CN103839684A - Graphene-ionic liquid composite electrode material and preparation method and application thereof - Google Patents
Graphene-ionic liquid composite electrode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a graphene-ionic liquid composite electrode material. A graphene composite electrode comprises graphene and ionic liquid, wherein the ionic liquid is dispersed in intervals of the graphene, and the mass ratio between the graphene and the ionic liquid is 5-10:1-2. The ionic liquid is added to the graphene electrode material with a high specific area and high electrical conductivity, so that the graphene-ionic liquid composite electrode material is formed. The graphene-ionic liquid composite electrode material has the advantages of high specific capacity, good electrical conductivity and good wettability with an ionic liquid electrolyte solution. The invention further relates to a preparation method of the graphene-ionic liquid composite electrode material, and an electrode plate and an electrochemical capacitor containing the graphene-ionic liquid composite electrode material.
Description
Technical field
The present invention relates to electrochemical capacitor field, particularly relate to a kind of Graphene-ionic liquid combination electrode material and its 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 electrochemical capacitor development and application, explore energy density how to carry electrochemical capacitor and be the emphasis of this area research at present.
According to the computing formula E=1/2CV of energy density
2, 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.
The voltage window of electrochemical capacitor is main relevant with the withstand voltage scope of electrolyte.Ionic liquid is a kind of electrolyte of withstand voltage wider range, and its chemical window can reach 4-6V, can improve the voltage window of electrochemical capacitor, significantly increases the energy density of electrochemical capacitor; And Graphene is as the two-dimentional monolayer material of one, there is higher specific area and higher conductivity, be a kind of desirable electrochemical capacitor electrode material.But ionic liquid is because viscosity is large, poor to the wettability of electrode material, this makes the more difficult raising of specific capacity of electrode material.
Summary of the invention
Based on this, being necessary to provide a kind of has higher infiltrating Graphene-ionic liquid combination electrode material and preparation method thereof with il electrolyte.
A preparation method for Graphene-ionic liquid combination electrode material, comprises the steps:
Graphite is added in the mixed solution of the concentrated sulfuric acid and red fuming nitric acid (RFNA), under 0 ℃ of environment, be uniformly mixed, then in mixed solution, add potassium permanganate, after mixing, under 85 ℃ of environment, react, keep again temperature to add deionized water dilution in reaction system, finally add hydrogenperoxide steam generator, stirring reaction is removed unreacted potassium permanganate, the mixture obtaining is carried out to suction filtration processing, the solids that suction filtration obtains uses watery hydrochloric acid and deionized water washing successively, after being dried, obtains graphite oxide;
Described graphite oxide is added in deionized water, ultrasonic dispersion, then the dispersion obtaining is carried out to suction filtration processing, the solids obtaining after suction filtration obtains graphene oxide after being dried;
In protective gas atmosphere, with the heating rate of 15-30 ℃/min, described graphene oxide is slowly heated to 500-700 ℃ from room temperature and carries out deoxygenation, the cooling Graphene that obtains after reaction;
The ratio that is 5 ~ 10:1 ~ 2 according to the mass ratio of Graphene and ionic liquid takes described Graphene and ionic liquid, and the described Graphene taking and described ionic liquid are added to in solvent, to make the concentration of described Graphene be 8 ~ 10mg/mL, ultrasonic dispersion, again the mixed solution obtaining is placed in to vacuum environment and stirs, obtain described Graphene-ionic liquid combination electrode material except after desolventizing.
In an embodiment, described solvent is isopropyl alcohol or methyl pyrrolidone therein.
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.
A kind of Graphene-ionic liquid combination electrode material, adopts said method to prepare.
This Graphene-ionic liquid combination electrode material forms combination electrode material by increase ionic liquid in the Graphene electrodes material with higher specific area and conductivity, the ionic liquid increasing in this combination electrode material, can increase the wettability of combination electrode material and il electrolyte, thereby improve the specific capacity of combination electrode material.Therefore, above-mentioned combination electrode material, has high specific capacity, good conductivity and has higher infiltrating advantage with il electrolyte.
And the preparation process of this Graphene-ionic liquid combination electrode material is simple, low for equipment requirements, can wide popularization and application.
In addition the electrochemical capacitor that, is also necessary to provide a kind of electrode slice that contains above-mentioned Graphene-ionic liquid combination electrode material and preparation method thereof and uses this electrode slice.
A kind of electrode slice, comprise collector and be coated in the electrode slurry on described collector, described electrode slurry comprises conductive agent, bonding agent and Graphene-ionic liquid combination electrode material, and described Graphene-ionic liquid combination electrode material is the Graphene-ionic liquid combination electrode material that adopts said method to prepare.
In an embodiment, described conductive agent is acetylene black therein, and described bonding agent is Kynoar, and described collector is aluminium foil.
A preparation method for electrode slice, comprises the steps:
The ratio that is 5 ~ 10:1 ~ 2 according to the mass ratio of Graphene and ionic liquid takes described Graphene and ionic liquid, and the described Graphene taking and described ionic liquid are added to in solvent, to make the concentration of described Graphene be 8 ~ 10mg/mL, ultrasonic dispersion, again the mixed solution obtaining is placed in to vacuum environment and stirs, obtain the solution that contains Graphene-ionic liquid combination electrode material;
The ratio that is 85:5:10 according to the mass ratio of Graphene-ionic liquid combination electrode material, bonding agent and conductive agent, mixes the described solution that contains Graphene-ionic liquid combination electrode material, bonding agent with conductive agent, obtain electrode slurry;
Described electrode slurry is coated on collector, through 80 ℃ of dry 2 hours, 250 ℃ processing in dry 2 hours, after section, obtains described electrode slice successively.
In an embodiment, described preparation method also comprises the preparation process of Graphene, as follows therein:
Graphite is added in the mixed solution of the concentrated sulfuric acid and red fuming nitric acid (RFNA), under 0 ℃ of environment, be uniformly mixed, then in mixed solution, add potassium permanganate, after mixing, under 85 ℃ of environment, react, keep again temperature to add deionized water dilution in reaction system, finally add hydrogenperoxide steam generator, stirring reaction is removed unreacted potassium permanganate, the mixture obtaining is carried out to suction filtration processing, the solids that suction filtration obtains uses watery hydrochloric acid and deionized water washing successively, after being dried, obtains graphite oxide;
Described graphite oxide is added in deionized water, ultrasonic dispersion, then the dispersion obtaining is carried out to suction filtration processing, the solids obtaining after suction filtration obtains graphene oxide after being dried;
In protective gas atmosphere, with the heating rate of 15-30 ℃/min, described graphene oxide is slowly heated to 500-700 ℃ from room temperature and carries out deoxygenation, the cooling Graphene that obtains after reaction.
In an embodiment, described conductive agent is acetylene black therein, and described bonding agent is Kynoar, and described collector is aluminium foil.
This electrode slice is because using above-mentioned Graphene-ionic liquid combination electrode material, has high specific capacity, good conductivity and has higher infiltrating advantage with il electrolyte.
A kind of electrochemical capacitor, comprise housing and be placed in battery core and the electrolyte in described housing, described battery core comprise positive plate and the negative plate being oppositely arranged and be arranged on described positive plate and described negative plate between barrier film, described positive plate and described negative plate are the electrode slice as described in claim 5-6 any one.
This electrochemical capacitor is by add above-mentioned Graphene-ionic liquid combination electrode material of function admirable in electrode slice, thereby makes above-mentioned electrochemical capacitor have that charge-discharge velocity is fast, power density is high, have extended cycle life and have the higher advantage such as stored energy capacitance and multiplying power property.
Accompanying drawing explanation
Fig. 1 is the preparation method's of the electrode slice of an execution mode flow chart.
Embodiment
Below in conjunction with drawings and the specific embodiments, Graphene-ionic liquid combination electrode material and preparation method thereof and related application are further described.
The preparation method of Graphene-ionic liquid combination electrode material of one execution mode, comprises the steps:
The ratio that is 5 ~ 10:1 ~ 2 according to the mass ratio of Graphene and ionic liquid takes described Graphene and ionic liquid, and the described Graphene taking and described ionic liquid are added to in solvent, to make the concentration of described Graphene be 8 ~ 10mg/mL, ultrasonic dispersion, again the mixed solution obtaining is placed in to vacuum environment and stirs, obtain described Graphene-ionic liquid combination electrode material except after desolventizing.
Wherein, Graphene can prepare as follows:
Graphite is added in the mixed solution of the concentrated sulfuric acid and red fuming nitric acid (RFNA), under 0 ℃ of environment, be uniformly mixed, then in mixed solution, add potassium permanganate, after mixing, under 85 ℃ of environment, react, keep again temperature to add deionized water dilution in reaction system, finally adding mass fraction is 30% hydrogenperoxide steam generator, stirring reaction is removed unreacted potassium permanganate, the mixture obtaining is carried out to suction filtration processing, the solids that suction filtration obtains uses watery hydrochloric acid and deionized water washing successively, after being dried, obtains graphite oxide;
Graphite oxide is added in deionized water, ultrasonic dispersion, then the dispersion obtaining is carried out to suction filtration processing, the solids obtaining after suction filtration obtains graphene oxide after being dried;
In protective gas atmosphere, with the heating rate of 15-30 ℃/min, graphene oxide is slowly heated to 500-700 ℃ from room temperature and carries out deoxygenation, after reaction, the cooling compound obtaining is Graphene.
Wherein, protective gas atmosphere can be the anaerobic atmosphere such as nitrogen or inert gas.
In the present embodiment, ionic liquid is two fluoroform sulfimide salt ([the EMIM] [Tf of 1-ethyl-3-methylimidazole
2n]) or two fluoroform sulfimide salt ([the BMIM] [Tf of 1-butyl-3-methylimidazole
2n]).
The preparation process of this Graphene-ionic liquid combination electrode material is simple, low for equipment requirements, can wide popularization and application.
In addition, present embodiment also provides a kind of Graphene-ionic liquid combination electrode material, and it is to adopt said method to prepare, and ionic liquid is attracted in the space of Graphene.
This Graphene-ionic liquid combination electrode material forms combination electrode material by increase ionic liquid in the Graphene electrodes material with higher specific area and conductivity, the ionic liquid increasing in this combination electrode material, can increase the wettability of combination electrode material and il electrolyte, thereby improve the specific capacity of combination electrode material.Therefore, above-mentioned combination electrode material, has high specific capacity, good conductivity and has higher infiltrating advantage with il electrolyte.
In addition, present embodiment also provides a kind of electrode slice that contains above-mentioned Graphene-ionic liquid combination electrode material and preparation method thereof and has used the electrochemical capacitor of this electrode slice.
A kind of electrode slice, comprise collector and be coated in the electrode slurry on described collector, described electrode slurry comprises conductive agent, bonding agent and Graphene-ionic liquid combination electrode material, and described Graphene-ionic liquid combination electrode material is for adopting said method to prepare.
Wherein, conductive agent is acetylene black.Bonding agent is Kynoar.Collector is aluminium foil.Ionic liquid is the two fluoroform sulfimide salt of 1-ethyl-3-methylimidazole or the two fluoroform sulfimide salt of 1-butyl-3-methylimidazole.
As shown in Figure 1, a kind of preparation method of electrode slice, comprises the steps:
Step S110, the ratio that is 5 ~ 10:1 ~ 2 according to the mass ratio of Graphene and ionic liquid takes described Graphene and ionic liquid, and the described Graphene taking and described ionic liquid are added to in solvent, to make the concentration of described Graphene be 8 ~ 10mg/mL, ultrasonic dispersion, again the mixed solution obtaining is placed in to vacuum environment and stirs, obtain the solution that contains Graphene-ionic liquid combination electrode material.
Step S120, the ratio that is 85:5:10 according to the mass ratio of Graphene-ionic liquid combination electrode material, bonding agent and conductive agent, the described solution that contains Graphene-ionic liquid combination electrode material, bonding agent are mixed with conductive agent, obtain electrode slurry.
Step S130, is coated in electrode slurry on collector, through 80 ℃ of dry 2 hours, 250 ℃ processing in dry 2 hours, obtains electrode slice after section successively.
This electrode slice is because using above-mentioned Graphene-ionic liquid combination electrode material, has high specific capacity, good conductivity and has higher infiltrating advantage with il electrolyte.
A kind of electrochemical capacitor, comprises housing and is placed in battery core and the electrolyte in housing, battery core comprise positive plate and the negative plate being oppositely arranged and be arranged on positive plate and negative plate between barrier film, positive plate and negative plate are above-mentioned electrode slice.
This electrochemical capacitor is by add above-mentioned Graphene-ionic liquid combination electrode material of function admirable in electrode slice, thereby makes above-mentioned electrochemical capacitor have that charge-discharge velocity is fast, power density is high, have extended cycle life and have the higher advantage such as stored energy capacitance and multiplying power property.
Be below specific embodiment part:
Embodiment 1
The preparation of graphite oxide: the graphite that is 99.5% by 1g purity adds in the mixed solution being made up of the 90mL98wt% concentrated sulfuric acid and 25mL65wt% red fuming nitric acid (RFNA), obtains mixture; Mixture is placed in to frozen water mixing bath to be stirred after 20 minutes; In mixture, add 6g potassium permanganate at leisure, and stir 1 hour; Then mixture is heated to 85 ℃ and keep after 30 minutes; In mixture, add 92mL deionized water, at 85 ℃, continue to keep after 30 minutes; In mixture, add 10mL30wt% hydrogenperoxide steam generator, and 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; Finally solid matter is placed in to 60 ℃ of vacuum drying ovens dry 12 hours, obtains graphite oxide.
The preparation of graphene oxide: the graphite oxide deionized water suspension that compound concentration is 1mg/mL; Above-mentioned suspension is carried out to ultrasonic processing, and wherein, ultrasonic power is 500W, and the time is 1 hour; Then above-mentioned suspension is carried out to suction filtration, obtain solid matter; The solid matter obtaining is placed in to vacuum drying oven and at 60 ℃, is dried 12 hours, obtain graphene oxide.
The preparation of Graphene: the graphite oxide preparing is placed under the argon atmosphere of flow velocity 400mL/min, make graphite oxide temperature around rise to 500 ℃ with the heating rate of 20 ℃/min from room temperature, at 500 ℃, keep after 2 hours, under the argon atmosphere of flow velocity 400mL/min, the temperature around graphite oxide is down to room temperature, obtains Graphene.
The preparation of Graphene-ionic liquid combination electrode material: add [EMIM] [Tf in isopropyl alcohol
2n] and the above-mentioned Graphene preparing, mixture obtained; Wherein, [EMIM] [Tf
2n] final concentration be 2mg/mL, the final concentration of Graphene is 10mg/mL;
Mixture is carried out to ultrasonic processing, and wherein, ultrasonic power is 500W, and the time is 6 hours; Then the mixture after ultrasonic is placed under vacuum environment and is stirred 6 hours, obtain described Graphene-ionic liquid combination electrode material.
Embodiment 2
The preparation of graphite oxide: the graphite that is 99.5% by 5g purity adds in the mixed solution being made up of the 475mL98wt% concentrated sulfuric acid and 120mL65wt% red fuming nitric acid (RFNA), obtains mixture; Mixture is placed in to frozen water mixing bath to be stirred after 20 minutes; In mixture, add 20g potassium permanganate at leisure, and stir 1 hour; Then mixture is heated to 85 ℃ and keep after 30 minutes; In mixture, add 92mL deionized water, at 85 ℃, continue to keep after 30 minutes; In mixture, add the hydrogenperoxide steam generator of 30mL30wt%, and 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; Finally solid matter is placed in to 60 ℃ of vacuum drying ovens dry 12 hours, obtains graphite oxide.
The preparation of graphene oxide: the graphite oxide deionized water suspension that compound concentration is 0.5mg/mL; Above-mentioned suspension is carried out to ultrasonic processing, and wherein, ultrasonic power is 800W, and the time is 2 hours; Then above-mentioned suspension is carried out to suction filtration, obtain solid matter; The solid matter obtaining is placed in to vacuum drying oven and at 60 ℃, is dried 12 hours, obtain graphene oxide.
The preparation of Graphene: the graphite oxide preparing is placed under the argon atmosphere of flow velocity 400mL/min, make graphite oxide temperature around rise to 700 ℃ with the heating rate of 25 ℃/min from room temperature, at 700 ℃, keep after 1 hour, under the argon atmosphere of flow velocity 400mL/min, the temperature around graphite oxide is down to room temperature, obtains Graphene.
The preparation of Graphene-ionic liquid combination electrode material: add [EMIM] [Tf in isopropyl alcohol
2n] and the above-mentioned Graphene preparing, mixture obtained; Wherein, [EMIM] [Tf
2n] final concentration be 2mg/mL, the final concentration of Graphene is 8mg/mL;
Mixture is carried out to ultrasonic processing, and wherein, ultrasonic power is 500W, and the time is 10 hours; Then the mixture after ultrasonic is placed under vacuum environment and is stirred 10 hours, obtain described Graphene-ionic liquid combination electrode material.
Embodiment 3
The preparation of graphite oxide: the graphite that is 99.5% by 2g purity adds in the mixed solution being made up of the 170mL98wt% concentrated sulfuric acid and 48mL65wt% red fuming nitric acid (RFNA), obtains mixture; Mixture is placed in to frozen water mixing bath to be stirred after 20 minutes; In mixture, add 8g potassium permanganate at leisure, and stir 1 hour; Then mixture is heated to 85 ℃ and keep after 30 minutes; In mixture, add 92mL deionized water, at 85 ℃, continue to keep after 30 minutes; In mixture, add 16mL30wt% hydrogenperoxide steam generator, and 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; Finally solid matter is placed in to 60 ℃ of vacuum drying ovens dry 12 hours, obtains graphite oxide.
The preparation of graphene oxide: the graphite oxide deionized water suspension that compound concentration is 0.5mg/mL; Above-mentioned suspension is carried out to ultrasonic processing, and wherein, ultrasonic power is 500W, and the time is 2 hours; Then above-mentioned suspension is carried out to suction filtration, obtain solid matter; The solid matter obtaining is placed in to vacuum drying oven and at 60 ℃, is dried 12 hours, obtain graphene oxide.
The preparation of Graphene: the graphite oxide preparing is placed under the argon atmosphere of flow velocity 400mL/min, make graphite oxide temperature around rise to 600 ℃ with the heating rate of 15 ℃/min from room temperature, at 600 ℃, keep after 0.5 hour, under the argon atmosphere of flow velocity 400mL/min, the temperature around graphite oxide is down to room temperature, obtains Graphene.
The preparation of Graphene-ionic liquid combination electrode material: add [BMIM] [Tf in isopropyl alcohol
2n] and the above-mentioned Graphene preparing, mixture obtained; Wherein, [BMIM] [Tf
2n] final concentration be 4mg/mL, the final concentration of Graphene is 10mg/mL;
Mixture is carried out to ultrasonic processing, and wherein, ultrasonic power is 500W, and the time is 8 hours; Then the mixture after ultrasonic is placed under vacuum environment and is stirred 8 hours, obtain described Graphene-ionic liquid combination electrode material.
Embodiment 4
The preparation of graphite oxide: the graphite that is 99.5% by 1g purity adds in the mixed solution being made up of the 90mL98wt% concentrated sulfuric acid and 25mL65wt% red fuming nitric acid (RFNA), obtains mixture; Mixture is placed in to frozen water mixing bath to be stirred after 20 minutes; In mixture, add 4g potassium permanganate at leisure, and stir 1 hour; Then mixture is heated to 85 ℃ and keep after 30 minutes; In mixture, add 92mL deionized water, at 85 ℃, continue to keep after 30 minutes; In mixture, add the hydrogenperoxide steam generator of 10mL30wt%, and 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; Finally solid matter is placed in to 60 ℃ of vacuum drying ovens dry 12 hours, obtains graphite oxide.
The preparation of graphene oxide: the graphite oxide deionized water suspension that compound concentration is 0.5mg/mL; Above-mentioned suspension is carried out to ultrasonic processing, and wherein, ultrasonic power is 500W, and the time is 1 hour; Then above-mentioned suspension is carried out to suction filtration, obtain solid matter; The solid matter obtaining is placed in to vacuum drying oven and at 60 ℃, is dried 12 hours, obtain graphene oxide.
The preparation of Graphene: the graphite oxide preparing is placed under the argon atmosphere of flow velocity 400mL/min, make graphite oxide temperature around rise to 500 ℃ with the heating rate of 30 ℃/min from room temperature, at 500 ℃, keep after 2 hours, under the argon atmosphere of flow velocity 400mL/min, the temperature around graphite oxide is down to room temperature, obtains Graphene.
The preparation of Graphene-ionic liquid combination electrode material: add [BMIM] [Tf in isopropyl alcohol
2n] and the above-mentioned Graphene preparing, mixture obtained; Wherein, [BMIM] [Tf
2n] final concentration be 1mg/mL, the final concentration of Graphene is 10mg/mL;
Mixture is carried out to ultrasonic processing, and wherein, ultrasonic power is 500W, and the time is 8 hours; Then the mixture after ultrasonic is placed under vacuum environment and is stirred 8 hours, obtain described Graphene-ionic liquid combination electrode material.
Embodiment 5
The ratio that is 85:5:10 according to mass ratio, Graphene-ionic liquid combination electrode material, Kynoar binding agent and acetylene black conductor that embodiment 1 is prepared mix, and obtain slurry; Slurry is coated on aluminium foil; Then by the aluminium foil that is coated with slurry prior to 80 ℃ after dry 2 hours, then after dry 2 hours, obtain slurry film in 250 ℃; By the section of slurry film, make electrochemical capacitor electrode sheet.
Successively above-mentioned electrode slice, barrier film, electrode slice lamination assembling are obtained to battery core; At battery core outer cladding battery container, by battery core sealing, then in battery container, inject ionic liquid [EMIM] [Tf by the liquid injection port being arranged on battery container
2n], after sealing liquid injection port, obtain electrochemical capacitor.
Embodiment 6
The ratio that is 85:5:10 according to mass ratio, Graphene-ionic liquid combination electrode material, Kynoar binding agent and acetylene black conductor that embodiment 2 is prepared mix, and obtain slurry; Slurry is coated on aluminium foil; Then by the aluminium foil that is coated with slurry prior to 80 ℃ after dry 2 hours, then after dry 2 hours, obtain slurry film in 250 ℃; By the section of slurry film, make electrochemical capacitor electrode sheet.
Successively electrode slice, barrier film, electrode slice lamination assembling are obtained to battery core; At battery core outer cladding battery container, by battery core sealing, then in battery container, inject ionic liquid [EMIM] [Tf by the liquid injection port being arranged on battery container
2n], after sealing liquid injection port, obtain electrochemical capacitor.
Embodiment 7
The ratio that is 85:5:10 according to mass ratio, Graphene-ionic liquid combination electrode material, Kynoar binding agent and acetylene black conductor that embodiment 3 is prepared mix, and obtain slurry; Slurry is coated on aluminium foil; Then by the aluminium foil that is coated with slurry prior to 80 ℃ after dry 2 hours, then after dry 2 hours, obtain slurry film in 250 ℃; By the section of slurry film, make electrochemical capacitor electrode sheet.
Successively electrode slice, barrier film, electrode slice lamination assembling are obtained to battery core; At battery core outer cladding battery container, by battery core sealing, then in battery container, inject ionic liquid [BMIM] [Tf by the liquid injection port being arranged on battery container
2n], after sealing liquid injection port, obtain electrochemical capacitor.
Embodiment 8
The ratio that is 85:5:10 according to mass ratio, Graphene-ionic liquid combination electrode material, Kynoar binding agent and acetylene black conductor that embodiment 4 is prepared mix, and obtain slurry; Slurry is coated on aluminium foil; Then by the aluminium foil that is coated with slurry prior to 80 ℃ after dry 2 hours, then after dry 2 hours, obtain slurry film in 250 ℃; By the section of slurry film, make electrochemical capacitor electrode sheet.
Successively electrode slice, barrier film, electrode slice lamination assembling are obtained to battery core; At battery core outer cladding battery container, by battery core sealing, then in battery container, inject ionic liquid [BMIM] [Tf by the liquid injection port being arranged on battery container
2n], after sealing liquid injection port, obtain electrochemical capacitor.
Performance test:
Respectively the electrochemical capacitor of assembling in embodiment 5 ~ 8 is carried out to charge-discharge test, voltage window is 4V, and current density is respectively 0.5A/g, and test result is as table 1.
Table 1 is the specific capacity that embodiment 5 ~ 8 carries out respectively charge-discharge test under 0.5A/g current density
| ? | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 |
| Specific capacity (F/g) under 0.5A/g | 221 | 236 | 248 | 202 |
The specific capacity test result of embodiment 5 ~ 8 under 0.5A/g current density show, the combination electrode material in embodiment 5 ~ 8 has excellent energy-storage property.
The above embodiment has only expressed several execution mode 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 range of patent of the present invention should be as the criterion with claims.
Claims (10)
1. a preparation method for Graphene-ionic liquid combination electrode material, is characterized in that, comprises the steps:
Graphite is added in the mixed solution of the concentrated sulfuric acid and red fuming nitric acid (RFNA), under 0 ℃ of environment, be uniformly mixed, then in mixed solution, add potassium permanganate, after mixing, under 85 ℃ of environment, react, keep again temperature to add deionized water dilution in reaction system, finally add hydrogenperoxide steam generator, stirring reaction is removed unreacted potassium permanganate, the mixture obtaining is carried out to suction filtration processing, the solids that suction filtration obtains uses watery hydrochloric acid and deionized water washing successively, after being dried, obtains graphite oxide;
Described graphite oxide is added in deionized water, ultrasonic dispersion, then the dispersion obtaining is carried out to suction filtration processing, the solids obtaining after suction filtration obtains graphene oxide after being dried;
In protective gas atmosphere, with the heating rate of 15-30 ℃/min, described graphene oxide is slowly heated to 500-700 ℃ from room temperature and carries out deoxygenation, the cooling Graphene that obtains after reaction;
The ratio that is 5 ~ 10:1 ~ 2 according to the mass ratio of Graphene and ionic liquid takes described Graphene and ionic liquid, and the described Graphene taking and described ionic liquid are added to in solvent, to make the concentration of described Graphene be 8 ~ 10mg/mL, ultrasonic dispersion, again the mixed solution obtaining is placed in to vacuum environment and stirs, obtain described Graphene-ionic liquid combination electrode material except after desolventizing.
2. the preparation method of Graphene-ionic liquid combination 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. the preparation method of Graphene-ionic liquid combination electrode material according to claim 1 and 2, is characterized in that, described solvent is isopropyl alcohol or methyl pyrrolidone.
4. Graphene-ionic liquid combination electrode material, is characterized in that, adopts method as described in claim 1-3 any one to prepare.
5. an electrode slice, comprise collector and be coated in the electrode slurry on described collector, it is characterized in that, described electrode slurry comprises conductive agent, bonding agent and Graphene-ionic liquid combination electrode material, and described Graphene-ionic liquid combination electrode material is Graphene-ionic liquid combination electrode material claimed in claim 4.
6. electrode slice according to claim 5, is characterized in that, described conductive agent is acetylene black, and described bonding agent is Kynoar, and described collector is aluminium foil.
7. a preparation method for electrode slice, is characterized in that, comprises the steps:
The ratio that is 5 ~ 10:1 ~ 2 according to the mass ratio of Graphene and ionic liquid takes described Graphene and ionic liquid, and the described Graphene taking and described ionic liquid are added to in solvent, to make the concentration of described Graphene be 8 ~ 10mg/mL, ultrasonic dispersion, again the mixed solution obtaining is placed in to vacuum environment and stirs, obtain the solution that contains Graphene-ionic liquid combination electrode material;
The ratio that is 85:5:10 according to the mass ratio of Graphene-ionic liquid combination electrode material, bonding agent and conductive agent, mixes the described solution that contains Graphene-ionic liquid combination electrode material, bonding agent with conductive agent, obtain electrode slurry;
Described electrode slurry is coated on collector, through 80 ℃ of dry 2 hours, 250 ℃ processing in dry 2 hours, after section, obtains described electrode slice successively.
8. the preparation method of electrode slice according to claim 7, is characterized in that, also comprises the preparation process of Graphene, as follows:
Graphite is added in the mixed solution of the concentrated sulfuric acid and red fuming nitric acid (RFNA), under 0 ℃ of environment, be uniformly mixed, then in mixed solution, add potassium permanganate, after mixing, under 85 ℃ of environment, react, keep again temperature to add deionized water dilution in reaction system, finally add hydrogenperoxide steam generator, stirring reaction is removed unreacted potassium permanganate, the mixture obtaining is carried out to suction filtration processing, the solids that suction filtration obtains uses watery hydrochloric acid and deionized water washing successively, after being dried, obtains graphite oxide;
Described graphite oxide is added in deionized water, ultrasonic dispersion, then the dispersion obtaining is carried out to suction filtration processing, the solids obtaining after suction filtration obtains graphene oxide after being dried;
In protective gas atmosphere, with the heating rate of 15-30 ℃/min, described graphene oxide is slowly heated to 500-700 ℃ from room temperature and carries out deoxygenation, the cooling Graphene that obtains after reaction.
9. the preparation method of electrode slice according to claim 7, is characterized in that, described conductive agent is acetylene black, and described bonding agent is Kynoar, and described collector is aluminium foil.
10. an electrochemical capacitor, comprise housing and be placed in battery core and the electrolyte in described housing, described battery core comprise positive plate and the negative plate being oppositely arranged and be arranged on described positive plate and described negative plate between barrier film, it is characterized in that, described positive plate and described negative plate are the electrode slice as described in claim 5-6 any one.
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| CN102142294A (en) * | 2010-01-29 | 2011-08-03 | 海洋王照明科技股份有限公司 | Graphene-ionic liquid composite material and preparation method thereof |
| CN102723211A (en) * | 2012-05-08 | 2012-10-10 | 海博瑞恩电子科技无锡有限公司 | High performance super capacitor and manufacturing process thereof |
| CN102750998A (en) * | 2012-07-09 | 2012-10-24 | 深圳市贝特瑞纳米科技有限公司 | Transparent graphene conductive thin film and preparation method thereof |
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| CN102142294A (en) * | 2010-01-29 | 2011-08-03 | 海洋王照明科技股份有限公司 | Graphene-ionic liquid composite material and preparation method thereof |
| CN102723211A (en) * | 2012-05-08 | 2012-10-10 | 海博瑞恩电子科技无锡有限公司 | High performance super capacitor and manufacturing process thereof |
| CN102750998A (en) * | 2012-07-09 | 2012-10-24 | 深圳市贝特瑞纳米科技有限公司 | Transparent graphene conductive thin film and preparation method thereof |
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| QINGMIN JI等: "Layer-by-Layer Films of Graphene and Ionic Liquids for Highly Selective Gas Sensing", 《ANGEWANDTE CHEMIE INTERNATIONAL EDITION》 * |
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