CN103839685A - Graphene-polyion liquid composite electrode material and preparation method and application thereof - Google Patents
Graphene-polyion liquid composite electrode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a graphene-polyion liquid composite electrode material. A graphene composite electrode comprises graphene and polyion liquid, wherein the polyion liquid is dispersed in intervals of the graphene, and the mass ratio between the graphene and the polyion liquid is 2.5-10:1. The polyion liquid is added to the graphene electrode material with a high specific area and high electrical conductivity, so that the graphene-polyion liquid composite electrode material is formed. The graphene-polyion 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-polyion liquid composite electrode material, and an electrode plate and an electrochemical capacitor containing the graphene-polyion liquid composite electrode material.
Description
Technical field
The present invention relates to electrochemical capacitor field, particularly relate to a kind of Graphene-poly ion 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-poly ion liquid combination electrode material and preparation method thereof with il electrolyte.
A preparation method for Graphene-poly ion 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;
The ratio that is 2.5 ~ 10:1 according to the mass ratio of graphene oxide and poly ion liquid takes described graphene oxide and poly ion liquid, and the described graphene oxide taking and described poly ion liquid are added to in solvent, to make the concentration of described graphene oxide be 8 ~ 10mg/mL, ultrasonic dispersion, the mixed solution obtaining is placed in to vacuum environment to be filtered, again the solid product obtaining after filtering is heated to 200 ~ 250 ° of C, thermal reduction obtains described Graphene-poly ion liquid combination electrode material.
In an embodiment, described poly ion liquid is poly-(1-vinyl-3 ethyl imidazol(e)) two fluoroform sulfimide salt therein; Described poly ion liquid adopts following steps preparation:
The ratio that is 40 ~ 50:50 ~ 70:1:55 ~ 90 according to the mol ratio of 1-vinyl imidazole, bromoethane, azo-bis-isobutyl cyanide and two fluoroform sulfimide lithium salts takes described 1-vinyl imidazole, described bromoethane, described azo-bis-isobutyl cyanide and described pair of fluoroform sulfimide lithium salts;
The described 1-vinyl imidazole taking is mixed under the condition stirring with described bromoethane, and at 40 ℃ stirring reaction, afterwards the temperature of reaction system is adjusted to 60 ℃, and add described azo-bis-isobutyl cyanide, reaction adds two fluoroform sulfimide lithium salts and distilled water in reacted system, continues stirring reaction, the mixed liquor obtaining is reacted in last vacuum filtration, and the solids of collection is gathered (1-vinyl-3 ethyl imidazol(e)) two fluoroform sulfimide salt poly ion liquids after being dried.
A kind of Graphene-poly ion liquid combination electrode material, adopts said method to make.
This Graphene-poly ion liquid combination electrode material forms combination electrode material by increase poly ion liquid in the Graphene electrodes material with higher specific area and conductivity, the poly ion 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-poly ion 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-poly ion 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-poly ion liquid combination electrode material, and described Graphene-poly ion liquid combination electrode material comprises Graphene and the poly ion liquid that said method makes.
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 2.5 ~ 10:1 according to the mass ratio of graphene oxide and poly ion liquid takes described graphene oxide and poly ion liquid, and the described graphene oxide taking and described poly ion liquid are added to in solvent, to make the concentration of described graphene oxide be 8 ~ 10mg/mL, ultrasonic dispersion, the mixed solution obtaining is placed in to vacuum environment to be filtered, again the solid product obtaining after filtering is heated to 200 ~ 250 ° of C, thermal reduction obtains described Graphene-poly ion liquid combination electrode material;
The ratio that is 85:5:10 according to the mass ratio of Graphene-poly ion liquid combination electrode material, bonding agent and conductive agent, mixes described Graphene-poly ion 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 graphene oxide adopts following steps preparation 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 an embodiment, described poly ion liquid adopts following steps preparation therein:
The ratio that is 40 ~ 50:50 ~ 70:1:55 ~ 90 according to the mol ratio of 1-vinyl imidazole, bromoethane, azo-bis-isobutyl cyanide and two fluoroform sulfimide lithium salts takes described 1-vinyl imidazole, described bromoethane, described azo-bis-isobutyl cyanide and described pair of fluoroform sulfimide lithium salts;
The described 1-vinyl imidazole taking is mixed under the condition stirring with described bromoethane, stirring reaction at 40 ℃, afterwards the temperature of reaction system is adjusted to 60 ℃, and add described azo-bis-isobutyl cyanide, reaction adds two fluoroform sulfimide lithium salts and distilled water in reacted system, continues stirring reaction, the mixed liquor obtaining is reacted in last vacuum filtration, and the solids of collection is gathered (1-vinyl-3 ethyl imidazol(e)) two fluoroform sulfimide salt poly ion liquids after being dried.
This electrode slice is because using above-mentioned Graphene-poly ion 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-poly ion 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-poly ion liquid combination electrode material and preparation method thereof and related application are further described.
The preparation method of Graphene-poly ion liquid combination electrode material of one execution mode, comprises the steps:
The ratio that is 2.5 ~ 10:1 according to the mass ratio of graphene oxide and poly ion liquid takes graphene oxide and poly ion liquid, and the graphene oxide taking and poly ion liquid are added to in solvent, to make the concentration of graphene oxide be 8 ~ 10mg/mL, ultrasonic dispersion, the mixed solution obtaining is placed in to vacuum environment to be filtered, again the solid product obtaining after filtering is heated to 200 ~ 250 ° of C, thermal reduction obtains Graphene-poly ion liquid combination electrode material.
Wherein, graphene oxide 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.
Wherein, protective gas atmosphere can be the anaerobic atmosphere such as nitrogen or inert gas.
Poly ion liquid is poly-(1-vinyl-3 ethyl imidazol(e)) two fluoroform sulfimide salt, and its preparation process comprises the steps:
The ratio that is 40 ~ 50:50 ~ 70:1:55 ~ 90 according to the mol ratio of 1-vinyl imidazole, bromoethane, azo-bis-isobutyl cyanide and two fluoroform sulfimide lithium salts takes described 1-vinyl imidazole, described bromoethane, described azo-bis-isobutyl cyanide and described pair of fluoroform sulfimide lithium salts;
The described 1-vinyl imidazole taking is mixed under the condition stirring with described bromoethane, and at 40 ℃ stirring reaction, afterwards the temperature of reaction system is adjusted to 60 ℃, and add described azo-bis-isobutyl cyanide, reaction adds two fluoroform sulfimide lithium salts and distilled water in reacted system, continues stirring reaction, the mixed liquor obtaining is reacted in last vacuum filtration, and the solids of collection is gathered (1-vinyl-3 ethyl imidazol(e)) two fluoroform sulfimide salt poly ion liquids after being dried.
In a preferred embodiment, bromoethane is 1:1 with the mol ratio of two fluoroform sulfimide lithium salts.
The preparation process of this Graphene-poly ion liquid combination electrode material is simple, low for equipment requirements, can wide popularization and application.
Said method makes Graphene-poly ion liquid combination electrode material, and poly ion liquid is attracted in the space of Graphene, and the mass ratio of Graphene and poly ion liquid is 2.5 ~ 10:1.This Graphene-poly ion liquid combination electrode material forms combination electrode material by increase poly ion liquid in the Graphene electrodes material with higher specific area and conductivity, the poly ion 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-poly ion 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-poly ion liquid combination electrode material, described Graphene-poly ion liquid combination electrode material comprises Graphene and poly ion liquid, wherein, described poly ion liquid is attracted in the space of described Graphene, and the mass ratio of described Graphene and described poly ion liquid is 2.5 ~ 10:1.
Wherein, conductive agent is acetylene black.Bonding agent is Kynoar.Collector is aluminium foil.
As shown in Figure 1, a kind of preparation method of electrode slice, comprises the steps:
Step S110, the ratio that is 2.5 ~ 10:1 according to the mass ratio of graphene oxide and poly ion liquid takes graphene oxide and poly ion liquid, and the graphene oxide taking and poly ion liquid are added to in solvent, to make the concentration of graphene oxide be 8 ~ 10mg/mL, ultrasonic dispersion, the mixed solution obtaining is placed in to vacuum environment to be filtered, again the solid product obtaining after filtering is heated to 200 ~ 250 ° of C, thermal reduction obtains Graphene-poly ion liquid combination electrode material.
Step S120, the ratio that is 85:5:10 according to the mass ratio of Graphene-poly ion liquid combination electrode material, bonding agent and conductive agent, mixes described Graphene-poly ion liquid combination electrode material, bonding agent 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-poly ion 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-poly ion 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 90mL 98wt% concentrated sulfuric acid and 25mL 65wt% 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 10mL 30wt% 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 poly ion liquid: get 5mol 1-vinyl imidazole and be placed in vial, stir, in the situation that stirring, add 5.5mol bromoethane, the mixed liquor obtaining stirring reaction under 40 ° of C after 16 hours is adjusted to the temperature of mixture 60 ° of C, in reaction system, add 0.1mol azo-bis-isobutyl cyanide, react 10 hours; In the mixed liquor having reacted, add distilled water (wherein, the quality of the mixed liquor having reacted and the volume ratio of distilled water are 1g:20mL) and the two fluoroform sulfimide lithium salts of 5.5mol (Li[TFSI]), after stirring reaction 1 hour, vacuum filtration, wash solid product with deionized water, dry, gathered (1-vinyl-3 ethyl imidazol(e)) two fluoroform sulfimide salt.
The preparation of Graphene-poly ion liquid combination electrode material: get the above-mentioned 1g graphene oxide preparing and add in 100ml propene carbonate, the concentration of graphene oxide is 10mg/mL, adding poly-(1-vinyl-3 ethyl imidazol(e)) the two fluoroform sulfimide salt of 0.2g to make its concentration in mixed solution is 2mg/mL again, the ultrasonic machine that is 500W with power ultrasonic 6 hours to mixed solution; By the mixed solution vacuum filtration after ultrasonic, the solid product obtaining after filtering is placed under air atmosphere again, is heated to 220 ° of C, keep 1 hour, obtain Graphene-poly ion liquid composite 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 475mL 98wt% concentrated sulfuric acid and 120mL 65wt% 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 30mL 30wt%, 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 poly ion liquid: get 10mol 1-vinyl imidazole and be placed in vial, stir, in the situation that stirring, add 14mol bromoethane, the mixed liquor obtaining stirring reaction under 40 ° of C after 16 hours is adjusted to the temperature of mixture 60 ° of C, in reaction system, add 0.2mol azo-bis-isobutyl cyanide, react 10 hours; In the mixed liquor having reacted, add distilled water (wherein, the quality of the mixed liquor having reacted and the volume ratio of distilled water are 1g:20mL) and the two fluoroform sulfimide lithium salts of 14mol (Li[TFSI]), after stirring reaction 1 hour, vacuum filtration, wash solid product with deionized water, dry, gathered (1-vinyl-3 ethyl imidazol(e)) two fluoroform sulfimide salt.
The preparation of Graphene-poly ion liquid combination electrode material: get the above-mentioned 0.8g graphene oxide preparing and add in 100ml propene carbonate, the concentration of graphene oxide is 8mg/mL, adding poly-(1-vinyl-3 ethyl imidazol(e)) the two fluoroform sulfimide salt of 0.2g to make its concentration in mixed solution is 2mg/mL again, the ultrasonic machine that is 500W with power ultrasonic 10 hours to mixed solution; By the mixed solution vacuum filtration after ultrasonic, the solid product obtaining after filtering is placed under air atmosphere again, is heated to 200 ° of C, keep 1 hour, obtain Graphene-poly ion liquid composite 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 170mL 98wt% concentrated sulfuric acid and 48mL 65wt% 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 16mL 30wt% 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 poly ion liquid: get 2mol 1-vinyl imidazole and be placed in vial, stir, in the situation that stirring, add 2.5mol bromoethane, the mixed liquor obtaining stirring reaction under 40 ° of C after 16 hours is adjusted to the temperature of mixture 60 ° of C, in reaction system, add 0.05mol azo-bis-isobutyl cyanide, react 10 hours; In the mixed liquor having reacted, add distilled water (wherein, the quality of the mixed liquor having reacted and the volume ratio of distilled water are 1g:20mL) and the two fluoroform sulfimide lithium salts of 2.5mol (Li[TFSI]), after stirring reaction 1 hour, vacuum filtration, wash solid product with deionized water, dry, gathered (1-vinyl-3 ethyl imidazol(e)) two fluoroform sulfimide salt;
The preparation of Graphene-poly ion liquid combination electrode material: get the above-mentioned 2g graphene oxide preparing and add in 200ml propene carbonate, the concentration of graphene oxide is 10mg/mL, adding poly-(1-vinyl-3 ethyl imidazol(e)) the two fluoroform sulfimide salt of 0.8g to make its concentration in mixed solution is 4mg/mL again, the ultrasonic machine that is 500W with power ultrasonic 8 hours to mixed solution; By the mixed solution vacuum filtration after ultrasonic, the solid product obtaining after filtering is placed under air atmosphere again, is heated to 250 ° of C, keep 0.5 hour, obtain Graphene-poly ion liquid composite 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 90mL 98wt% concentrated sulfuric acid and 25mL 65wt% 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 10mL 30wt%, 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 poly ion liquid: get 20mol 1-vinyl imidazole and be placed in vial, stir, in the situation that stirring, add 30mol bromoethane, the mixed liquor obtaining stirring reaction under 40 ° of C after 16 hours is adjusted to the temperature of mixture 60 ° of C, in reaction system, add 0.5mol azo-bis-isobutyl cyanide, react 10 hours; In the mixed liquor having reacted, add distilled water (wherein, the quality of the mixed liquor having reacted and the volume ratio of distilled water are 1g:20mL) and the two fluoroform sulfimide lithium salts of 30mol (Li[TFSI]), after stirring reaction 1 hour, vacuum filtration, wash solid product with deionized water, dry, gathered (1-vinyl-3 ethyl imidazol(e)) two fluoroform sulfimide salt;
The preparation of Graphene-poly ion liquid combination electrode material: get the above-mentioned 1g graphene oxide preparing and add in 100ml propene carbonate, the concentration of graphene oxide is 10mg/mL, adding poly-(1-vinyl-3 ethyl imidazol(e)) the two fluoroform sulfimide salt of 0.1g to make its concentration in mixed solution is 1mg/mL again, the ultrasonic machine that is 500W with power ultrasonic 8 hours to mixed solution; By the mixed solution vacuum filtration after ultrasonic, the solid product obtaining after filtering is placed under air atmosphere again, is heated to 240 ° of C, keep 0.5 hour, obtain Graphene-poly ion liquid composite material.
Embodiment 5
The ratio that is 85:5:10 according to mass ratio, Graphene-poly ion 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, the aluminium foil that is coated with slurry prior to 80 ℃ after dry 2 hours, then after dry 2 hours, is obtained to 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 Li[TFSI by the liquid injection port being arranged on battery container], after sealing liquid injection port, obtain electrochemical capacitor.
Embodiment 6
The ratio that is 85:5:10 according to mass ratio, Graphene-poly ion 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 Li[TFSI by the liquid injection port being arranged on battery container], after sealing liquid injection port, obtain electrochemical capacitor.
Embodiment 7
The ratio that is 85:5:10 according to mass ratio, Graphene-poly ion 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 Li[TFSI by the liquid injection port being arranged on battery container], after sealing liquid injection port, obtain electrochemical capacitor.
Embodiment 8
The ratio that is 85:5:10 according to mass ratio, Graphene-poly ion 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 Li[TFSI by the liquid injection port being arranged on battery container], 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 | 214 | 226 | 235 | 191 |
The specific capacity of the electrochemical capacitor of embodiment 5 ~ 8 under 0.5A/g current density is all more than 191F/g, be up to 235F/g, 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-poly ion 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;
The ratio that is 2.5 ~ 10:1 according to the mass ratio of graphene oxide and poly ion liquid takes described graphene oxide and poly ion liquid, and the described graphene oxide taking and described poly ion liquid are added to in solvent, to make the concentration of described graphene oxide be 8 ~ 10mg/mL, ultrasonic dispersion, the mixed solution obtaining is placed in to vacuum environment to be filtered, again the solid product obtaining after filtering is heated to 200 ~ 250 ° of C, thermal reduction obtains described Graphene-poly ion liquid combination electrode material.
2. Graphene-poly ion liquid combination electrode material according to claim 1, is characterized in that, described poly ion liquid is poly-(1-vinyl-3 ethyl imidazol(e)) two fluoroform sulfimide salt.
3. the preparation method of Graphene-poly ion liquid combination electrode material according to claim 1 and 2, is characterized in that, described poly ion liquid adopts following steps preparation:
The ratio that is 40 ~ 50:50 ~ 70:1:55 ~ 90 according to the mol ratio of 1-vinyl imidazole, bromoethane, azo-bis-isobutyl cyanide and two fluoroform sulfimide lithium salts takes described 1-vinyl imidazole, described bromoethane, described azo-bis-isobutyl cyanide and described pair of fluoroform sulfimide lithium salts;
The described 1-vinyl imidazole taking is mixed under the condition stirring with described bromoethane, and at 40 ℃ stirring reaction, afterwards the temperature of reaction system is adjusted to 60 ℃, and add described azo-bis-isobutyl cyanide, reaction adds two fluoroform sulfimide lithium salts and distilled water in reacted system, continues stirring reaction, the mixed liquor obtaining is reacted in last vacuum filtration, and the solids of collection is gathered (1-vinyl-3 ethyl imidazol(e)) two fluoroform sulfimide salt poly ion liquids after being dried.
4. Graphene-poly ion liquid combination electrode material, is characterized in that, adopts the arbitrary described method of claims 1 to 3 to make.
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-poly ion liquid combination electrode material, and described Graphene-poly ion liquid combination electrode material adopts Graphene-poly ion 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 2.5 ~ 10:1 according to the mass ratio of graphene oxide and poly ion liquid takes described graphene oxide and poly ion liquid, and the described graphene oxide taking and described poly ion liquid are added to in solvent, to make the concentration of described graphene oxide be 8 ~ 10mg/mL, ultrasonic dispersion, the mixed solution obtaining is placed in to vacuum environment to be filtered, again the solid product obtaining after filtering is heated to 200 ~ 250 ° of C, thermal reduction obtains described Graphene-poly ion liquid combination electrode material;
The ratio that is 85:5:10 according to the mass ratio of Graphene-poly ion liquid combination electrode material, bonding agent and conductive agent, mixes described Graphene-poly ion 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, described graphene oxide adopts following steps preparation:
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.
9. the preparation method of electrode slice according to claim 7, is characterized in that, described poly ion liquid adopts following steps preparation:
The ratio that is 40 ~ 50:50 ~ 70:1:55 ~ 90 according to the mol ratio of 1-vinyl imidazole, bromoethane, azo-bis-isobutyl cyanide and two fluoroform sulfimide lithium salts takes described 1-vinyl imidazole, described bromoethane, described azo-bis-isobutyl cyanide and described pair of fluoroform sulfimide lithium salts;
The described 1-vinyl imidazole taking is mixed under the condition stirring with described bromoethane, stirring reaction at 40 ℃, afterwards the temperature of reaction system is adjusted to 60 ℃, and add described azo-bis-isobutyl cyanide, reaction adds two fluoroform sulfimide lithium salts and distilled water in reacted system, continues stirring reaction, the mixed liquor obtaining is reacted in last vacuum filtration, and the solids of collection is gathered (1-vinyl-3 ethyl imidazol(e)) two fluoroform sulfimide salt poly ion liquids after being dried.
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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| CN107057409A (en) * | 2017-06-09 | 2017-08-18 | 宁波工程学院 | A kind of preparation method of graphene-based electrically conductive ink filler |
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