy density comparison diagram of the ultracapacitor that adopts the electrode material in above-described embodiment 1 and comparative example 1～3 to make; Fig. 7 (e) is the equivalent series resistance comparison diagram of the ultracapacitor that adopts the electrode material in above-described embodiment 1 and comparative example 1～3 to make; Fig. 7 (f) be the ultracapacitor that adopts the electrode material in above-described embodiment 1 and comparative example 1～3 to make 10mV/s sweep under speed than electric capacity comparison diagram.From Fig. 7 (a)～7(f) can find out that adding microwave peels off the absorbent charcoal based ultracapacitor of graphene conductive agent and have excellent chemical property, for example from Fig. 7 (a), can obtain, its high rate performance is good, when current density is increased to 2A/g from 0.5A/g, it still retains 95% than electric capacity; From Fig. 7 (b), can obtain, its degree of depth charge and discharge cycles is more than 1000 times, and the specific volume decay is only 8%, and the absorbent charcoal based ultracapacitor that this reflected microwave is peeled off the graphene conductive agent has longer cycle life; From Fig. 7 (c), can obtain, its power density reaches 150KW/kg; From Fig. 7 (d), can obtain, its specific energy is up to 10.2Wh/kg.From Fig. 7 (a)～7(f) contrast can find out, with traditional conductive agent, compare, the absorbent charcoal based electrode that adds the graphene conductive agent has high rate performance preferably, outstanding cyclical stability, lower equivalent series resistance, larger power density, larger energy density and larger ratio electric capacity.
Above-described embodiment has been described in detail technical scheme of the present invention; be understood that and the foregoing is only specific embodiments of the invention; be not limited to the present invention; all any modifications of making in principle scope of the present invention, supplement or similar fashion substitutes etc., within all should being included in protection scope of the present invention.
Claims (10)
1. the electrode material for ultracapacitor, it is characterized in that: active carbon, Graphene and binding agent, consist of, wherein, graphene uniform is interspersed between activated carbon granule; The described Graphene number of plies is 2 layers～7 layers, and the BET specific area is at 300m
2more than/g; And the mass ratio of described Graphene and activated carbon is 1:19～1:1.
2. the electrode material for ultracapacitor as claimed in claim 1, it is characterized in that: the number of plies of described Graphene is 3 layers～5 layers.
3. the electrode material for ultracapacitor as claimed in claim 1, it is characterized in that: the BET specific area of described Graphene is at 350m
2/ g～1000m
2/ g.
4. the electrode material for ultracapacitor as claimed in claim 1, it is characterized in that: the mass ratio of described Graphene and activated carbon is 1:15～1:7.
5. the electrode material for ultracapacitor as claimed in claim 1, it is characterized in that: the mass ratio of described Graphene and activated carbon is 1:9.
6. the electrode material for ultracapacitor as described as arbitrary claim in claim 1 to 5 is characterized in that: described binding agent comprise Kynoar,, Kynoar, polyvinyl alcohol, sodium carboxymethylcellulose.
7. the electrode material for ultracapacitor as described as arbitrary claim in claim 1 to 5, it is characterized in that: the preparation method of described Graphene comprises electrochemical stripping method, chemical reduction method, catalytic growth method.
8. the electrode material for ultracapacitor as claimed in claim 7, it is characterized in that: the preparation method of described Graphene is: adopt Hummer ' s chemical method to prepare graphite oxide, this graphite oxide is scattered in deionized water and forms dispersion liquid, after processing, Freeze Drying Technique obtains graphite oxide, then this graphite oxide is put into to microwave oven, adopt the microwave thermal reduction technique to make it peel off that to be reduced to graphite rare.
9. the preparation method of the electrode material for ultracapacitor as claimed in claim 1, it is characterized in that: active carbon, sheet Graphene and binding agent evenly are blended in solvent and form slurry, then this slurry evenly is coated in to substrate material surface, drying is processed rear compression molding, obtains electrode material.
10. the preparation method of the electrode material for ultracapacitor as claimed in claim 1, it is characterized in that: described solvent comprises ethanol, propyl alcohol, the tert-butyl alcohol, 1-METHYLPYRROLIDONE; Described basis material comprises porous foam nickel material, aluminum foil material, titanium material.
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