CN103956275A - Method for preparing three-dimensional graphene network enhanced activated carbon supercapacitor electrode piece - Google Patents
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Abstract
The invention provides a method for preparing a three-dimensional graphene network enhanced activated carbon supercapacitor electrode piece. The method mainly comprises the steps that a chemical vapour deposition (CVD) technique is mainly utilized, foam metal is used as a graphene growth catalyst for preparing a graphene network skeleton, then activated carbon slurry is injected to form a supercapacitor electrode piece structure supporting the activated carbon structure of the graphene network skeleton, organic combining of the graphene and the activated carbon is achieved, the conductivity of activated carbon materials is improved, and meanwhile the graphene skeleton provides capacitance for improving the energy density and the power density. The graphene skeleton is applied to supercapacitor electrode materials to improve the comprehensive performance of a supercapacitor. Accordingly, the method can be applied to preparation of novel supercapacitor electrode materials.
Description
The invention belongs to new material device preparation field, relate to a kind of method of preparing three-dimensional grapheme network strengthen active carbon ultracapacitor pole piece.
Background technology
The consumption 80%-90% of world energy sources comes from the use of fossil fuel, produces problems thereupon: the CO2 that reduces gradually and give off due to combustion of fossil fuel of world's fossil fuel storage amount makes global warming, this be we profound lesson arrive.Therefore, a kind of development of sustainable renewable new energy source is particularly crucial for meeting following requirement clean, safety energy.Electric chemical super capacitor is the daily traffic the mankind as important new forms of energy storage system, is bringing into play irreplaceable important function in the lives such as communication.Ultracapacitor is a kind of very important electrochemistry electric energy storage device, belongs to the complete series low-carbon economy core product of standard.It is fast that ultracapacitor has a lot of characteristics (1) charging rate.Ultracapacitor can charge and not affect its performance under very high current density, so the required charging interval is very short, and can supplement the more than 95% of rated capacity even several seconds with money.(2) power density is large.There is not redox reaction in electric double layer type ultracapacitor, fake capacitance type ultracapacitor is also surface oxidation reduction reaction, large compared with the power density of battery.(3) have extended cycle life.Electric double layer type is due to just electrostatic charge effect, and its cycle life can reach hundreds of thousands, and memory-less effect, far away higher than the cycle life of battery.(4) safety and environmental protection.The electrode material and the electrolyte that use all can keep the safety in production, use, store, phase (SEI) in the middle of can producing in charge and discharge process unlike lithium battery.(5) operating temperature range is wide.Due to the electrolyte of ultracapacitor, to choose restrictive condition few, can be-40 ℃ of work and unaffected.It is more that the electrolyte of lithium battery is chosen restriction.Therefore, the growth and development of ultracapacitor has attracted numerous scientific workers' concern.Meanwhile, in view of its various features, be widely used in consumer electronics sector, intelligent power system, the field of traffic such as new-energy automobile, the military fields such as ELECTROMAGNETIC BOMB, tank startup system.Yet, energy density and relative high system equivalent internal resistance that ultracapacitor is lower, especially the performance under large charging and discharging currents density, has limited further developing of ultracapacitor.Internal resistance restriction due to ultracapacitor itself, in larger current density, discharge and recharge under condition and can produce very large voltage drop, cause memory capacity sharply to reduce, meanwhile, produced very large heat and caused super capacitor system overheated and cause a series of safety problems.The electrode material of development of new structure, keeps ultracapacitor inherent characteristic, improves the energy density of ultracapacitor, and reducing internal resistance is an important developing direction and the challenge facing.
Active carbon has high volumetric surface area, and cost is low, with the feature such as electrolyte is compatible good, is the most widely used electrode material for super capacitor.Yet active carbon, due to conductivity very low (10 ~ 100 S/m), is prepared in the process of electrode material for super capacitor in industry, need to conductive additive for example carbon black mix use.
Graphene is the newcomer in the Carbon Materials family finding for 2004, has unique physical property and wide application prospect.Due to the initiative experimental study aspect Graphene, its finder A. K. Geim and K. S. Novoselov have won 2010 annual Nobel Prizes in physics.As the basis of Graphene research, the preparation of Graphene receives much concern always, and its progress of research is also very fast.From tape stripping method the earliest, to SiC single crystal epitaxial growth method, chemical stripping method subsequently, until chemical vapor deposition (CVD) method is constantly improved and develops round realizing the application of this peculiar material of Graphene all the time.From early stage physical property research, till now as energy and material at lithium ion battery, ultracapacitor, as electronics material at transistor, radio-frequency devices, as power, electrically reinforcement is at composite material, especially the use in transparent conductive film, Graphene more shines charming glamour.Graphene be at present the thinnest be in the world the hardest nano material also, it is almost completely transparent, only absorbs 2.3% light; Conductive coefficient is up to 5300 W/mK, and higher than carbon nano-tube and diamond, under normal temperature, its electron mobility surpasses 15000 cm
2/ Vs, ratio nano carbon pipe or silicon wafer height again, and resistivity only approximately 10
-6Ω cm, lower than copper or silver, be the current material of resistivity minimum in the world.Because its resistivity is extremely low, the speed that electronics runs is exceedingly fast, and is therefore expected to can be used to develop thinner, conduction speed electronic component of new generation or transistor faster.Because Graphene is in fact a kind of transparent, good conductor, be also applicable to for manufacturing transparent touch screen, tabula rasa or even solar cell.In addition, single-layer graphene as the specific area of two-dimensional material up to 2630 m
2/ g, high conductivity in addition, grapheme material is considered to a kind of desirable electrochemistry electric energy accumulating material, is one of the most promising material of preparation applying electronic equipment of future generation.
And conventional conductive black contrasts electric capacity without any contribution in industry, if can reduce the ratio of conductive black, with high-quality grapheme material, replace, can increase the ratio of original active carbon active material simultaneously, so just can improve energy density and the power density of ultracapacitor, reduce internal resistance simultaneously, reduce thermal losses, improve system security reliability.How utilizing the graphene film of a large amount of nanoscales, at lower cost and pressing close under industrial processes requirement, be prepared into high-quality energy storage electrode material, is one of significant challenge facing at present.The preparation method of graphene nanometer sheet has a lot, and oxidation-reduction method can be prepared a tonne grapheme material, reproducible, especially, in energy storage material field, is considered to one of the important channel that can accomplish scale production.Oxidation-reduction method comprises graphite oxidation obtained to graphite oxide, then reduced and prepared the graphene nanometer sheet of different size by reducing process.Yet due to the restriction of oxide-reduction method itself, the Graphene quality prepared lower (for example conductivity only >1500 S/m), Graphene defect is many, has a strong impact on the performance of its performance.Chemical vapour deposition technique (CVD) is one of important method of preparing high-quality graphene film, and along with the development of technology of preparing, the output of CVD method also can meet the requirement of large-scale production.CVD method can utilize gaseous state, liquid state, solid matter as carbon source, to carry out the growth of graphene film.
It is target that the present invention take that Graphene network and active carbon organically combine, first prepare Graphene three-dimensional network, in Graphene network, inject the ultracapacitor pole piece that active carbon slurry is prepared into high-quality Graphene three-dimensional network support active carbon structure again, in order to improve super capacitor energy/power density, reduction system equivalent internal resistance, improves system security reliability.
Summary of the invention
Goal of the invention: Graphene has high conductivity under certain condition has high specific area simultaneously, and this provides theoretical foundation for its application in electrochemical energy storage field.Graphene is a kind of two-dimensional material, and being only prepared into macroscopic material could its using value in the middle of reality.Therefore, first the present invention prepares Graphene network skeleton by chemical vapour deposition technique, again active carbon slurry is injected in skeleton, form the ultracapacitor pole piece structure that Graphene network skeleton supports active carbon structure, realize Graphene and active carbon and organically combined, improved the conductivity of absorbent charcoal material, kept the superiority of active carbon itself not introduce again negative effect simultaneously, apply and electrode material for super capacitor, improve the combination property of ultracapacitor.
Therefore, the invention provides a kind of method of preparing three-dimensional grapheme network strengthen active carbon ultracapacitor pole piece, comprising:
(1) first CVD stove to remain on vacuum degree be 1-500mTorr, simultaneous temperature remains within the scope of 500-1200 ° of C, heating rate scope is 1-10 ℃/min; Then foam metal is placed in to CVD stove and keeps 10-30min, be connected with protective atmosphere and gaseous carbon source simultaneously, gas volume flow weight range is 0.1-500sccm, air pressure range 0.1-50 Torr; Afterwards foam metal is shifted out from CVD stove central area rapidly and cool to room temperature;
In step of the present invention (1), foam metal is the commercialization finished product with certain porosity, porosity >95%, foam metal material can comprise that any one has the metal material of catalytic growth Graphene function, comprises Cu, Ni, Fe, Ga, Au, Co, Pt, Ir, Ru, Deng, the industrial equipment that the equipment that described chemical vapour deposition technique is used is standard for CVD growth furnace;
Described protective atmosphere can be the mist of hydrogen and argon gas, or single a kind of inert gas comprises argon gas, and helium etc. are preferably the mist of hydrogen and argon gas;
Described gaseous carbon source, is mainly hydro carbons source of the gas, comprises methane, ethene, and acetylene etc., are preferably methane.
(2), the foam metal of the Graphene of having grown is placed in to corrosive liquid the Graphene network that grows out and body of metal foam is departed from, etching time scope is 1-24h; The three-dimensional network of Graphene is passed through rinsing again until pH is 7-10,120 ° of C of bake out temperature, drying time scope 1-24h.Described corrosive liquid is determined according to foam metal matrix used, mainly comprises ferric ion solutions, aqueous acid etc.; Through these technical processs, will obtain high-quality Graphene network structural material, Graphene is preferably 3-5 atomic layer level thickness, and process is as shown in Figure 1.
(3), the Graphene network obtaining through step of the present invention (2) is sticked on metal collector finished industrial product and through coating or spraying technology, active carbon slurry is injected in Graphene network skeleton, adhere to simultaneously and on collector, form the ultracapacitor pole piece structure that Graphene network skeleton supports active carbon structure; Coating speed 1.5m/s, pole piece thickness 100-150 μ m.Process as shown in Figure 2.The conductivity test of pole piece adopts four point probe method of testing.Described active carbon can be the industrialization finished product that is applied to super electrode capacitor electrode material.
As a kind of best mode: CVD stove of the present invention is warming up to 900-1050 ℃, and vacuum degree is at 100 m Torr, and heating rate is 10 ℃/min; Foam Ni is placed in to CVDLu center warm area and keeps 10 minutes, pass into 50 sccm hydrogen and 500 sccm argon gas, air pressure 30 Torr, 5-12sccm methane simultaneously.Effect is best with this understanding, and the specific surface of preparing Graphene three-dimensional network in this condition is about 1000 m
2/ g, its conductivity is 3000 S/m.The high-quality Graphene three-dimensional network of preparing is sticked in metal collector, form Graphene skeleton, in order to strengthen the conductivity of ultracapacitor absorbent charcoal material, the Conductivity Ratio of pole piece adds the raising at least 20% of conductive black originally.Graphene three-dimensional network also has contribution (1000 m to ultracapacitor total capacity simultaneously
2/ g, 20 μ F/m
2).Reached reduction internal resistance, raising capacity, the object of power/energy density.
Technology point of the present invention has:
A, CVD stove intensification temperature: CVD stove is warming up to lower than 900 or higher than 1050 ℃, to prepare Graphene second-rate;
B, catalyst are selected Ni, find that foam Ni makes catalyst effect best through great many of experiments;
C, 50 sccm hydrogen and 500 sccm argon gas,, air pressure 30 Torr, 5-12sccm methane is also that the present invention prepares Graphene key factor, through great many of experiments, finds, this ratio best results, other proportionate relationships are all worse than condition of the present invention.
Concrete reaction principle is:
(1) utilize chemical vapour deposition technique (Chemical Vapor Deposition, CVD), take foam metal as catalysis matrix, according to certain condition at metal surface catalytic growth Graphene
(2) with chemical corrosion method, Graphene and foam metal matrix are departed from, obtain self-existent (Free-standing) Graphene network;
(3) Graphene network is sticked in metal collector, utilize spraying or coating technique to inject active carbon super capacitor electrode paste simultaneously in Graphene network, take and form Graphene network as the pole piece structure of skeleton structure support absorbent charcoal material.
Beneficial effect:
Method of the present invention can be used for preparing on a large scale active carbon and Graphene three-dimensional net structure ultracapacitor pole piece.Prepared active carbon and Graphene three-dimensional net structure pole piece have kept the original high volumetric surface area of active carbon and pore structure and distribution.Utilize and the good combination of Graphene simultaneously, greatly improved the conductivity of pole piece itself.In addition, due to the intervention of high-quality graphene network configuration, also can be to the ratio electric capacity of the ultracapacitor (theoretical value: specific area 2630 m that contributes
2/ g, 20 μ F/m
2).Therefore, method of the present invention can be applicable to Novel super capacitor electrode material preparation field, can improve ultracapacitor combination property.
Specifically: the three-dimensional grapheme network strengthen active carbon ultracapacitor pole piece being prepared by this inventive method, kept the characteristic of original active carbon, for example high specific area (is generally greater than 1500m
2/ g), the compatibility good with solvent, simultaneously due to the introducing of high-quality CVD Graphene network skeleton, the conduction not only having improved between active carbon connects, and Graphene itself also has contribution (20 μ F/m to capacitance
2), for as electrode material for super capacitor, there is good application prospect.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in further detail.
Fig. 1 is the schematic diagram that CVD prepares Graphene network, and a is nickel foam substrate; B is CVD growing graphene; C is free-stangding Graphene network;
Fig. 2 prepares three-dimensional grapheme network strengthen active carbon ultracapacitor pole piece schematic diagram.
Embodiment
For understanding better the present invention, below in connection with embodiment, describe the present invention, but will be appreciated that these embodiment are only for to carry out example explanation to the present invention, and unrestricted the present invention.
The compound using in following examples or reagent are commercially available to be obtained, or can prepare by conventional method well known by persons skilled in the art; The laboratory apparatus using can be buied by commercial sources.
Active carbon described in embodiment is the industrialization finished product that is applied to super electrode capacitor electrode material, and foam metal is commercialization finished product coiled material.
Embodiment 1: select a kind of electrode material for super capacitor-active carbon (KURARAY, YP-50F), foam metal WeiNi(Hefei section is brilliant).(Hefei section is brilliant, GSL-1100X-III-D11-8) is warming up to 900 ° of C, and vacuum degree is at 100 m Torr, and heating rate is 10 ℃/min for CVD stove; Foam Ni is placed in to CVDLu center warm area and keeps 30 minutes, pass into hydrogen (50 sccm) and argon gas (500 sccm) simultaneously, and methane 5sccm, air pressure 30 Torr; The rapid CongCVDLu of foam Ni center warm area is shifted out and cool to room temperature.The sample of the Graphene of having grown is corroded to 8h with aqueous hydrochloric acid solution, then pass through rinsing until PH is 7-10,120 ° of C of bake out temperature, dry 24h.The Graphene network final sample obtaining is sticked on aluminium foil, utilize coating technique that active carbon slurry is coated on Graphene skeleton and aluminium foil, through drying, finally obtain Graphene network enhanced activity charcoal super capacitor pole piece.Coating speed 1m/s, pole piece thickness 100 μ m.Bake out temperature 100oC.The conductivity test of pole piece adopts four point probe method of testing.
Embodiment 2: select a kind of electrode material for super capacitor-active carbon (KURARAY, YP-50F), foam metal WeiNi(Hefei section is brilliant).(Hefei section is brilliant, GSL-1100X-III-D11-8) is warming up to 950 ° of C, and vacuum degree is at 100 m Torr, and heating rate is 10 °/min for CVD stove; Foam Ni is placed in to CVDLu center warm area and keeps 20 minutes, pass into hydrogen (50 sccm) and argon gas (500 sccm) simultaneously, and methane 8sccm, air pressure 30 Torr; The rapid CongCVDLu of foam Ni center warm area is shifted out and cool to room temperature.The sample of the Graphene of having grown is corroded to 10h with aqueous hydrochloric acid solution, then pass through rinsing until PH is 7-10,120 ° of C of bake out temperature, dry 24h.The Graphene network final sample obtaining is sticked on aluminium foil, utilize coating technique that active carbon slurry is coated on Graphene skeleton and aluminium foil, through drying, finally obtain Graphene network enhanced activity charcoal super capacitor pole piece.Coating speed 1.5m/s, pole piece thickness 110 μ m.Bake out temperature 100oC.The conductivity test of pole piece adopts four point probe method of testing.
Embodiment 3: select a kind of electrode material for super capacitor-active carbon (KURARAY, YP-50F), foam metal WeiNi(Hefei section is brilliant).(Hefei section is brilliant, GSL-1100X-III-D11-8) is warming up to 1050 ° of C, and vacuum degree is at 100 m Torr, and heating rate is 10 °/min for CVD stove; Foam Ni is placed in to CVDLu center warm area and keeps 10 minutes, pass into hydrogen (50 sccm) and argon gas (500 sccm) simultaneously, and methane 10sccm, air pressure 30 Torr; The rapid CongCVDLu of foam Ni center warm area is shifted out and cool to room temperature.The sample of the Graphene of having grown is corroded to 12h with aqueous hydrochloric acid solution, then pass through rinsing until PH is 7-10,120 ° of C of bake out temperature, dry 24h.The Graphene network final sample obtaining is sticked on aluminium foil, utilize coating technique that active carbon slurry is coated on Graphene skeleton and aluminium foil, through drying, finally obtain Graphene network enhanced activity charcoal super capacitor pole piece.Coating speed 2m/s, pole piece thickness 120 μ m.Bake out temperature 100oC.The conductivity test of pole piece adopts four point probe method of testing.
Embodiment 4: select a kind of electrode material for super capacitor-active carbon (KURARAY, YP-50F), foam metal WeiNi(Hefei section is brilliant).(Hefei section is brilliant, GSL-1100X-III-D11-8) is warming up to 1050 ° of C, and vacuum degree is at 100 m Torr, and heating rate is 10 °/min for CVD stove; Foam Ni is placed in to CVDLu center warm area and keeps 10 minutes, pass into hydrogen (50 sccm) and argon gas (500 sccm), air pressure 30 Torr, methane 12sccm simultaneously; The rapid CongCVDLu of foam Ni center warm area is shifted out and cool to room temperature.The sample of the Graphene of having grown is corroded to 12h with aqueous hydrochloric acid solution, then pass through rinsing until PH is 7-10,120 ° of C of bake out temperature, dry 24h.The Graphene network final sample obtaining is sticked on aluminium foil, utilize coating technique that active carbon slurry is coated on Graphene skeleton and aluminium foil, through drying, finally obtain Graphene network enhanced activity charcoal super capacitor pole piece.Coating speed 2m/s, pole piece thickness 150 μ m.Bake out temperature 100oC.The conductivity test of pole piece adopts four point probe method of testing.
Comparative example 1: select a kind of electrode material for super capacitor-active carbon (KURARAY, YP-50F), in the direct coating of active carbon slurry and aluminium foil that utilizes coating technique that the same terms is prepared, obtain the active carbon ultracapacitor pole piece that does not have Graphene network to strengthen.Coating speed 2m/s, pole piece thickness 150 μ m.Bake out temperature 100oC.The conductivity test of pole piece adopts four point probe method of testing.
Test result is as shown in table 1.
Each embodiment properties of sample test result of table 1.
| ? | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example |
| Electricity (S/cm) | 1570 | 1600 | 1580 | 1610 | 513 |
Discuss: see the above table 1, its conductivity of sample that adopts the present invention to prepare is 1570-1610, is much better than and does not adopt method of the present invention (conductivity 513).
Although the present invention has been carried out to example explanation in conjunction with specific embodiments, but what those skilled in the art will recognize that is, in the situation that not departing from purport of the present invention and scope, can described embodiment be changed or be improved, the scope of the invention limits by appended claims.
Claims (3)
1. the preparation method of three-dimensional grapheme network strengthen active carbon ultracapacitor pole piece, is characterized in that realizing as follows:
(1) first CVD stove to remain on vacuum degree be 1-500mTorr, simultaneous temperature remains within the scope of 500-1200 ℃, heating rate scope is 1-10 ℃/min; Then foam metal is placed in to CVD stove and keeps 10-30min, be connected with protective atmosphere and gaseous carbon source simultaneously, gas volume flow weight range is 0.1-500sccm, air pressure range 0.1-50 Torr; Afterwards foam metal is shifted out from CVD stove central area rapidly and cool to room temperature;
(2) foam metal of the Graphene of having grown is placed in to corrosive liquid the Graphene network and the body of metal foam that grow out are departed from, etching time scope is 1-24h; The three-dimensional network of Graphene is passed through rinsing again until pH is 7-10,120 ° of C of bake out temperature, drying time scope 1-24h;
(3), the Graphene network obtaining through step of the present invention (2) is sticked on metal collector finished industrial product and through coating or spraying technology, active carbon slurry is injected in Graphene network skeleton, adhere to simultaneously and on collector, form the ultracapacitor pole piece structure that Graphene network skeleton supports active carbon structure; Coating speed 1.5m/s, pole piece thickness 100-150 μ m.
2. the preparation method of three-dimensional grapheme network strengthen active carbon ultracapacitor pole piece according to claim 1, the porosity >95% that it is characterized in that the foam metal described in step (1), foam metal material comprises Cu, Ni, Fe, Ga, Au, Co, Pt, Ir and Ru; Described protective atmosphere is the mist of hydrogen and argon gas, or single a kind of inert gas is as argon gas, helium; Described gaseous carbon source is hydro carbons source of the gas, comprises methane, ethene, acetylene.
3. the preparation method of three-dimensional grapheme network strengthen active carbon ultracapacitor pole piece according to claim 2, is characterized in that
In step (1), CVD stove is warming up to 900-1050 ° of C, and vacuum degree is at 100 m Torr, and heating rate is 10 °/min; Foam Ni is placed in to CVDLu center warm area and keeps 10 minutes, pass into 50 sccm hydrogen and 500 sccm argon gas, air pressure 30 Torr, 5-12sccm methane simultaneously;
(2) foam metal of the Graphene of having grown is placed in to corrosive liquid the Graphene network and the body of metal foam that grow out are departed from, etching time scope is 1-24h; The three-dimensional network of Graphene is passed through rinsing again until pH is 7-10,120 ° of C of bake out temperature, drying time scope 1-24h;
(3), the Graphene network obtaining through step of the present invention (2) is sticked on metal collector finished industrial product and through coating or spraying technology, active carbon slurry is injected in Graphene network skeleton, adhere to simultaneously and on collector, form the ultracapacitor pole piece structure that Graphene network skeleton supports active carbon structure; Coating speed 1.5m/s, pole piece thickness 100-150 μ m.
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