CN102757040A - Graphene-based hydrogel and preparation method thereof as well as preparation method and application of supercapacitor electrode taking graphene-based hydrogel as active material - Google Patents
Graphene-based hydrogel and preparation method thereof as well as preparation method and application of supercapacitor electrode taking graphene-based hydrogel as active material Download PDFInfo
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Abstract
The invention discloses graphene-based hydrogel and a preparation method thereof as well as a preparation method and an application of a supercapacitor electrode taking the graphene-based hydrogel as an active material, and relates to a graphene material and a preparation method thereof as well as a preparation method of a supercapacitor electrode. The invention aims at solving the technical problems that a conventional preparation method of the graphene-based hydrogel utilizes a toxic reducing agent and is complex in operation. The graphene-based hydrogel disclosed by the invention is hydrogel formed by graphene or graphene and an ungraphitised carbon material. The preparation method comprises the following steps of: after oxidizing graphite into graphite oxide, dispersing the graphite oxide separately or with the ungraphitised carbon material in water to obtain graphene-based colloidal dispersion through reduction; after rotary evaporation or rotary centrifugal treatment at reduced pressure, obtaining the graphene-based hydrogel through leaching or washing; and after coating the graphene-based hydrogel on an electrode current collector, immersing the electrode current collector in electrolyte for dipping to obtain the supercapacitor electrode which can be used as the anode and/or cathode of a supercapacitor.
Description
Technical field
The present invention relates to grapheme material, its preparation method and by its ultracapacitor that assembles.
Background technology
Graphene is by sp
2The monoatomic layer carbon film two-dimensional material that the hydridization carbon atom is formed according to six side's solid matter structures is owing to possess good conductivity, outstanding heat conductivility, good chemicalstability, excellent mechanical property, and high theoretical specific surface area (2630m
2/ g), become the research focus of energy storage, catalysis, sensing, electronics, prepare composite, have broad application prospects.But; Owing to have strong model ylid bloom action power between the Graphene lamella; Piling up again of graphene nanometer sheet very easily taken place in the preparation of Graphene and use; Lamella piles up and makes the surface of sheet interlayer not to be utilized effectively closely, and the actual specific surface-area is well below the theoretical value (2630m of expection
2/ g), seriously hindered the application of Graphene.In order to solve the problem that graphene film piles up again; A kind of technical scheme is the form that Graphene is prepared into hydrogel; A large amount of moisture that exist form the significant interval between graphene nanometer sheet, kept the separation between the graphene film, have guaranteed the contact of the aqueous solution to the graphene film laminar surface.
(X. Yang et al., Adv.Mater., 2011,23 (25): 2833-2838 such as Dan Li; X. Yang et al., Angew.Chem.Int.Ed., 2011,50 (32): 7325-7328.) adopt Hydrazine Hydrate 80 as reductive agent, the method through vacuum filtration has prepared the Graphene hydrogel; Publication number is that the Chinese patent of CN101941693A discloses employing Hydrazine Hydrate 80, Peng Qinghuana, lithium aluminum hydride, formaldehyde, saccharide compound, xitix, amino acid as reductive agent, prepares the method for Graphene hydrogel through the method that leaves standstill processing.The reductive agent Hydrazine Hydrate 80, the Peng Qinghuana that adopt in this method have toxicity; And vacuum filtration, to leave standstill treating processes very long, the operating procedure more complicated, so the technical problem that this area presses for solution is to select novel reductive agent; Improve processing condition, simplify the preparation process.
Summary of the invention
The present invention will solve the reductive agent that existing Graphene hydrogel preparation method utilized to have the technical problem of toxicity and complicated operation, thereby graphene-based hydrogel, its preparation method is provided and with its preparation method and application as the electrode of super capacitor of active substance.
Graphene-based hydrogel of the present invention is the hydrogel that is formed by Graphene, 90%～99.5% of the water accounts total mass in the hydrogel.
The preparation method of above-mentioned graphene-based hydrogel carries out according to the following steps:
One, takes by weighing graphite and reductive agent; Wherein the mass ratio of graphite and reductive agent is 1: (1～1000); Reductive agent is a kind of or wherein several kinds the combination in KOH, NaOH, LiOH and the ammoniacal liquor;
Two, the graphite oxidation that step 1 is taken by weighing becomes graphite oxide;
Three, the concentration by graphite oxide is 0.01mg/mL～50mg/mL, and the graphite oxide that step 2 is obtained adds in the entry, ultrasonicly peels off, disperses, and obtains the graphene oxide aqueous dispersions;
Four, the graphene oxide aqueous dispersions that step 3 is obtained is under 4 ℃～100 ℃ the condition in temperature, adds reductive agent, is that 20～100KHz, power are that the ultrasound condition of 40～1000W reduces 0.2h～6h down in frequency, obtains the Graphene colloidal dispersion;
Five, it is that 90%～99.5% gel is separated out from the Graphene colloidal dispersion that Graphene colloidal dispersion decompression rotary evaporation that step 4 is obtained or rotating centrifugal are handled to water cut; And then gel carried out the washing of dialysis or vacuum filtration, obtain graphene-based hydrogel.
Different reductive agent reducing degree is different, and prepared Graphene surface oxygen functional group kind, content are also inequality, and thus obtained Graphene hydrogel is in structure, there are differences in nature.The reductive agent that the present invention adopts is a kind of or wherein several kinds the combination in KOH, NaOH, LiOH and the ammoniacal liquor; There is more oxygen-containing functional group in gained Graphene surface; During as the active substance of electrode of super capacitor oxygen-containing functional group take place will definitely be contrary redox reaction; Thereby bigger fake capacitance electric current is provided, can improves and compare capacitance.
Graphene-based hydrogel of the present invention can also be the composite aquogel that is formed by Graphene and non-graphitic carbon material, 90%～99.5% of the water accounts total mass in the hydrogel; Non-graphitic carbon material is a kind of or wherein several kinds the combination in carbon nanotube, carbon black, acetylene black, thomel, carbon nano-particle and the gac; The mass ratio of non-graphitic carbon material and Graphene is (0.01～20): 1.
The preparation method of above-mentioned graphene-based hydrogel carries out according to the following steps:
One, the mass ratio in graphite, non-graphitic carbon material and reductive agent is 1: (0.01～20): the ratio of (1～1000) takes by weighing graphite, non-graphitic carbon material and reductive agent respectively, and wherein non-graphitic carbon material is a kind of or wherein several kinds the combination in carbon nanotube, carbon black, acetylene black, thomel, carbon nano-particle and the gac; Reductive agent is a kind of or wherein several kinds the combination in KOH, NaOH, LiOH and the ammoniacal liquor;
Two, the graphite oxidation that step 1 is taken by weighing becomes graphite oxide;
Three, the concentration by graphite oxide is 0.01mg/mL～50mg/mL; The graphite oxide that step 2 is obtained adds in the entry; Ultrasonicly peel off, disperse, obtain the graphene oxide aqueous dispersions, the non-graphitic carbon material that again step 1 is taken by weighing joins in the graphene oxide aqueous dispersions; Through stirring and/or ultransonic method it is uniformly dispersed, obtains graphite oxide thiazolinyl aqueous dispersions;
Four, the graphite oxide thiazolinyl aqueous dispersions that step 3 is obtained is under 4 ℃～100 ℃ the condition in temperature; Add reductive agent; In frequency is that 20～100KHz, power are reduction 0.2h～6h under the ultrasound condition of 40～1000W, obtains graphene-based colloidal dispersion;
Five, it is that 90%～99.5% gel is separated out from graphene-based colloidal dispersion that graphene-based colloidal dispersion decompression rotary evaporation that step 4 is obtained or rotating centrifugal are handled to water cut; And then gel carried out the washing of dialysis or vacuum filtration, obtain graphene-based hydrogel.
Preparing method as the electrode of super capacitor of active substance carries out according to the following steps with above-mentioned graphene-based hydrogel: be immersed in after being coated in graphene-based hydrogel on the electrode current collecting body in the electrolytic solution of ultracapacitor and flood 1h～24h, obtain with the electrode of super capacitor of graphene-based hydrogel as active substance.
Above-mentioned with graphene-based hydrogel as the application of the electrode of super capacitor of active substance be with graphene-based hydrogel as the electrode of super capacitor of active substance positive pole and/or negative pole as ultracapacitor.
Compared with prior art, the present invention has the following advantages:
Graphene-based hydrogel of the present invention; Be to make as reductive agent by a kind of or its arbitrary combination in KOH, NaOH, LiOH and the ammoniacal liquor; There is more oxygen-containing functional group in gained Graphene surface; During as the active substance of electrode of super capacitor oxygen-containing functional group take place will definitely be contrary redox reaction, thereby bigger fake capacitance electric current is provided, can improve and compare capacitance.
The present invention expands simple Graphene hydrogel for having comprised the graphene-based composite gel system of non-graphitic carbon material; When adding non-graphitic carbon material; Because generally possessing the delocalized pi-bond of surperficial hydrophobic character and graphene oxide sheet, carbon material has stronger interaction, therefore can homodisperse in the graphene oxide dispersion liquid; In gel formation process subsequently, be evenly distributed in the gel; Graphene nanometer sheet is played interval action, kept porous, larger aperture and higher effective area, strengthened the compartmentation of water in the hydrogel; In addition; Be distributed in non-graphitic carbon material in the graphene-based hydrogel and also have other beneficial effect; For example in the graphene-carbon nano tube composite aquogel, the conduction that carbon nanotube has strengthened between the graphene nanometer sheet connects, and has also improved the physical strength of hydrogel.And in Graphene-acetylene black composite aquogel, acetylene black has also improved the water retention capacity of hydrogel.The These characteristics of graphene-based hydrogel helps to improve ratio electric capacity and the high rate capability by the ultracapacitor of its assembling, is especially suitable for use as the electrode materials of ultracapacitor.
Among the preparation technology of graphene-based hydrogel of the present invention, a kind of or its arbitrary combination in employing KOH, NaOH, LiOH and the ammoniacal liquor is as nontoxic reductive agent, and only the supersound process through the short period of time can obtain the reductive Graphene, and raw material is simple, and technology is quick.In forming the process of gel, adopt decompression rotary evaporation technology to steam moisture rapidly, make the concentration of graphene-based aqueous dispersions reach threshold value rapidly and form gel, much more quick than vacuum filtration, the method that leaves standstill; In the process that forms gel, adopt rotating centrifugal to handle and also can make Graphene form the heavy-gravity gel in the short period of time together with non-graphitic carbon material, separate from aqueous phase, be deposited on the bottom of centrifuge tube.Therefore, technical scheme of the present invention has the characteristics of simple and fast, and green non-pollution.
Description of drawings
Fig. 1 is the stereoscan photograph of the film that after drying at room temperature, obtains of graphene-based hydrogel that test prepares in one;
Fig. 2 is the ratio electric capacity-potential curve that converts at the cyclic voltammetry curve under the different scanning speed as the electrode of super capacitor of electrode active material with graphene-based hydrogel of preparation in the test one; A is that sweep velocity is the ratio electric capacity-potential curve under the 0.01V/s; B is that sweep velocity is the ratio electric capacity-potential curve under the 0.02V/s; C is that sweep velocity is the ratio electric capacity-potential curve under the 0.05V/s; D is that sweep velocity is the ratio electric capacity-potential curve under the 0.1V/s; E is that sweep velocity is the ratio electric capacity-potential curve under the 0.2V/s; F is that sweep velocity is the ratio electric capacity-potential curve under the 0.5V/s; G is that sweep velocity is the ratio electric capacity-potential curve under the 1V/s;
Fig. 3 be the test one in the preparation with electrode of super capacitor the constant current charge-discharge curve under different electric flow density of graphene-based hydrogel as electrode active material; Wherein a is that current density is the constant current charge-discharge curve under the 2A/g condition; B is that current density is the constant current charge-discharge curve under the 5A/g condition; C is that current density is the constant current charge-discharge curve under the 10A/g condition; D is that current density is the constant current charge-discharge curve under the 50A/g condition;
Fig. 4 be in the test one preparation with graphene-based hydrogel as the discharge of electrode of super capacitor constant current charge-discharge under the different electric flow density of electrode active material than electric capacity-current density curve;
Fig. 5 is a stereoscan photograph of testing the Graphene-film that the multi-walled carbon nano-tubes composite aquogel obtains for preparing in two after drying at room temperature;
Fig. 6 be the test three the preparation with electrode of super capacitor the ratio electric capacity-potential curve under different scanning speed of Graphene-acetylene black composite aquogel as electrode active material; A is that sweep velocity is the ratio electric capacity-potential curve under the 0.02V/s; B is that sweep velocity is the ratio electric capacity-potential curve under the 0.05V/s; C is that sweep velocity is the ratio electric capacity-potential curve under the 0.1V/s; D is that sweep velocity is the ratio electric capacity-potential curve under the 0.2V/s; E is that sweep velocity is the ratio electric capacity-potential curve under the 0.5V/s; F is that sweep velocity is the ratio electric capacity-potential curve under the 1V/s; G is that sweep velocity is the ratio electric capacity-potential curve under the 2V/s; H is that sweep velocity is the ratio electric capacity-potential curve under the 5V/s;
Fig. 7 be the test three the preparation with electrode of super capacitor the constant current charge-discharge curve under different electric flow density of Graphene-acetylene black composite aquogel as electrode active material; Wherein a is that current density is the constant current charge-discharge curve under the 2A/g condition; B is that current density is the constant current charge-discharge curve under the 5A/g condition; C is that current density is the constant current charge-discharge curve under the 10A/g condition; D is that current density is the constant current charge-discharge curve under the 50A/g condition;
Fig. 8 be test three preparations with Graphene-acetylene black composite aquogel as the discharge of electrode of super capacitor constant current charge-discharge under the different electric flow density of electrode active material than electric capacity-current density curve.
Embodiment
Technical scheme of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the graphene-based hydrogel of this embodiment is the hydrogel that is formed by Graphene, 90%～99.5% of the water accounts total mass in the hydrogel.
Embodiment two: this embodiment and embodiment one are different be in the hydrogel water accounts total mass 93%～99%.Other is identical with embodiment one.
Embodiment three: the preparation method of embodiment one described graphene-based hydrogel carries out according to the following steps:
One, takes by weighing graphite and reductive agent; Wherein the mass ratio of graphite and reductive agent is 1: (1～1000); Reductive agent is a kind of or wherein several kinds the combination in KOH, NaOH, LiOH and the ammoniacal liquor; When reductive agent was compsn, each reductive agent was pressed arbitrarily than combination;
Two, the graphite oxidation that step 1 is taken by weighing becomes graphite oxide;
Three, the concentration by graphite oxide is 0.01mg/mL～50mg/mL, and the graphite oxide that step 2 is obtained adds in the entry, ultrasonicly peels off, disperses, and obtains the graphene oxide aqueous dispersions;
Four, the graphene oxide aqueous dispersions that step 3 is obtained is under 4 ℃～100 ℃ the condition in temperature, adds reductive agent, is that 20～100KHz, power are that the ultrasound condition of 40～1000W reduces 0.2h～6h down in frequency, obtains the Graphene colloidal dispersion;
Five, it is that 90%～99.5% gel is separated out from the Graphene colloidal dispersion that Graphene colloidal dispersion decompression rotary evaporation that step 4 is obtained or rotating centrifugal are handled to water cut; And then gel carried out the washing of dialysis or vacuum filtration, obtain graphene-based hydrogel.
Embodiment four: this embodiment and embodiment three are different is that the mass ratio of graphite and reductive agent is 1 in the step 1: (5～100).Other is identical with embodiment three.
Embodiment five: this embodiment is different with embodiment three or four be in the step 2 graphite oxidation to become the method for graphite oxide following: in the exsiccant beaker, add the 460mL mass percentage concentration and be 98% H
2SO
4, then beaker is placed ice-water bath, add 20g graphite and 10g NaNO
3, stir with 50～500 rev/mins speed, add the Powdered KMnO of 60g simultaneously gradually
4, under ice-water bath, agitation condition, continue reaction 2h; The continuous reaction of thermostatical oil bath relaying 35min with 35 ± 1 ℃ of beaker immigrations; Be that controlled temperature is constant at 98 ℃, continues isothermal reaction 1h after slowly adding 920mL zero(ppm) water under 50～500 rev/mins the agitation condition at rotating speed; To 2000mL, adding 200mL mass percentage concentration is 30% ydrogen peroxide 50, suction filtration while hot with 40 ℃ distilled water dilutings; The use mass percentage concentration is 5% hydrochloric acid cleaning filter cake, in filtrating, does not have SO
4 2-Ion (is used BaCl
2Solution detects), use the zero(ppm) water filtering and washing again; Take out filter cake,, obtain graphite oxide at 80 ℃ of following vacuum-drying 24h.Other is identical with embodiment three or four.
Embodiment six: this embodiment is different with one of embodiment three to five is that ultrasonic in the step 3 is to be that 20～100KHz, power are to carry out under the condition of 40～1000W in frequency.Other is identical with one of embodiment three to five.
Embodiment seven: this embodiment is different with one of embodiment three to six is that the graphene oxide aqueous dispersions is under 30 ℃～80 ℃ the condition in temperature in the step 4; Adding reductive agent, is that 40～80KHz, power are that the ultrasound condition of 50～500W reduces 1h～5h down in frequency.Other is identical with one of embodiment three to six.
Embodiment eight: this embodiment is different with one of embodiment three to seven be the decompression rotary evaporation described in the step 5 vacuum tightness for-0.07MPa～-0.1MPa, temperature is 30 ℃～90 ℃, rotating speed is 20 rev/mins～500 rev/mins.Other is identical with one of embodiment three to seven.
Embodiment nine: this embodiment is different with one of embodiment three to seven is that the rotating speed of the rotating centrifugal described in the step 5 is 500 rev/mins～20000 rev/mins.Other is identical with one of embodiment three to seven.
Embodiment ten: the graphene-based hydrogel of this embodiment is the hydrogel that is formed by Graphene and non-graphitic carbon material, 90%～99.5% of the water accounts total mass in the hydrogel; Non-graphitic carbon material is a kind of or wherein several kinds the combination in carbon nanotube, carbon black, acetylene black, thomel, carbon nano-particle and the gac; The mass ratio of non-graphitic carbon material and Graphene is (0.01～20): 1.
This embodiment adds non-graphitic carbon material in the Graphene hydrogel; Because generally possessing the delocalized pi-bond of surperficial hydrophobic character and graphene oxide sheet, carbon material has stronger interaction, therefore can homodisperse in the graphene oxide dispersion liquid; Be evenly distributed on the non-graphitic carbon material in the hydrogel that forms subsequently; Graphene nanometer sheet is played interval action, kept porous, larger aperture and higher effective area, strengthened the compartmentation of water in the hydrogel; In addition; Be distributed in non-graphitic carbon material in the graphene-based hydrogel and also have other beneficial effect; For example in the graphene-carbon nano tube composite aquogel, the conduction that carbon nanotube has strengthened between the graphene nanometer sheet connects, and has also improved the physical strength of hydrogel.And in Graphene-acetylene black composite aquogel, acetylene black has also improved the water retention capacity of hydrogel.The These characteristics of graphene-based hydrogel helps to improve ratio electric capacity and the high rate capability by the ultracapacitor of its assembling, is especially suitable for use as the electrode materials of ultracapacitor.
Embodiment 11: this embodiment and embodiment ten are different be in the hydrogel water accounts total mass 93%～99%.Other is identical with embodiment ten.
Embodiment 12: the preparation method of embodiment ten described graphene-based hydrogels carries out according to the following steps:
One, the mass ratio in graphite, non-graphitic carbon material and reductive agent is 1: (0.01～20): the ratio of (1～1000) takes by weighing graphite, non-graphitic carbon material and reductive agent respectively, and wherein non-graphitic carbon material is a kind of or wherein several kinds the combination in carbon nanotube, carbon black, acetylene black, thomel, carbon nano-particle and the gac; Reductive agent is a kind of or wherein several kinds the combination in KOH, NaOH, LiOH and the ammoniacal liquor;
Two, the graphite oxidation that step 1 is taken by weighing becomes graphite oxide;
Three, the concentration by graphite oxide is 0.01mg/mL～50mg/mL; The graphite oxide that step 2 is obtained adds in the entry; Ultrasonicly peel off, disperse, obtain the graphene oxide aqueous dispersions, the non-graphitic carbon material that again step 1 is taken by weighing joins in the graphene oxide aqueous dispersions; Through stirring and/or ultransonic method it is uniformly dispersed, obtains graphite oxide thiazolinyl aqueous dispersions;
Four, the graphite oxide thiazolinyl aqueous dispersions that step 3 is obtained is under 4 ℃～100 ℃ the condition in temperature; Add reductive agent; In frequency is that 20～100KHz, power are reduction 0.2h～6h under the ultrasound condition of 40～1000W, obtains graphene-based colloidal dispersion;
Five, it is that 90%～99.5% gel is separated out from graphene-based colloidal dispersion that graphene-based colloidal dispersion decompression rotary evaporation that step 4 is obtained or rotating centrifugal are handled to water cut; And then gel carried out the washing of dialysis or vacuum filtration, obtain graphene-based hydrogel.
When the carbon material in the step 1 was compsn, various carbon materials were pressed arbitrarily than combination.
This embodiment adopts the method for simple and fast and green non-pollution to prepare graphene-based hydrogel.In the Graphene hydrogel, add non-graphitic carbon material; Because generally possessing the delocalized pi-bond of surperficial hydrophobic character and graphene oxide sheet, carbon material has stronger interaction, therefore can homodisperse in the graphene oxide dispersion liquid; Be evenly distributed on the non-graphitic carbon material in the hydrogel that forms subsequently; Graphene nanometer sheet is played interval action, kept porous, larger aperture and higher effective area, strengthened the compartmentation of water in the hydrogel; In addition; Be distributed in non-graphitic carbon material in the graphene-based hydrogel and also have other beneficial effect; For example in the graphene-carbon nano tube composite aquogel, the conduction that carbon nanotube has strengthened between the graphene nanometer sheet connects, and has also improved the physical strength of hydrogel.And in Graphene-acetylene black composite aquogel, acetylene black has also improved the water retention capacity of hydrogel.The These characteristics of graphene-based hydrogel helps to improve ratio electric capacity and the high rate capability by the ultracapacitor of its assembling, is especially suitable for use as the electrode materials of ultracapacitor.
Embodiment 13: this embodiment and embodiment 12 are different is that the mass ratio of graphite in the step 1, non-graphitic carbon material and reductive agent is 1: (0.1～5): (5～100).Other is identical with embodiment 12.
Embodiment 14: this embodiment is different with embodiment 12 or 13 be in the step 2 graphite oxidation to become the method for graphite oxide following: in the exsiccant beaker, add the 460mL mass percentage concentration and be 98% H
2SO
4, then beaker is placed ice-water bath, add 20g graphite and 10g NaNO
3, stir with 50～500 rev/mins speed, add the Powdered KMnO of 60g simultaneously gradually
4, under ice-water bath, agitation condition, continue reaction 2h; The continuous reaction of thermostatical oil bath relaying 35min with 35 ± 1 ℃ of beaker immigrations; Be that controlled temperature is constant at 98 ℃, continues isothermal reaction 1h after slowly adding 920mL zero(ppm) water under 50～500 rev/mins the agitation condition at rotating speed; To 2000mL, adding 200mL mass percentage concentration is 30% ydrogen peroxide 50, suction filtration while hot with 40 ℃ distilled water dilutings; The use mass percentage concentration is 5% hydrochloric acid cleaning filter cake, in filtrating, does not have SO
4 2-Ion (is used BaCl
2Solution detects), use the zero(ppm) water filtering and washing again; Take out filter cake,, obtain graphite oxide at 80 ℃ of following vacuum-drying 24h.Other is identical with embodiment 12 or 13.
Embodiment 15: what this embodiment was different with one of embodiment 12 to 14 is to stir in the step 3 to be mechanical stirring or induction stirring, and mixing speed is 20 rev/mins～2000 rev/mins.Other is identical with one of embodiment 12 to 14.
Embodiment 16: this embodiment is different with one of embodiment 12 to 15 is that ultrasonic in the step 3 is to be that 20～100KHz, power are to carry out under the condition of 40～1000W in frequency.Other is identical with one of embodiment 12 to 15.
Embodiment 17: this embodiment is different with one of embodiment 12 to 16 is that graphite oxide thiazolinyl aqueous dispersions is under 30 ℃～80 ℃ the condition in temperature in the step 4; Adding reductive agent, is that 40～80KHz, power are that the ultrasound condition of 50～500W reduces 1h～5h down in frequency.Other is identical with one of embodiment 12 to 16.
Embodiment 18: this embodiment is different with one of embodiment 12 to 17 be the decompression rotary evaporation described in the step 5 vacuum tightness for-0.07MPa～-0.1MPa; Temperature is 30 ℃～90 ℃, and rotating speed is 20 rev/mins～500 rev/mins.Other is identical with one of embodiment 12 to 17.
Embodiment 19: this embodiment is different with one of embodiment 12 to 17 is that the rotating speed of the rotating centrifugal described in the step 5 is 500 rev/mins～20000 rev/mins.Other is identical with one of embodiment 12 to 17.
Embodiment 20: the preparation method as the electrode of super capacitor of electrode active material carries out according to the following steps with embodiment one or embodiment ten described graphene-based hydrogels: be immersed in after being coated in graphene-based hydrogel on the electrode current collecting body in the electrolytic solution of ultracapacitor and flood 1h～24h, obtain with the electrode of super capacitor of graphene-based hydrogel as electrode active material.
Embodiment 21: embodiment 20 is described with the application of graphene-based hydrogel as the electrode of super capacitor of electrode active material, be with graphene-based hydrogel as the electrode of super capacitor of active substance positive pole and/or negative pole as ultracapacitor.
With following verification experimental verification beneficial effect of the present invention:
Test one: the preparation method of the graphene-based hydrogel of this test one carries out according to the following steps:
One, takes by weighing 1g graphite and 5gKOH;
Two, the graphite oxidation that step 1 is taken by weighing becomes graphite oxide: concrete operations are: adding 23mL mass percentage concentration is 98% H in the exsiccant beaker
2SO
4, be placed on then in the ice-water bath, add 1g graphite and 0.5g NaNO
3, stir with 100 rev/mins speed, add the Powdered KMnO of 3g simultaneously gradually
4, under ice-water bath, agitation condition, continue reaction 2h; The continuous reaction of thermostatical oil bath relaying 35min with 35 ± 1 ℃ of beaker immigrations; Be that controlled temperature is constant at 98 ℃, continues isothermal reaction 1h after slowly adding 46mL zero(ppm) water under 100 rev/mins the agitation condition at rotating speed; To 100mL, adding 10mL mass percentage concentration is 30% ydrogen peroxide 50, suction filtration while hot with 40 ℃ distilled water dilutings; Using an amount of mass percentage concentration is that 5% hydrochloric acid cleans filter cake, in filtrating, does not have SO
4 2-Ion (is used BaCl
2Solution detects), use the zero(ppm) water filtering and washing again; Take out filter cake,, obtain graphite oxide at 80 ℃ of following vacuum-drying 24h;
Three, the concentration by graphite oxide is 1mg/mL, and the graphite oxide that step 2 is obtained adds in the entry, is that 40KHz, power are ultrasonicly under the condition of 50W to peel off, disperse 1h in frequency, obtains the graphene oxide aqueous dispersions;
Four, the graphene oxide aqueous dispersions that step 3 is obtained is under 50 ℃ the condition in temperature, adds the KOH that step 1 takes by weighing, and is that 40KHz, power are that the ultrasound condition of 50W reduces 1h down in frequency, obtains the Graphene colloidal dispersion;
Five, the Graphene colloidal dispersion that step 4 is obtained joins in the flask of Rotary Evaporators; In vacuum tightness is that 70 ℃, rotating speed are that decompression rotary evaporation to water cut is that 96.5% gel is separated out in the Graphene colloidal dispersion under 70 rev/mins the condition for-0.09MPa, temperature; The molecular weight that dams of packing into after will scraping attached to the gel on the flask inwall then is in 8000～14000 the dialysis bag; Again dialysis bag is immersed in dialysis 72h in the zero(ppm) water, obtains the Graphene hydrogel.
The graphene-based hydrogel that this test one obtains is coated on the clean sheet glass, treats that room temperature places dry laggard line scanning electron microscopic observation, and the stereoscan photograph of the graphene-based aquagel membrane of gained is as shown in Figure 1.As can beappreciated from fig. 1, the graphene-based hydrogel of this test one preparation is after applying, and Graphene lamella self-assembly oriented alignment forms very orderly laminar structured in tens micrometer ranges.
Carry out according to the following steps as the preparation method of the electrode of super capacitor of electrode active material to test the graphene-based hydrogel that obtains: be immersed in after being coated in graphene-based hydrogel on the titanium foil electrode current collecting body in the electrolytic solution of ultracapacitor and flood 12h, obtain with the electrode of super capacitor of graphene-based hydrogel as active substance; Wherein electrolytic solution is that density is the aqueous sulfuric acid of 1.28g/mL.
With above-mentioned with graphene-based hydrogel as the electrode of super capacitor of electrode active material as the research electrode; With the Graphite Electrodes is counter electrode; With mercury/mercurous sulfate electrode is reference electrode; Form three-electrode system, test is with the super capacitor characteristic of graphene-based hydrogel as the electrode of super capacitor of electrode active material.
Test is with the cyclic voltammetry curve of graphene-based hydrogel as the electrode of super capacitor of electrode active material; And cyclic voltammetry curve converted to than electric capacity-potential curve; Ratio electric capacity-the potential curve that obtains is as shown in Figure 2, and a is that sweep velocity is the ratio electric capacity-potential curve under the 0.01V/s; B is that sweep velocity is the ratio electric capacity-potential curve under the 0.02V/s; C is that sweep velocity is the ratio electric capacity-potential curve under the 0.05V/s; D is that sweep velocity is the ratio electric capacity-potential curve under the 0.1V/s; E is that sweep velocity is the ratio electric capacity-potential curve under the 0.2V/s; F is that sweep velocity is the ratio electric capacity-potential curve under the 0.5V/s; G is that sweep velocity is the ratio electric capacity-potential curve under the 1V/s.As can beappreciated from fig. 2; Exist a pair of on the curve at a distance of nearer oxidation-reduction peak; And along with the increase peak separation of sweeping speed increases, show this to the oxidation-reduction peak corresponding one will definitely be contrary electrochemical reaction, i.e. the redox reaction of oxygen-containing functional group on the Graphene surface.In addition, commutate moment at potential scan, electric current rises rapidly, shows good capacitance characteristic.When especially sweep velocity was up to 1V/s, curve still approached rectangle, and it is few to descend during with respect to 0.01V/s than electric capacity, explains that graphene-based hydrogel electrode has splendid high rate capability.
Graphene-based hydrogel electrode is carried out constant current charge-discharge under the different electric flow density, it is as shown in Figure 3 that corresponding constant current charges and discharge curve.Wherein a is that current density is the constant current charge-discharge curve under the 2A/g condition; B is that current density is the constant current charge-discharge curve under the 5A/g condition; C is that current density is the constant current charge-discharge curve under the 10A/g condition; D is that current density is the constant current charge-discharge curve under the 50A/g condition.Visible by Fig. 3, good at different electric flow density lower electrode capacitance characteristic.When current density reached 50A/g, electrode can be emitted most of capacity in a few times in second.
The discharge of constant current charge-discharge under the different electric flow density is mapped with current density than electric capacity, and the ratio electric capacity that obtains and the relation curve of current density are as shown in Figure 4.Visible by Fig. 4, under the 1A/g current density than electric capacity up to 214.6F/g, milder with the increase of current density than electric capacity suppression ratio, when current density still reaches 90.1F/g than electric capacity during up to 200A/g.
More than these experimental results show that all graphene-based hydrogel electrode has high ratio capacitance in sulfuric acid electrolyte, also have extraordinary high power charging-discharging characteristic, is fit to very much do the electrode of ultracapacitor.These good characteristics be derived from the Graphene hydrogel moisture at interval graphene nanometer sheet, guaranteed high electrode surface and bigger nano level hole, for electrolytic solution provides abundant contact area and broad quick transmission path.Simultaneously, the fake capacitance electric current of Graphene surface oxygen functional group has also improved the ratio capacitance of electrode.
Test two: the preparation method of the graphene-based hydrogel of this test two carries out according to the following steps:
One, taking by weighing 1g graphite, 0.33g multi-walled carbon nano-tubes and 20g mass percentage concentration is 25% ammoniacal liquor;
Two, the graphite oxidation that step 1 is taken by weighing becomes graphite oxide: concrete operations are: adding 23mL mass percentage concentration is 98% H in the exsiccant beaker
2SO
4, be placed on then in the ice-water bath, add 1g graphite and 0.5g NaNO
3, stir with 200 rev/mins speed, add the Powdered KMnO of 3g gradually
4, under ice-water bath, agitation condition, continue reaction 2h; The continuous reaction of thermostatical oil bath relaying 35min with 35 ± 1 ℃ of beaker immigrations; Be that controlled temperature is constant at 98 ℃, continues isothermal reaction 1h after slowly adding 46mL zero(ppm) water under 200 rev/mins the agitation condition at rotating speed; To 100mL, adding 10mL mass percentage concentration is 30% ydrogen peroxide 50, suction filtration while hot with 40 ℃ distilled water dilutings; Using an amount of mass percentage concentration is that 5% hydrochloric acid cleans filter cake, in filtrating, does not have SO
4 2-Ion (is used BaCl
2Solution detects), use the zero(ppm) water filtering and washing again; Take out filter cake,, obtain graphite oxide at 80 ℃ of following vacuum-drying 24h;
Three, the concentration by graphite oxide is 1mg/mL; The graphite oxide that step 2 is obtained adds in the entry; In frequency is that 40KHz, power are ultrasonicly under the condition of 100W to peel off, disperse 1h, obtains the graphene oxide aqueous dispersions, and the multi-walled carbon nano-tubes that again step 1 is taken by weighing joins in the graphene oxide aqueous dispersions; Be to stir 20min under 1000 rev/mins the condition at rotating speed, obtain graphene oxide-multi-walled carbon nano-tubes aqueous dispersions;
Four, the graphene oxide that step 3 is obtained-multi-walled carbon nano-tubes aqueous dispersions is under 25 ℃ the condition in temperature; The mass percentage concentration that the adding step 1 takes by weighing is 25% ammoniacal liquor; In frequency is that 40KHz, power are reduction 1h under the ultrasound condition of 100W, obtains Graphene-multi-walled carbon nano-tubes colloidal dispersion;
Five, the Graphene that step 4 is obtained-multi-walled carbon nano-tubes colloidal dispersion joins in the centrifuge tube of whizzer; Be under 15000 rev/mins the condition at the rotating speed of rotating centrifugal; Centrifugal is that 98% gel is separated out in Graphene-multi-walled carbon nano-tubes colloidal dispersion to water cut; The molecular weight that dams of packing into after the gel that will be deposited on centrifuge tube bottom then scrapes is in the dialysis bag of 8000-14000; Again dialysis bag is immersed in the zero(ppm) water dialysis 72 hours, obtains Graphene-multi-walled carbon nano-tubes hydrogel.
The Graphene that this test two obtains-multi-walled carbon nano-tubes hydrogel is coated on the clean sheet glass, treats that room temperature places dry laggard line scanning electron microscopic observation, and the stereoscan photograph of the Graphene of gained-multi-walled carbon nano-tubes aquagel membrane is as shown in Figure 5.As can beappreciated from fig. 5, in the Graphene-multi-walled carbon nano-tubes hydrogel of this test two preparations, multi-walled carbon nano-tubes is evenly distributed between the Graphene lamella, has played graphene nanometer sheet at interval, keeps orderly laminated structure, keeps the effect of hole.
Test three: the preparation method of the graphene-based hydrogel of this test three carries out according to the following steps:
One, takes by weighing 1g graphite, 0.33g acetylene black and 5gKOH;
Two, the graphite oxidation that step 1 is taken by weighing becomes graphite oxide, and concrete operations are: adding 23mL mass percentage concentration is 98% H in the exsiccant beaker
2SO
4, be placed on then in the ice-water bath, add 1g graphite and 0.5g NaNO
3, stir with 200 rev/mins speed, add the Powdered KMnO of 3g gradually
4, under ice-water bath, agitation condition, continue reaction 2h; The continuous reaction of thermostatical oil bath relaying 35min with 35 ± 1 ℃ of beaker immigrations; Be that controlled temperature is constant at 98 ℃, continues isothermal reaction 1h after slowly adding 46mL zero(ppm) water under 200 rev/mins the agitation condition at rotating speed; To 100mL, adding 10mL mass percentage concentration is 30% ydrogen peroxide 50, suction filtration while hot with 40 ℃ distilled water dilutings; Using an amount of mass percentage concentration is that 5% hydrochloric acid cleans filter cake, in filtrating, does not have SO
4 2-Ion (is used BaCl
2Solution detects), use the zero(ppm) water filtering and washing again; Take out filter cake,, obtain graphite oxide at 80 ℃ of following vacuum-drying 24h;
Three, the concentration by graphite oxide is 1mg/mL; The graphite oxide that step 2 is obtained adds in the entry; In frequency is that 40KHz, power are ultrasonicly under the condition of 50W to peel off, disperse 1h, obtains the graphene oxide aqueous dispersions, and the acetylene black that again step 1 is taken by weighing joins in the graphene oxide aqueous dispersions; In frequency is that 40KHz, power are ultra-sonic dispersion 1h under the condition of 50W, obtains graphene oxide-acetylene black aqueous dispersions;
Four, the graphene oxide that step 3 is obtained-acetylene black aqueous dispersions is under 50 ℃ the condition in temperature, adds the KOH that step 1 takes by weighing, and is that 40KHz, power are that the ultrasound condition of 50W reduces 1h down in frequency, obtains Graphene-acetylene black colloidal dispersion;
Five, the Graphene that step 4 is obtained-acetylene black colloidal dispersion joins in the flask of Rotary Evaporators; In vacuum tightness is that 70 ℃, rotating speed are that decompression rotary evaporation to water cut is that 98.7% gel is separated out in the Graphene colloidal dispersion under 70 rev/mins the condition for-0.09MPa, temperature; To scrape attached to the gel on the flask inwall then; Carry out the vacuum filtration washing, obtain Graphene-acetylene black hydrogel.
Carry out according to the following steps as the preparation method of the electrode of super capacitor of electrode active material to test three Graphene-acetylene black hydrogels of obtaining: be immersed in after being coated in Graphene-acetylene black hydrogel on the titanium foil electrode current collecting body in the electrolytic solution of ultracapacitor and flood 12h, obtain with the electrode of super capacitor of Graphene-acetylene black hydrogel as active substance; Wherein electrolytic solution is that density is the aqueous sulfuric acid of 1.28g/mL.
With above-mentioned with Graphene-acetylene black hydrogel as the electrode of super capacitor of electrode active material as the research electrode; With the Graphite Electrodes is counter electrode; With mercury/mercurous sulfate electrode is reference electrode; Form three-electrode system, test is with the super capacitor characteristic of Graphene-acetylene black hydrogel as the electrode of super capacitor of electrode active material.
Test is with the cyclic voltammetry curve of Graphene-acetylene black hydrogel as the electrode of super capacitor of electrode active material, and cyclic voltammetry curve is converted to than electric capacity-potential curve, and the ratio electric capacity-potential curve that obtains is as shown in Figure 6.A is that sweep velocity is the ratio electric capacity-potential curve under the 0.02V/s; B is that sweep velocity is the ratio electric capacity-potential curve under the 0.05V/s; C is that sweep velocity is the ratio electric capacity-potential curve under the 0.1V/s; D is that sweep velocity is the ratio electric capacity-potential curve under the 0.2V/s; E is that sweep velocity is the ratio electric capacity-potential curve under the 0.5V/s; F is that sweep velocity is the ratio electric capacity-potential curve under the 1V/s; G is that sweep velocity is the ratio electric capacity-potential curve under the 2V/s; H is that sweep velocity is the ratio electric capacity-potential curve under the 5V/s.As can beappreciated from fig. 6; Exist a pair of on the curve at a distance of nearer oxidation-reduction peak; And along with the increase peak separation of sweeping speed increases, show this to the oxidation-reduction peak corresponding one will definitely be contrary electrochemical reaction, i.e. the redox reaction of oxygen-containing functional group on the Graphene surface.In addition, commutate moment at potential scan, electric current rises rapidly, shows good capacitance characteristic.When sweep velocity during up to 1V/s, the curve of curve during with 0.01V/s still is more or less the same the numerical value when still being in close proximity to 0.01V/s than electric capacity.And when sweep velocity during up to 5V/s, curve still approaches rectangle very much, explains that the electrode of super capacitor of this test three preparations has splendid high rate capability.
Graphene-acetylene black hydrogel electrode is carried out constant current charge-discharge under the different electric flow density, it is as shown in Figure 7 that corresponding constant current charges and discharge curve, and wherein a is that current density is the constant current charge-discharge curve under the 2A/g condition; B is that current density is the constant current charge-discharge curve under the 5A/g condition; C is that current density is the constant current charge-discharge curve under the 10A/g condition; D is that current density is the constant current charge-discharge curve under the 50A/g condition; Visible by Fig. 7, good at different electric flow density lower electrode capacitance characteristic.When current density reached 50A/g, electrode can be emitted most of capacity in a few times in second.
The discharge of constant current charge-discharge under the different electric flow density is mapped with current density than electric capacity, and the ratio electric capacity that obtains and the relation curve of current density are as shown in Figure 8.Visible by Fig. 8, under the 1A/g current density, reach 139.8F/g than electric capacity, along with the increase of current density, than electric capacity through almost no longer reducing after the decline at initial stage, when current density still reaches 115.2F/g than electric capacity during up to 500A/g.
All these experimental results all show; Graphene-acetylene black the hydrogel of test three preparations shows the fake capacitance electric current of surface oxygen functional group in sulfuric acid electrolyte as the electrode of super capacitor of electrode active material; Has higher specific capacitance; Also have extraordinary high power charging-discharging characteristic, its high magnification characteristic even be superior to testing pure Graphene hydrogel electrode in is fit to do the electrode materials of ultracapacitor very much.These good characteristics be derived from the graphene-based hydrogel moisture and acetylene black at interval graphene nanometer sheet, guaranteed high electrode surface and bigger nano level hole, for electrolytic solution provides abundant contact area and broad quick transmission path.And the fake capacitance electric current of Graphene surface oxygen functional group has also improved the ratio capacitance of electrode.Simultaneously,, good water retention property is arranged also, make the supply of gel electrode electrolyte inside abundant by the existing good conductive characteristic of chain-cluster body that the acetylene black of tens nanometer particle sizes is formed.
Claims (10)
1. graphene-based hydrogel is characterized in that graphene-based hydrogel is the hydrogel that is formed by Graphene, 90%～99.5% of the water accounts total mass in the hydrogel.
2. the preparation method of graphene-based hydrogel as claimed in claim 1 is characterized in that the preparation method of graphene-based hydrogel carries out according to the following steps:
One, takes by weighing graphite and reductive agent; Wherein the mass ratio of graphite and reductive agent is 1: (1～1000); Reductive agent is a kind of or wherein several kinds the combination in KOH, NaOH, LiOH and the ammoniacal liquor;
Two, the graphite oxidation that step 1 is taken by weighing becomes graphite oxide;
Three, the concentration by graphite oxide is 0.01mg/mL～50mg/mL, and the graphite oxide that step 2 is obtained adds in the entry, ultrasonicly peels off, disperses, and obtains the graphene oxide aqueous dispersions;
Four, the graphene oxide aqueous dispersions that step 3 is obtained is under 4 ℃～100 ℃ the condition in temperature, adds reductive agent, is that 20～100KHz, power are that the ultrasound condition of 40～1000W reduces 0.2h～6h down in frequency; Obtain the Graphene colloidal dispersion;
Five, it is that 90%～99.5% gel is separated out from the Graphene colloidal dispersion that Graphene colloidal dispersion decompression rotary evaporation that step 4 is obtained or rotating centrifugal are handled to water cut; And then gel carried out the washing of dialysis or vacuum filtration, obtain graphene-based hydrogel.
3. the preparation method of graphene-based hydrogel according to claim 2 is characterized in that ultrasonic in the step 3 peeled off, disperseed is to be that 20～100KHz, power are to carry out under the condition of 40～1000W in frequency.
4. the preparation method of graphene-based hydrogel according to claim 2, the vacuum tightness that it is characterized in that the decompression rotary evaporation described in the step 5 for-0.07MPa～-0.1MPa, temperature is 30 ℃～90 ℃, rotating speed is 20 rev/mins～500 rev/mins.
5. the preparation method of graphene-based hydrogel according to claim 2, the rotating speed that it is characterized in that the rotating centrifugal described in the step 5 is 500 rev/mins～20000 rev/mins.
6. graphene-based hydrogel is characterized in that graphene-based hydrogel is the hydrogel that is formed by Graphene and non-graphitic carbon material, 90%～99.5% of the water accounts total mass in the hydrogel; Non-graphitic carbon material is a kind of or wherein several kinds the combination in carbon nanotube, carbon black, acetylene black, thomel, carbon nano-particle and the gac; The mass ratio of non-graphitic carbon material and Graphene is (0.01～20): 1.
7. the method for preparing graphene-based hydrogel as claimed in claim 6 is characterized in that the preparation method of graphene-based hydrogel carries out according to the following steps:
One, the mass ratio in graphite, non-graphitic carbon material and reductive agent is 1: (0.01～20): the ratio of (1～1000) takes by weighing graphite, non-graphitic carbon material and reductive agent respectively, and wherein non-graphitic carbon material is a kind of or wherein several kinds the combination in carbon nanotube, carbon black, acetylene black, thomel, carbon nano-particle and the gac; Reductive agent is a kind of or wherein several kinds the combination in KOH, NaOH, LiOH and the ammoniacal liquor;
Two, the graphite oxidation that step 1 is taken by weighing becomes graphite oxide;
Three, the concentration by graphite oxide is 0.01mg/mL～50mg/mL; The graphite oxide that step 2 is obtained adds in the entry; Ultrasonicly peel off, disperse, obtain the graphene oxide aqueous dispersions, the non-graphitic carbon material that again step 1 is taken by weighing joins in the graphene oxide aqueous dispersions; Through stirring and/or ultransonic method it is uniformly dispersed, obtains graphite oxide thiazolinyl aqueous dispersions;
Four, the graphite oxide thiazolinyl aqueous dispersions that step 3 is obtained is under 4 ℃～100 ℃ the condition in temperature, adds reductive agent, is that 20～100KHz, power are that the ultrasound condition of 40～1000W reduces 0.2h～6h down in frequency; Obtain graphene-based colloidal dispersion;
Five, it is that 90%～99.5% gel is separated out from graphene-based colloidal dispersion that graphene-based colloidal dispersion decompression rotary evaporation that step 4 is obtained or rotating centrifugal are handled to water cut; And then gel carried out the washing of dialysis or vacuum filtration, obtain graphene-based hydrogel.
8. the preparation method of graphene-based hydrogel according to claim 7, the mass ratio that it is characterized in that graphite in the step 1, non-graphitic carbon material and reductive agent is 1: (0.1～5): (5～100).
9. with claim 1 or 6 described graphene-based hydrogels preparation method as the electrode of super capacitor of electrode active material; It is characterized in that it carries out according to the following steps: be immersed in after being coated in graphene-based hydrogel on the electrode current collecting body in the electrolytic solution of ultracapacitor and flood 1h～24h, obtain with the electrode of super capacitor of graphene-based hydrogel as electrode active material.
10. claim 9 is described with the application of graphene-based hydrogel as the electrode of super capacitor of electrode active material, it is characterized in that with graphene-based hydrogel as the electrode of super capacitor of active substance positive pole and/or negative pole as ultracapacitor.
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|---|---|---|---|---|
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-
2012
- 2012-07-25 CN CN201210259710.7A patent/CN102757040B/en active Active
Non-Patent Citations (1)
| Title |
|---|
| 徐宇曦: "功能化石墨烯的制备、组装及其应用", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 * |
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