CN103787309A - Preparation method of boron doped graphene film and electrochemical capacitor - Google Patents
Preparation method of boron doped graphene film and electrochemical capacitor Download PDFInfo
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Abstract
A preparation method of a boron doped graphene film comprises the steps of: oxidizing graphite to obtain graphite oxide; dispersing the graphite oxide in deionized water, conducting ultrasonic treatment, filtering and drying to obtain the graphene oxide; placing the graphene oxide in a mixed atmosphere of boron trichloride and inert gas, heating to 800-1000 DEG C for reaction, and insulating for 30-120 min to obtain the boron doped graphene; and adding the boron doped graphene into methyl pyrrolidone to obtain a boron doped graphene solution, conducting ultrasonic treatment on the boron doped graphene solution, carrying out vacuum filtration, subjecting filtration substances to freeze drying in an environment with temperature lower than -25 DEG C for 3-5 h, then subjecting filtration substances to freeze drying in an environment with temperature lower than -60 DEG C and pressure lower than 5 Pa for 12-24 h, so as to obtain the boron doped graphene film. The invention utilizes freeze drying technology to greatly reduce agglomeration of graphene sheet layers and effectively improve the storage performance of graphene. The invention also provides a preparation method of an electrochemical capacitor using the boron doped graphene film.
Description
Technical field
The present invention relates to graphene composite material field, particularly relate to the preparation method of boron doped graphene film and use the preparation method of the electrochemical capacitor of this boron doped graphene film.
Background technology
Graphene is a kind of two-dimentional unimolecular layer material, has excellent character, as high-specific surface area, and high conductivity, high mechanical strength and excellent toughness etc., have the potential of application in a lot of fields, be therefore subject to investigator's extensive concern.
At present, there is the matrix material of doped graphene, form boron doped graphene as carried out boron doping on Graphene, due to the electronegativity of boron, can improve Graphene energy storage efficiency, thereby raising stored energy capacitance, makes boron doped graphene have the advantages such as specific conductivity is high, Stability Analysis of Structures, is a kind of ideal electrochemical capacitor electrode material.The preparation method of traditional boron doped graphene is synthetic boron doped graphene in reactor, then boron doped graphene is purified.In preparation process Graphene be difficult to after disperseing or disperseing easily reunite, directly affected the energy-storage property of electrode materials.This has limited development and the application of graphene composite material greatly.
Summary of the invention
Based on this, the preparation method who is necessary to provide a kind of preparation method of the boron doped graphene film that can improve energy-storage property and uses the electrochemical capacitor of this boron doped graphene film.
A preparation method for boron doped graphene film, 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 placed under the mixed atmosphere of boron trichloride and rare gas element, is warming up at the temperature of 800 ℃ ~ 1000 ℃ and reacts, and be incubated 30 minutes ~ 120 minutes, obtain boron doped graphene; And
Described boron doped graphene is joined in methyl-2-pyrrolidone, obtain boron doped graphene solution, described boron doped graphene solution is carried out to the filtration of supersound process final vacuum, then the environment lyophilize below filtrate being placed in to-25 ℃ 3 hours ~ 5 hours, be placed in again-60 ℃ of following and pressure lower than the environment lyophilize of 5Pa 12 hours ~ 24 hours, obtain boron doped graphene film.
In an embodiment, the described step of preparing graphite oxide comprises therein:
Graphite is added in the mixing solutions of the vitriol oil and concentrated nitric acid, at-2 ℃ ~ 2 ℃ temperature, stir;
Add potassium permanganate in described mixing solutions and be heated to 80 ℃ ~ 90 ℃ and react, and be incubated 20 minutes ~ 30 minutes;
Add deionized water to the mixing solutions that has added potassium permanganate, continue at 80 ℃ ~ 90 ℃, to keep 20 minutes ~ 30 minutes;
Add hydrogen peroxide to having added in the mixing solutions of deionized water;
The mixing solutions that has added hydrogen peroxide is carried out to suction filtration also to be washed solids with dilute hydrochloric acid and deionized water; And
Dry described solids, obtains graphite oxide.
In an embodiment, the purity of described graphite is 99.5% therein.
In an embodiment, in the mixed atmosphere of described boron trichloride and rare gas element, the flow velocity of described boron trichloride is 200mL/min ~ 400mL/min therein, and the flow velocity of described rare gas element is 200mL/min ~ 400mL/min.
Therein in an embodiment, the temperature rise rate of described temperature-rise period is 10 ℃/min ~ 20 ℃/min.
In an embodiment, the concentration of described boron doped graphene solution is 0.5g/L ~ 2.0g/L therein.
A preparation method for electrochemical capacitor, comprising:
Above-mentioned boron doped graphene film is carried out after roll-in, and drying and slicing treatment, obtain electrode slice;
Stack gradually assembling according to the order of described electrode slice, barrier film and described electrode slice and obtain battery core; And
At described battery core outer cladding housing, and inject electrolytic solution in described housing, after sealing, obtain electrochemical capacitor.
Therein in an embodiment, described being dried as at 80 ℃ of temperature dry 2 hours.
In an embodiment, described electrolytic solution is ionic liquid therein.
In an embodiment, described ionic liquid is 1-butyl-3-Methylimidazole hexafluoro borate ([BMIM] [BF therein
6]).
In preparation method in preparation method and the electrochemical capacitor of above-mentioned boron doped graphene film, by graphite oxide is adulterated with boron in the mixed atmosphere of boron trichloride and rare gas element, obtain boron doped graphene, then under low-temp low-pressure, carry out lyophilize and process acquisition boron doped graphene film.Utilize Freeze Drying Technique, be directly gaseous state the solvent of boron doped graphene sheet interlayer from solid state transformation, effectively reduce the reunion of sheet interlayer, therefore can effectively improve the energy storage surface of Graphene, make this material when 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 film of an embodiment schema;
Fig. 2 is the preparation method's of the boron doped graphene thin film electrochemistry electrical condenser of an embodiment schema.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the preparation method of boron doped graphene film is described in further detail.
Refer to Fig. 1, the preparation method of the boron doped graphene film 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, in frozen water mixes and bathes, keeping temperature is to stir under the condition of-2 ℃ ~ 2 ℃ of left and right; 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 80 ℃ ~ 90 ℃ and reacts, and be incubated 20 minutes ~ 30 minutes, in this insulating process, can further be oxidized graphite; Add deionized water, continue at 80 ℃ ~ 90 ℃, to keep 20 minutes ~ 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 temperature dry 12 hours, obtain graphite oxide.
In the present embodiment, graphite can be 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 can be 0.5g/L ~ 1.0g/L, and ultrasonic power is 500W, and ultrasonic time is 2 hours ~ 4 hours.Dry process is for being placed in solids 60 ℃ of vacuum chambers dry 12 hours.
S103, is placed in graphene oxide the mixed atmosphere of boron trichloride and rare gas element, is warming up at 800 ℃ ~ 1000 ℃ temperature and reacts, and be incubated 30 minutes ~ 120 minutes, obtains boron doped graphene.
In the present embodiment, in the gas mixed atmosphere of boron trichloride and rare gas element, the flow velocity of boron trichloride can be 200mL/min ~ 400mL/min, and the flow velocity of rare gas element can be 200mL/min ~ 400mL/min.Rare gas element can be argon gas, helium etc.Temperature-rise period is warming up to 800 ℃ ~ 1000 ℃ and keep temperature take temperature rise rate as the speed of 10 ℃/min ~ 20 ℃/min.In insulating process, graphene oxide is peeled off and is mutually adulterated with boron, then cuts off boron trichloride gas, under the atmosphere that is 400mL/min, makes temperature cool to room temperature at the flow velocity of rare gas element, obtains boron doped graphene.
S104, is placed in methyl-2-pyrrolidone supersound process by boron doped graphene, obtains boron doped graphene solution, and boron doped graphene solution for vacuum is filtered, and obtains filtrate; It is-25 ℃ of following environment 3 hours ~ 5 hours that filtrate is placed in to temperature, then to be placed in temperature be-60 ℃ of following and pressure lower than the environment of 5Pa 12 hours ~ 24 hours, obtains boron doped graphene film.
In the present embodiment, the concentration of boron doped graphene solution can be 0.5g/L ~ 2.0g/L, and the ultrasonic time can be 3 hours ~ 5 hours, and boron doped graphene can be dispersed in methyl-2-pyrrolidone preferably.Filtration procedure obtains filtrate after boron doped graphene solution for vacuum is slowly filtered.
In the preparation method of above-mentioned boron doped graphene film, by graphite oxide is adulterated with boron in the mixed atmosphere of boron trichloride and rare gas element, obtain boron doped graphene, then under low-temp low-pressure, carry out lyophilize and process acquisition boron doped graphene film.On Graphene, carry out boron doping and form boron doped graphene film.Due to the electronegativity of boron, can improve Graphene energy storage efficiency, thereby improve stored energy capacitance.In preparation process, utilize Freeze Drying Technique, be directly gaseous state the solvent of boron doped graphene sheet interlayer from solid state transformation, reduce significantly the reunion of graphene sheet layer, effectively improve the energy storage surface of Graphene.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, carries out above-mentioned boron doped graphene film after roll-in, and drying and slicing treatment, obtain electrode slice.
In the present embodiment, drying process is to be dried 2 hours at 80 ℃ of temperature.
S202, stacks gradually assembling according to the order of electrode slice, barrier film and electrode slice and obtains battery core.
S203 at battery core outer cladding housing, and injects electrolytic solution in housing, obtains electrochemical capacitor after sealing.
In the present embodiment, inject electrolytic solution to housing from the spout of housing, then seal spout, obtain electrochemical capacitor.Wherein, the electrolytic solution of injection is ionic liquid, and ionic liquid can be [BMIM] [BF
6].
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
The technical process of preparing boron doped graphene film is as follows:
Graphite → graphite oxide → graphene oxide → boron doped graphene → boron doped graphene film.
(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 ℃ and keep 30 minutes; Add afterwards 92mL deionized water to continue at 85 ℃, to keep 30 minutes; 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.Wherein once washing process is for first solids being placed in to dilute hydrochloric acid, and suction filtration is poured deionized water into after waiting filtrate to drain again and carried out suction filtration.Finally by solids dry graphite oxide that obtains for 12 hours in 60 ℃ of vacuum drying ovens.
(2) preparation of graphene oxide: the graphite oxide obtaining in (1) is dispersed in deionized water, and obtaining concentration is 0.5g/L graphite oxide solution; The ultrasonic apparatus that is 500W with power is filtered after ultrasonic 2 hours graphite oxide solution; Solids after filtering is placed in to vacuum drying oven dry 12 hours, obtains graphene oxide.
(3) preparation of boron doped graphene: get the graphene oxide obtaining in (2) and be placed in the atmosphere of argon gas and boron trichloride, wherein the flow velocity of argon gas is 200mL/min, and the flow velocity of boron trichloride is 200mL/min; Then with 20 ℃/min temperature rise rate, graphene oxide temperature is around risen to 800 ° of C, and keep 30 minutes; Finally turn off boron trichloride gas, the atmosphere that is 400mL/min at the flow velocity of argon gas makes temperature drop to room temperature, obtains boron doped graphene.
(4) preparation of boron doped graphene film: be placed in methyl-2-pyrrolidone by obtaining boron doped graphene in (3), obtaining concentration is the boron doped graphene solution of 1g/L; Ultrasonic boron doped graphene solution 3 hours final vacuums are filtered; It is the environment 5 hours of-30 ℃ that filtrate after filtering is placed in to temperature; In the environment that to move to temperature again and be-60 ℃ and pressure be 1Pa, continue 12 hours, obtain boron doped graphene film.
Embodiment 2
The technical process of preparing boron doped graphene film is as follows:
Graphite → graphite oxide → graphene oxide → boron doped graphene → boron doped graphene film.
(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 ℃ and keep 30 minutes; Add afterwards 150mL deionized water to continue at 85 ℃, to keep 30 minutes; 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, obtains the graphite oxide solution that concentration is 1g/L, the ultrasonic apparatus that is 500W with power is filtered after ultrasonic 2 hours graphite oxide solution; Solids after filtering is placed in to vacuum drying oven dry 12 hours, obtains graphene oxide.
(3) preparation of boron doped graphene: get the graphene oxide obtaining in (2) and be placed in helium and boron trichloride atmosphere, wherein the flow velocity of helium is 200mL/min, and the flow velocity of boron trichloride is 300mL/min; Then with 15 ℃/min temperature rise rate, graphene oxide temperature is around risen to 900 ℃, and keep 30 minutes; Finally turn off boron trichloride gas, the atmosphere that is 400mL/min at the flow velocity of helium makes temperature drop to room temperature, obtains boron doped graphene.
(4) preparation of boron doped graphene film: be placed in methyl-2-pyrrolidone by obtaining boron doped graphene in (3), obtaining concentration is the boron doped graphene solution of 0.5g/L; Ultrasonic boron doped graphene solution 3 hours final vacuums are filtered; It is the environment 4 hours of-40 ℃ that filtrate after filtering is placed in to temperature; Move to again in the environment that temperature-80 ℃ and pressure are 1Pa, continue 12 hours, obtain boron doped graphene film.
Embodiment 3
The technical process of preparing boron doped graphene film is as follows:
Graphite → graphite oxide → graphene oxide → boron doped graphene → boron doped graphene film.
(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 under 2 ℃ of environment and is stirred 20 minutes; In mixing solutions, add 20g potassium permanganate at leisure again, stir 1 hour; Then mixing solutions is heated to 85 ℃ and keep 30 minutes; Add afterwards 300mL deionized water to continue at 80 ℃, to keep 30 minutes; 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 vacuum drying ovens.
(2) preparation of graphene oxide: the graphite oxide obtaining in (1) is dispersed in deionized water, obtains the graphite oxide solution that concentration is 1g/L; The ultrasonic apparatus that is 500W with power is filtered after ultrasonic 3 hours graphite oxide solution; Solids after filtering is placed in to vacuum drying oven dry 12 hours, obtains graphene oxide.
(3) preparation of boron doped graphene: get the graphene oxide obtaining in (2) and be placed in the atmosphere of argon gas and boron trichloride, wherein the flow velocity of argon gas is 200mL/min, and the flow velocity of boron trichloride is 400mL/min; Then with 15 ℃/min temperature rise rate, graphene oxide temperature is around risen to 1000 ℃, and keep 30 minutes; Finally turn off boron trichloride gas, the atmosphere that is 400mL/min at the flow velocity of argon gas makes temperature drop to room temperature, obtains boron doped graphene.
(4) preparation of boron doped graphene film: be placed in methyl-2-pyrrolidone by obtaining boron doped graphene in (3), obtaining concentration is the boron doped graphene solution of 1g/L; Ultrasonic boron doped graphene solution 3 hours final vacuums are filtered; It is the environment 3 hours of-35 ℃ that filtrate after filtering is placed in to temperature; In the environment that filtrate to be moved to temperature again and be-70 ℃ and pressure be 2Pa, continue 12 hours, obtain boron doped graphene film.
Embodiment 4
The technical process of preparing boron doped graphene film is as follows:
Graphite → graphite oxide → graphene oxide → boron doped graphene → boron doped graphene film
(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 under-2 ° of C and stirs 20 minutes; In mixing solutions, add 4g potassium permanganate at leisure again, stir 1 hour; Then mixing solutions is heated to 90 ℃ and keep 20 minutes; Add afterwards 92mL deionized water to continue at 90 ℃, to keep 20 minutes; 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 vacuum drying ovens.
(2) preparation of graphene oxide: the graphite oxide obtaining in (1) is dispersed in deionized water, obtains the graphite oxide solution that concentration is 1g/L; The ultrasonic apparatus that is 500W with power is filtered after ultrasonic 4 hours graphite oxide solution; Solids after filtering is placed in to vacuum drying oven dry 12 hours, obtains graphene oxide.
(3) preparation of boron doped graphene: get the graphene oxide obtaining in (2) and be placed under the atmosphere of argon gas and boron trichloride, wherein the flow velocity of argon gas is 400mL/min, and the flow velocity of boron trichloride is 400mL/min; Then with 20 ℃/min temperature rise rate, graphene oxide temperature is around risen to 800 ℃, and keep 120 minutes; Finally turn off boron trichloride gas, the atmosphere that is 400mL/min at the flow velocity of argon gas makes temperature be down to room temperature, obtains boron doped graphene.
(4) preparation of boron doped graphene film: be placed in methyl-2-pyrrolidone by obtaining boron doped graphene in (3), obtaining concentration is the boron doped graphene solution of 2g/L, filters ultrasonic boron doped graphene solution 5 hours final vacuums; Filtrate after filtering is placed in to the environment 4 hours of-40 ℃; Move to again temperature and be in the environment of-80 ℃ and pressure 1Pa, continue 24 hours, obtain boron doped graphene film.
Embodiment 5
The technical process of preparing boron doped graphene is as follows:
Graphite → graphite oxide → graphene oxide → boron doped graphene
(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 at 85 ℃, to keep 30 minutes; 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 vacuum drying ovens.
(2) preparation of graphene oxide: the graphite oxide obtaining in (1) is dispersed in deionized water, obtains the graphite oxide solution that concentration is 1g/L; The ultrasonic apparatus that is 500W with power is filtered after ultrasonic 4 hours graphite oxide solution; Solids after filtering is placed in to vacuum drying oven dry 12 hours, obtains graphene oxide.
(3) preparation of boron doped graphene: get the graphene oxide obtaining in (2) and be placed under the atmosphere of argon gas and boron trichloride, wherein the flow velocity of argon gas is 200mL/min, and the flow velocity of boron trichloride is 200mL/min; Then with 20 ℃/min temperature rise rate, graphene oxide temperature is around risen to 800 ℃, and keep 30 minutes; Finally turn off boron trichloride gas, the atmosphere that is 400mL/min at the flow velocity of argon gas makes temperature be down to room temperature, obtains boron doped graphene.
Embodiment 6
The technical process of preparing electrochemical capacitor is as follows:
(1) the boron doped graphene film of being prepared by embodiment 1 carries out roll-in, at 80 ℃ of temperature, is dried and carries out slicing treatment after 2 hours, makes electrode slice.
(2) according to being stacked gradually to assembling, the order of the electrode slice, barrier film and the electrode slice that obtain in (1) obtains battery core.
(3), by the battery core obtaining in housing seal (2), in housing, inject [BMIM] [BF toward the spout being arranged on housing subsequently
6], sealing spout, obtains electrochemical capacitor.
Embodiment 7
The technical process of preparing electrochemical capacitor is as follows:
(1) the boron doped graphene film of being prepared by embodiment 2 carries out roll-in, is dried slicing treatment after 2 hours at 80 ℃ of temperature, makes electrode slice.
(2) according to being stacked gradually to assembling, the order of the electrode slice, barrier film and the electrode slice that obtain in (1) obtains battery core.
(3), by the battery core obtaining in housing seal (2), in housing, inject [BMIM] [BF toward the spout being arranged on housing subsequently
6], sealing spout, obtains electrochemical capacitor.
Embodiment 8
The technical process of preparing electrochemical capacitor is as follows:
(1) the boron doped graphene film of being prepared by embodiment 3 carries out roll-in, at 80 ℃ of temperature, is dried and carries out slicing treatment after 2 hours, makes electrode slice.
(2) according to being stacked gradually to assembling, the order of the electrode slice, barrier film and the electrode slice that obtain in (1) obtains battery core.
(3), by the battery core obtaining in housing seal (2), in housing, inject [BMIM] [BF toward the spout being arranged on housing subsequently
6], sealing spout, obtains electrochemical capacitor.
Embodiment 9
The technical process of preparing electrochemical capacitor is as follows:
(1) the boron doped graphene film of being prepared by embodiment 4 carries out roll-in, at 80 ℃ of temperature, is dried and carries out slicing treatment after 2 hours, makes electrode slice.
(2) according to being stacked gradually to assembling, the order of the electrode slice, barrier film and the electrode slice that obtain in (1) obtains battery core.
(3), by the battery core obtaining in housing seal (2), in housing, inject [BMIM] [BF toward the spout being arranged on housing subsequently
6], sealing spout, obtains electrochemical capacitor.
Embodiment 10
The technical process of preparing electrochemical capacitor is as follows:
(1) the boron doped graphene prepared by embodiment 5, acetylene carbon black, polyvinylidene difluoride (PVDF) are in mass ratio for 80:10:10 is mixed into slurry.
(2) slurry in (1) is coated on aluminium foil, at 80 ℃ of temperature, slicing treatment is carried out in vacuum-drying after 8 hours, makes electrode slice.
(3) according to being stacked gradually to assembling, the order of the electrode slice, barrier film and the electrode slice that obtain in (2) obtains battery core.
(4), by the battery core obtaining in housing seal (3), in housing, inject [BMIM] [BF toward the spout being arranged on housing subsequently
6], sealing spout, obtains electrochemical capacitor.
Electrochemical capacitor to assembling in embodiment 6 ~ embodiment 10 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 6 ~ 10
As shown in Table 1, embodiment 6 ~ embodiment 9 is the electrochemical capacitors that utilize the film preparation of boron doped graphene, and the specific storage under 0.5A/g current density all, more than 200F/g left and right, is up to 213F/g.Embodiment 5 is the electrochemical capacitors that utilize boron doped graphene to prepare, and under identical testing conditions, its specific storage is only 125F/g.By relatively drawing, above-mentioned boron doped graphene film has excellent energy-storage property.
Claims (10)
1. a preparation method for boron doped graphene film, 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 placed under the mixed atmosphere of boron trichloride and rare gas element, is warming up at the temperature of 800 ℃ ~ 1000 ℃ and reacts, and be incubated 30 minutes ~ 120 minutes, obtain boron doped graphene; And
Described boron doped graphene is joined in methyl-2-pyrrolidone, obtain boron doped graphene solution, described boron doped graphene solution is carried out to the filtration of supersound process final vacuum, then the environment lyophilize below filtrate being placed in to-25 ℃ 3 hours ~ 5 hours, be placed in again-60 ℃ of following and pressure lower than the environment lyophilize of 5Pa 12 hours ~ 24 hours, obtain boron doped graphene film.
2. the preparation method of boron doped graphene film according to claim 1, is characterized in that, the described step of preparing graphite oxide comprises:
Graphite is added in the mixing solutions of the vitriol oil and concentrated nitric acid, at-2 ℃ ~ 2 ℃ temperature, stir;
Add potassium permanganate in described mixing solutions and be heated to 80 ℃ ~ 90 ℃ and react, and be incubated 20 minutes ~ 30 minutes;
Add deionized water to the mixing solutions that has added potassium permanganate, continue at 80 ℃ ~ 90 ℃, to keep 20 minutes ~ 30 minutes;
Add hydrogen peroxide to having added in the mixing solutions of deionized water;
The mixing solutions that has added hydrogen peroxide is carried out to suction filtration also to be washed solids with dilute hydrochloric acid and deionized water; And
Dry described solids, obtains graphite oxide.
3. the preparation method of boron doped graphene film according to claim 1, is characterized in that, the purity of described graphite is 99.5%.
4. the preparation method of boron doped graphene film according to claim 1, it is characterized in that, in the mixed atmosphere of described boron trichloride and rare gas element, the flow velocity of described boron trichloride is 200mL/min ~ 400mL/min, and the flow velocity of described rare gas element is 200mL/min ~ 400mL/min.
5. the preparation method of boron doped graphene film according to claim 1, is characterized in that, the temperature rise rate of described temperature-rise period is 10 ℃/min ~ 20 ℃/min.
6. the preparation method of boron doped graphene film according to claim 1, is characterized in that, the concentration of described boron doped graphene solution is 0.5g/L ~ 2.0g/L.
7. a preparation method for electrochemical capacitor, is characterized in that, comprising:
Boron doped graphene film described in claim 1 is carried out after roll-in, and drying and slicing treatment, obtain electrode slice;
Stack gradually assembling according to the order of described electrode slice, barrier film and described electrode slice and obtain battery core; And
At described battery core outer cladding housing, and inject electrolytic solution in described housing, after sealing, obtain electrochemical capacitor.
8. the preparation method of electrochemical capacitor according to claim 7, is characterized in that, described being dried as be dried 2 hours at 80 ℃ of temperature.
9. the preparation method of electrochemical capacitor according to claim 7, is characterized in that, described electrolytic solution is ionic liquid.
10. the preparation method of electrochemical capacitor according to claim 9, is characterized in that, described ionic liquid is [BMIM] [BF
6].
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108417403A (en) * | 2018-03-09 | 2018-08-17 | 西安交通大学 | A kind of preparation method of the porous nitrogen-doped graphene membrane electrodes of 3D |
| CN111653436A (en) * | 2020-06-10 | 2020-09-11 | 贵州梅岭电源有限公司 | Application of carbon aerogel/graphene film in flexible supercapacitor |
| CN113896188A (en) * | 2021-10-22 | 2022-01-07 | 中国科学院兰州化学物理研究所 | Preparation method of boron-doped graphene heat-conducting film |
-
2012
- 2012-10-31 CN CN201210428397.5A patent/CN103787309A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108417403A (en) * | 2018-03-09 | 2018-08-17 | 西安交通大学 | A kind of preparation method of the porous nitrogen-doped graphene membrane electrodes of 3D |
| CN111653436A (en) * | 2020-06-10 | 2020-09-11 | 贵州梅岭电源有限公司 | Application of carbon aerogel/graphene film in flexible supercapacitor |
| CN111653436B (en) * | 2020-06-10 | 2022-07-05 | 贵州梅岭电源有限公司 | Application of carbon aerogel/graphene film in flexible supercapacitor |
| CN113896188A (en) * | 2021-10-22 | 2022-01-07 | 中国科学院兰州化学物理研究所 | Preparation method of boron-doped graphene heat-conducting film |
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