CN103839697A - Graphene/C60 composite material and preparation method and applications thereof - Google Patents
Graphene/C60 composite material and preparation method and applications thereof Download PDFInfo
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- CN103839697A CN103839697A CN201210484403.9A CN201210484403A CN103839697A CN 103839697 A CN103839697 A CN 103839697A CN 201210484403 A CN201210484403 A CN 201210484403A CN 103839697 A CN103839697 A CN 103839697A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention pertains to the field of electrochemistry materials, and discloses a graphene/C60 composite material and a preparation method and applications thereof. The electrode material comprises, by mass, 50%-85% of grapheme and 15%-50% of C60. According to the graphene/C60 composite material provided in the invention, the grapheme sheet has the advantage of low aggregation, so the advantage of high energy storage capacity can be realized when the composite material is used as the electrochemistry capacitor electrode material.
Description
Technical field
The present invention relates to electrochemical material field, relate in particular to a kind of Graphene/C
60composite material 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 computing 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 capacity that improves electrode material 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 monolayer material of one, there is higher specific area and higher 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, the Graphene/C that provides a kind of stored energy capacitance higher is provided problem to be solved by this invention
60the preparation method of composite material.
Technical scheme of the present invention is as follows:
The invention provides a kind of Graphene/C
60the preparation method of composite material, comprises the steps:
Graphite oxide is placed in to 1 ~ 5L deionized water and is configured to the graphite oxide solution that concentration is 0.5 ~ 1mg/ml, ultrasonic processing graphite oxide solution subsequently, then again toward the C that adds 0.2 ~ 0.8g in graphite oxide solution
60obtain mixture, to described mixture carry out heated sealed processing, magnetic agitation, subsequent filtration, dry, obtain Graphene/C
60composite material; Wherein, graphite oxide and C
60mass ratio be 10:1 ~ 10:5.
Described Graphene/C
60the preparation method of composite material, wherein, described graphite oxide is adopted with the following method and is made:
Graphite is added in the mixed acid solution of the concentrated sulfuric acid and red fuming nitric acid (RFNA), 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 oxidation processes, remove subsequently potassium permanganate, suction filtration, cyclic washing 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.
Described Graphene/C
60the preparation method of composite material, wherein, in described mixed acid solution, the volume ratio of the concentrated sulfuric acid and red fuming nitric acid (RFNA) is 90:25 ~ 475:120.
Described Graphene/C
60the preparation method of composite material, wherein, it is 30min ~ 1h that described mixed acid solution is heated to the time that 85 ° of C carry out oxidation processes.
Described Graphene/C
60the preparation method of composite material, wherein, the mass fraction of described hydrogen peroxide solution is 30%, the addition of this hydrogen peroxide solution is 9 ~ 30ml.
Described Graphene/C
60the preparation method of composite material wherein, time prepared by graphite oxide, is to adopt watery hydrochloric acid and deionized water cyclic washing to the washing of screening.
Described Graphene/C
60the preparation method of composite material, wherein, when described heat treated, heating-up temperature is 180 ~ 220 ℃, be 15 ~ 24h heating time.
The present invention also provides the Graphene/C that adopts above-mentioned preparation method to make
60composite material.
The present invention also provides above-mentioned Graphene/C
60composite material in electrochemical capacitor as the application of electrode active material.
Graphene/C provided by the invention
60composite material, the reunion of its graphene sheet layer is lower, has higher stored energy capacitance while making this composite material as electrochemical capacitor electrode material.
Embodiment
The invention provides Graphene/C
60concrete preparation technology's flow process of composite material is as follows:
Graphite → graphite oxide → Graphene/C
60composite material
(1) prepare graphite oxide: the graphite that is 99.5% by purity adds in the mixed solution of the concentrated sulfuric acid and red fuming nitric acid (RFNA), mix in bath (temperature is controlled at 0 ℃) and stir at frozen water, in mixed solution, add potassium permanganate at leisure more afterwards, graphite is oxidized, then mixed solution being heated to 85 ° of C keeps 30min ~ 1h to be at high temperature further oxidized graphite, finally add hydrogen peroxide (mass fraction is 30%) to remove potassium permanganate, suction filtration, solids is carried out to cyclic washing with watery 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/C
60composite material: graphite oxide is placed in to 1 ~ 5L deionized water and is configured to the graphite oxide solution that concentration is 0.5 ~ 1mg/ml, ultrasonic 2h; Add again the C of 0.2～0.8g
60obtain mixture, make described C
60concentration be 0.1 ~ 0.5mg/ml, obtain mixture, the heated sealed of carrying out to described mixture at 180～220 ℃ is processed 15 ~ 24h, carries out magnetic agitation simultaneously, slowly filters with final vacuum, with being placed at 60 ℃ dry 12h, obtains Graphene/C
60composite material; Wherein, graphite oxide and C
60mass ratio be 10:1 ~ 10:5; Wherein, ultrasonic effect is that graphite oxide is peeled off as graphene oxide; The effect of heated sealed processing, magnetic agitation is to make graphene oxide and C
60reaction, make C
60graphene oxide is reduced into Graphene.
The preparation method of combination electrode material adopts oxidation-reduction method, and equipment, technique are simple, and convenient operation, easily realizes large-scale industrial production.
Graphene/the C that adopts said method to make
60composite material, according to mass ratio, comprises 50% ~ 85% Graphene and 15% ~ 50% C
60; Wherein, C
60be simple by carbon atom in conjunction with the stable molecule forming, it has 60 summits and 32 faces, wherein 12 is regular pentagon, 20 is regular hexagon.This Graphene/C
60composite material, the reunion of its graphene sheet layer is lower, has higher stored energy capacitance while making this composite material as electrochemical capacitor electrode material.
Graphene/C below
60the application of composite material
Graphene/C
60composite material is generally used for the electrode material of electrochemical capacitor, below introduces the method that uses this material to be made into electrochemical capacitor.
First, the ratio that is 85:5:10 according to mass ratio, by Graphene/C
60composite material Kynoar binding agent and acetylene black conductor mix, and obtain slurry;
Secondly, slurry is coated on aluminium foil, through 80 ° of C vacuumizes 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, use again battery housing seal battery core, in battery container, inject electrolyte (preferred ion liquid) toward the liquid injection port being arranged on battery container subsequently, sealing liquid injection port, obtains electrochemical capacitor.
Below preferred embodiment of the present invention is described in further detail.
Embodiment 1 ~ 4th, Graphene/C
60the preparation method of composite material
Embodiment 1
The present invention prepares Graphene/C
60the technological process of composite material is as follows:
Graphite → graphite oxide → Graphene/C
60composite material
(1) graphite: purity 99.5%;
(2) graphite oxide: take the graphite 1g that (1) moderate purity is 99.5% and add in the mixed solution being formed by the 90ml concentrated sulfuric acid (mass fraction is 98%) and 25ml red fuming nitric acid (RFNA) (mass fraction 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 hydrogenperoxide steam generator (mass fraction 30%), stir 10 minutes, mixture is carried out to suction filtration, with 100ml watery 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/C60 composite 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 0.2g C
60, C
60solubility be 0.2mg/ml, mixture is moved in polytetrafluoroethylene bottle, sealing, and rises to 200 ° of C by this temperature, magnetic agitation 15 hours is filtered, and solid product is placed in to dry 12 hours of the vacuum environment of 60 ° of C, obtains Graphene/C60 composite material.
Embodiment 2
The present invention prepares Graphene/C
60the technological process of composite material is as follows:
Graphite → graphite oxide → Graphene/C
60composite material
(1) graphite: purity 99.5%;
(2) graphite oxide: take the graphite 5g that (1) moderate purity is 99.5% and add in the mixed solution being formed by the 475ml concentrated sulfuric acid (mass fraction is 98%) and 120ml red fuming nitric acid (RFNA) (mass fraction 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 hydrogenperoxide steam generator (mass fraction 30%), stir 10 minutes, mixture is carried out to suction filtration, with 300ml watery 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/C
60composite 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 2 hours; Add again the C of 0.5g
60, C
60solubility be 0.1mg/ml, mixture is moved in polytetrafluoroethylene bottle, sealing, and rises to 180 ° of C by this temperature, magnetic agitation 24 hours is filtered, and solid product is placed in to dry 12 hours of the vacuum environment of 60 ° of C, obtains Graphene/C60 composite material.
Embodiment 3
The present invention prepares Graphene/C
60the technological process of composite material is as follows:
Graphite → graphite oxide → Graphene/C
60composite material
(1) graphite: purity 99.5%;
(2) graphite oxide: take the graphite 2g that (1) moderate purity is 99.5% and add in the mixed solution being formed by the 170ml concentrated sulfuric acid (mass fraction is 98%) and 48ml red fuming nitric acid (RFNA) (mass fraction 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 hydrogenperoxide steam generator (mass fraction 30%), stir 10 minutes, mixture is carried out to suction filtration, with 250ml watery 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/C60 composite 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 the C of 0.8g
60, C
60solubility be 0.2mg/ml, mixture is moved in polytetrafluoroethylene bottle, sealing, and rises to 220 ° of C by this temperature, magnetic agitation 16 hours is filtered, and solid product is placed in to dry 12 hours of the vacuum environment of 60 ° of C, obtains Graphene/C60 composite material.
Embodiment 4
The present invention prepares Graphene/C
60the technological process of composite material is as follows:
Graphite → graphite oxide → Graphene/C
60composite material
(1) graphite: purity 99.5%;
(2) graphite oxide: take the graphite 1g that (1) moderate purity is 99.5% and add in the mixed solution being formed by the 90ml concentrated sulfuric acid (mass fraction is 98%) and 25ml red fuming nitric acid (RFNA) (mass fraction 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 hydrogenperoxide steam generator (mass fraction 30%), stir 10 minutes, mixture is carried out to suction filtration, with 100ml watery 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/C60 composite material: the 1g graphite oxide of preparation in (2) is added in 2L deionized water, and the solubility of graphite oxide in water is 0.5mg/ml, ultrasonic 2 hours; Add again the C of 0.5g
60, C
60solubility be 0.25mg/ml, mixture is moved in polytetrafluoroethylene bottle, sealing, and rises to 180 ° of C by this temperature, magnetic agitation 20 hours is filtered, and solid product is placed in to dry 12 hours of the vacuum environment of 60 ° of C, obtains Graphene/C60 composite material.
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 85:5:10 according to mass ratio, Graphene/C that embodiment 1 is obtained
60composite material Kynoar binding agent and acetylene black conductor 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, in battery container, inject [BMIM] [PF by the liquid injection port being arranged on battery container subsequently
6], sealing liquid injection port, 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 both positive and negative polarity of battery is connected with the both positive and negative polarity of test macro, recall the test program 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 capacity of the 3rd circle as the specific capacity of material.
Embodiment 6 ~ 8 is identical with the process of preparing of embodiment 5, and difference is that the electrode material adopting is respectively the prepared electrode material out of embodiment 2 ~ 4.
The electrochemical capacitor that embodiment 5 ~ 8 is made carries out charge-discharge test under current density 0.5A/g, and its specific capacity is as shown in table 1:
Table 1
| Embodiment | 5 | 6 | 7 | 8 |
| Specific capacity (F/g) | 182 | 171 | 211 | 165 |
As shown in table 1, Graphene/C60 composite material prepared by the present invention specific capacity under 0.5A/g current density all, more than 160F/g, is up to 211F/g, illustrates that composite material 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 (9)
1. a Graphene/C
60the preparation method of composite material, is characterized in that, comprises the steps:
Graphite oxide is placed in to 1 ~ 5L deionized water and is configured to the graphite oxide solution that concentration is 0.5 ~ 1mg/ml, ultrasonic processing graphite oxide solution subsequently, then again toward the C that adds 0.2 ~ 0.8g in graphite oxide solution
60, obtain mixture, to described mixture carry out heated sealed processing, magnetic agitation, subsequent filtration, dry, obtain Graphene/C
60composite material; Wherein, graphite oxide and C
60mass ratio be 10:1 ~ 10:5.
2. Graphene/C according to claim 1
60the preparation method of composite material, is characterized in that, graphite oxide is adopted with the following method and made:
Graphite is added in the mixed acid solution of the concentrated sulfuric acid and red fuming nitric acid (RFNA), 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 oxidation processes, remove subsequently potassium permanganate, suction filtration, cyclic washing 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. Graphene/C according to claim 2
60the preparation method of composite material, is characterized in that, in described mixed acid solution, the volume ratio of the concentrated sulfuric acid and red fuming nitric acid (RFNA) is 90:25 ~ 475:120.
4. Graphene/C according to claim 2
60the preparation method of composite material, is characterized in that, it is 30min ~ 1h that described mixed acid solution is heated to the time that 85 ° of C carry out oxidation processes.
5. Graphene/C according to claim 2
60the preparation method of composite material, is characterized in that, the mass fraction of described hydrogen peroxide solution is 30%, and the addition of this hydrogen peroxide solution is 9 ~ 30ml.
6. Graphene/C according to claim 2
60the preparation method of composite material, is characterized in that, time prepared by graphite oxide, is to adopt watery hydrochloric acid and deionized water cyclic washing to the washing of screening.
7. Graphene/C according to claim 1
60the preparation method of composite material, is characterized in that, when described heat treated, heating-up temperature is 180 ~ 220 ℃, and be 15 ~ 24h heating time.
8. a Graphene/C
60composite material, is characterized in that, adopts the arbitrary described method of claim 1 to 7 to make.
9. Graphene/C claimed in claim 8
60composite material in electrochemical capacitor as the application of electrode active material.
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Cited By (2)
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| CN105679553A (en) * | 2016-04-22 | 2016-06-15 | 青岛科技大学 | Super capacitor based on fullerene nano fiber/polyaniline composite |
| CN106847535A (en) * | 2016-12-16 | 2017-06-13 | 吴中区穹窿山天仲高分子材料技术研究所 | A kind of Graphene fulvene compounding material and preparation method and purposes |
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