CN103787310A - Boron-doped graphene composite thin film electrode material and preparation method thereof, and electrochemical capacitor and preparation method of electrochemical capacitor - Google Patents
Boron-doped graphene composite thin film electrode material and preparation method thereof, and electrochemical capacitor and preparation method of electrochemical capacitor Download PDFInfo
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Abstract
A boron-doped graphene composite thin film electrode material comprises a boron-doped graphene thin film and an ionic liquid adsorbed on the boron-doped graphene thin film. A preparation method of the electrode material comprises the steps: oxidating graphite to obtain graphite oxide; dispersing the graphite oxide in deionized water, carrying out ultrasonic treatment, filtering, drying, and thus obtaining graphene oxide; mixing the graphene oxide with diboron trioxide, then placing in an inert gas atmosphere, heating up to 800 DEG C to 1300 DEG C, carrying out heat preservation for 0.5 hour to 2 hours, then cooling to the room temperature, removing residual diboron trioxide, washing, carrying out ultrasonic treatment, carrying out vacuum filtration, and thus obtaining the boron-doped graphene thin film; and soaking the boron-doped graphene thin film in deionized water, then taking out, removing the water on the surface, next soaking in the ionic liquid, placing the boron-doped graphene thin film adsorbed with the ionic liquid in a vacuum environment, then heating for 12 hours to 24 hours at the temperature of 100-120 DEG C, carrying out suction filtration, and thus obtaining the boron-doped graphene composite thin film electrode material having higher energy storage specific capacity. The invention also provides an electrochemical capacitor and a preparing method thereof.
Description
Technical field
The present invention relates to graphene composite material field, particularly relate to boron doped graphene composite film electrode material and preparation method thereof and use electrochemical capacitor of this boron doped graphene composite film electrode material and preparation method thereof.
Background technology
Electrochemical capacitor, as a kind of novel energy-storing device, due to advantages such as its charge-discharge velocity are fast, power density is high, have extended cycle life, is the another energy storage device that has application potential and exploitation value after lithium ion.But energy density lower be a key factor of restriction ultracapacitor development and application, according to the calculation formula E=1/2CV of energy density
2, improve energy density and mainly start with from two aspects, be the voltage window that improves electrochemical capacitor on the one hand; The specific storage that improves electrode materials in addition on the one hand.The voltage window withstand voltage scope main and electrolytic solution of electrochemical capacitor has light, in order to improve the voltage window of electrochemical capacitor, start at present to adopt ionic liquid as electrolytic solution, its chemical window can reach 4V ~ 6V, can significantly increase the energy density of electrochemical capacitor, but ionic liquid is because viscosity is large, poor to the wetting property of electrode materials, this makes the more difficult raising of specific storage of electrode materials.
Graphene is as the two-dimentional unimolecular layer material of one, there is higher specific surface area and higher specific conductivity, Graphene is after boron-doping, due to the electronegativity of boron, make the energy storage efficiency of Graphene higher, boron doped graphene is a kind of desirable electrochemical capacitor electrode material, but this material is easily reunited, cause its actual specific surface area little, and poor with the wetting property of ionic liquid, and the stored energy ratio capacity obtaining is not high.
Summary of the invention
Based on this, be necessary to provide boron doped graphene composite film electrode material that a kind of stored energy ratio capacity is higher and preparation method thereof, used electrochemical capacitor of this boron doped graphene composite film electrode material and preparation method thereof.
A kind of boron doped graphene composite film electrode material, comprises boron doped graphene film and is adsorbed in the ionic liquid on described boron doped graphene film.
In an embodiment, described ionic liquid is two fluoroform sulfimide salt ([EMIM] TF of 1-ethyl-3-methylimidazole therein
2or two fluoroform sulfimide salt ([BMIM] TF of 1-butyl-3-Methylimidazole N)
2n).
In an embodiment, the mass ratio of described boron doped graphene film and described ionic liquid is 1:20 ~ 1:50 therein.
A preparation method for boron doped graphene composite film electrode material, comprising:
Graphite is oxidized, obtains graphite oxide;
Described graphite oxide is dispersed in deionized water, ultrasonic 2 hours ~ 4 hours, filter, dry, obtain graphene oxide;
Described graphene oxide is mixed with boron trioxide under the atmosphere that is placed on rare gas element, be warming up to 800 ° of C ~ 1300 ° C and be incubated 0.5 hour ~ after 2 hours, be cooled to room temperature, obtain mixture, remove remaining boron trioxide, washing, solids after washing is placed in to deionized water for ultrasonic, after vacuum filtration, obtains boron doped graphene film, then described boron doped graphene film is immersed in deionized water; And
Described boron doped graphene film is taken out from deionized water, remove after the moisture of boron doped graphene film surface, described boron doped graphene film is placed in to ionic liquid to be soaked, then absorption there is is the boron doped graphene film of ionic liquid to be placed in 100 ° of C ~ 120 of vacuum environment ° C heating 12 hours ~ 24 hours, suction filtration, obtains boron doped graphene composite film electrode material.
In an embodiment, the mass ratio of described graphene oxide and boron trioxide is 0.5:1 ~ 4:1 therein.
Therein in an embodiment, described in be warming up to 800 ° of C ~ 1300 ° C and be incubated 0.5 hour ~ temperature rise rate that is cooled to room temperature after 2 hours is 10 ° of C/min ~ 30 ° C/min.
In an embodiment, described ionic liquid is the two fluoroform sulfimide salt of 1-ethyl-3-methylimidazole or the two fluoroform sulfimide salt of 1-butyl-3-Methylimidazole therein.
Therein in an embodiment, described in to remove remaining boron trioxide be that described mixture is placed in to massfraction is that 10% hydrochloric acid stirs after 2 hours and filters.
A kind of electrochemical capacitor, comprises housing and is housed in positive plate, negative plate, barrier film and the electrolytic solution in described housing;
Described positive plate and negative plate comprise boron doped graphene composite film electrode material;
Described electrolytic solution is ionic liquid.
A preparation method for electrochemical capacitor, comprising:
Boron doped graphene composite film electrode material is dried and slicing treatment, obtains positive plate and negative plate;
Stack gradually assembling according to the order of described positive plate, barrier film and described negative plate and obtain battery core; And
At described battery core outer cladding housing, and inject the electrolytic solution being formed by ionic liquid in described housing, after sealing, obtain electrochemical capacitor.
Above-mentioned boron doped graphene composite film electrode material and preparation method thereof and electrochemical capacitor and preparation method in, boron doped graphene film is first immersed in deionized water and is preserved, and then be placed in ionic liquid, utilize the exchange between water and ionic liquid, greatly reduce the reunion of graphene sheet layer, effectively improve the energy storage surface of Graphene.Simultaneously because boron doped graphene composite film electrode material contains ionic liquid, the electrolytic solution using is also ionic liquid, can improve the wetting property of boron doped graphene composite film electrode material in electrolytic solution, the wetting property of this material and electrolytic solution is improved greatly.While finally making this material as electrochemical capacitor electrode material, there is excellent energy-storage property.
Accompanying drawing explanation
Fig. 1 is the preparation method's of the boron doped graphene composite film electrode material of an embodiment schema;
Fig. 2 is the preparation method's of the electrochemical capacitor of an embodiment schema.
Embodiment
Below in conjunction with embodiment and accompanying drawing, boron doped graphene composite film electrode material and preparation method thereof and electrochemical capacitor that uses this boron doped graphene composite film electrode material and preparation method thereof are described in further detail.
The boron doped graphene composite film electrode material of one embodiment, comprises boron doped graphene film and is adsorbed in the ionic liquid on described boron doped graphene film.
In the present embodiment, ionic liquid is preferably the two fluoroform sulfimide salt of 1-ethyl-3-methylimidazole or the two fluoroform sulfimide salt of 1-butyl-3-Methylimidazole.The mass ratio of boron doped graphene film and ionic liquid is preferably 1:20 ~ 1:50.
In above-mentioned boron doped graphene composite film electrode material, there is good energy-storage property, due to the existence of ionic liquid, make boron doped graphene film be difficult for reuniting, and improve the wetting property of this material and electrolytic solution, while making this material as electrochemical capacitor electrode material, there is excellent energy-storage property.
Refer to Fig. 1, the preparation method of the boron doped graphene composite film electrode material of an embodiment comprises the following steps:
S101, is oxidized graphite, obtains graphite oxide.
Its concrete steps are: graphite is added in the mixing solutions of the vitriol oil and concentrated nitric acid, mixes in bath at frozen water, keeping temperature is to stir under the condition about 0 ° of C; Then add at leisure potassium permanganate to mixing solutions, because potassium permanganate has strong oxidizing property under acidic conditions, can be oxidized graphite; Again mixing solutions is heated to 85 ° of C and reacts, and be incubated 30 minutes, in this insulating process, can further be oxidized graphite; Add deionized water, continue to keep 85 ° of C temperature 30 minutes; Then add hydrogen peroxide to mixing solutions, remove excessive potassium permanganate, obtain graphite oxide solution; Graphite oxide solution is carried out to suction filtration, obtains solids, and with dilute hydrochloric acid and deionized water to solids repetitive scrubbing, remove impurity, by solids in vacuum drying oven at 60 ° of C temperature dry 12 hours, obtain graphite oxide.
In the present embodiment, graphite is preferably 99.5% graphite.The massfraction of the vitriol oil is 98%, and the massfraction of concentrated nitric acid is 65%.The massfraction of hydrogen peroxide is 30%.
S102, is dispersed in graphite oxide in deionized water, and ultrasonic 2 hours ~ 4 hours, filter, dry, obtain graphene oxide.
Its concrete steps are: the graphite oxide that S101 is made is dispersed in and in deionized water, forms graphite oxide solution; Graphite oxide solution is carried out after supersound process, graphite oxide solution being filtered, obtain solids; Drying solid thing obtains graphene oxide.
In the present embodiment, the concentration of graphite oxide is preferably 0.5g/L ~ 1.0g/L, and ultrasonic power is preferably 500W, and ultrasonic time is preferably 2 hours ~ and 4 hours.Dry process is preferably solids is placed in to 60 ° of C of vacuum chamber dry 12 hours.
S103, mixes graphene oxide under the atmosphere that is placed on rare gas element with boron trioxide, is warming up to 800 ° of C ~ 1300 ° C and is incubated 0.5 hour ~ after 2 hours, is cooled to room temperature, obtains mixture; Remove remaining boron trioxide, washing, is placed in deionized water for ultrasonic by the solids after washing, obtains boron doped graphene film after vacuum filtration, and boron doped graphene film is placed in to deionized water.
In the present embodiment, the mass ratio of graphene oxide and boron trioxide is preferably 0.5:1 ~ 4:1.Rare gas element is preferably argon gas or neon, and the flow velocity of rare gas element is preferably 100mL/min ~ 400mL/min.Temperature rise rate in temperature-rise period is preferably 10 ° of C/min ~ 30 ° C/min.The concrete steps of removing remaining boron trioxide are preferably after the graphene oxide making until S102 reacts with boron trioxide and obtain mixture, the sodium hydroxide solution that mixture is placed in to 3mol/L stirs 2 hours, responseless boron trioxide is dissolved, then filter.Washing step is preferably and adopts deionized water wash filtrate.
S104, boron doped graphene film is taken out from deionized water, remove after the moisture of boron doped graphene film surface, boron doped graphene film is placed in to ionic liquid to be soaked, then absorption there is is the boron doped graphene film of ionic liquid to be placed in vacuum environment ° C heating 12 hours ~ 24 hours in 100 ° of C ~ 120, suction filtration, obtains boron doped graphene composite film electrode material.
In the present embodiment, the moisture of removing boron doped graphene film surface is preferably and adopts filter paper that its surperficial moisture is blotted.Ionic liquid is preferably the two fluoroform sulfimide salt of 1-ethyl-3-methylimidazole or the two fluoroform sulfimide salt of 1-butyl-3-Methylimidazole.Suction filtration is mainly in order to remove unnecessary ionic liquid.
In the preparation method of above-mentioned boron doped graphene composite film electrode material, first boron doped graphene film submergence is kept in deionized water, and then be placed in ionic liquid, utilize the exchange between water and ionic liquid, greatly reduce the reunion of graphene sheet layer, effectively improve the energy storage surface of Graphene, and the existence of ionic liquid, the wetting property of boron doped graphene composite film electrode material and electrolytic solution is improved greatly, while making this material as electrochemical capacitor electrode material, there is excellent energy-storage property.And this preparation method's technique is simple, easy to operate, there is the prospect of good industrial applications.
The electrochemical capacitor of one embodiment, comprises housing and is housed in positive plate, negative plate, barrier film and the electrolytic solution in described housing; Positive plate and negative plate comprise above-mentioned boron doped graphene composite film electrode material; Electrolytic solution is ionic liquid.
In the present embodiment, ionic liquid is preferably the two fluoroform sulfimide salt of 1-ethyl-3-methylimidazole or the two fluoroform sulfimide salt of 1-butyl-3-Methylimidazole.
Above-mentioned electrochemical capacitor adopts boron doped graphene composite film electrode material as electrode slice, because boron doped graphene composite film electrode material has good energy-storage property, while making this material as electrochemical capacitor electrode material, there is excellent energy-storage property.
Refer to Fig. 2, the preparation method of the electrochemical capacitor of an embodiment comprises the following steps:
S201, is dried above-mentioned boron doped graphene composite film electrode material and slicing treatment, obtains positive plate and negative plate;
In the present embodiment, drying process is preferably prior to being dried 2 hours at 80 ℃ of temperature, then is dried 2 hours at 250 ℃ of temperature.
S202, stacks gradually assembling according to the order of positive plate, barrier film and negative plate and obtains battery core.
S203 at battery core outer cladding housing, and injects the electrolytic solution being formed by ionic liquid in housing, obtains electrochemical capacitor after sealing.
In the present embodiment, inject ionic liquid to housing from the spout of housing, then seal spout, obtain electrochemical capacitor.Ionic liquid is preferably the two fluoroform sulfimide salt of 1-ethyl-3-methylimidazole or the two fluoroform sulfimide salt of 1-butyl-3-Methylimidazole.
Preparation method's step of above-mentioned electrochemical capacitor is simple, operate controlled, be applicable to large-scale industrial production.
Describe below in conjunction with specific embodiment.
Embodiment 1
(1) preparation of graphite oxide: take purity and be 99.5% graphite 1g, in the mixing solutions that the concentrated nitric acid that the vitriol oil that to add by 90mL massfraction be 98% and 25mL massfraction are 65% forms, mixing solutions is placed in to frozen water and mixes to bathe under environment and stir 20 minutes; In mixing solutions, add 6g potassium permanganate at leisure again, stir 1 hour; Then mixing solutions is heated to 85 ° of C and keeps 30 minutes; Add afterwards 92mL deionized water to continue to keep 30 minutes under 85 ° of C; Finally add the superoxol of 10mL massfraction 30%, stir 10 minutes; Mixing solutions is carried out to suction filtration, then with 100mL dilute hydrochloric acid and 150mL deionized water, solids is washed respectively successively, wash altogether three times, finally by solids dry graphite oxide that obtains for 12 hours in 60 ° of C vacuum drying ovens.
(2) preparation of graphene oxide: the graphite oxide obtaining in (1) is dispersed in deionized water, the concentration of graphite oxide is 1g/L, under the condition that is 500W at power with Ultrasonic Cleaners, after ultrasonic 2 hours, filter and obtain solids, the vacuum drying oven that solids is placed in to 60 ° of C is dried 12 hours, obtains graphene oxide.
(3) preparation of boron doped graphene film: get the graphene oxide obtaining in (2) and mix and obtain mixture with boron trioxide, wherein the mass ratio of graphene oxide and boron trioxide is 4:1; Then be placed under the argon gas atmosphere that flow velocity is 400mL/min, with 20 ° of C/min temperature rise rates, mixture temperature around risen to 800 ° of C, and keep 30 minutes; The argon gas atmosphere that is 400mL/min at flow velocity drops to room temperature; The sodium hydroxide solution that mixture is placed in to 3mol/L stirs 2 hours, filtration obtains filtrate, with after deionized water washing and filtering thing, filtrate after washing is placed in to deionized water for ultrasonic, vacuum is slowly filtered and is obtained boron doped graphene film, boron doped graphene film is placed in to deionized water and preserves.
(4) preparation of boron doped graphene composite film electrode material: the boron doped graphene film obtaining in (3) is taken out from deionized water, blot its surperficial water with filter paper, boron doped graphene film is immersed in to [EMIM] TF completely
2in N, boron doped graphene film and [EMIM] TF
2n mass ratio is 1:20, then mixture is placed under the vacuum environment of 120 ° of C and heats 12 hours, finally unnecessary ionic liquid suction filtration is removed, and obtains boron doped graphene composite film electrode material.
Embodiment 2
(1) preparation of graphite oxide: take purity and be 99.5% graphite 3g, the vitriol oil that to add by 285mL massfraction be 98% and 72mL massfraction are in the mixing solutions that forms of 65% concentrated nitric acid, mixing solutions is placed in to frozen water and mixes to bathe under environment and stir 20 minutes; In mixing solutions, add 12g potassium permanganate at leisure again, stir 1 hour; Then mixing solutions is heated to 85 ° of C and keeps 30 minutes; Add afterwards 150mL deionized water to continue to keep 30 minutes under 85 ° of C; Finally add the superoxol of 18mL massfraction 30%, stir 10 minutes; Mixing solutions is carried out to suction filtration, then with 200mL dilute hydrochloric acid and 30mL deionized water, solids is washed respectively successively, wash altogether three times, finally by solids dry graphite oxide that obtains for 12 hours in 60 ° of C vacuum drying ovens.
(2) preparation of graphene oxide: the graphite oxide obtaining in (1) is dispersed in deionized water, and the concentration of graphite oxide solution is 1g/L, the ultrasonic apparatus that is 500W with power is filtered after ultrasonic 2 hours graphite oxide solution; The vacuum drying oven that solids after filtering is placed in to 60 ° of C is dried 12 hours, obtains graphene oxide.
(3) preparation of boron doped graphene film: get the graphene oxide obtaining in (2) and mix and obtain mixture with boron trioxide, wherein the mass ratio of graphene oxide and boron trioxide is 2:1; Then be placed under the argon gas atmosphere that flow velocity is 400mL/min, with 30 ° of C/min temperature rise rates, mixture temperature around risen to 1100 ° of C, and keep 2 hours; The argon gas atmosphere that is 400mL/min at flow velocity drops to room temperature; The sodium hydroxide solution that mixture is placed in to 3mol/L stirs 2 hours, filtration obtains filtrate, with after deionized water washing and filtering thing, filtrate after washing is placed in to deionized water for ultrasonic, vacuum is slowly filtered and is obtained boron doped graphene film, boron doped graphene film is placed in to deionized water and preserves.
(4) preparation of boron doped graphene composite film electrode material: the boron doped graphene film obtaining in (3) is taken out from deionized water, blot its surperficial water with filter paper, boron doped graphene film is immersed in to [EMIM] TF completely
2in N, boron doped graphene film and [EMIM] TF
2n mass ratio is 1:30, then mixture is placed under the vacuum environment of 100 ° of C and heats 24 hours, finally unnecessary ionic liquid suction filtration is removed, and obtains boron doped graphene composite film electrode material.
Embodiment 3
(1) preparation of graphite oxide: take purity and be 99.5% graphite 5g, in the mixing solutions that the concentrated nitric acid that the vitriol oil that to add by 420mL massfraction be 98% and 120mL massfraction are 65% forms, mixing solutions is placed in to frozen water and mixes to bathe under environment and stir 20 minutes; In mixing solutions, add 20g potassium permanganate at leisure again, stir 1 hour; Then mixing solutions is heated to 85 ° of C and keeps 30 minutes; Add afterwards 300mL deionized water to continue to keep 30 minutes under 85 ° of C; Finally add the superoxol of 40mL massfraction 30%, stir 10 minutes; Mixing solutions is carried out to suction filtration, then with 400mL dilute hydrochloric acid and 800mL deionized water, solids is washed respectively successively, wash altogether three times, last solids is the dry graphite oxide that obtains for 12 hours in 60 ° of C vacuum drying ovens.
(2) preparation of graphene oxide: the graphite oxide obtaining in (1) is dispersed in deionized water, and the concentration of graphite oxide solution is 1g/L; The ultrasonic apparatus that is 500W with power is filtered after ultrasonic 3 hours graphite oxide solution; The vacuum drying oven that solids after filtering is placed in to 60 ° of C is dried 12 hours, obtains graphene oxide.
(3) preparation of boron doped graphene film: get the graphene oxide obtaining in (2) and mix and obtain mixture with boron trioxide, wherein the mass ratio of graphene oxide and boron trioxide is 1:1; Then being placed in flow velocity is under the neon atmosphere of 200mL/min, with 10 ° of C/min temperature rise rates, mixture temperature is around risen to 1000 ° of C, and keeps 30 minutes; The neon atmosphere that is 200mL/min at flow velocity drops to room temperature, the sodium hydroxide solution that mixture is placed in to 3mol/L stirs 2 hours, filtration obtains filtrate, with after deionized water washing and filtering thing, filtrate after washing is placed in to deionized water for ultrasonic, vacuum is slowly filtered and is obtained boron doped graphene film, boron doped graphene film is placed in to deionized water and preserves.
(4) preparation of boron doped graphene composite film electrode material: the boron doped graphene film obtaining in (3) is taken out from deionized water, blot its surperficial water with filter paper, boron doped graphene film is immersed in to [BMIM] TF completely
2in N, boron doped graphene film and [EMIM] TF
2n mass ratio is 1:40, then mixture is placed under the vacuum environment of 100 ° of C and heats 24 hours, finally unnecessary ionic liquid suction filtration is removed, and obtains boron doped graphene composite film electrode material.
Embodiment 4
(1) preparation of graphite oxide: take purity and be 99.5% graphite 1g, in the mixing solutions that the concentrated nitric acid that the vitriol oil that to add by 90mL massfraction be 98% and 25mL massfraction are 65% forms, mixing solutions is placed in to frozen water and mixes to bathe under environment and stir 20 minutes; In mixing solutions, add 4g potassium permanganate at leisure again, stir 1 hour; Then mixing solutions is heated to 85 ° of C and keeps 30 minutes; Add afterwards 92mL deionized water to continue to keep 30 minutes under 85 ° of C; Finally add the superoxol of 9mL massfraction 30%, stir 10 minutes; Mixing solutions is carried out to suction filtration, then with 100mL dilute hydrochloric acid and 150mL deionized water, solids is washed respectively successively, wash altogether three times, last solids is the dry graphite oxide that obtains for 12 hours in 60 ° of C vacuum drying ovens.
(2) preparation of graphene oxide: the graphite oxide obtaining in (1) is dispersed in deionized water, and the concentration of graphite oxide solution is 1g/L; The ultrasonic apparatus that is 500W with power is filtered after ultrasonic 4 hours graphite oxide solution; The vacuum drying oven that solids after filtering is placed in to 60 ° of C is dried 12 hours, obtains graphene oxide.
(3) preparation of boron doped graphene film: get the graphene oxide obtaining in (2) and mix and obtain mixture with boron trioxide, wherein the mass ratio of graphene oxide and boron trioxide is 0.5:1; Then be placed under the argon gas atmosphere that flow velocity is 1 00mL/min, with 20 ° of C/min temperature rise rates, mixture temperature is around risen to 1300 ° of C, and keep 1 hour, the last argon gas atmosphere that is 100mL/min at flow velocity drops to room temperature, the sodium hydroxide solution that mixture is placed in to 3mol/L stirs 2 hours, filtration obtains filtrate, with after deionized water washing and filtering thing, filtrate after washing is placed in to deionized water for ultrasonic, vacuum is slowly filtered and is obtained boron doped graphene film, boron doped graphene film is placed in to deionized water and preserves.
(4) preparation of boron doped graphene composite film electrode material: the boron doped graphene film obtaining in (3) is taken out from deionized water, blot its surperficial water with filter paper, boron doped graphene film is immersed in to [BMIM] TF completely
2in N, boron doped graphene film and [EMIM] TF
2n mass ratio is 1:50, then mixture is placed under the vacuum environment of 100 ° of C and heats 24 hours, finally unnecessary ionic liquid suction filtration is removed, and obtains boron doped graphene composite film electrode material.
Embodiment 5
The technical process of preparing electrochemical capacitor is as follows:
(1) the boron doped graphene composite film electrode material of being prepared by embodiment 1 is dried 2 hours at 80 ° of C temperature, then at 250 ℃ of temperature, is dried and carries out slicing treatment after 2 hours, makes positive plate and negative plate.
(2) according to being stacked gradually to assembling, the order of the positive plate, barrier film and the negative plate that obtain in (1) obtains battery core.
(3), by the battery core obtaining in housing seal (2), in housing, inject [EMIM] TF toward the spout being arranged on housing subsequently
2n, sealing spout, obtains electrochemical capacitor.
Embodiment 6
The technical process of preparing electrochemical capacitor is as follows:
(1) the boron doped graphene composite film electrode material of being prepared by embodiment 2 carries out roll-in, at 80 ° of C temperature, is dried 2 hours, then at 250 ℃ of temperature, is dried slicing treatment after 2 hours, makes positive plate and negative plate.
(2) according to being stacked gradually to assembling, the order of the positive plate, barrier film and the negative plate that obtain in (1) obtains battery core.
(3), by the battery core obtaining in housing seal (2), in housing, inject [EMIM] TF toward the spout being arranged on housing subsequently
2n, sealing spout, obtains electrochemical capacitor.
Embodiment 7
The technical process of preparing electrochemical capacitor is as follows:
(1) the boron doped graphene composite film electrode material of being prepared by embodiment 3 is dried 2 hours at 80 ° of C temperature, then at 250 ℃ of temperature, is dried and carries out slicing treatment after 2 hours, makes positive plate and negative plate.
(2) according to being stacked gradually to assembling, the order of the positive plate, barrier film and the negative plate that obtain in (1) obtains battery core.
(3), by the battery core obtaining in housing seal (2), in housing, inject [BMIM] TF toward the spout being arranged on housing subsequently
2n, sealing spout, obtains electrochemical capacitor.
Embodiment 8
The technical process of preparing electrochemical capacitor is as follows:
(1) the boron doped graphene composite film electrode material of being prepared by embodiment 4 is dried 2 hours at 80 ° of C temperature, then at 250 ℃ of temperature, is dried and carries out slicing treatment after 2 hours, makes positive plate and negative plate.
(2) according to being stacked gradually to assembling, the order of the positive plate, barrier film and the negative plate that obtain in (1) obtains battery core.
(3), by the battery core obtaining in housing seal (2), in housing, inject [BMIM] TF toward the spout being arranged on housing subsequently
2n, sealing spout, obtains electrochemical capacitor.
Electrochemical capacitor to assembling in embodiment 5 ~ 8 carries out charge-discharge test.The voltage window of its test is 4V, and current density is 0.5A/g.Test result is as shown in table 1.
The electrochemical capacitor charge-discharge test result of table 1 embodiment 5 ~ 8
| Sample | Specific storage (F/g) |
| Embodiment 5 | 232 |
| Embodiment 6 | 265 |
| Embodiment 7 | 258 |
| Embodiment 8 | 274 |
As shown in Table 1, the specific storage according to the electrochemical capacitor of embodiment 5 ~ 8 preparations under 0.5A/g current density all, more than 230F/g left and right, is up to 274F/g, has excellent energy-storage property.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. a boron doped graphene composite film electrode material, is characterized in that, comprises boron doped graphene film and is adsorbed in the ionic liquid on described boron doped graphene film.
2. boron doped graphene composite film electrode material according to claim 1, is characterized in that, described ionic liquid is the two fluoroform sulfimide salt of 1-ethyl-3-methylimidazole or the two fluoroform sulfimide salt of 1-butyl-3-Methylimidazole.
3. boron doped graphene composite film electrode material according to claim 1, is characterized in that, the mass ratio of described boron doped graphene film and described ionic liquid is 1:20 ~ 1:50.
4. a preparation method for boron doped graphene composite film electrode material, is characterized in that, comprising:
Graphite is oxidized, obtains graphite oxide;
Described graphite oxide is dispersed in deionized water, ultrasonic 2 hours ~ 4 hours, filter, dry, obtain graphene oxide;
Described graphene oxide is mixed with boron trioxide under the atmosphere that is placed on rare gas element, be warming up to 800 ° of C ~ 1300 ° C and be incubated 0.5 hour ~ after 2 hours, be cooled to room temperature, obtain mixture, remove remaining boron trioxide, washing, solids after washing is placed in to deionized water for ultrasonic, after vacuum filtration, obtains boron doped graphene film, then described boron doped graphene film is immersed in deionized water; And
Described boron doped graphene film is taken out from deionized water, remove after the moisture of boron doped graphene film surface, described boron doped graphene film is placed in to ionic liquid to be soaked, then absorption there is is the boron doped graphene film of ionic liquid to be placed under vacuum environment in 100 ° of C ~ 120 ° C heating 12 hours ~ 24 hours, suction filtration, obtains boron doped graphene composite film electrode material.
5. the preparation method of boron doped graphene composite film electrode material according to claim 4, is characterized in that, the mass ratio of described graphene oxide and boron trioxide is 0.5:1 ~ 4:1.
6. the preparation method of boron doped graphene composite film electrode material according to claim 4, it is characterized in that, described in be warming up to 800 ° of C ~ 1300 ° C and be incubated 0.5 hour ~ temperature rise rate that is cooled to room temperature after 2 hours is 10 ° of C/min ~ 30 ° C/min.
7. the preparation method of boron doped graphene composite film electrode material according to claim 4, described ionic liquid is the two fluoroform sulfimide salt of 1-ethyl-3-methylimidazole or the two fluoroform sulfimide salt of 1-butyl-3-Methylimidazole.
8. the preparation method of boron doped graphene composite film electrode material according to claim 4, is characterized in that, described in to remove remaining boron trioxide be that sodium hydroxide solution that described mixture is placed in to matter 3mol/L stirs after 2 hours and filters.
9. an electrochemical capacitor, is characterized in that, comprises housing and is housed in positive plate, negative plate, barrier film and the electrolytic solution in described housing;
Described positive plate and negative plate comprise the doped graphene of boron described in claim 1 composite film electrode material;
Described electrolytic solution is ionic liquid.
10. a preparation method for electrochemical capacitor, is characterized in that, comprising:
Boron doped graphene composite film electrode material described in claim 1 is dried and slicing treatment, obtains positive plate and negative plate;
Stack gradually assembling according to the order of described positive plate, barrier film and described negative plate and obtain battery core; And
At described battery core outer cladding housing, and inject the electrolytic solution being formed by ionic liquid in described housing, after sealing, obtain electrochemical capacitor.
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