CN102757040B - 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 the preparation method of grapheme material.
Background technology
Graphene is by sp
2the monoatomic layer carbon film two-dimensional material that hydridization carbon atom forms according to six side's solid matter structures, owing to possessing good conductivity, outstanding heat conductivility, good chemical stability, excellent mechanical property, and high theoretical specific surface area (2630m
2/ g), become the study hotspot of energy storage, catalysis, sensing, electronics, prepare composite, have broad application prospects.But, owing to there being strong model ylid bloom action power between graphene sheet layer, in the preparation of Graphene and use procedure, very easily there is the stacking again of graphene nanometer sheet, the stacking surface that makes sheet interlayer of lamella can not be utilized effectively closely, and actual specific surface-area is well below the theoretical value (2630m of expection
2/ g), seriously hinder the application of Graphene.In order to solve graphene film stacking problem again, a kind of technical scheme is the form that Graphene is prepared into hydrogel, a large amount of moisture existing forms significant interval between graphene nanometer sheet, has maintained the separation between graphene film, has guaranteed the contact of the aqueous solution to graphene sheet layer 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 as reductive agent, prepare Graphene hydrogel by the method for vacuum filtration; Publication number is that the Chinese patent of CN101941693A discloses employing hydrazine hydrate, sodium borohydride, lithium aluminum hydride, formaldehyde, saccharide compound, xitix, amino acid as reductive agent, prepares the method for Graphene hydrogel by leaving standstill the method for processing.The reductive agent hydrazine hydrate, the sodium borohydride that in the method, adopt have toxicity, and vacuum filtration, leave standstill treating processes very long, operating procedure more complicated, therefore this area technical problem in the urgent need to address be select novel reducer, improve processing condition, simplify preparation process.
Summary of the invention
The present invention will solve the reductive agent that existing Graphene hydrogel preparation method utilizes to have the technical problem of toxicity and complicated operation, thereby the preparation method of graphene-based hydrogel is provided.
Graphene-based hydrogel of the present invention is the hydrogel being formed by Graphene, and the moisture in hydrogel accounts for 90%～99.5% of total mass.
The preparation method of above-mentioned graphene-based hydrogel carries out according to the following steps:
One, take graphite and reductive agent; Wherein the mass ratio of graphite and reductive agent is 1:(1～1000); Reductive agent is a kind of in KOH, NaOH, LiOH and ammoniacal liquor or wherein several combination;
Two, graphite oxidation step 1 being taken becomes graphite oxide;
Three, be 0.01mg/mL～50mg/mL by the concentration of graphite oxide, the graphite oxide that step 2 is obtained is added to the water, and ultrasonicly peels off, disperses, and obtains graphene oxide aqueous dispersions;
Four, graphene oxide aqueous dispersions step 3 being obtained is, under the condition of 4 ℃～100 ℃, to add reductive agent in temperature, is under 20～100KHz, the power ultrasound condition that is 40～1000W, to reduce 0.2h～6h in frequency, obtains Graphene colloidal dispersion;
Five, Graphene colloidal dispersion decompression rotary evaporation step 4 being obtained or rotating centrifugal are processed to water content to be 90%～99.5% gel is separated out from Graphene colloidal dispersion, and then gel is carried out to dialysis or vacuum filtration washing, obtain graphene-based hydrogel.
Different reductive agent reducing degree differences, prepared Graphene surface oxygen functional group kind, content are not identical yet, 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 in KOH, NaOH, LiOH and ammoniacal liquor or wherein several combination, there is more oxygen-containing functional group in gained Graphene surface, during as the active substance of electrode of super capacitor there is redox reaction that will definitely be contrary in oxygen-containing functional group, thereby larger fake capacitance electric current is provided, can improves and compare capacitance.
Graphene-based hydrogel of the present invention can also be the composite aquogel being formed by Graphene and non-graphitic carbon material, and the moisture in hydrogel accounts for 90%～99.5% of total mass; Non-graphitic carbon material is a kind of in carbon nanotube, carbon black, acetylene black, carbon fiber, carbon nano-particle and gac or wherein several combination; 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, be 1:(0.01～20 in the mass ratio of graphite, non-graphitic carbon material and reductive agent): the ratio of (1～1000) takes respectively graphite, non-graphitic carbon material and reductive agent, and wherein non-graphitic carbon material is a kind of in carbon nanotube, carbon black, acetylene black, carbon fiber, carbon nano-particle and gac or wherein several combination; Reductive agent is a kind of in KOH, NaOH, LiOH and ammoniacal liquor or wherein several combination;
Two, graphite oxidation step 1 being taken becomes graphite oxide;
Three, be 0.01mg/mL～50mg/mL by the concentration of graphite oxide, the graphite oxide that step 2 is obtained is added to the water, ultrasonicly peel off, disperse, obtain graphene oxide aqueous dispersions, the non-graphitic carbon material again step 1 being taken joins in graphene oxide aqueous dispersions, by stirring and/or ultrasonic method, it is uniformly dispersed, obtains graphite oxide thiazolinyl aqueous dispersions;
Four, graphite oxide thiazolinyl aqueous dispersions step 3 being obtained is under the condition of 4 ℃～100 ℃ in temperature, add reductive agent, be under 20～100KHz, the power ultrasound condition that is 40～1000W, to reduce 0.2h～6h in frequency, obtain graphene-based colloidal dispersion;
Five, graphene-based colloidal dispersion decompression rotary evaporation step 4 being obtained or rotating centrifugal are processed to water content to be 90%～99.5% gel is separated out from graphene-based colloidal dispersion, and then gel is carried out to dialysis or vacuum filtration washing, obtain graphene-based hydrogel.
Preparation method using above-mentioned graphene-based hydrogel as the electrode of super capacitor of active substance carries out according to the following steps: after graphene-based hydrogel is coated on electrode current collecting body, be immersed in the electrolytic solution of ultracapacitor and flood 1h～24h, obtain the electrode of super capacitor using graphene-based hydrogel as active substance.
The application of the above-mentioned electrode of super capacitor using graphene-based hydrogel as active substance is positive pole and/or the negative pole as ultracapacitor by the electrode of super capacitor using graphene-based hydrogel as active substance.
Compared with prior art, the present invention has the following advantages:
Graphene-based hydrogel of the present invention, to be made as reductive agent by a kind of or its arbitrary combination in KOH, NaOH, LiOH and ammoniacal liquor, there is more oxygen-containing functional group in gained Graphene surface, during as the active substance of electrode of super capacitor there is redox reaction that will definitely be contrary in oxygen-containing functional group, thereby larger fake capacitance electric current is provided, can improves and compare capacitance.
The graphene-based composite gel system for having comprised non-graphitic carbon material expanded by simple Graphene hydrogel by the present invention, in the time adding non-graphitic carbon material, because carbon material generally possesses surperficial hydrophobic character, there is stronger interaction with the delocalized pi-bond of graphene oxide sheet, therefore can be dispersed in graphene oxide dispersion liquid, in gel formation process subsequently, be evenly distributed in gel, graphene nanometer sheet is played to interval action, maintain porous, larger aperture and higher useful area, strengthened the compartmentation of water in hydrogel; In addition, be distributed in the beneficial effect that non-graphitic carbon material in graphene-based hydrogel also has other, for example, in graphene-carbon nano tube composite aquogel, the conduction that carbon nanotube has strengthened between 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 contributes 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.
In the preparation technology of graphene-based hydrogel of the present invention, a kind of or its arbitrary combination in employing KOH, NaOH, LiOH and ammoniacal liquor, as nontoxic reductive agent, only can obtain the Graphene of reduction by the supersound process of short period of time, and raw material is simple, and technique is quick.Forming in the process of gel, adopt decompression rotary evaporation technology can steam rapidly moisture, make the concentration of graphene-based aqueous dispersions reach rapidly threshold value and form gel, than vacuum filtration, to leave standstill method much quick; Forming in the process of gel, adopt rotating centrifugal to process and also can make in the short period of time Graphene form the gel of thickness together with non-graphitic carbon material, from water, separate, be deposited on the bottom of centrifuge tube.Therefore, technical scheme of the present invention has the feature of simple and fast, and green non-pollution.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of the film that obtains after drying at room temperature of graphene-based hydrogel that test prepares in one;
Fig. 2 tests ratio electric capacity-potential curve that the cyclic voltammetry curve of the electrode of super capacitor using graphene-based hydrogel as electrode active material of preparing under different scanning speed converts to; A is that sweep velocity is the ratio electric capacity-potential curve under 0.01V/s; B is that sweep velocity is the ratio electric capacity-potential curve under 0.02V/s; C is that sweep velocity is the ratio electric capacity-potential curve under 0.05V/s; D is that sweep velocity is the ratio electric capacity-potential curve under 0.1V/s; E is that sweep velocity is the ratio electric capacity-potential curve under 0.2V/s; F is that sweep velocity is the ratio electric capacity-potential curve under 0.5V/s; G is that sweep velocity is the ratio electric capacity-potential curve under 1V/s;
Fig. 3 tests the constant current charge-discharge curve of the electrode of super capacitor using graphene-based hydrogel as electrode active material of preparing under different current densities; Wherein a is that current density is the constant current charge-discharge curve under 2A/g condition; B is that current density is the constant current charge-discharge curve under 5A/g condition; C is that current density is the constant current charge-discharge curve under 10A/g condition; D is that current density is the constant current charge-discharge curve under 50A/g condition;
Fig. 4 tests the electric discharge of the constant current charge-discharge under different current densities of the electrode of super capacitor using graphene-based hydrogel as electrode active material of preparation in than electric capacity-current density curve;
Fig. 5 is the stereoscan photograph of the film that obtains after drying at room temperature of Graphene-multi-walled carbon nano-tubes composite aquogel that test prepares in two;
Fig. 6 tests the ratio electric capacity-potential curve of three electrode of super capacitor using Graphene-acetylene black composite aquogel as electrode active material of preparing under different scanning speed; A is that sweep velocity is the ratio electric capacity-potential curve under 0.02V/s; B is that sweep velocity is the ratio electric capacity-potential curve under 0.05V/s; C is that sweep velocity is the ratio electric capacity-potential curve under 0.1V/s; D is that sweep velocity is the ratio electric capacity-potential curve under 0.2V/s; E is that sweep velocity is the ratio electric capacity-potential curve under 0.5V/s; F is that sweep velocity is the ratio electric capacity-potential curve under 1V/s; G is that sweep velocity is the ratio electric capacity-potential curve under 2V/s; H is that sweep velocity is the ratio electric capacity-potential curve under 5V/s;
Fig. 7 tests the constant current charge-discharge curve of three electrode of super capacitor using Graphene-acetylene black composite aquogel as electrode active material of preparing under different current densities; Wherein a is that current density is the constant current charge-discharge curve under 2A/g condition; B is that current density is the constant current charge-discharge curve under 5A/g condition; C is that current density is the constant current charge-discharge curve under 10A/g condition; D is that current density is the constant current charge-discharge curve under 50A/g condition;
Fig. 8 tests the electric discharge of the three electrode of super capacitor constant current charge-discharges under different current densities using Graphene-acetylene black composite aquogel as electrode active material of preparing than electric capacity-current density curve.
Embodiment
Technical solution 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 present embodiment is the hydrogel being formed by Graphene, and the moisture in hydrogel accounts for 90%～99.5% of total mass.
Embodiment two: what present embodiment was different from embodiment one is, and in hydrogel, moisture accounts for total mass 93%～99%.Other is identical with embodiment one.
Embodiment three: the preparation method of the graphene-based hydrogel described in embodiment one carries out according to the following steps:
One, take graphite and reductive agent; Wherein the mass ratio of graphite and reductive agent is 1:(1～1000); Reductive agent is a kind of in KOH, NaOH, LiOH and ammoniacal liquor or wherein several combination; In the time that reductive agent is composition, each reductive agent is by any combination;
Two, graphite oxidation step 1 being taken becomes graphite oxide;
Three, be 0.01mg/mL～50mg/mL by the concentration of graphite oxide, the graphite oxide that step 2 is obtained is added to the water, and ultrasonicly peels off, disperses, and obtains graphene oxide aqueous dispersions;
Four, graphene oxide aqueous dispersions step 3 being obtained is, under the condition of 4 ℃～100 ℃, to add reductive agent in temperature, is under 20～100KHz, the power ultrasound condition that is 40～1000W, to reduce 0.2h～6h in frequency, obtains Graphene colloidal dispersion;
Five, Graphene colloidal dispersion decompression rotary evaporation step 4 being obtained or rotating centrifugal are processed to water content to be 90%～99.5% gel is separated out from Graphene colloidal dispersion, and then gel is carried out to dialysis or vacuum filtration washing, obtain graphene-based hydrogel.
Embodiment four: the mass ratio of what present embodiment was different from embodiment three is in step 1 graphite and reductive agent is 1:(5～100).Other is identical with embodiment three.
Embodiment five: the method for what present embodiment was different from embodiment three or four is in step 2 graphite oxidation becomes graphite oxide is as follows: adding 460mL mass percentage concentration in dry beaker is 98% H
2sO
4, then beaker is placed in to ice-water bath, add 20g graphite and 10g NaNO
3, stir with the speed of 50～500 revs/min, add gradually the Powdered KMnO of 60g simultaneously
4, under ice-water bath, agitation condition, continue reaction 2h; Beaker is moved into the continuous reaction of the thermostatical oil bath relaying 35min of 35 ± 1 ℃; Be slowly to add after 920mL distilled water under the agitation condition of 50～500 revs/min at rotating speed, control homo(io)thermism in 98 ℃, continue isothermal reaction 1h; With the distilled water diluting of 40 ℃, to 2000mL, adding 200mL mass percentage concentration is 30% hydrogen peroxide, suction filtration while hot; The hydrochloric acid cleaning filter cake that is 5% by mass percentage concentration, until in filtrate without SO
4 2-ion (is used BaCl
2solution detects), then use distilled water filtering and washing; Take out filter cake, at 80 ℃, vacuum-drying 24h, obtains graphite oxide.Other is identical with embodiment three or four.
Embodiment six: it is ultrasonic that what present embodiment was different from one of embodiment three to five is in step 3 is to be to carry out under 20～100KHz, the power condition that is 40～1000W in frequency.Other is identical with one of embodiment three to five.
Embodiment seven: under graphene oxide aqueous dispersions in temperature the is condition of 30 ℃～80 ℃ that what present embodiment was different from one of embodiment three to six is in step 4, adding reductive agent, is under 40～80KHz, the power ultrasound condition that is 50～500W, to reduce 1h～5h in frequency.Other is identical with one of embodiment three to six.
Embodiment eight: the vacuum tightness of what present embodiment was different from one of embodiment three to seven the is decompression rotary evaporation described in step 5 is-0.07MPa～-0.1MPa, and temperature is 30 ℃～90 ℃, and rotating speed is 20 revs/min～500 revs/min.Other is identical with one of embodiment three to seven.
Embodiment nine: the rotating speed of what present embodiment was different from one of embodiment three to seven the is rotating centrifugal described in step 5 is 500 revs/min～20000 revs/min.Other is identical with one of embodiment three to seven.
Embodiment ten: the graphene-based hydrogel of present embodiment is the hydrogel being formed by Graphene and non-graphitic carbon material, and the moisture in hydrogel accounts for 90%～99.5% of total mass; Non-graphitic carbon material is a kind of in carbon nanotube, carbon black, acetylene black, carbon fiber, carbon nano-particle and gac or wherein several combination; The mass ratio of non-graphitic carbon material and Graphene is (0.01～20): 1.
Present embodiment adds non-graphitic carbon material in Graphene hydrogel, because carbon material generally possesses surperficial hydrophobic character, there is stronger interaction with the delocalized pi-bond of graphene oxide sheet, therefore can be dispersed in graphene oxide dispersion liquid, be evenly distributed on the non-graphitic carbon material in the hydrogel forming subsequently, graphene nanometer sheet is played to interval action, maintained porous, larger aperture and higher useful area, strengthened the compartmentation of water in hydrogel; In addition, be distributed in the beneficial effect that non-graphitic carbon material in graphene-based hydrogel also has other, for example, in graphene-carbon nano tube composite aquogel, the conduction that carbon nanotube has strengthened between 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 contributes 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: what present embodiment was different from embodiment ten is, and in hydrogel, moisture accounts for total mass 93%～99%.Other is identical with embodiment ten.
Embodiment 12: the preparation method of the graphene-based hydrogel described in embodiment ten carries out according to the following steps:
One, be 1:(0.01～20 in the mass ratio of graphite, non-graphitic carbon material and reductive agent): the ratio of (1～1000) takes respectively graphite, non-graphitic carbon material and reductive agent, and wherein non-graphitic carbon material is a kind of in carbon nanotube, carbon black, acetylene black, carbon fiber, carbon nano-particle and gac or wherein several combination; Reductive agent is a kind of in KOH, NaOH, LiOH and ammoniacal liquor or wherein several combination;
Two, graphite oxidation step 1 being taken becomes graphite oxide;
Three, be 0.01mg/mL～50mg/mL by the concentration of graphite oxide, the graphite oxide that step 2 is obtained is added to the water, ultrasonicly peel off, disperse, obtain graphene oxide aqueous dispersions, the non-graphitic carbon material again step 1 being taken joins in graphene oxide aqueous dispersions, by stirring and/or ultrasonic method, it is uniformly dispersed, obtains graphite oxide thiazolinyl aqueous dispersions;
Four, graphite oxide thiazolinyl aqueous dispersions step 3 being obtained is under the condition of 4 ℃～100 ℃ in temperature, add reductive agent, be under 20～100KHz, the power ultrasound condition that is 40～1000W, to reduce 0.2h～6h in frequency, obtain graphene-based colloidal dispersion;
Five, graphene-based colloidal dispersion decompression rotary evaporation step 4 being obtained or rotating centrifugal are processed to water content to be 90%～99.5% gel is separated out from graphene-based colloidal dispersion, and then gel is carried out to dialysis or vacuum filtration washing, obtain graphene-based hydrogel.
In the time that the carbon material in step 1 is composition, various carbon materials are by any combination.
Present embodiment adopts the method for simple and fast and green non-pollution to prepare graphene-based hydrogel.In Graphene hydrogel, add non-graphitic carbon material, because carbon material generally possesses surperficial hydrophobic character, there is stronger interaction with the delocalized pi-bond of graphene oxide sheet, therefore can be dispersed in graphene oxide dispersion liquid, be evenly distributed on the non-graphitic carbon material in the hydrogel forming subsequently, graphene nanometer sheet is played to interval action, maintained porous, larger aperture and higher useful area, strengthened the compartmentation of water in hydrogel; In addition, be distributed in the beneficial effect that non-graphitic carbon material in graphene-based hydrogel also has other, for example, in graphene-carbon nano tube composite aquogel, the conduction that carbon nanotube has strengthened between 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 contributes 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: the mass ratio of what present embodiment was different from embodiment 12 is graphite in step 1, non-graphitic carbon material and reductive agent is 1:(0.1～5): (5～100).Other is identical with embodiment 12.
Embodiment 14: the method for what present embodiment was different from embodiment 12 or 13 is in step 2 graphite oxidation becomes graphite oxide is as follows: adding 460mL mass percentage concentration in dry beaker is 98% H
2sO
4, then beaker is placed in to ice-water bath, add 20g graphite and 10g NaNO
3, stir with the speed of 50～500 revs/min, add gradually the Powdered KMnO of 60g simultaneously
4, under ice-water bath, agitation condition, continue reaction 2h; Beaker is moved into the continuous reaction of the thermostatical oil bath relaying 35min of 35 ± 1 ℃; Be slowly to add after 920mL distilled water under the agitation condition of 50～500 revs/min at rotating speed, control homo(io)thermism in 98 ℃, continue isothermal reaction 1h; With the distilled water diluting of 40 ℃, to 2000mL, adding 200mL mass percentage concentration is 30% hydrogen peroxide, suction filtration while hot; The hydrochloric acid cleaning filter cake that is 5% by mass percentage concentration, until in filtrate without SO
4 2-ion (is used BaCl
2solution detects), then use distilled water filtering and washing; Take out filter cake, at 80 ℃, vacuum-drying 24h, obtains graphite oxide.Other is identical with embodiment 12 or 13.
Embodiment 15: what present embodiment was different from one of embodiment 12 to 14 is to stir in step 3 as mechanical stirring or induction stirring, and mixing speed is 20 revs/min～2000 revs/min.Other is identical with one of embodiment 12 to 14.
Embodiment 16: it is ultrasonic that what present embodiment was different from one of embodiment 12 to 15 is in step 3 is to be to carry out under 20～100KHz, the power condition that is 40～1000W in frequency.Other is identical with one of embodiment 12 to 15.
Embodiment 17: under graphite oxide thiazolinyl aqueous dispersions in temperature the is condition of 30 ℃～80 ℃ that what present embodiment was different from one of embodiment 12 to 16 is in step 4, adding reductive agent, is under 40～80KHz, the power ultrasound condition that is 50～500W, to reduce 1h～5h in frequency.Other is identical with one of embodiment 12 to 16.
Embodiment 18: the vacuum tightness of what present embodiment was different from one of embodiment 12 to 17 the is decompression rotary evaporation described in step 5 is-0.07MPa～-0.1MPa, temperature is 30 ℃～90 ℃, and rotating speed is 20 revs/min～500 revs/min.Other is identical with one of embodiment 12 to 17.
Embodiment 19: the rotating speed of what present embodiment was different from one of embodiment 12 to 17 the is rotating centrifugal described in step 5 is 500 revs/min～20000 revs/min.Other is identical with one of embodiment 12 to 17.
Embodiment 20: carry out according to the following steps as the preparation method of the electrode of super capacitor of electrode active material using the graphene-based hydrogel described in embodiment one or embodiment ten: be immersed in after graphene-based hydrogel is coated on electrode current collecting body in the electrolytic solution of ultracapacitor and flood 1h～24h, obtain the electrode of super capacitor using graphene-based hydrogel as electrode active material.
Embodiment 21: the application of the electrode of super capacitor using graphene-based hydrogel as electrode active material described in embodiment 20 is positive pole and/or the negative pole as ultracapacitor by the electrode of super capacitor using graphene-based hydrogel as active substance.
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, take 1g graphite and 5gKOH;
Two, graphite oxidation step 1 being taken becomes graphite oxide: concrete operations are: in dry beaker, adding 23mL mass percentage concentration is 98% H
2sO
4, be then placed in ice-water bath, add 1g graphite and 0.5g NaNO
3, stir with the speed of 100 revs/min, add gradually the Powdered KMnO of 3g simultaneously
4, under ice-water bath, agitation condition, continue reaction 2h; Beaker is moved into the continuous reaction of the thermostatical oil bath relaying 35min of 35 ± 1 ℃; Be slowly to add after 46mL distilled water under the agitation condition of 100 revs/min at rotating speed, control homo(io)thermism in 98 ℃, continue isothermal reaction 1h; With the distilled water diluting of 40 ℃, to 100mL, adding 10mL mass percentage concentration is 30% hydrogen peroxide, suction filtration while hot; The hydrochloric acid cleaning filter cake that is 5% by appropriate mass percentage concentration, until in filtrate without SO
4 2-ion (is used BaCl
2solution detects), then use distilled water filtering and washing; Take out filter cake, at 80 ℃, vacuum-drying 24h, obtains graphite oxide;
Three, be 1mg/mL by the concentration of graphite oxide, the graphite oxide that step 2 is obtained is added to the water, and is ultrasonicly under 40KHz, the power condition that is 50W to peel off, disperse 1h in frequency, obtains graphene oxide aqueous dispersions;
Four, graphene oxide aqueous dispersions step 3 being obtained is under the condition of 50 ℃ in temperature, and the KOH that adds step 1 to take is under 40KHz, the power ultrasound condition that is 50W, to reduce 1h in frequency, obtains Graphene colloidal dispersion;
Five, Graphene colloidal dispersion step 4 being obtained joins in the flask of Rotary Evaporators, in vacuum tightness be-0.09MPa, temperature is that 70 ℃, rotating speed are that the gel that rotary evaporation to water content is 96.5% that reduces pressure under the condition of 70 revs/min is separated out in Graphene colloidal dispersion, then by being attached to, after gel on flask inwall scrapes, to pack the molecular weight that dams into be in 8000～14000 dialysis bag, again dialysis bag is immersed in to dialysis 72h in distilled water, obtains Graphene hydrogel.
The graphene-based hydrogel that this test one obtains is coated on clean sheet glass, treats the dry laggard line scanning electron microscopic observation of room temperature placement, and the stereoscan photograph of the graphene-based aquagel membrane of gained as shown in Figure 1.As can be seen from Figure 1, the graphene-based hydrogel of this test one preparation is after applying, and graphene sheet layer 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 a graphene-based hydrogel obtaining: after graphene-based hydrogel is coated on titanium foil electrode current collecting body, be immersed in the electrolytic solution of ultracapacitor and flood 12h, obtain the electrode of super capacitor using graphene-based hydrogel as active substance; Wherein electrolytic solution is that density is the aqueous sulfuric acid of 1.28g/mL.
By the above-mentioned electrode of super capacitor using graphene-based hydrogel as electrode active material as Electrode, take Graphite Electrodes as to electrode, take mercury/Mercurous sulfate electrode as reference electrode, composition three-electrode system, the supercapacitor properties of the electrode of super capacitor of test using graphene-based hydrogel as electrode active material.
The cyclic voltammetry curve of the electrode of super capacitor of test using graphene-based hydrogel as electrode active material, and cyclic voltammetry curve is converted to than electric capacity-potential curve, as shown in Figure 2, a is that sweep velocity is the ratio electric capacity-potential curve under 0.01V/s to the ratio electric capacity-potential curve obtaining; B is that sweep velocity is the ratio electric capacity-potential curve under 0.02V/s; C is that sweep velocity is the ratio electric capacity-potential curve under 0.05V/s; D is that sweep velocity is the ratio electric capacity-potential curve under 0.1V/s; E is that sweep velocity is the ratio electric capacity-potential curve under 0.2V/s; F is that sweep velocity is the ratio electric capacity-potential curve under 0.5V/s; G is that sweep velocity is the ratio electric capacity-potential curve under 1V/s.As can be seen from Figure 2, on curve, exist a pair of at a distance of nearer oxidation-reduction peak, and increase along with sweeping fast increase peak separation, show this to oxidation-reduction peak correspondence one will definitely be contrary electrochemical reaction, i.e. the redox reaction of oxygen-containing functional group on Graphene surface.In addition, in potential scan commutation moment, electric current rises rapidly, shows good capacitance characteristic.Especially when sweep velocity is up to 1V/s, curve is still close to rectangle, declines during with respect to 0.01V/s few than electric capacity, illustrates that graphene-based hydrogel electrode has splendid high rate capability.
Graphene-based hydrogel electrode is carried out to constant current charge-discharge under different current densities, and corresponding constant current charges and discharge curve as shown in Figure 3.Wherein a is that current density is the constant current charge-discharge curve under 2A/g condition; B is that current density is the constant current charge-discharge curve under 5A/g condition; C is that current density is the constant current charge-discharge curve under 10A/g condition; D is that current density is the constant current charge-discharge curve under 50A/g condition.As seen from Figure 3, good at different current density lower electrode capacitance characteristics.In the time that current density reaches 50A/g, electrode can be emitted most of capacity in several seconds.
The electric discharge of constant current charge-discharge under different current densities is mapped with current density than electric capacity, and the ratio electric capacity obtaining and the relation curve of current density are as shown in Figure 4.As seen from Figure 4, under 1A/g current density than electric capacity up to 214.6F/g, milder than electric capacity suppression ratio with the increase of current density, when current density still reaches 90.1F/g than electric capacity during up to 200A/g.
These experimental results all show above, and graphene-based hydrogel electrode has high ratio capacitance in sulfuric acid electrolyte, also has extraordinary high power charging-discharging characteristic, is applicable to very much doing the electrode of ultracapacitor.These good characteristics have been derived from moisture interval in Graphene hydrogel graphene nanometer sheet, has guaranteed high electrode surface and larger nano level hole, for electrolytic solution provides abundant contact area and broad fast transport passage.Meanwhile, 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, take the ammoniacal liquor that 1g graphite, 0.33g multi-walled carbon nano-tubes and 20g mass percentage concentration are 25%;
Two, graphite oxidation step 1 being taken becomes graphite oxide: concrete operations are: in dry beaker, adding 23mL mass percentage concentration is 98% H
2sO
4, be then placed in ice-water bath, add 1g graphite and 0.5g NaNO
3, stir with the speed of 200 revs/min, add gradually the Powdered KMnO of 3g
4, under ice-water bath, agitation condition, continue reaction 2h; Beaker is moved into the continuous reaction of the thermostatical oil bath relaying 35min of 35 ± 1 ℃; Be slowly to add after 46mL distilled water under the agitation condition of 200 revs/min at rotating speed, control homo(io)thermism in 98 ℃, continue isothermal reaction 1h; With the distilled water diluting of 40 ℃, to 100mL, adding 10mL mass percentage concentration is 30% hydrogen peroxide, suction filtration while hot; The hydrochloric acid cleaning filter cake that is 5% by appropriate mass percentage concentration, until in filtrate without SO
4 2-ion (is used BaCl
2solution detects), then use distilled water filtering and washing; Take out filter cake, at 80 ℃, vacuum-drying 24h, obtains graphite oxide;
Three, be 1mg/mL by the concentration of graphite oxide, the graphite oxide that step 2 is obtained is added to the water, be ultrasonicly under 40KHz, the power condition that is 100W to peel off, disperse 1h in frequency, obtain graphene oxide aqueous dispersions, the multi-walled carbon nano-tubes again step 1 being taken joins in graphene oxide aqueous dispersions, be to stir 20min under the condition of 1000 revs/min at rotating speed, obtain graphene oxide-multi-walled carbon nano-tubes aqueous dispersions;
Four, graphene oxide-multi-walled carbon nano-tubes aqueous dispersions step 3 being obtained is under the condition of 25 ℃ in temperature, add the ammoniacal liquor that mass percentage concentration that step 1 takes is 25%, be under 40KHz, the power ultrasound condition that is 100W, to reduce 1h in frequency, obtain Graphene-multi-walled carbon nano-tubes colloidal dispersion;
Five, Graphene-multi-walled carbon nano-tubes colloidal dispersion step 4 being obtained joins in the centrifuge tube of whizzer, be under the condition of 15000 revs/min at the rotating speed of rotating centrifugal, the centrifugal gel that is 98% to water content is separated out in Graphene-multi-walled carbon nano-tubes colloidal dispersion, then after the gel that is deposited on centrifuge tube bottom being scraped, packing the molecular weight that dams into is in the dialysis bag of 8000-14000, again dialysis bag is immersed in distilled water to dialysis 72 hours, obtains Graphene-multi-walled carbon nano-tubes hydrogel.
Graphene-multi-walled carbon nano-tubes hydrogel that this test two obtains is coated on clean sheet glass, treats the dry laggard line scanning electron microscopic observation of room temperature placement, and the stereoscan photograph of Graphene-multi-walled carbon nano-tubes aquagel membrane of gained as shown in Figure 5.As can be seen from Figure 5, in Graphene-multi-walled carbon nano-tubes hydrogel of this test two preparations, multi-walled carbon nano-tubes is evenly distributed between graphene sheet layer, has played interval graphene nanometer sheet, maintains 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, take 1g graphite, 0.33g acetylene black and 5gKOH;
Two, graphite oxidation step 1 being taken becomes graphite oxide, and concrete operations are: in dry beaker, adding 23mL mass percentage concentration is 98% H
2sO
4, be then placed in ice-water bath, add 1g graphite and 0.5g NaNO
3, stir with the speed of 200 revs/min, add gradually the Powdered KMnO of 3g
4, under ice-water bath, agitation condition, continue reaction 2h; Beaker is moved into the continuous reaction of the thermostatical oil bath relaying 35min of 35 ± 1 ℃; Be slowly to add after 46mL distilled water under the agitation condition of 200 revs/min at rotating speed, control homo(io)thermism in 98 ℃, continue isothermal reaction 1h; With the distilled water diluting of 40 ℃, to 100mL, adding 10mL mass percentage concentration is 30% hydrogen peroxide, suction filtration while hot; The hydrochloric acid cleaning filter cake that is 5% by appropriate mass percentage concentration, until in filtrate without SO
4 2-ion (is used BaCl
2solution detects), then use distilled water filtering and washing; Take out filter cake, at 80 ℃, vacuum-drying 24h, obtains graphite oxide;
Three, be 1mg/mL by the concentration of graphite oxide, the graphite oxide that step 2 is obtained is added to the water, be ultrasonicly under 40KHz, the power condition that is 50W to peel off, disperse 1h in frequency, obtain graphene oxide aqueous dispersions, the acetylene black again step 1 being taken joins in graphene oxide aqueous dispersions, be ultrasonic dispersion 1h under 40KHz, the power condition that is 50W in frequency, obtain graphene oxide-acetylene black aqueous dispersions;
Four, graphene oxide-acetylene black aqueous dispersions step 3 being obtained is under the condition of 50 ℃ in temperature, and the KOH that adds step 1 to take is under 40KHz, the power ultrasound condition that is 50W, to reduce 1h in frequency, obtains Graphene-acetylene black colloidal dispersion;
Five, Graphene-acetylene black colloidal dispersion step 4 being obtained joins in the flask of Rotary Evaporators, in vacuum tightness be-0.09MPa, temperature is that 70 ℃, rotating speed are that the gel that rotary evaporation to water content is 98.7% that reduces pressure under the condition of 70 revs/min is separated out in Graphene colloidal dispersion, then the gel being attached on flask inwall is scraped, carry out 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 the three Graphene-acetylene black hydrogels that obtain: after Graphene-acetylene black hydrogel is coated on titanium foil electrode current collecting body, be immersed in the electrolytic solution of ultracapacitor and flood 12h, obtain the electrode of super capacitor using Graphene-acetylene black hydrogel as active substance; Wherein electrolytic solution is that density is the aqueous sulfuric acid of 1.28g/mL.
By the above-mentioned electrode of super capacitor using Graphene-acetylene black hydrogel as electrode active material as Electrode, take Graphite Electrodes as to electrode, take mercury/Mercurous sulfate electrode as reference electrode, composition three-electrode system, the supercapacitor properties of test using Graphene-acetylene black hydrogel as the electrode of super capacitor of electrode active material.
The cyclic voltammetry curve of test using 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, the ratio electric capacity-potential curve obtaining is as shown in Figure 6.A is that sweep velocity is the ratio electric capacity-potential curve under 0.02V/s; B is that sweep velocity is the ratio electric capacity-potential curve under 0.05V/s; C is that sweep velocity is the ratio electric capacity-potential curve under 0.1V/s; D is that sweep velocity is the ratio electric capacity-potential curve under 0.2V/s; E is that sweep velocity is the ratio electric capacity-potential curve under 0.5V/s; F is that sweep velocity is the ratio electric capacity-potential curve under 1V/s; G is that sweep velocity is the ratio electric capacity-potential curve under 2V/s; H is that sweep velocity is the ratio electric capacity-potential curve under 5V/s.As can be seen from Figure 6, on curve, exist a pair of at a distance of nearer oxidation-reduction peak, and increase along with sweeping fast increase peak separation, show this to oxidation-reduction peak correspondence one will definitely be contrary electrochemical reaction, i.e. the redox reaction of oxygen-containing functional group on Graphene surface.In addition, in potential scan commutation moment, electric current rises rapidly, shows good capacitance characteristic.When sweep velocity is during up to 1V/s, the curve of curve during with 0.01V/s is still more or less the same, the numerical value while being still in close proximity to 0.01V/s than electric capacity.And when sweep velocity is during up to 5V/s, curve, still very close to rectangle, illustrates that the electrode of super capacitor of this test three preparations has splendid high rate capability.
Graphene-acetylene black hydrogel electrode is carried out to constant current charge-discharge under different current densities, and corresponding constant current charges and discharge curve as shown in Figure 7, and wherein a is that current density is the constant current charge-discharge curve under 2A/g condition; B is that current density is the constant current charge-discharge curve under 5A/g condition; C is that current density is the constant current charge-discharge curve under 10A/g condition; D is that current density is the constant current charge-discharge curve under 50A/g condition; As seen from Figure 7, good at different current density lower electrode capacitance characteristics.In the time that current density reaches 50A/g, electrode can be emitted most of capacity in several seconds.
The electric discharge of constant current charge-discharge under different current densities is mapped with current density than electric capacity, and the ratio electric capacity obtaining and the relation curve of current density are as shown in Figure 8.As seen from Figure 8, under 1A/g current density, reach 139.8F/g than electric capacity, along with the increase of current density, almost no longer reducing after the decline at initial stage than electric capacity, 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 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, there is higher ratio capacitance, also there is extraordinary high power charging-discharging characteristic, its high magnification characteristic is even better than testing pure Graphene hydrogel electrode in, is applicable to very much doing the electrode materials of ultracapacitor.These good characteristics have been derived from moisture in graphene-based hydrogel and acetylene black interval graphene nanometer sheet, has guaranteed high electrode surface and larger nano level hole, for electrolytic solution provides abundant contact area and broad fast transport passage.And the fake capacitance electric current of Graphene surface oxygen functional group has also improved the ratio capacitance of electrode.Meanwhile, the existing good conductive characteristic of chain-cluster body being formed by the acetylene black of tens nanometer particle sizes, the water retention property also having had, makes the supply of gel electrode electrolyte inside abundant.
Claims (6)
1. the preparation method of graphene-based hydrogel, is characterized in that the preparation method of graphene-based hydrogel carries out according to the following steps:
One, take graphite and reductive agent; Wherein the mass ratio of graphite and reductive agent is 1:(1～1000); Reductive agent is a kind of in KOH, NaOH, LiOH and ammoniacal liquor or wherein several combination;
Two, graphite oxidation step 1 being taken becomes graphite oxide;
Three, be 0.01mg/mL～50mg/mL by the concentration of graphite oxide, the graphite oxide that step 2 is obtained is added to the water, and ultrasonicly peels off, disperses, and obtains graphene oxide aqueous dispersions;
Four, graphene oxide aqueous dispersions step 3 being obtained is, under the condition of 4 ℃～100 ℃, to add reductive agent in temperature, is under 20～100KHz, the power ultrasound condition that is 40～1000W, to reduce 0.2h～6h in frequency; Obtain Graphene colloidal dispersion;
Five, Graphene colloidal dispersion decompression rotary evaporation step 4 being obtained or rotating centrifugal are processed to water content to be 90%～99.5% gel is separated out from Graphene colloidal dispersion, and then gel is carried out to dialysis or vacuum filtration washing, obtain graphene-based hydrogel; Moisture in this hydrogel accounts for 90%～99.5% of total mass, and this graphene-based hydrogel is the gel with the thickness of two-dimentional laminated structure.
2. the preparation method of graphene-based hydrogel according to claim 1, is characterized in that ultrasonic in step 3 peeled off, disperseed is to be to carry out under 20～100KHz, the power condition that is 40～1000W in frequency.
3. the preparation method of graphene-based hydrogel according to claim 1, is characterized in that the vacuum tightness of the decompression rotary evaporation described in step 5 is-0.07MPa～-0.1MPa, and temperature is 30 ℃～90 ℃, and rotating speed is 20 revs/min～500 revs/min.
4. the preparation method of graphene-based hydrogel according to claim 1, the rotating speed that it is characterized in that the rotating centrifugal described in step 5 is 500 revs/min～20000 revs/min.
5. the preparation method of graphene-based hydrogel, is characterized in that the preparation method of graphene-based hydrogel carries out according to the following steps:
One, be 1:(0.01～20 in the mass ratio of graphite, non-graphitic carbon material and reductive agent): the ratio of (1～1000) takes respectively graphite, non-graphitic carbon material and reductive agent, and wherein non-graphitic carbon material is a kind of in carbon nanotube, carbon black, acetylene black, carbon fiber and gac or wherein several combination; Reductive agent is a kind of in KOH, NaOH, LiOH and ammoniacal liquor or wherein several combination;
Two, graphite oxidation step 1 being taken becomes graphite oxide;
Three, be 0.01mg/mL～50mg/mL by the concentration of graphite oxide, the graphite oxide that step 2 is obtained is added to the water, ultrasonicly peel off, disperse, obtain graphene oxide aqueous dispersions, the non-graphitic carbon material again step 1 being taken joins in graphene oxide aqueous dispersions, by stirring and/or ultrasonic method, it is uniformly dispersed, obtains graphite oxide thiazolinyl aqueous dispersions;
Four, graphite oxide thiazolinyl aqueous dispersions step 3 being obtained is, under the condition of 4 ℃～100 ℃, to add reductive agent in temperature, is under 20～100KHz, the power ultrasound condition that is 40～1000W, to reduce 0.2h～6h in frequency; Obtain graphene-based colloidal dispersion;
Five, graphene-based colloidal dispersion decompression rotary evaporation step 4 being obtained or rotating centrifugal are processed to water content to be 90%～99.5% gel is separated out from graphene-based colloidal dispersion, and then gel is carried out to dialysis or vacuum filtration washing, obtain graphene-based hydrogel; Moisture in this hydrogel accounts for 90%～99.5% of total mass, and this graphene-based hydrogel is the gel with the thickness of two-dimentional laminated structure.
6. the preparation method of graphene-based hydrogel according to claim 5, the mass ratio that it is characterized in that graphite in step 1, non-graphitic carbon material and reductive agent is 1:(0.1～5): (5～100).
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