CN103839684B - 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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- CN103839684B CN103839684B CN201210491421.XA CN201210491421A CN103839684B CN 103839684 B CN103839684 B CN 103839684B CN 201210491421 A CN201210491421 A CN 201210491421A CN 103839684 B CN103839684 B CN 103839684B
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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, more particularly to a kind of Graphene-ionic liquid combination electrode material
And its preparation method and application.
Background technology
Electrochemical capacitor as a kind of new type of energy storage device, because its charge-discharge velocity is fast, power density is high, the circulation longevity
The advantages of order long, is the energy storage device of another great application potential and Development volue after lithium ion battery.But energy density
The relatively low key factor being restriction electrochemical capacitor development and applying, the energy how exploration carries electrochemical capacitor is close
Degree is the emphasis of this area research current.
Computing formula e=1/2cv according to energy density2, improve energy density and mainly start with terms of two, on the one hand carry
The voltage window of high electrochemical capacitor；Still further aspect is to improve the specific capacity of electrode material, and the raising of these two aspects all can
Bring the raising of energy density.
The voltage window of electrochemical capacitor is mainly relevant with the pressure scope of electrolyte.Ionic liquid is a kind of pressure model
Enclose wider electrolyte, its chemical window can reach 4-6v, can improve the voltage window of electrochemical capacitor, dramatically increase electrification
Learn the energy density of capacitor；And Graphene, as a kind of two dimension monolayer material, has higher specific surface area and higher
Electrical conductivity, be a kind of preferable electrochemical capacitor electrode material.But ionic liquid is big due to viscosity, the leaching to electrode material
Lubricant nature is poor, and this makes the more difficult raising of specific capacity of electrode material.
Content of the invention
Based on this it is necessary to offer is a kind of has higher infiltrating Graphene-ionic liquid with il electrolyte
Combination electrode material and preparation method thereof.
A kind of preparation method of Graphene-ionic liquid combination electrode material, comprises the steps:
Graphite is added to the mixed solution of concentrated sulphuric acid and concentrated nitric acid, is uniformly mixed under 0 DEG C of environment, Ran Houxiang
Potassium permanganate is added, mix homogeneously reacts under 85 DEG C of environment, then keeping temperature adds in reaction system in mixed solution
Deionized water dilutes, and is eventually adding hydrogenperoxide steam generator, and stirring reaction removes unreacted potassium permanganate, to the mixture obtaining
Carry out sucking filtration process, the solidss that sucking filtration obtains, successively using dilute hydrochloric acid and deionized water wash, obtain graphite oxide after being dried；
Described graphite oxide is added to deionized water, ultrasonic disperse, then the dispersion obtaining is carried out at sucking filtration
Reason, the solidss obtaining after sucking filtration obtain graphene oxide after being dried；
In protective gas atmosphere, with 15-30 DEG C/min of heating rate, described graphene oxide is slowly added from room temperature
Heat carries out deoxygenation to 500-700 DEG C, and cooling after reaction obtains Graphene；
Mass ratio according to Graphene and ionic liquid is that the ratio of 5 ~ 10:1 ~ 2 weighs described Graphene and ionic liquid,
And the described Graphene weighing and described ionic liquid added make the concentration of described Graphene be 8 ~ 10mg/ml to solvent,
Ultrasonic disperse, then the mixed solution obtaining is placed in stirring in vacuum environment, obtain described Graphene-ionic liquid after removing solvent
Bluk recombination electrode material.
Wherein in an embodiment, described solvent is isopropanol or methyl pyrrolidone.
Wherein in an embodiment, described ionic liquid is 1- ethyl-3-methylimidazole bis-trifluoromethylsulfoandimide salt
Or 1- butyl -3- Methylimidazole. bis-trifluoromethylsulfoandimide salt.
A kind of Graphene-ionic liquid combination electrode material, is prepared using said method.
This Graphene-ionic liquid combination electrode material passes through in the Graphene with higher specific surface area and electrical conductivity
Increase ionic liquid in electrode material and form combination electrode material, the ionic liquid increasing in this combination electrode material, can increase
Combination electrode material and the wellability of il electrolyte, thus improve the specific capacity of combination electrode material.Therefore, above-mentioned multiple
Composite electrode material, have high specific capacity, excellent electrical conductivity and with il electrolyte have higher infiltrating excellent
Point.
And the preparation process of this Graphene-ionic liquid combination electrode material is simple, low for equipment requirements, can extensively push away
Wide application.
Additionally, there is a need to offer a kind of electrode slice containing above-mentioned Graphene-ionic liquid combination electrode material and its
Preparation method and the electrochemical capacitor using this electrode slice.
A kind of electrode slice, including collector and be coated in electrode slurry on described collector, described electrode slurry bag
Include conductive agent, bonding agent and Graphene-ionic liquid combination electrode material, described Graphene-ionic liquid combination electrode material
Material is the Graphene-ionic liquid combination electrode material being prepared using said method.
Wherein in an embodiment, described conductive agent is acetylene black, and described bonding agent is Kynoar, described afflux
Body is aluminium foil.
A kind of preparation method of electrode slice, comprises the steps:
Mass ratio according to Graphene and ionic liquid is that the ratio of 5 ~ 10:1 ~ 2 weighs described Graphene and ionic liquid,
And the described Graphene weighing and described ionic liquid added make the concentration of described Graphene be 8 ~ 10mg/ml to solvent,
Ultrasonic disperse, then the mixed solution obtaining is placed in stirring in vacuum environment, obtain containing Graphene-ionic liquid combination electrode
The solution of material；
Mass ratio according to Graphene-ionic liquid combination electrode material, bonding agent and conductive agent is the ratio of 85:5:10
Example, is mixed homogeneously described with conductive agent containing Graphene-solution of ionic liquid combination electrode material, bonding agent, obtains electricity
Pole slurry；
Described electrode slurry is coated on a current collector, processes within 2 hours through 80 DEG C of dryings 2 hours, 250 DEG C of dryings successively,
Described electrode slice is obtained after section.
Wherein in an embodiment, described preparation method also includes the preparation process of Graphene, as follows:
Graphite is added to the mixed solution of concentrated sulphuric acid and concentrated nitric acid, is uniformly mixed under 0 DEG C of environment, Ran Houxiang
Potassium permanganate is added, mix homogeneously reacts under 85 DEG C of environment, then keeping temperature adds in reaction system in mixed solution
Deionized water dilutes, and is eventually adding hydrogenperoxide steam generator, and stirring reaction removes unreacted potassium permanganate, to the mixture obtaining
Carry out sucking filtration process, the solidss that sucking filtration obtains, successively using dilute hydrochloric acid and deionized water wash, obtain graphite oxide after being dried；
Described graphite oxide is added to deionized water, ultrasonic disperse, then the dispersion obtaining is carried out at sucking filtration
Reason, the solidss obtaining after sucking filtration obtain graphene oxide after being dried；
In protective gas atmosphere, with 15-30 DEG C/min of heating rate, described graphene oxide is slowly added from room temperature
Heat carries out deoxygenation to 500-700 DEG C, and cooling after reaction obtains Graphene.
Wherein in an embodiment, described conductive agent is acetylene black, and described bonding agent is Kynoar, described afflux
Body is aluminium foil.
This electrode slice is because using above-mentioned Graphene-ionic liquid combination electrode material, having high specific capacity, excellent electricity
Conductance and have higher infiltrating advantage with il electrolyte.
A kind of electrochemical capacitor, including housing and be placed in the battery core in described housing and electrolyte, described battery core includes
The positive plate being oppositely arranged and negative plate and be arranged on barrier film between described positive plate and described negative plate, described positive plate
It is the electrode slice as described in any one of claim 5-6 with described negative plate.
This electrochemical capacitor passes through to add the above-mentioned Graphene-ionic liquid combination electrode of function admirable in electrode slice
Material, so that above-mentioned electrochemical capacitor has, charge-discharge velocity is fast, power density is high, have extended cycle life and have
The advantages of higher stored energy capacitance and multiplying power property.
Brief description
Fig. 1 is the flow chart of the preparation method of the electrode slice of an embodiment.
Specific embodiment
Below in conjunction with the accompanying drawings and specific embodiment is to Graphene-ionic liquid combination electrode material and preparation method thereof and phase
Close application to be further described.
The preparation method of the Graphene of one embodiment-ionic liquid combination electrode material, comprises the steps:
Mass ratio according to Graphene and ionic liquid is that the ratio of 5 ~ 10:1 ~ 2 weighs described Graphene and ionic liquid,
And the described Graphene weighing and described ionic liquid added make the concentration of described Graphene be 8 ~ 10mg/ml to solvent,
Ultrasonic disperse, then the mixed solution obtaining is placed in stirring in vacuum environment, obtain described Graphene-ionic liquid after removing solvent
Bluk recombination electrode material.
Wherein, Graphene can be made by the steps and obtain:
Graphite is added to the mixed solution of concentrated sulphuric acid and concentrated nitric acid, is uniformly mixed under 0 DEG C of environment, Ran Houxiang
Potassium permanganate is added, mix homogeneously reacts under 85 DEG C of environment, then keeping temperature adds in reaction system in mixed solution
Deionized water dilutes, and is eventually adding the hydrogenperoxide steam generator that mass fraction is 30%, and stirring reaction removes unreacted permanganic acid
Potassium, carries out sucking filtration process to the mixture obtaining, and the solidss that sucking filtration obtains, successively using dilute hydrochloric acid and deionized water wash, are done
Graphite oxide is obtained after dry；
Graphite oxide is added to deionized water, ultrasonic disperse, then sucking filtration process is carried out to the dispersion obtaining, take out
The solidss obtaining after filter obtain graphene oxide after being dried；
In protective gas atmosphere, with 15-30 DEG C/min of heating rate, graphene oxide is slowly heated to from room temperature
500-700 DEG C carries out deoxygenation, cools down the compound obtaining and be Graphene after reaction.
Wherein, protective gas atmosphere can be the anaerobic atmosphere such as nitrogen or noble gases.
In the present embodiment, ionic liquid is 1- ethyl-3-methylimidazole bis-trifluoromethylsulfoandimide salt ([emim]
[tf2N]) or 1- butyl -3- Methylimidazole. bis-trifluoromethylsulfoandimide salt ([bmim] [tf2N]).
The preparation process of this Graphene-ionic liquid combination electrode material is simple, low for equipment requirements, can be widely popularized
Application.
Additionally, present embodiment additionally provides a kind of Graphene-ionic liquid combination electrode material, it is using above-mentioned side
Method prepares, and ionic liquid is attracted in the space of Graphene.
This Graphene-ionic liquid combination electrode material passes through in the Graphene with higher specific surface area and electrical conductivity
Increase ionic liquid in electrode material and form combination electrode material, the ionic liquid increasing in this combination electrode material, can increase
Combination electrode material and the wellability of il electrolyte, thus improve the specific capacity of combination electrode material.Therefore, above-mentioned multiple
Composite electrode material, have high specific capacity, excellent electrical conductivity and with il electrolyte have higher infiltrating excellent
Point.
Additionally, present embodiment additionally provides a kind of electrode containing above-mentioned Graphene-ionic liquid combination electrode material
Piece and preparation method thereof and the electrochemical capacitor using this electrode slice.
A kind of electrode slice, including collector and be coated in electrode slurry on described collector, described electrode slurry bag
Include conductive agent, bonding agent and Graphene-ionic liquid combination electrode material, described Graphene-ionic liquid combination electrode material
Material is to be prepared using said method.
Wherein, conductive agent is acetylene black.Bonding agent is Kynoar.Collector is aluminium foil.Ionic liquid be 1- ethyl-
3- Methylimidazole. bis-trifluoromethylsulfoandimide salt or 1- butyl -3- Methylimidazole. bis-trifluoromethylsulfoandimide salt.
As shown in figure 1, a kind of preparation method of electrode slice, comprise the steps:
Step s110, according to Graphene and ionic liquid mass ratio be 5 ~ 10:1 ~ 2 ratio weigh described Graphene and
Ionic liquid, and the described Graphene weighing and described ionic liquid are added make to solvent described Graphene concentration be 8 ~
10mg/ml, ultrasonic disperse, then the mixed solution obtaining is placed in stirring in vacuum environment, obtain containing Graphene-ionic liquid
The solution of combination electrode material.
Step s120, the mass ratio according to Graphene-ionic liquid combination electrode material, bonding agent and conductive agent is 85:
The ratio of 5:10, is mixed described all with conductive agent containing Graphene-solution of ionic liquid combination electrode material, bonding agent
Even, obtain electrode slurry.
Step s130, electrode slurry is coated on a current collector, successively through 80 DEG C of dryings 2 hours, 250 DEG C of dryings 2 hours
Process, after section, obtain electrode slice.
This electrode slice is because using above-mentioned Graphene-ionic liquid combination electrode material, having high specific capacity, excellent electricity
Conductance and have higher infiltrating advantage with il electrolyte.
A kind of electrochemical capacitor, including housing and be placed in the battery core in housing and electrolyte, battery core includes being oppositely arranged
Positive plate and negative plate and be arranged on barrier film between positive plate and negative plate, positive plate and negative plate are above-mentioned electrode
Piece.
This electrochemical capacitor passes through to add the above-mentioned Graphene-ionic liquid combination electrode of function admirable in electrode slice
Material, so that above-mentioned electrochemical capacitor has, charge-discharge velocity is fast, power density is high, have extended cycle life and have
The advantages of higher stored energy capacitance and multiplying power property.
It is below specific embodiment part:
Embodiment 1
The preparation of graphite oxide: the graphite that 1g purity is 99.5% adds by 90ml98wt% concentrated sulphuric acid and 25ml65wt%
In the mixed solution of concentrated nitric acid composition, obtain mixture；Mixture is placed in after stirring 20 minutes in frozen water mixing bath；At leisure
Add 6g potassium permanganate toward in mixture, and stir 1 hour；Then after heating the mixture to 85 DEG C and keeping 30 minutes；Past
92ml deionized water is added, after continuing at 85 DEG C to keep 30 minutes in mixture；10ml30wt% peroxide is added toward in mixture
Change hydrogen solution, and stir 10 minutes；Sucking filtration is carried out to mixture；Use 100ml dilute hydrochloric acid and 150ml deionized water more successively respectively
Solidss are washed, washs three times altogether；Finally solid matter is placed in 60 DEG C of vacuum drying ovens and is dried 12 hours, that is, obtain
Graphite oxide.
The preparation of graphene oxide: compound concentration is the graphite oxide deionized water suspension of 1mg/ml；To above-mentioned suspension
Liquid carries out supersound process, and wherein, ultrasonic power is 500w, and the time is 1 hour；Then sucking filtration is carried out to above-mentioned suspension, obtain
Solid matter；The solid matter obtaining is placed in vacuum drying oven and is dried 12 hours at 60 DEG C, that is, obtain graphene oxide.
The preparation of Graphene: the graphite oxide preparing is placed under the argon atmosphere of flow velocity 400ml/min, makes oxidation
Temperature around graphite rises to 500 DEG C with the heating rate of 20 DEG C/min from room temperature, after keeping 2 hours at 500 DEG C, in flow velocity
Under the argon atmosphere of 400ml/min, the temperature around graphite oxide is down to room temperature, that is, obtains Graphene.
The preparation of Graphene-ionic liquid combination electrode material: add [emim] [tf in isopropanol2N] and above-mentioned
The Graphene preparing, obtains mixture；Wherein, [emim] [tf2N] final concentration of 2mg/ml, the final concentration of Graphene
For 10mg/ml；
Supersound process is carried out to mixture, wherein, ultrasonic power is 500w, and the time is 6 hours；Then after will be ultrasonic
Mixture is placed in and stirs 6 hours under vacuum environment, that is, obtain described Graphene-ionic liquid combination electrode material.
Embodiment 2
The preparation of graphite oxide: the graphite that 5g purity is 99.5% add by 475ml98wt% concentrated sulphuric acid and
In the mixed solution of 120ml65wt% concentrated nitric acid composition, obtain mixture；Mixture is placed in frozen water mixing bath and stirs 20 points
Zhong Hou；Add 20g potassium permanganate toward in mixture at leisure, and stir 1 hour；Then heat the mixture to 85 DEG C and keep
After 30 minutes；Add 92ml deionized water toward in mixture, after continuing at 85 DEG C to keep 30 minutes；Add toward in mixture
The hydrogenperoxide steam generator of 30ml30wt%, and stir 10 minutes；Sucking filtration is carried out to mixture；Use 300ml dilute hydrochloric acid more successively respectively
With 450ml deionized water, solidss are washed, wash three times altogether；Finally solid matter is placed in 60 DEG C of vacuum drying ovens dry
Dry 12 hours, that is, obtain graphite oxide.
The preparation of graphene oxide: compound concentration is the graphite oxide deionized water suspension of 0.5mg/ml；To above-mentioned outstanding
Supernatant liquid carries out supersound process, and wherein, ultrasonic power is 800w, and the time is 2 hours；Then sucking filtration is carried out to above-mentioned suspension, obtain
To solid matter；The solid matter obtaining is placed in vacuum drying oven and is dried 12 hours at 60 DEG C, that is, obtain graphene oxide.
The preparation of Graphene: the graphite oxide preparing is placed under the argon atmosphere of flow velocity 400ml/min, makes oxidation
Temperature around graphite rises to 700 DEG C with the heating rate of 25 DEG C/min from room temperature, after keeping 1 hour at 700 DEG C, in flow velocity
Under the argon atmosphere of 400ml/min, the temperature around graphite oxide is down to room temperature, that is, obtains Graphene.
The preparation of Graphene-ionic liquid combination electrode material: add [emim] [tf in isopropanol2N] and above-mentioned
The Graphene preparing, obtains mixture；Wherein, [emim] [tf2N] final concentration of 2mg/ml, the final concentration of Graphene
For 8mg/ml；
Supersound process is carried out to mixture, wherein, ultrasonic power is 500w, and the time is 10 hours；Then after will be ultrasonic
Mixture be placed under vacuum environment stir 10 hours, that is, obtain described Graphene-ionic liquid combination electrode material.
Embodiment 3
The preparation of graphite oxide: the graphite that 2g purity is 99.5% adds by 170ml98wt% concentrated sulphuric acid and 48ml65wt%
In the mixed solution of concentrated nitric acid composition, obtain mixture；Mixture is placed in after stirring 20 minutes in frozen water mixing bath；At leisure
Add 8g potassium permanganate toward in mixture, and stir 1 hour；Then after heating the mixture to 85 DEG C and keeping 30 minutes；Past
92ml deionized water is added, after continuing at 85 DEG C to keep 30 minutes in mixture；16ml30wt% peroxide is added toward in mixture
Change hydrogen solution, and stir 10 minutes；Sucking filtration is carried out to mixture；Use 250ml dilute hydrochloric acid and 300ml deionized water more successively respectively
Solidss are washed, washs three times altogether；Finally solid matter is placed in 60 DEG C of vacuum drying ovens and is dried 12 hours, that is, obtain
Graphite oxide.
The preparation of graphene oxide: compound concentration is the graphite oxide deionized water suspension of 0.5mg/ml；To above-mentioned outstanding
Supernatant liquid carries out supersound process, and wherein, ultrasonic power is 500w, and the time is 2 hours；Then sucking filtration is carried out to above-mentioned suspension, obtain
To solid matter；The solid matter obtaining is placed in vacuum drying oven and is dried 12 hours at 60 DEG C, that is, obtain graphene oxide.
The preparation of Graphene: the graphite oxide preparing is placed under the argon atmosphere of flow velocity 400ml/min, makes oxidation
Temperature around graphite rises to 600 DEG C with the heating rate of 15 DEG C/min from room temperature, after keeping 0.5 hour at 600 DEG C, in stream
Under the argon atmosphere of fast 400ml/min, the temperature around graphite oxide is down to room temperature, that is, obtains Graphene.
The preparation of Graphene-ionic liquid combination electrode material: add [bmim] [tf in isopropanol2N] and above-mentioned
The Graphene preparing, obtains mixture；Wherein, [bmim] [tf2N] final concentration of 4mg/ml, the final concentration of Graphene
For 10mg/ml；
Supersound process is carried out to mixture, wherein, ultrasonic power is 500w, and the time is 8 hours；Then after will be ultrasonic
Mixture is placed in and stirs 8 hours under vacuum environment, that is, obtain described Graphene-ionic liquid combination electrode material.
Embodiment 4
The preparation of graphite oxide: the graphite that 1g purity is 99.5% adds by 90ml98wt% concentrated sulphuric acid and 25ml65wt%
In the mixed solution of concentrated nitric acid composition, obtain mixture；Mixture is placed in after stirring 20 minutes in frozen water mixing bath；At leisure
Add 4g potassium permanganate toward in mixture, and stir 1 hour；Then after heating the mixture to 85 DEG C and keeping 30 minutes；Past
92ml deionized water is added, after continuing at 85 DEG C to keep 30 minutes in mixture；The mistake of 10ml30wt% is added toward in mixture
Hydrogen peroxide solution, and stir 10 minutes；Sucking filtration is carried out to mixture；Use 100ml dilute hydrochloric acid and 150ml deionization more successively respectively
Water washs to solidss, washs three times altogether；Finally solid matter is placed in 60 DEG C of vacuum drying ovens and is dried 12 hours, obtain final product
To graphite oxide.
The preparation of graphene oxide: compound concentration is the graphite oxide deionized water suspension of 0.5mg/ml；To above-mentioned outstanding
Supernatant liquid carries out supersound process, and wherein, ultrasonic power is 500w, and the time is 1 hour；Then sucking filtration is carried out to above-mentioned suspension, obtain
To solid matter；The solid matter obtaining is placed in vacuum drying oven and is dried 12 hours at 60 DEG C, that is, obtain graphene oxide.
The preparation of Graphene: the graphite oxide preparing is placed under the argon atmosphere of flow velocity 400ml/min, makes oxidation
Temperature around graphite rises to 500 DEG C with the heating rate of 30 DEG C/min from room temperature, after keeping 2 hours at 500 DEG C, in flow velocity
Under the argon atmosphere of 400ml/min, the temperature around graphite oxide is down to room temperature, that is, obtains Graphene.
The preparation of Graphene-ionic liquid combination electrode material: add [bmim] [tf in isopropanol2N] and above-mentioned
The Graphene preparing, obtains mixture；Wherein, [bmim] [tf2N] final concentration of 1mg/ml, the final concentration of Graphene
For 10mg/ml；
Supersound process is carried out to mixture, wherein, ultrasonic power is 500w, and the time is 8 hours；Then after will be ultrasonic
Mixture is placed in and stirs 8 hours under vacuum environment, that is, obtain described Graphene-ionic liquid combination electrode material.
Embodiment 5
According to the ratio for 85:5:10 for the mass ratio, the Graphene that embodiment 1 is prepared-ionic liquid combination electrode
Material, Kynoar binding agent and acetylene black conductor mix homogeneously, obtain slurry；Slurry is coated on aluminium foil；Then
Be coated with the aluminium foil of slurry prior to 80 DEG C of dryings 2 hours after, after 250 DEG C of dryings 2 hours, obtain slurry film；By slurry
Film is cut into slices, that is, electrochemical capacitor electrode piece is obtained.
Successively above-mentioned electrode slice, barrier film, electrode slice lamination assembling are obtained battery core；In battery core outer cladding battery container, will
Battery core seals, and then the liquid injection port by being arranged on battery container injects ionic liquid [emim] toward in battery container
[tf2N], after sealing liquid injection port, that is, obtain electrochemical capacitor.
Embodiment 6
According to the ratio for 85:5:10 for the mass ratio, the Graphene that embodiment 2 is prepared-ionic liquid combination electrode
Material, Kynoar binding agent and acetylene black conductor mix homogeneously, obtain slurry；Slurry is coated on aluminium foil；Then
Be coated with the aluminium foil of slurry prior to 80 DEG C of dryings 2 hours after, after 250 DEG C of dryings 2 hours, obtain slurry film；By slurry
Film is cut into slices, that is, electrochemical capacitor electrode piece is obtained.
Successively electrode slice, barrier film, electrode slice lamination assembling are obtained battery core；In battery core outer cladding battery container, by battery core
Sealing, then the liquid injection port by being arranged on battery container injects ionic liquid [emim] [tf toward in battery container2N], close
After envelope liquid injection port, that is, obtain electrochemical capacitor.
Embodiment 7
According to the ratio for 85:5:10 for the mass ratio, the Graphene that embodiment 3 is prepared-ionic liquid combination electrode
Material, Kynoar binding agent and acetylene black conductor mix homogeneously, obtain slurry；Slurry is coated on aluminium foil；Then
Be coated with the aluminium foil of slurry prior to 80 DEG C of dryings 2 hours after, after 250 DEG C of dryings 2 hours, obtain slurry film；By slurry
Film is cut into slices, that is, electrochemical capacitor electrode piece is obtained.
Successively electrode slice, barrier film, electrode slice lamination assembling are obtained battery core；In battery core outer cladding battery container, by battery core
Sealing, then the liquid injection port by being arranged on battery container injects ionic liquid [bmim] [tf toward in battery container2N], close
After envelope liquid injection port, that is, obtain electrochemical capacitor.
Embodiment 8
According to the ratio for 85:5:10 for the mass ratio, the Graphene that embodiment 4 is prepared-ionic liquid combination electrode
Material, Kynoar binding agent and acetylene black conductor mix homogeneously, obtain slurry；Slurry is coated on aluminium foil；Then
Be coated with the aluminium foil of slurry prior to 80 DEG C of dryings 2 hours after, after 250 DEG C of dryings 2 hours, obtain slurry film；By slurry
Film is cut into slices, that is, electrochemical capacitor electrode piece is obtained.
Successively electrode slice, barrier film, electrode slice lamination assembling are obtained battery core；In battery core outer cladding battery container, by battery core
Sealing, then the liquid injection port by being arranged on battery container injects ionic liquid [bmim] [tf toward in battery container2N], close
After envelope liquid injection port, that is, obtain electrochemical capacitor.
Performance test:
Respectively charge-discharge test is carried out to the electrochemical capacitor of assembling in embodiment 5 ~ 8, voltage window is 4v, electric current is close
Degree is respectively 0.5a/g, test result such as table 1.
Table 1 carries out the specific capacity of charge-discharge test respectively for embodiment 5 ~ 8 under 0.5a/g electric current density
| Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | |
| Specific capacity (f/g) under 0.5a/g | 221 | 236 | 248 | 202 |
Specific capacity test result under 0.5a/g electric current density for the embodiment 5 ~ 8 shows, the combination electrode in embodiment 5 ~ 8
Material has excellent energy-storage property.
Embodiment described above only have expressed the several embodiments of the present invention, and its description is more concrete and detailed, but simultaneously
Therefore the restriction to the scope of the claims of the present invention can not be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, some deformation can also be made and improve, these broadly fall into the guarantor of the present invention
Shield scope.Therefore, the protection domain of patent of the present invention should be defined by claims.
Claims (8)
1. a kind of electrode slice, including collector and be coated in electrode slurry on described collector it is characterised in that described electricity
Pole slurry includes conductive agent, bonding agent and Graphene-ionic liquid combination electrode material, and wherein, Graphene-ionic liquid is multiple
The mass ratio of composite electrode material, bonding agent and conductive agent is 85:5:10；
Described electrode slice is to mix the described solution containing Graphene-ionic liquid combination electrode material, bonding agent and conductive agent
Close uniformly, obtain electrode slurry, more described electrode slurry is coated on a current collector, successively through 80 DEG C of dryings 2 hours, 250 DEG C
It is dried 2 hours and processes, obtain after section；
Described Graphene-ionic liquid combination electrode material adopts following steps to prepare:
Graphite is added to the mixed solution of concentrated sulphuric acid and concentrated nitric acid, is uniformly mixed under 0 DEG C of environment, then to mixing
Add potassium permanganate in solution, mix homogeneously reacts under 85 DEG C of environment, then keeping temperature add in reaction system go from
Sub- water dilution, is eventually adding hydrogenperoxide steam generator, stirring reaction removes unreacted potassium permanganate, and the mixture obtaining is carried out
Sucking filtration is processed, and the solidss that sucking filtration obtains, successively using dilute hydrochloric acid and deionized water wash, obtain graphite oxide after being dried；
Described graphite oxide is added to deionized water, ultrasonic disperse, then sucking filtration process is carried out to the dispersion obtaining, take out
The solidss obtaining after filter obtain graphene oxide after being dried；
In protective gas atmosphere, with 15-30 DEG C/min of heating rate, described graphene oxide is slowly heated to from room temperature
500-700 DEG C carries out deoxygenation, and cooling after reaction obtains Graphene；
Mass ratio according to Graphene and ionic liquid is that the ratio of 5～10:1～2 weighs described Graphene and ionic liquid, and
The described Graphene weighing and described ionic liquid are added and makes the concentration of described Graphene be 8～10mg/ml to solvent, surpass
Sound disperses, then the mixed solution obtaining is placed in stirring in vacuum environment, obtains described Graphene-ionic liquid after removing solvent
Combination electrode material.
2. it is characterised in that described conductive agent is acetylene black, described bonding agent is poly- to electrode slice according to claim 1
Vinylidene, described collector is aluminium foil.
3. electrode slice according to claim 1 is it is characterised in that described ionic liquid is 1- ethyl-3-methylimidazole pair
Trifluoro sulfonamide or 1- butyl -3- Methylimidazole. bis-trifluoromethylsulfoandimide salt.
4. the electrode slice according to claim 1 or 3 is it is characterised in that described solvent is isopropanol or methyl pyrrolidone.
5. a kind of preparation method of electrode slice is it is characterised in that comprise the steps:
Mass ratio according to Graphene and ionic liquid is that the ratio of 5～10:1～2 weighs described Graphene and ionic liquid, and
The described Graphene weighing and described ionic liquid are added and makes the concentration of described Graphene be 8～10mg/ml to solvent, surpass
Sound disperses, then the mixed solution obtaining is placed in stirring in vacuum environment, obtains containing Graphene-ionic liquid combination electrode material
The solution of material；
Mass ratio according to Graphene-ionic liquid combination electrode material, bonding agent and conductive agent is the ratio of 85:5:10, will
Described mix homogeneously with conductive agent containing Graphene-solution of ionic liquid combination electrode material, bonding agent, obtain electrode slurry
Material；
Described electrode slurry is coated on a current collector, processes within 2 hours through 80 DEG C of dryings 2 hours, 250 DEG C of dryings successively, section
After obtain described electrode slice.
6. the preparation method of electrode slice according to claim 5 is it is characterised in that also include the preparation process of Graphene,
As follows:
Graphite is added to the mixed solution of concentrated sulphuric acid and concentrated nitric acid, is uniformly mixed under 0 DEG C of environment, then to mixing
Add potassium permanganate in solution, mix homogeneously reacts under 85 DEG C of environment, then keeping temperature add in reaction system go from
Sub- water dilution, is eventually adding hydrogenperoxide steam generator, stirring reaction removes unreacted potassium permanganate, and the mixture obtaining is carried out
Sucking filtration is processed, and the solidss that sucking filtration obtains, successively using dilute hydrochloric acid and deionized water wash, obtain graphite oxide after being dried；
Described graphite oxide is added to deionized water, ultrasonic disperse, then sucking filtration process is carried out to the dispersion obtaining, take out
The solidss obtaining after filter obtain graphene oxide after being dried；
In protective gas atmosphere, with 15-30 DEG C/min of heating rate, described graphene oxide is slowly heated to from room temperature
500-700 DEG C carries out deoxygenation, and cooling after reaction obtains Graphene.
7. the preparation method of electrode slice according to claim 5 is it is characterised in that described conductive agent is acetylene black, described
Bonding agent is Kynoar, and described collector is aluminium foil.
8. a kind of electrochemical capacitor, including housing and be placed in the battery core in described housing and electrolyte, described battery core includes phase
Positive plate to setting and negative plate and be arranged on barrier film between described positive plate and described negative plate it is characterised in that
Described positive plate and described negative plate are the electrode slice as described in any one of claim 1-4.
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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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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
Non-Patent Citations (1)
| Title |
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| Layer-by-Layer Films of Graphene and Ionic Liquids for Highly Selective Gas Sensing;Qingmin Ji等;《Angewandte Chemie International Edition》;20101112;第49卷(第50期);第9737-9739页 * |
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