CN103996546A - Graphene composite material and preparation method thereof, electrochemical capacitor and electrode thereof - Google Patents
Graphene composite material and preparation method thereof, electrochemical capacitor and electrode thereof Download PDFInfo
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Abstract
The invention relates to a graphene composite material that is formed by combination of graphene, ruthenium oxide, and a carbon nano tube. The mass ratio of the graphene to the ruthenium oxide to the carbon nano tube is 0.5-1:0.1-1:0.1-1. The provided graphene composite material has the high specific capacity. In addition, the invention also relates to a preparation method of the graphene composite material, and an electrochemical capacitor and an electrode thereof.
Description
Technical field
The present invention relates to electrochemical capacitor field, particularly a kind of graphene composite material and preparation method thereof, use this graphene composite material electrochemical capacitor electrode and use the electrochemical capacitor as electrode material of this graphene composite material.
Background technology
Electrochemical capacitor is a kind of energy storage device of high power type, applies to some extent in a lot of fields.But energy density low be restriction its key factor further developing, the energy density that therefore how to improve electrochemical capacitor be this field in study emphasis.Improve energy density and mainly start with from two aspects, improve on the one hand the voltage window of electrochemical capacitor; The specific capacity that improves electrode material in addition on the one hand.The raising of this two aspect all can bring the raising of energy density.At present, mainly contain material with carbon element, conducting polymer and metal oxide three major types for the material of electrochemical capacitor electrode, but all there is as electrode the problem that specific capacity is lower in this three classes material, directly causes the energy density of electrochemical capacitor lower.
Summary of the invention
Given this, be necessary to provide graphene composite material that a kind of specific capacity is higher and preparation method thereof, use this graphene composite material electrochemical capacitor electrode and use the electrochemical capacitor as electrode material of this graphene composite material.
A kind of graphene composite material, Graphene, ruthenium-oxide and carbon nano-tube that described graphene composite material is 0.5 ~ 1:0.1 ~ 1:0.1 ~ 1 by mass ratio are compounded to form.
A preparation method for graphene composite material, comprises the steps:
Use graphite-made for graphite oxide;
In the environment of inert gas, described graphite oxide is heated to 700 DEG C ~ 900 DEG C insulation reaction 0.5 hour ~ 2 hours, through cooling, obtain Graphene; And
Be 1ml:0.5mg ~ 1mg:0.1mg ~ 1mg:0.1mg ~ 1mg according to volume mass ratio, in deionized water, add successively described Graphene, ruthenium trichloride and carbon nano-tube, after ultrasonic mixing, in continuing to drip hydrogen peroxide under the condition stirring, stop dripping and be placed on 80 DEG C ~ 90 DEG C back flow reaction 2 hours ~ 6 hours, after filtration, clean and dry, obtain the graphene composite material being compounded to form by described Graphene, ruthenium-oxide and described carbon nano-tube; Wherein, the mass ratio of the described hydrogen peroxide of described ruthenium trichloride and dropping is 1:80 ~ 400.
In an embodiment, use described graphite-made to comprise for the step of described graphite oxide therein:
Be 1g:109ml ~ 119ml according to mass volume ratio, described graphite is joined in the mixed liquor being made up of the concentrated sulfuric acid and red fuming nitric acid (RFNA), and be placed in frozen water and mix to bathe and be uniformly mixed formation mixed solution; And
Be 1:4 ~ 6 according to the mass ratio of described graphite and potassium permanganate, described potassium permanganate is joined in described mixed solution, stir and carry out intercalation in 0.5 hour ~ 3 hours, be then heated to 20 DEG C ~ 50 DEG C insulation reaction 10 minutes ~ 40 minutes, then add deionized water, be heated to again 60 DEG C ~ 95 DEG C insulation reaction 10 minutes ~ 40 minutes, obtain reactant liquor, in described reactant liquor, add hydrogen peroxide, through suction filtration, and use successively watery hydrochloric acid and deionized water washing, then drying, graphite oxide obtained; Wherein, the mass volume ratio of described potassium permanganate and described deionized water is 1g:15ml ~ 50ml; And the described hydrogen peroxide adding and the mass ratio of described potassium permanganate are 0.63 ~ 0.95:1.
In an embodiment, heating rate when described graphite oxide heating is 15 DEG C/min ~ 30 DEG C/min therein.
In an embodiment, the drop rate of described hydrogen peroxide is 0.05mg/ minute ~ 0.5mg/ minute therein.
In an embodiment, the condition of described lasting stirring is therein: stir speed (S.S.) is 200 revs/min ~ 300 revs/min.
In an embodiment, the reactant liquor that described back flow reaction obtains cleaning step is after filtering therein: the filter residue that the reactant liquor of described back flow reaction is obtained after filtering uses acetone and deionized water washing successively.
Therein in an embodiment, the drying condition of the reactant liquor that described back flow reaction obtains after filtration and after cleaning is: 50 DEG C ~ 80 DEG C vacuumize 8 hours ~ 16 hours.
An electrode for electrochemical capacitor, the material of the electrode of described electrochemical capacitor is graphene composite material, Graphene, ruthenium-oxide and carbon nano-tube that described graphene composite material is 0.5 ~ 1:0.1 ~ 1:0.1 ~ 1 by mass ratio are compounded to form.
A kind of electrochemical capacitor, the material of described electrode is graphene composite material, Graphene, ruthenium-oxide and carbon nano-tube that described graphene composite material is 0.5 ~ 1:0.1 ~ 1:0.1 ~ 1 by mass ratio are compounded to form.
Graphene, ruthenium-oxide and carbon nano-tube that above-mentioned graphene composite material is 0.5 ~ 1:0.1 ~ 1:0.1 ~ 1 by mass ratio are compounded to form, not only can reduce the reunion that independent use ruthenium-oxide causes, can also form conductive network, and there is higher conductivity, make the graphene composite material obtaining there is the specific capacity higher compared with ruthenium-oxide and excellent high rate performance.
Brief description of the drawings
Fig. 1 is preparation method's flow chart of the graphene composite material of an execution mode.
Embodiment
Mainly in conjunction with the drawings and the specific embodiments graphene composite material and preparation method thereof, electrochemical capacitor and electrode thereof are described in further detail below.
The graphene composite material of one execution mode, Graphene, ruthenium-oxide and carbon nano-tube that graphene composite material is 0.5 ~ 1:0.1 ~ 1:0.1 ~ 1 by mass ratio are compounded to form.
Graphene, ruthenium-oxide and carbon nano-tube that above-mentioned graphene composite material is 0.5 ~ 1:0.1 ~ 1:0.1 ~ 1 by mass ratio are compounded to form, because ruthenium-oxide has higher specific capacity (being greater than 1000F/g) and conductivity (being greater than 100S/cm), can be used as the electrode material of high-energy-density electrochemical capacitor, but due to ruthenium-oxide agglomeration especially severe, the efficiency of energy storage when use can reduce it greatly as electrode material separately; And Graphene is a kind of two-dimentional monolayer material, there is higher specific area and higher conductivity, and carbon nano-tube also has higher conductivity, and have compared with high length-diameter ratio, by common to Graphene and carbon nano-tube and ruthenium-oxide synthetic composite material, not only reduce the reunion causing of independent use ruthenium-oxide, can also form conductive network, improve conductivity, make the graphene composite material obtaining there is the specific capacity higher compared with ruthenium-oxide and excellent high rate performance.
As shown in Figure 1, the preparation method of the graphene composite material of an execution mode, comprises the steps:
Step S110: use graphite-made for graphite oxide.
Wherein, graphite-made can adopt routine to prepare the obtaining of method of graphite oxide for graphite oxide, preferred, uses graphite-made to comprise for the step of graphite oxide:
Be 1g:109ml ~ 119ml according to mass volume ratio, graphite is joined in the mixed liquor being made up of the concentrated sulfuric acid and red fuming nitric acid (RFNA), and be placed in frozen water and mix to bathe and be uniformly mixed formation mixed solution; And
Be 1:4 ~ 6 according to the mass ratio of graphite and potassium permanganate, potassium permanganate is joined in mixed solution, stir and carry out intercalation in 0.5 hour ~ 3 hours, be then heated to 20 DEG C ~ 50 DEG C insulation reaction 10 minutes ~ 40 minutes, then add deionized water, be heated to again 60 DEG C ~ 95 DEG C insulation reaction 10 minutes ~ 40 minutes, obtain reactant liquor, in reactant liquor, add hydrogen peroxide, through suction filtration, and use successively watery hydrochloric acid and deionized water washing, then drying, graphite oxide obtained; Wherein, the mass volume ratio of potassium permanganate and deionized water is 1g:15ml ~ 50ml; And the hydrogen peroxide adding and the mass ratio of potassium permanganate are 0.63 ~ 0.95:1.
Wherein, graphite can be the conventional graphite in this area, is preferably purity and is 99.5% graphite.
Wherein, to refer to mass fraction be 98% sulfuric acid to the concentrated sulfuric acid; It is 65% nitric acid that red fuming nitric acid (RFNA) refers to mass fraction.Preferably, in the mixed liquor being made up of the concentrated sulfuric acid and red fuming nitric acid (RFNA), the volume ratio of the concentrated sulfuric acid and red fuming nitric acid (RFNA) is 85:24 ~ 95:24.
Wherein, it is 20 minutes that graphite joins the time of stirring in the mixed liquor being made up of the concentrated sulfuric acid and red fuming nitric acid (RFNA), by stirring, graphite can be dispersed in the mixed liquor being made up of the concentrated sulfuric acid and red fuming nitric acid (RFNA) more fully.
In specific embodiment, need to lentamente potassium permanganate be joined in mixed solution.
After being joined to mixed solution, potassium permanganate reacts by stirring, in the process of reaction, emit heat, potassium permanganate is oxidized the edge of graphite aspect, sulfate ion in mixed solution and sulfuric acid molecule are adsorbed on the edge of graphite aspect by the effect of static simultaneously, along with the continuation of stirring, heat is constantly emitted in potassium permanganate reaction, the cellular lattice plane of graphite gradually becomes the large molecule of plane of positively charged, sulfate ion and sulfuric acid molecule are inserted into the interlayer of graphite, form sulfuric acid-compound between graphite layers.
It is 0.5 hour ~ 3 hours that the intercalation time is carried out in stirring, makes to have more abundant that time enough is undertaken by intercalation.
Then be heated to 20 DEG C ~ 50 DEG C insulation reaction 10 minutes ~ 40 minutes, can make sulfuric acid-compound between graphite layers that the more oxidation of the degree of depth occurs.
Then by adding deionized water, and be heated to 60 DEG C ~ 95 DEG C insulation reaction 10 minutes ~ 40 minutes, in order to make sulfuric acid-compound between graphite layers generation hydrolysis, large quantity of moisture enters into sulfuric acid-compound between graphite layers, the distance of graphite layers increases, and volumetric expansion, by being heated to 60 DEG C ~ 95 DEG C insulation reaction 10 minutes ~ 40 minutes, sulfuric acid-compound between graphite layers is peeled off, thereby forms graphite oxide.
The mass volume ratio of potassium permanganate and deionized water is 1g:(15ml ~ 50ml), thus potassium permanganate better dissolved.
Reactant liquor added hydrogen peroxide before suction filtration in reactant liquor, can remove remaining potassium permanganate in reactant liquor, and the mass ratio of the hydrogen peroxide adding and potassium permanganate is 0.63 ~ 0.95:1, to ensure that in reactant liquor, remaining potassium permanganate is completely removed.
In specific embodiment, watery hydrochloric acid and deionized water washing are three times altogether, thereby wash the remaining concentrated sulfuric acid, red fuming nitric acid (RFNA) and hydrogen peroxide etc. in reactant liquor.
Preferably, the drying condition of reactant liquor after filtration and after cleaning is: 50 DEG C ~ 80 DEG C vacuumize 8 hours ~ 16 hours.
Step S120: in the environment of inert gas, graphite oxide is heated to 700 DEG C ~ 900 DEG C insulation reaction 0.5 hour ~ 2 hours, through cooling, obtains Graphene.
Wherein, the environment of inert gas can be the environment such as nitrogen, helium, argon gas.In specific embodiment, by passing into inert gas with the speed of 200ml/ minute ~ 400ml/ minute, form the environment of inert gas.
Preferably, heating rate when graphite oxide heats is 15 DEG C/min ~ 30 DEG C/min.Be rapidly heated by using heating rate to be 15 DEG C/min ~ 30 DEG C/min, accelerate the cracking of graphite oxide.
Step S130: be 1ml:0.5mg ~ 1mg:0.1mg ~ 1mg:0.1mg ~ 1mg according to volume mass ratio, in deionized water, add successively Graphene, ruthenium trichloride and carbon nano-tube, after ultrasonic mixing, in continuing to drip hydrogen peroxide under the condition stirring, stop dripping and be placed on 80 DEG C ~ 90 DEG C back flow reaction 2 hours ~ 6 hours, after filtration, clean and dry, obtain the graphene composite material being compounded to form by Graphene, ruthenium-oxide and carbon nano-tube; Wherein, the mass ratio of the hydrogen peroxide of ruthenium trichloride and dropping is 1:80 ~ 400.
Preferably, the reactant liquor that back flow reaction obtains cleaning step is after filtering: the filter residue that the reactant liquor of back flow reaction is obtained after filtering uses acetone and deionized water washing successively.
Preferably, the drying condition of the reactant liquor that back flow reaction obtains after filtration and after cleaning is: 50 DEG C ~ 80 DEG C vacuumize 8 hours ~ 16 hours.
Preferably, the drop rate of hydrogen peroxide is 0.05mg/ minute ~ 0.5mg/ minute, thereby controls the generation of ruthenium-oxide.
Preferably, the condition that continues to stir is: the speed of stirring is 200 revs/min ~ 300 revs/min, and this speed is conducive to the carrying out of reaction.
The preparation method of above-mentioned graphene composite material, by the graphene composite material that adopts above-mentioned preparation process to prepare, not only reduce the reunion causing of independent use ruthenium-oxide, can also form conductive network, and there is higher conductivity, make the graphene composite material obtaining there is the specific capacity higher compared with ruthenium-oxide and excellent high rate performance.
The preparation method of above-mentioned graphene composite material is low for equipment requirements, technique is simple, easily realizes large-scale production.
The electrode of the electrochemical capacitor of one execution mode, the material of the electrode of electrochemical capacitor is graphene composite material, Graphene, ruthenium-oxide and carbon nano-tube that graphene composite material is 0.5 ~ 1:0.1 ~ 1:0.1 ~ 1 by mass ratio are compounded to form.
The material of the electrode of above-mentioned electrochemical capacitor is graphene composite material, and because this graphene composite material has higher specific capacity, makes the electrode of electrochemical capacitor have higher specific capacity.
The electrochemical capacitor of one execution mode, comprises electrode, and the material of electrode is graphene composite material, and Graphene, ruthenium-oxide and carbon nano-tube that graphene composite material is 0.5 ~ 1:0.1 ~ 1:0.1 ~ 1 by mass ratio are compounded to form.
Above-mentioned electrochemical capacitor, due to having compared with the graphene composite material of height ratio capacity as electrode material of using, makes the electrode of electrochemical capacitor have higher specific capacity, thereby makes above-mentioned electrochemical capacitor have higher energy density.
Be below specific embodiment part:
Embodiment 1
Being prepared as follows of the graphene composite material of the present embodiment:
(1) in the mixed liquor that the red fuming nitric acid (RFNA) that the concentrated sulfuric acid that 1g graphite (mass fraction 99.5%) to be joined by 90 milliliters of mass fractions be 98% and 25 milliliters of mass fractions are 65% forms, and be placed in frozen water and mix to bathe and be uniformly mixed 20 minutes, form mixed solution.
(2) 6g potassium permanganate is slowly joined in mixed solution, stir and within 1 hour, carry out intercalation, then be heated to 20 DEG C of insulation reaction 30 minutes, then add the deionized water of 92ml, be heated to again 85 DEG C of insulation reaction 30 minutes, obtain reactant liquor, in reactant liquor, add 10ml hydrogen peroxide (mass fraction is 30%) to remove potassium permanganate, use successively the watery hydrochloric acid of 100ml and the deionized water of 150ml to wash totally three times through the filter residue of suction filtration, then in 60 DEG C of vacuum drying ovens, be dried 12 hours, obtain graphite oxide.
(3) graphite oxide is placed in to argon gas (passing into speed is 400ml/ minute) environment, is heated to 700 DEG C of insulation reaction 2 hours with the heating rate of 30 DEG C/min, in argon gas (passing into speed is 400ml/ minute) environment, be cooled to room temperature, obtain Graphene.
(4) be 1ml:1mg:0.5mg:0.5mg according to volume mass ratio, in deionized water, add successively Graphene, ruthenium trichloride and carbon nano-tube, the ultrasonic mixing that is 500W through power 4 hours, then continuing to stir under the condition of (stir speed (S.S.) is 200 revs/min), drip the hydrogen peroxide of 100mg with the speed of 0.1mg/ minute, stop dripping and be placed in 90 DEG C back flow reaction 4 hours, obtain reactant liquor, obtain after filtering filter residue, filter residue is used and uses successively acetone and deionized water washing, then 60 DEG C of vacuum drying ovens are dried 12 hours, obtain by Graphene, the graphene composite material that ruthenium-oxide and carbon nano-tube are compounded to form.
Embodiment 2
Being prepared as follows of the graphene composite material of the present embodiment:
(1) in the mixed liquor that the red fuming nitric acid (RFNA) that the concentrated sulfuric acid that 1g graphite (mass fraction 99.5%) to be joined by 95 milliliters of mass fractions be 98% and 24 milliliters of mass fractions are 65% forms, and be placed in frozen water and mix to bathe and be uniformly mixed 20 minutes, form mixed solution.
(2) 4g potassium permanganate is slowly joined in mixed solution, stir and within 0.5 hour, carry out intercalation, then be heated to 40 DEG C of insulation reaction 10 minutes, then add the deionized water of 60ml, be heated to again 65 DEG C of insulation reaction 30 minutes, obtain reactant liquor, in reactant liquor, add 6ml hydrogen peroxide (mass fraction is 30%) to remove potassium permanganate, use successively the watery hydrochloric acid of 100ml and the deionized water of 150ml to wash totally three times through the filter residue of suction filtration, then in 50 DEG C of vacuum drying ovens, be dried 16 hours, obtain graphite oxide.
(3) graphite oxide is placed in to argon gas (passing into speed is 300ml/ minute) environment, is heated to 800 DEG C of insulation reaction 1 hour with the heating rate of 25 DEG C/min, in argon gas (passing into speed is 300ml/ minute) environment, be cooled to room temperature, obtain Graphene.
(4) be 1ml:0.5mg:0.5mg:0.5mg according to volume mass ratio, in deionized water, add successively Graphene, ruthenium trichloride and carbon nano-tube, the ultrasonic mixing that is 500W through power 4 hours, then continuing to stir under the condition of (stir speed (S.S.) is 200 revs/min), drip the hydrogen peroxide of 120mg with the speed of 0.05mg/ minute, stop dripping and be placed in 80 DEG C back flow reaction 6 hours, obtain reactant liquor, obtain after filtering filter residue, filter residue is used and uses successively acetone and deionized water washing, then 50 DEG C of vacuum drying ovens are dried 16 hours, obtain by Graphene, the graphene composite material that ruthenium-oxide and carbon nano-tube are compounded to form.
Embodiment 3
Being prepared as follows of the graphene composite material of the present embodiment:
(1) in the mixed liquor that the red fuming nitric acid (RFNA) that the concentrated sulfuric acid that 1g graphite (mass fraction 99.5%) to be joined by 85 milliliters of mass fractions be 98% and 24 milliliters of mass fractions are 65% forms, and be placed in frozen water and mix to bathe and be uniformly mixed 20 minutes, form mixed solution.
(2) 4g potassium permanganate is slowly joined in mixed solution, stir and within 3 hours, carry out intercalation, then be heated to 50 DEG C of insulation reaction 20 minutes, then add the deionized water of 200ml, be heated to again 95 DEG C of insulation reaction 10 minutes, obtain reactant liquor, in reactant liquor, add 8ml hydrogen peroxide (mass fraction is 30%) to remove potassium permanganate, use successively the watery hydrochloric acid of 100ml and the deionized water of 150ml to wash totally three times through the filter residue of suction filtration, then in 80 DEG C of vacuum drying ovens, be dried 8 hours, obtain graphite oxide.
(3) graphite oxide is placed in to argon gas (passing into speed is 400ml/ minute) environment, be heated to 900 DEG C of insulation reaction 0.5 hour with the heating rate of 30 DEG C/min, in argon gas (passing into speed is 400ml/ minute) environment, be cooled to room temperature, obtain Graphene.
(4) be 1ml:1mg:0.2mg:0.2mg according to volume mass ratio, in deionized water, add successively Graphene, ruthenium trichloride and carbon nano-tube, the ultrasonic mixing that is 500W through power 2 hours, then continuing to stir under the condition of (stir speed (S.S.) is 200 revs/min), drip the hydrogen peroxide of 80mg with the speed of 0.5mg/ minute, stop dripping and be placed in 85 DEG C back flow reaction 2 hours, obtain reactant liquor, obtain after filtering filter residue, filter residue is used to acetone and deionized water washing, then 80 DEG C of vacuum drying ovens are dried 8 hours, obtain by Graphene, the graphene composite material that ruthenium-oxide and carbon nano-tube are compounded to form.
Embodiment 4
Being prepared as follows of the graphene composite material of the present embodiment:
(1) in the mixed liquor that the red fuming nitric acid (RFNA) that the concentrated sulfuric acid that 1g graphite (mass fraction 99.5%) to be joined by 90 milliliters of mass fractions be 98% and 25 milliliters of mass fractions are 65% forms, and be placed in frozen water and mix to bathe and be uniformly mixed 20 minutes, form mixed solution.
(2) 4g potassium permanganate is slowly joined in mixed solution, stir and within 1 hour, carry out intercalation, then be heated to 35 DEG C of insulation reaction 40 minutes, then add the deionized water of 92ml, be heated to again 60 DEG C of insulation reaction 40 minutes, obtain reactant liquor, in reactant liquor, add 9ml hydrogen peroxide (mass fraction is 30%) to remove potassium permanganate, use successively the watery hydrochloric acid of 100ml and the deionized water of 150ml to wash totally three times through the filter residue of suction filtration, then in 60 DEG C of vacuum drying ovens, be dried 12 hours, obtain graphite oxide.
(3) graphite oxide is placed in to argon gas (passing into speed is 200ml/ minute) environment, is heated to 700 DEG C of insulation reaction 2 hours with the heating rate of 15 DEG C/min, in argon gas (passing into speed is 200ml/ minute) environment, be cooled to room temperature, obtain Graphene.
(4) be 1ml:1mg:0.1mg:0.1mg according to volume mass ratio, in deionized water, add successively Graphene, ruthenium trichloride and carbon nano-tube, the ultrasonic mixing that is 500W through power 1 hour, then continuing to stir under the condition of (stir speed (S.S.) is 200 revs/min), drip the hydrogen peroxide of 300mg with the speed of 0.1mg/ minute, stop dripping and be placed in 90 DEG C back flow reaction 6 hours, obtain reactant liquor, obtain after filtering filter residue, filter residue is used and uses successively acetone and deionized water washing, then 60 DEG C of vacuum drying ovens are dried 12 hours, obtain by Graphene, the graphene composite material that ruthenium-oxide and carbon nano-tube are compounded to form.
Embodiment 5
Being prepared as follows of the electrochemical capacitor of the present embodiment:
(1) ratio that is 85:5:10 according to mass ratio, graphene composite material prepared by embodiment 1, Kynoar binding agent and conductive agent acetylene black mix, and obtain slurry;
(2) slurry is coated on Copper Foil, drying, slicing treatment, make electrochemical capacitor electrode sheet.
(3) by the electrode slice obtaining in the electrode slice obtaining in (2), barrier film and (2) in order stack of laminations dress up battery core, use again battery housing seal battery core, subsequently toward being arranged on liquid injection port on battery container toward the sulfuric acid/water electrolyte that injects 2mol/L in battery container, sealing liquid injection port, obtains electrochemical capacitor.
Embodiment 6
Being prepared as follows of the electrochemical capacitor of the present embodiment:
(1) ratio that is 85:5:10 according to mass ratio, graphene composite material prepared by embodiment 2, Kynoar binding agent and conductive agent acetylene black mix, and obtain slurry;
(2) slurry is coated on Copper Foil, drying, slicing treatment, make electrochemical capacitor electrode sheet.
(3) by the electrode slice obtaining in the electrode slice obtaining in (2), barrier film and (2) in order stack of laminations dress up battery core, use again battery housing seal battery core, subsequently toward being arranged on liquid injection port on battery container toward the sulfuric acid/water electrolyte that injects 2mol/L in battery container, sealing liquid injection port, obtains electrochemical capacitor.
Embodiment 7
Being prepared as follows of the electrochemical capacitor of the present embodiment:
(1) ratio that is 85:5:10 according to mass ratio, graphene composite material prepared by embodiment 3, Kynoar binding agent and conductive agent acetylene black mix, and obtain slurry;
(2) slurry is coated on Copper Foil, drying, slicing treatment, make electrochemical capacitor electrode sheet.
(3) by the electrode slice obtaining in the electrode slice obtaining in (2), barrier film and (2) in order stack of laminations dress up battery core, use again battery housing seal battery core, subsequently toward being arranged on liquid injection port on battery container toward the sulfuric acid/water electrolyte that injects 2mol/L in battery container, sealing liquid injection port, obtains electrochemical capacitor.
Embodiment 8
Being prepared as follows of the electrochemical capacitor of the present embodiment:
(1) ratio that is 85:5:10 according to mass ratio, graphene composite material prepared by embodiment 4, Kynoar binding agent and conductive agent acetylene black mix, and obtain slurry;
(2) slurry is coated on Copper Foil, drying, slicing treatment, make electrochemical capacitor electrode sheet.
(3) by the electrode slice obtaining in the electrode slice obtaining in (2), barrier film and (2) in order stack of laminations dress up battery core, use again battery housing seal battery core, subsequently toward being arranged on liquid injection port on battery container toward the sulfuric acid/water electrolyte that injects 2mol/L in battery container, sealing liquid injection port, obtains electrochemical capacitor.
The electrochemical capacitor of embodiment 5 ~ embodiment 8 that table 1 represents is the specific capacity data of carrying out charge-discharge test under 0.5A/g and 0.5A/g in current density respectively.
Table 1
| ? | Specific capacity (0.5A/g) (F/g) | Specific capacity (50A/g) (F/g) |
| Embodiment 5 | 786 | 711 |
| Embodiment 6 | 902 | 772 |
| Embodiment 7 | 716 | 631 |
| Embodiment 8 | 589 | 516 |
As can be seen from Table 1, the electrode that adopts the electrochemical capacitor that graphene composite material prepared by above-mentioned preparation method makes is that under 0.5A/g, height ratio capacity can reach 902F/g in current density, and the height ratio capacity of the electrode that uses the electrochemical capacitor that traditional material makes under 0.5A/g only has 432F/g; And in the time that current density rises to 50A/g from 0.5A/g, the conservation rate of the specific capacity of the electrode of the electrochemical capacitor that graphene composite material prepared by employing said method is made is all more than 85%, can reach 90%, and the specific capacity conservation rate of the electrode of the electrochemical capacitor that traditional material is made is 40%, the graphene composite material that above-mentioned preparation method prepares has excellent high rate performance.
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 graphene composite material, is characterized in that, Graphene, ruthenium-oxide and carbon nano-tube that described graphene composite material is 0.5 ~ 1:0.1 ~ 1:0.1 ~ 1 by mass ratio are compounded to form.
2. a preparation method for graphene composite material, is characterized in that, comprises the steps:
Use graphite-made for graphite oxide;
In the environment of inert gas, described graphite oxide is heated to 700 DEG C ~ 900 DEG C insulation reaction 0.5 hour ~ 2 hours, through cooling, obtain Graphene; And
Be 1ml:0.5mg ~ 1mg:0.1mg ~ 1mg:0.1mg ~ 1mg according to volume mass ratio, in deionized water, add successively described Graphene, ruthenium trichloride and carbon nano-tube, after ultrasonic mixing, in continuing to drip hydrogen peroxide under the condition stirring, stop dripping and be placed on 80 DEG C ~ 90 DEG C back flow reaction 2 hours ~ 6 hours, after filtration, clean and dry, obtain the graphene composite material being compounded to form by described Graphene, ruthenium-oxide and described carbon nano-tube; Wherein, the mass ratio of the described hydrogen peroxide of described ruthenium trichloride and dropping is 1:80 ~ 400.
3. the preparation method of graphene composite material according to claim 2, is characterized in that, uses described graphite-made to comprise for the step of described graphite oxide:
Be 1g:109ml ~ 119ml according to mass volume ratio, described graphite is joined in the mixed liquor being made up of the concentrated sulfuric acid and red fuming nitric acid (RFNA), and be placed in frozen water and mix to bathe and be uniformly mixed formation mixed solution; And
Be 1:4 ~ 6 according to the mass ratio of described graphite and potassium permanganate, described potassium permanganate is joined in described mixed solution, stir and carry out intercalation in 0.5 hour ~ 3 hours, be then heated to 20 DEG C ~ 50 DEG C insulation reaction 10 minutes ~ 40 minutes, then add deionized water, be heated to again 60 DEG C ~ 95 DEG C insulation reaction 10 minutes ~ 40 minutes, obtain reactant liquor, in described reactant liquor, add hydrogen peroxide, through suction filtration, and use successively watery hydrochloric acid and deionized water washing, then drying, graphite oxide obtained; Wherein, the mass volume ratio of described potassium permanganate and described deionized water is 1g:15ml ~ 50ml; And the described hydrogen peroxide adding and the mass ratio of described potassium permanganate are 0.63 ~ 0.95:1.
4. the preparation method of graphene composite material according to claim 2, is characterized in that, heating rate when described graphite oxide heating is 15 DEG C/min ~ 30 DEG C/min.
5. the preparation method of graphene composite material according to claim 2, is characterized in that, the drop rate of described hydrogen peroxide is 0.05mg/ minute ~ 0.5mg/ minute.
6. the preparation method of graphene composite material according to claim 2, is characterized in that, the condition of described lasting stirring is: stir speed (S.S.) is 200 revs/min ~ 300 revs/min.
7. the preparation method of graphene composite material according to claim 2, it is characterized in that, the reactant liquor that described back flow reaction obtains cleaning step is after filtering: the filter residue that the reactant liquor of described back flow reaction is obtained after filtering uses acetone and deionized water washing successively.
8. the preparation method of graphene composite material according to claim 2, is characterized in that, the drying condition of the reactant liquor that described back flow reaction obtains after filtration and after cleaning is: 50 DEG C ~ 80 DEG C vacuumize 8 hours ~ 16 hours.
9. the electrode of an electrochemical capacitor, it is characterized in that, the material of the electrode of described electrochemical capacitor is graphene composite material, and Graphene, ruthenium-oxide and carbon nano-tube that described graphene composite material is 0.5 ~ 1:0.1 ~ 1:0.1 ~ 1 by mass ratio are compounded to form.
10. an electrochemical capacitor, is characterized in that, comprises electrode, and the material of described electrode is graphene composite material, and Graphene, ruthenium-oxide and carbon nano-tube that described graphene composite material is 0.5 ~ 1:0.1 ~ 1:0.1 ~ 1 by mass ratio are compounded to form.
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