CN103832996A - Graphene/carbon nano-tube composite material, preparation method and application thereof - Google Patents
Graphene/carbon nano-tube composite material, preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of electrochemical materials, and discloses a graphene/carbon nano-tube composite material, a preparation method and an application thereof. The electrode material comprises, by mass, 50-90% of graphene and 10-50% of carbon nano-tubes. According to the graphene/carbon nano-tube composite material, agglomeration of the graphene lamellas is low, such that the high energy storage capacity is provided when the composite material is adopted as the electrochemical capacitor electrode material.
Description
Technical field
The present invention relates to electrochemical material field, relate in particular to a kind of graphene/carbon nanometer tube composite materials and preparation method and application.
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 battery.But energy density lower be a key factor of restriction ultracapacitor development and application, explore the energy density that how to improve ultracapacitor and be the emphasis of this area research at present.According to the calculation formula of energy density
, improve energy density and mainly start with from two aspects, improve on the one hand the voltage window of electrochemical capacitor; Be the specific storage that improves electrode materials on the one hand in addition, the raising of this two aspect all can bring the raising of energy density.
Graphene is as the two-dimentional unimolecular layer material of one, there is higher specific surface area and higher specific conductivity, it is a kind of desirable electrochemical capacitor electrode material, but graphene sheet layer is easily reunited, cause a lot of surfaces of graphene sheet layer can not be used for energy storage, thereby make the stored energy capacitance of Graphene not high.
Summary of the invention
Based on the problems referred to above, problem to be solved by this invention is to provide the preparation method of the graphene/carbon nanometer tube composite materials that a kind of stored energy capacitance is higher.
Technical scheme of the present invention is as follows:
The preparation method who the invention provides a kind of graphene/carbon nanometer tube composite materials, comprises the steps:
Graphite oxide is placed in to 0.5 ~ 5L deionized water and is configured to the graphite oxide solution that concentration is 0.5 ~ 2mg/ml, supersound process graphite oxide solution subsequently, then again toward the carbon nanotube that adds 0.05 ~ 0.8g in graphite oxide solution; Continue supersound process, carry out subsequently centrifugal treating, and after the object drying that centrifugal treating is obtained processing, obtain graphene oxide/carbon nano tube compound material;
Described graphene oxide/carbon nano tube compound material is placed in to the atmosphere that rare gas element forms, and at 700 ~ 900 DEG C, sintering processes 30min ~ 1h, is cooled to room temperature, obtains described graphene/carbon nanometer tube composite materials.
The preparation method of described graphene/carbon nanometer tube combination electrode material, wherein, described graphite oxide is adopted with the following method and is made:
Graphite is added in the mixed acid solution of the vitriol oil and concentrated nitric acid, mix in bath and stir at frozen water, in mixed acid solution, add potassium permanganate at leisure more afterwards, then mixed acid solution is heated to 85 ° of C carries out oxide treatment, remove subsequently potassium permanganate, suction filtration, repetitive scrubbing screening, dry, obtains graphite oxide; Wherein, the quality of graphite and mixed acid solution and volume ratio are 1 ~ 5g:115 ~ 595ml; The mass ratio of graphite and potassium permanganate is 1:4 ~ 6.
The preparation method of described graphene/carbon nanometer tube composite materials, wherein, in described mixed acid solution, the volume ratio of the vitriol oil and concentrated nitric acid is 90:25 ~ 475:120.
The preparation method of described graphene/carbon nanometer tube composite materials, wherein, it is 30min ~ 1h that described mixed acid solution is heated to the time that 85 ° of C carry out oxide treatment.
The preparation method of described graphene/carbon nanometer tube composite materials, wherein, the massfraction of described hydrogen peroxide solution is 30%, the add-on of this hydrogen peroxide solution is 9 ~ 30ml.
The preparation method of described graphene/carbon nanometer tube composite materials wherein, time prepared by graphite oxide, is to adopt dilute hydrochloric acid and deionized water repetitive scrubbing to the washing of screening.
The preparation method of described graphene/carbon nanometer tube composite materials, wherein, in described graphite oxide/carbon nano tube compound material preparation process, described in twice, the time of supersound process is 2 ~ 4h.
The preparation method of described graphene/carbon nanometer tube composite materials, wherein, when described centrifugal treating, centrifugal rotational speed is 3000 ~ 5000 revs/min, centrifugation time is 20 ~ 30 minutes.
The preparation method of described graphene/carbon nanometer tube composite materials wherein, when described sintering processes, is to adopt the temperature rise rate of 10 ~ 20 DEG C/min to be warming up to 800 ~ 1000 DEG C.
The present invention also provides the graphene/carbon nanometer tube composite materials that adopts above-mentioned preparation method to make.
The present invention also provides the application as electrode active material in electrochemical capacitor of above-mentioned graphene/carbon nanometer tube composite materials.
Graphene/carbon nanometer tube composite materials provided by the invention, the reunion of its graphene sheet layer is lower, centrifugal treating can make matrix material have good conductive grid, improve the specific conductivity of material, thereby there is higher stored energy capacitance and high rate performance while making this matrix material as electrochemical capacitor electrode material.
The preparation method of combination electrode material adopts oxidation reduction process, and equipment, technique are simple, and convenient operation, easily realizes large-scale industrial production.
Embodiment
The concrete preparation technology's flow process that the invention provides graphene/carbon nanometer tube composite materials is as follows:
Graphite → graphite oxide → graphene/carbon nanometer tube composite materials
(1) prepare graphite oxide: the graphite that is 99.5% by purity adds in the mixing solutions of the vitriol oil and concentrated nitric acid, mix in bath (temperature is controlled at 0 DEG C) and stir at frozen water, in mixing solutions, add potassium permanganate at leisure more afterwards, graphite is oxidized, then mixing solutions being heated to 85 ° of C keeps 30min ~ 1h to be at high temperature further oxidized graphite, finally add hydrogen peroxide (massfraction is 30%) to remove potassium permanganate, suction filtration, solids is carried out to repetitive scrubbing with dilute hydrochloric acid and deionized water, dry, obtain graphite oxide; Wherein, the quality of graphite and mixed acid solution and volume ratio are 1 ~ 5g:115 ~ 595ml; The mass ratio of graphite and potassium permanganate is 1:4 ~ 6;
(2) prepare graphene oxide/carbon nano tube compound material: graphite oxide is placed in to 0.5 ~ 5L deionized water and is configured to the graphite oxide solution that concentration is 0.5 ~ 2mg/ml, supersound process 2 ~ 4h; Then add the carbon nanotube of 0.05～0.8g, the concentration of described carbon nanotube in solution is 0.05 ~ 0.5mg/ml, continues supersound process 1 ~ 2h, carries out subsequently centrifugal treating, and the object drying processing that centrifugal treating is obtained, obtain graphene oxide/carbon nano tube compound material; Wherein, when described centrifugal treating, centrifugal rotational speed is 3000 ~ 5000 revs/min, and centrifugation time is 20 ~ 30 minutes; The true air environment that the object obtaining after centrifugal treating is placed in 60 ° of C is dried 12 hours;
(3) prepare graphene/carbon nanometer tube composite materials: the atmosphere that described graphene oxide/carbon nano tube compound material is placed in to rare gas element formation is (as the atmosphere of the gas mixture formation of argon gas, nitrogen or argon gas and nitrogen; Preferably argon gas atmosphere; In the time forming the atmosphere of rare gas element formation, its airshed is controlled at 400ml/min, be conducive to the formation of graphene/carbon nanometer tube composite materials) in, sintering processes 30min ~ 1h at 700 ~ 900 DEG C, under the protection of rare gas element (airshed: 400ml/ minute) atmosphere, be cooled to room temperature, obtain described graphene/carbon nanometer tube composite materials; Wherein, preferably, when described sintering processes, adopt the temperature rise rate of 10 ~ 20 DEG C/min to be warming up to 800 ~ 1000 DEG C; The effect of sintering processes is mainly that graphene oxide is cracked into Graphene.
The preparation method of combination electrode material adopts oxidation reduction process, and equipment, technique are simple, and convenient operation, easily realizes large-scale industrial production.
Adopt the graphene/carbon nanometer tube composite materials that makes of aforesaid method, according to mass ratio, comprise 50% ~ 90% Graphene and 10% ~ 50% carbon nanotube.This graphene/carbon nanometer tube composite materials, the reunion of its graphene sheet layer is lower, centrifugal treating can make matrix material have good conductive grid, improve the specific conductivity of material, thereby there is higher stored energy capacitance and high rate performance while making this matrix material as electrochemical capacitor electrode material.
The application of graphene/carbon nanometer tube composite materials below
Graphene/carbon nanometer tube composite materials is generally used for the electrode materials of electrochemical capacitor, below introduces the method that uses this material to be made into electrochemical capacitor.
First, the ratio that is 95:5 according to mass ratio, mixes graphene/carbon nanometer tube composite materials and polyvinylidene difluoride (PVDF) binding agent, obtains slurry;
Secondly, slurry is coated on aluminium foil, through 80 ° of C vacuum-dryings 2 hours, slicing treatment, made electrode slice;
Finally, take two plate electrode sheets, be respectively positive plate and negative plate; By positive plate, barrier film, negative plate in order stack of laminations dress up battery core, then use battery housing seal battery core, inject electrolytic solution (ionic liquid) toward the spout being arranged on battery container subsequently, sealing spout, obtains electrochemical capacitor.
Below preferred embodiment of the present invention is described in further detail.
Embodiment 1 ~ 4th, the preparation method of graphene/carbon nanometer tube composite materials
Embodiment 1
It is as follows that the present invention prepares the technical process of graphene/carbon nanometer tube composite materials:
Graphite → graphite oxide → graphene oxide/carbon nano tube compound material → graphene/carbon nanometer tube composite materials
(1) graphite: purity 99.5%;
(2) graphite oxide: take the graphite 1g that (1) moderate purity is 99.5% and add in the mixing solutions being formed by the 90ml vitriol oil (massfraction is 98%) and 25ml concentrated nitric acid (massfraction is 65%), mixture is placed under frozen water mixing bath environment and is stirred 20 minutes, in mixture, add 6g potassium permanganate at leisure again, stir 1 hour, then mixture 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 10ml superoxol (massfraction 30%), stir 10 minutes, mixture is carried out to suction filtration, with 100ml dilute hydrochloric acid and 150ml deionized water, solids is washed respectively successively again, wash altogether three times, last solid matter is the dry graphite oxide that obtains for 12 hours in 60 ° of C vacuum drying ovens,
(3) graphene oxide/carbon nano tube compound material: the 1g graphite oxide of preparation in (2) is added in 1L deionized water, and the solubility of graphite oxide in water is 1mg/ml, ultrasonic 2 hours; Add again 0.05g carbon nanotube, the solubility of carbon nanotube is 0.05mg/ml, continue ultrasonic 2 hours, carry out centrifugal to suspension, centrifugal revolution is 5000 revs/min, centrifugation time 20 minutes, the vacuum environment that the centrifugal solid product obtaining is placed in to 60 ° of C is dried 12 hours, obtains graphene oxide/carbon nano tube compound material;
(4) graphene/carbon nanometer tube composite materials: the graphene oxide/carbon nano tube compound material obtaining in (3) is placed in to argon gas (airshed: 400ml/ minute) environment; rise to 800 ° of C with 15 ° of temperature rise rates of C/ minute; and keep 1 hour; finally continue to be naturally down to room temperature under the protection of argon gas (airshed: 400ml/ minute), obtain graphene/carbon nanometer tube composite materials.
Embodiment 2
It is as follows that the present invention prepares the technical process of graphene/carbon nanometer tube composite materials:
Graphite → graphite oxide → graphene oxide/carbon nano tube compound material → graphene/carbon nanometer tube composite materials
(1) graphite: purity 99.5%;
(2) graphite oxide: take the graphite 5g that (1) moderate purity is 99.5% and add in the mixing solutions being formed by the 475ml vitriol oil (massfraction is 98%) and 120ml concentrated nitric acid (massfraction is 65%), mixture is placed under frozen water mixing bath environment and is stirred 20 minutes, in mixture, add 20g potassium permanganate at leisure again, stir 1 hour, then mixture 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 30ml superoxol (massfraction 30%), stir 10 minutes, mixture is carried out to suction filtration, with 300ml dilute hydrochloric acid and 450ml deionized water, solids is washed respectively successively again, wash altogether three times, last solid matter is the dry graphite oxide that obtains for 12 hours in 60 ° of C vacuum drying ovens,
(3) graphene oxide/carbon nano tube compound material: the 5g graphite oxide of preparation in (2) is added in 5L deionized water, and the solubility of graphite oxide in water is 1mg/ml, ultrasonic 3 hours; Add again 0.5g carbon nanotube, the solubility of carbon nanotube is 0.1mg/ml, continue ultrasonic 3 hours, carry out centrifugal to suspension, centrifugal revolution is 4000 revs/min, centrifugation time 25 minutes, the vacuum environment that the centrifugal solid product obtaining is placed in to 60 ° of C is dried 12 hours, obtains graphene oxide/carbon nano tube compound material;
(4) graphene/carbon nanometer tube composite materials: the graphene oxide/carbon nano tube compound material obtaining in (3) is placed in to argon gas (airshed: 400ml/ minute) environment; rise to 900 ° of C with 20 ° of temperature rise rates of C/ minute; and keep 0.5 hour; finally continue to be naturally down to room temperature under the protection of argon gas (airshed: 400ml/ minute), obtain graphene/carbon nanometer tube composite materials.
Embodiment 3
It is as follows that the present invention prepares the technical process of graphene/carbon nanometer tube composite materials:
Graphite → graphite oxide → graphene oxide/carbon nano tube compound material → graphene/carbon nanometer tube composite materials
(1) graphite: purity 99.5%;
(2) graphite oxide: take the graphite 2g that (1) moderate purity is 99.5% and add in the mixing solutions being formed by the 170ml vitriol oil (massfraction is 98%) and 48ml concentrated nitric acid (massfraction is 65%), mixture is placed under frozen water mixing bath environment and is stirred 20 minutes, in mixture, add 8g potassium permanganate at leisure again, stir 1 hour, then mixture 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 16ml superoxol (massfraction 30%), stir 10 minutes, mixture is carried out to suction filtration, with 250ml dilute hydrochloric acid and 300ml deionized water, solids is washed respectively successively again, wash altogether three times, last solid matter is the dry graphite oxide that obtains for 12 hours in 60 ° of C vacuum drying ovens,
(3) graphene oxide/carbon nano tube compound material: the 2g graphite oxide of preparation in (2) is added in 4L deionized water, and the solubility of graphite oxide in water is 0.5mg/ml, ultrasonic 2 hours; Add again 0.8g carbon nanotube, the solubility of carbon nanotube is 0.2mg/ml, continue ultrasonic 2 hours, carry out centrifugal to suspension, centrifugal revolution is 3000 revs/min, centrifugation time 30 minutes, the vacuum environment that the centrifugal solid product obtaining is placed in to 60 ° of C is dried 12 hours, obtains graphene oxide/carbon nano tube compound material;
(4) graphene/carbon nanometer tube composite materials: the graphene oxide/carbon nano tube compound material obtaining in (3) is placed in to argon gas (airshed: 400ml/ minute) environment; rise to 850 ° of C with 25 ° of temperature rise rates of C/ minute; and keep 1 hour; finally continue to be naturally down to room temperature under the protection of argon gas (airshed: 400ml/ minute), obtain graphene/carbon nanometer tube composite materials.
Embodiment 4
It is as follows that the present invention prepares the technical process of graphene/carbon nanometer tube composite materials:
Graphite → graphite oxide → graphene oxide/carbon nano tube compound material → graphene/carbon nanometer tube composite materials
(1) graphite: purity 99.5%;
(2) graphite oxide: take the graphite 1g that (1) moderate purity is 99.5% and add in the mixing solutions being formed by the 90ml vitriol oil (massfraction is 98%) and 25ml concentrated nitric acid (massfraction is 65%), mixture is placed under frozen water mixing bath environment and is stirred 20 minutes, in mixture, add 4g potassium permanganate at leisure again, stir 1 hour, then mixture 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 9ml superoxol (massfraction 30%), stir 10 minutes, mixture is carried out to suction filtration, with 100ml dilute hydrochloric acid and 150ml deionized water, solids is washed respectively successively again, wash altogether three times, last solid matter is the dry graphite oxide that obtains for 12 hours in 60 ° of C vacuum drying ovens,
(3) graphene oxide/carbon nano tube compound material: the 1g graphite oxide of preparation in (2) is added in 0.5L deionized water, and the solubility of graphite oxide in water is 2mg/ml, ultrasonic 4 hours; Add again 0.5g carbon nanotube, the solubility of carbon nanotube is 1mg/ml, continue ultrasonic 4 hours, carry out centrifugal to suspension, centrifugal revolution is 5000 revs/min, centrifugation time 20 minutes, the vacuum environment that the centrifugal solid product obtaining is placed in to 60 ° of C is dried 12 hours, obtains graphene oxide/carbon nano tube compound material;
(4) graphene/carbon nanometer tube composite materials: the graphene oxide/carbon nano tube compound material obtaining in (3) is placed in to argon gas (airshed: 400ml/ minute) environment; rise to 1000 ° of C with 10 ° of temperature rise rates of C/ minute; and keep 1 hour; finally continue to be naturally down to room temperature under the protection of argon gas (airshed: 400ml/ minute), obtain graphene/carbon nanometer tube composite materials.
Embodiment 5 ~ 8th, the material of embodiment 1 ~ 4 preparation is as the application of electrochemical capacitor electrode material
Embodiment 5
(1) ratio that is 95:5 according to mass ratio, graphene/carbon nanometer tube composite materials and polyvinylidene difluoride (PVDF) binding agent that embodiment 1 is obtained mix, and obtain slurry;
(2) slurry obtaining in (1) is coated on aluminium foil, through 80 ° of C of vacuum dry 2 hours, slicing treatment, makes electrode slice.
(3) take two plate electrode sheets in (2), be respectively positive plate and negative plate; By positive plate, barrier film, negative plate in order stack of laminations dress up battery core, then use battery housing seal battery core, inject [BMIM] [PF by the spout being arranged on battery container subsequently
6], sealing spout, obtains electrochemical capacitor.
The electrochemical capacitor that embodiment 5 is assembled carries out charge-discharge test with LAND battery test system, test process is: the positive and negative electrode of battery is connected with the positive and negative electrode of test macro, recall the test procedure of test macro, the current density discharging and recharging is made as to 0.5A/g, charge to 4V from 0V, be discharged to 0V from 4V again, three circles that so circulate, get the specific storage of the 3rd circle as the specific storage of material.
Embodiment 6 ~ 8 is identical with the process of preparing of embodiment 5, and difference is that the electrode materials adopting is respectively embodiment) ~ 4 prepared electrode materialss out.
The electrochemical capacitor that embodiment 5 ~ 8 is made carries out charge-discharge test under current density 0.5A/g, and its specific storage is as shown in table 1:
Table 1
| Embodiment | 5 | 6 | 7 | 8 |
| Specific storage (F/g) | 165 | 184 | 213 | 188 |
As shown in table 1, graphene/carbon nanometer tube composite materials prepared by the present invention specific storage under current density 0.5A/g all, more than 160F/g, is up to 213F/g, has excellent energy-storage property.
Should be understood that, the above-mentioned statement for preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, and scope of patent protection of the present invention should be as the criterion with claims.
Claims (10)
1. a preparation method for graphene/carbon nanometer tube composite materials, is characterized in that, comprises the steps:
Graphite oxide is placed in to 0.5 ~ 5L deionized water and is configured to the graphite oxide solution that concentration is 0.5 ~ 2mg/ml, supersound process graphite oxide solution subsequently, then again toward the carbon nanotube that adds 0.05 ~ 0.8g in graphite oxide solution; Continue supersound process, carry out subsequently centrifugal treating, and after the object drying that centrifugal treating is obtained processing, obtain graphene oxide/carbon nano tube compound material;
Described graphene oxide/carbon nano tube compound material is placed in to the atmosphere that rare gas element forms, and at 700 ~ 900 DEG C, sintering processes 30min ~ 1h, is cooled to room temperature, obtains described graphene/carbon nanometer tube composite materials.
2. the preparation method of graphene/carbon nanometer tube composite materials according to claim 1, is characterized in that, graphite oxide is adopted with the following method and made:
Graphite is added in the mixed acid solution of the vitriol oil and concentrated nitric acid, mix in bath and stir at frozen water, in mixed acid solution, add potassium permanganate at leisure more afterwards, then mixed acid solution is heated to 85 ° of C carries out oxide treatment, remove subsequently potassium permanganate, suction filtration, repetitive scrubbing screening, dry, obtains graphite oxide; Wherein, the quality of graphite and mixed acid solution and volume ratio are 1 ~ 5g:115 ~ 595ml; The mass ratio of graphite and potassium permanganate is 1:4 ~ 6.
3. the preparation method of graphene/carbon nanometer tube composite materials according to claim 2, is characterized in that, in described mixed acid solution, the volume ratio of the vitriol oil and concentrated nitric acid is 90:25 ~ 475:120.
4. the preparation method of graphene/carbon nanometer tube composite materials according to claim 2, is characterized in that, it is 30min ~ 1h that described mixed acid solution is heated to the time that 85 ° of C carry out oxide treatment.
5. the preparation method of graphene/carbon nanometer tube composite materials according to claim 2, is characterized in that, the massfraction of described hydrogen peroxide solution is 30%, and the add-on of this hydrogen peroxide solution is 9 ~ 30ml.
6. the preparation method of graphene/carbon nanometer tube composite materials according to claim 1, is characterized in that, in described graphite oxide/carbon nano tube compound material preparation process, described in twice, the time of supersound process is 2 ~ 4h.
7. the preparation method of graphene/carbon nanometer tube composite materials according to claim 1, is characterized in that, when described centrifugal treating, centrifugal rotational speed is 3000 ~ 5000 revs/min, and centrifugation time is 20 ~ 30 minutes.
8. the preparation method of graphene/carbon nanometer tube composite materials according to claim 1, is characterized in that, when described sintering processes, adopts the temperature rise rate of 10 ~ 20 DEG C/min to be warming up to 800 ~ 1000 DEG C.
9. a graphene/carbon nanometer tube composite materials, is characterized in that, adopts the arbitrary described method of claim 1 to 8 to make.
Graphene/carbon nanometer tube composite materials claimed in claim 9 in electrochemical capacitor as the application of electrode active material.
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| CN105645381A (en) * | 2016-01-12 | 2016-06-08 | 山东联星能源集团有限公司 | Method for preparing graphene/carbon nanotube composite material by intensive microwave process |
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