CN103626156A - Graphene and preparation method thereof, and application of graphene in electrochemical capacitor - Google Patents
Graphene and preparation method thereof, and application of graphene in electrochemical capacitor Download PDFInfo
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- CN103626156A CN103626156A CN201210299022.3A CN201210299022A CN103626156A CN 103626156 A CN103626156 A CN 103626156A CN 201210299022 A CN201210299022 A CN 201210299022A CN 103626156 A CN103626156 A CN 103626156A
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Abstract
The invention provides a preparation method for graphene. According to the method, a silica nanometer bead is used as a carrier, graphene is prepared through layer-upon-layer self-assembling, and the problem of agglomeration caused by stacking of graphene lamellas is avoided. The invention further provides graphene prepared by using the preparation method. The prepared graphene has a great specific surface area and great energy storage capacity. Moreover, the invention provides application of the graphene in an electrochemical capacitor. An electrochemical capacitor electrode material using the graphene has high energy storage capacity and excellent rate capability.
Description
Technical field
The present invention relates to electrochemical field, particularly relate to a kind of Graphene and preparation method thereof and the application in electrochemical capacitor.
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.At present, the material for electrochemical capacitor electrode mainly contains carbon material, conducting polymer and metal oxide three major types.
Graphene, as a kind of novel carbon material, due to its two-dimentional unimolecular layer structure, and has high specific conductivity (more than 10S/cm) and high theoretical specific surface area (2630m
2/ g) etc. advantage, is a kind of potential high-performance electric chemistry capacitor electrode material.Yet in reality, Graphene is very easy to reunite, cause the specific surface area of Graphene far below its theoretical specific surface area, the surface that makes reunion Graphene afterwards carry out energy storage reduces greatly, stored energy capacitance also just reduces greatly, and reunite and to be also unfavorable for that electrolyte ion transmits in grapheme material, cause high rate performance to decline.Therefore, how solving Graphene reunion is that Graphene is applied to a major issue before electrochemical capacitor electrode material.
Summary of the invention
For addressing the above problem, first aspect present invention aims to provide a kind of preparation method of Graphene, this preparation method be take silica nanometer bead and is made Graphene as the mode of carrier by self-assembly layer by layer, has avoided graphene sheet layer to be stacked and the agglomeration traits that causes.Second aspect present invention provides the Graphene being made by this preparation method, and this Graphene has large specific surface area and stored energy capacitance.And third aspect present invention provides the application of this Graphene in electrochemical capacitor, used the electrochemical capacitor electrode material of this Graphene to there is higher stored energy capacitance and excellent high rate performance.
First aspect, the invention provides a kind of preparation method of Graphene, comprises the following steps:
(1) get graphite oxide and be scattered in deionized water, ultrasonic, making concentration is the graphene oxide solution of 0.5～1mg/ml; Get the described graphene oxide solution of part, regulate pH value to 3～6, make electronegative graphene oxide solution; Separately get the described graphene oxide solution of part, in described graphene oxide solution, add dimethylaminopropyl ethyl carboxamide and quadrol, after reaction, make positively charged graphene oxide solution;
(2) get the silica nanometer bead aqueous solution that concentration is 20～30mg/ml, add described positively charged graphene oxide solution, mix, stir, centrifugal, after being dissolved in to deionized water, centrifugal sediment makes the silica nanometer bead aqueous solution that is coated with positively charged graphene oxide; Add subsequently described electronegative graphene oxide solution, mix, stir, centrifugal, after being dissolved in to deionized water, centrifugal sediment makes the silica nanometer bead aqueous solution that is coated with electronegative graphene oxide;
The above-mentioned operation 3～10 times that adds positively charged graphene oxide solution and add electronegative graphene oxide solution repeatedly, finally makes graphene oxide/silica nanometer bead matrix material after centrifugal;
(3) described graphene oxide/silica nanometer bead matrix material is placed under inert atmosphere, with the temperature rise rates of 15～30 ℃/min, rise to 700～900 ℃, keep 0.5～2 hour, after being down to subsequently room temperature, make the silica nanometer bead that is coated with Graphene, the ratio that is finally 1g: 0.5～2ml in solid-to-liquid ratio adds to the described silica nanometer bead that is coated with Graphene in hydrofluoric acid, stir, vacuum filtration, by deionized water washed solid to pH value, be neutral, vacuum-drying, makes Graphene.
In step (1), graphite oxide makes graphene oxide solution after ultrasonic dispersion.
Preferably, ultrasonic power is 500～800w, and ultrasonic time is 0.5～2 hour.
Preferably, graphite oxide makes as follows: get purity and be 99.5% graphite, adding massfraction is in the mix acid liquor of 98% the vitriol oil and the massfraction concentrated nitric acid that is 65%, at frozen water, mix in bath and stir, then add potassium permanganate, stir 1～2 hour, subsequently mixing solutions being heated to 85～95 ℃ keeps 30～60 minutes, finally adding massfraction is that 30% hydrogen peroxide is removed potassium permanganate, suction filtration, with dilute hydrochloric acid and deionized water, solids is carried out to repetitive scrubbing, vacuum-drying, makes graphite oxide.
More preferably, described graphite: the vitriol oil: concentrated nitric acid: potassium permanganate: the ratio of hydrogen peroxide is 1g: 85～95ml: 24～25ml: 4～6g: 6～10ml.
Graphene oxide surface is because of electronegative with oxygen-containing functional groups such as carboxyls.A described graphene oxide solution part, as by adding the material regulator solution pH values such as sodium carbonate or sodium bicarbonate, makes electronegative graphene oxide solution; Another part, as by being with upper amino with dimethylaminopropyl ethyl carboxamide and quadrol generation amidate action, makes positively charged graphene oxide solution.
Preferably, adding dimethylaminopropyl ethyl carboxamide to final concentration is 0.6～1mg/ml, and adding quadrol to final concentration is 4～6mg/ml.
In step (2), take silica nanometer bead as core, in the coated multilayer graphene oxide structure of its surface mode by self-assembly layer by layer, avoided graphene sheet layer to be stacked and the agglomeration traits that causes.First, in silica nanometer bead surface adsorption, thereby positively charged graphene oxide makes the silica nanometer bead aqueous solution that is coated with positively charged graphene oxide, and then by the magnetism between positive and negative charge, electronegative graphene oxide coated on positively charged graphene oxide surface, unnecessary unreacted graphene oxide solution will be removed in centrifugal process, so repeated multiple times subsequently, can make graphene oxide/silica nanometer bead matrix material.
Preferably, the particle diameter of described silica nanometer bead is 50～70nm.
Preferably, described positively charged graphene oxide solution mixes with the ratio that the described silica nanometer bead aqueous solution is 1: 50～400 in graphene oxide with the mass ratio of silica nanometer bead, and described electronegative graphene oxide solution mixes with the ratio that the described silica nanometer bead aqueous solution is 1: 150～400 in graphene oxide with the mass ratio of silica nanometer bead.
In step (3), comprise the process that graphene oxide high temperature reduction is made to Graphene, and comprise by adding hydrofluoric acid solution to remove the process of silica nanometer bead.After high temperature reduction, silica nanometer bead surface is coated as having the Graphene of vesicular structure.Add after hydrofluoric acid solution, hydrofluoric acid solution can pass in a large amount of pore texture of Graphene, because the silica nanometer bead as core texture can be dissolved, and remove silica nanometer bead by vacuum filtration subsequently, the graphene-structured that only retains hollow structure, makes after vacuum-drying and has large specific surface area and the Graphene of stored energy capacitance.
Second aspect, the invention provides a kind of Graphene, and described Graphene is for to make according to aforementioned preparation method.Described Graphene has large specific surface area and stored energy capacitance.
The third aspect, the invention provides the application of this Graphene in electrochemical capacitor.
A kind of Graphene provided by the invention and preparation method thereof and the application in electrochemical capacitor, have following excellent effect:
(1) preparation method of the present invention be take silica nanometer bead and is made Graphene as the mode of carrier by self-assembly layer by layer, has avoided graphene sheet layer to be stacked and the agglomeration traits that causes;
(2) by Graphene provided by the invention, there is large specific surface area and stored energy capacitance;
(3) used the electrochemical capacitor electrode material of this Graphene to there is higher stored energy capacitance and excellent high rate performance.
Accompanying drawing explanation
Fig. 1 is a kind of preparation method's of Graphene process flow sheet.
Embodiment
The following stated is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
First aspect, the invention provides a kind of preparation method of Graphene, as shown in Figure 1, comprises the following steps:
(1) get graphite oxide and be scattered in deionized water, ultrasonic, making concentration is the graphene oxide solution of 0.5～1mg/ml; Get the described graphene oxide solution of part, regulate pH value to 3～6, make electronegative graphene oxide solution; Separately get the described graphene oxide solution of part, in described graphene oxide solution, add dimethylaminopropyl ethyl carboxamide (EDC) and quadrol, after reaction, make positively charged graphene oxide solution;
(2) get the silica nanometer bead aqueous solution that concentration is 20～30mg/ml, add described positively charged graphene oxide solution, mix, stir, centrifugal, after being dissolved in to deionized water, centrifugal sediment makes the silica nanometer bead aqueous solution that is coated with positively charged graphene oxide; Add subsequently described electronegative graphene oxide solution, mix, stir, centrifugal, after being dissolved in to deionized water, centrifugal sediment makes the silica nanometer bead aqueous solution that is coated with electronegative graphene oxide;
The above-mentioned operation 3～10 times that adds positively charged graphene oxide solution and add electronegative graphene oxide solution repeatedly, finally makes graphene oxide/silica nanometer bead matrix material after centrifugal;
(3) described graphene oxide/silica nanometer bead matrix material is placed under inert atmosphere, with the temperature rise rates of 15～30 ℃/min, rise to 700～900 ℃, keep 0.5～2 hour, after being down to subsequently room temperature, make the silica nanometer bead that is coated with Graphene, the ratio that is finally 1g: 0.5～2ml in solid-to-liquid ratio adds to the described silica nanometer bead that is coated with Graphene in hydrofluoric acid, stir, vacuum filtration, by deionized water washed solid to pH value, be neutral, vacuum-drying, makes Graphene.
In step (1), graphite oxide makes graphene oxide solution after ultrasonic dispersion.
Ultrasonic power is 500～800w, and ultrasonic time is 0.5～2 hour.
Graphite oxide makes as follows: get purity and be 99.5% graphite, adding massfraction is in the mix acid liquor of 98% the vitriol oil and the massfraction concentrated nitric acid that is 65%, at frozen water, mix in bath and stir, then add potassium permanganate, stir 1～2 hour, subsequently mixing solutions being heated to 85～95 ℃ keeps 30～60 minutes, finally adding massfraction is that 30% hydrogen peroxide is removed potassium permanganate, suction filtration, with dilute hydrochloric acid and deionized water, solids is carried out to repetitive scrubbing, vacuum-drying, makes graphite oxide.
Described graphite: the vitriol oil: concentrated nitric acid: potassium permanganate: the ratio of hydrogen peroxide is 1g: 85～95ml: 24～25ml: 4～6g: 6～10ml.
Graphene oxide surface is because of electronegative with oxygen-containing functional groups such as carboxyls.A described graphene oxide solution part, as by adding the material regulator solution pH values such as sodium carbonate or sodium bicarbonate, makes electronegative graphene oxide solution; Another part, as by being with upper amino with dimethylaminopropyl ethyl carboxamide and quadrol generation amidate action, makes positively charged graphene oxide solution.
Adding dimethylaminopropyl ethyl carboxamide to final concentration is 0.6～1mg/ml, and adding quadrol to final concentration is 4～6mg/ml.
In step (2), take silica nanometer bead as core, in the coated multilayer graphene oxide structure of its surface mode by self-assembly layer by layer, avoided graphene sheet layer to be stacked and the agglomeration traits that causes.First, in silica nanometer bead surface adsorption, thereby positively charged graphene oxide makes the silica nanometer bead aqueous solution that is coated with positively charged graphene oxide, and then by the magnetism between positive and negative charge, electronegative graphene oxide coated on positively charged graphene oxide surface, unnecessary unreacted graphene oxide solution will be removed in centrifugal process, so repeated multiple times subsequently, can make graphene oxide/silica nanometer bead matrix material.
The particle diameter of described silica nanometer bead is 50～70nm.
Described positively charged graphene oxide solution mixes with the ratio that the described silica nanometer bead aqueous solution is 1: 150～400 in graphene oxide with the mass ratio of silica nanometer bead, and described electronegative graphene oxide solution mixes with the ratio that the described silica nanometer bead aqueous solution is 1: 150～400 in graphene oxide with the mass ratio of silica nanometer bead.
In step (3), comprise the process that graphene oxide high temperature reduction is made to Graphene, and comprise by adding hydrofluoric acid solution to remove the process of silica nanometer bead.After high temperature reduction, silica nanometer bead surface is coated as having the Graphene of vesicular structure.Add after hydrofluoric acid solution, hydrofluoric acid solution can pass in a large amount of pore texture of Graphene, because the silica nanometer bead as core texture can be dissolved, and remove silica nanometer bead by vacuum filtration subsequently, the graphene-structured that only retains hollow structure, makes after vacuum-drying and has large specific surface area and the Graphene of stored energy capacitance.
Second aspect, the invention provides a kind of Graphene, and described Graphene is for to make according to aforementioned preparation method.Described Graphene has large specific surface area and stored energy capacitance.
The third aspect, the invention provides the application of this Graphene in electrochemical capacitor.
Described electrochemical capacitor is prepared as follows:
First, according to mass ratio, be 80～90: 5～10: 5～10 ratio, Graphene of the present invention, polyvinylidene difluoride (PVDF) binding agent and conductive agent acetylene black are mixed, make slurry;
Secondly, slurry is coated on aluminium foil, drying, slicing treatment, make electrochemical capacitor electrode sheet;
Finally, by Graphene electrodes sheet, barrier film, Graphene electrodes sheet in order stack of laminations dress up battery core, use again battery housing seal battery core, toward the spout being arranged on battery container, in battery container, inject electrolytic solution subsequently, the ionogen in described electrolytic solution adopts organic electrolyte tetraethyl ammonium a tetrafluoro borate/propylene carbonate (1mol/L Et
4nBF
4/ PC), sealing spout, makes electrochemical capacitor, and electrochemical capacitor is carried out to electro-chemical test.
Embodiment mono-
A preparation method for Graphene, comprises the following steps:
(1) taking purity is that 99.5% graphite 1g adds in the mix acid liquor being comprised of the 90ml vitriol oil (massfraction is 98%) and 25ml concentrated nitric acid (massfraction is 65%), be placed under frozen water mixing bath environment and stir 20 minutes, in mixing solutions, add 6g potassium permanganate at leisure again, stir 1 hour, then mixing solutions is heated to 85 ℃ and keep 30 minutes, add afterwards 92ml deionized water to continue at 85 ℃, to keep 30 minutes, finally add 10ml superoxol (massfraction is 30%), stir 10 minutes, mixing solutions is carried out to suction filtration, with 100ml dilute hydrochloric acid and 150ml deionized water, solids is washed respectively successively again, wash altogether three times, last solid matter is the dry graphite oxide that makes for 12 hours in 60 ℃ of vacuum drying ovens,
The graphite oxide making is added in deionized water, carry out ultrasonicly, ultrasonic power is 500W, and after ultrasonic 1 hour, making concentration is the graphene oxide solution of 1mg/ml; Graphene oxide solution is divided into two parts, in a solution, adds sodium carbonate, the pH value of solution is adjusted to 6, make electronegative graphene oxide solution; Toward adding dimethylaminopropyl ethyl carboxamide (EDC) to final concentration in other a solution, be that 1mg/ml and quadrol to final concentration are 5mg/ml, stirring at room 1 hour, makes positively charged graphene oxide solution after reaction;
(2) get the silica nanometer bead aqueous solution that 50ml concentration is 20mg/ml, the particle diameter of described silica nanometer bead is 50nm, add positively charged graphene oxide solution described in 5ml, mix, stir 30 minutes, centrifugal three times, after being dissolved in to deionized water, centrifugal sediment makes the silica nanometer bead aqueous solution that 50ml is coated with positively charged graphene oxide; Add subsequently electronegative graphene oxide solution described in 5ml, mix, stir 30 minutes, centrifugal three times, make the silica nanometer bead aqueous solution that is coated with electronegative graphene oxide after centrifugal sediment is dissolved in to deionized water;
The above-mentioned operation 3 times that adds positively charged graphene oxide solution and add electronegative graphene oxide solution repeatedly, finally makes graphene oxide/silica nanometer bead matrix material after centrifugal;
(3) described graphene oxide/silica nanometer bead matrix material is placed under inert atmosphere, with the temperature rise rates of 20 ℃/min, rise to 800 ℃, keep 0.5 hour, after being down to room temperature, make the silica nanometer bead that is coated with Graphene, the ratio that is finally 1g: 2ml in solid-to-liquid ratio adds to the described silica nanometer bead that is coated with Graphene in hydrofluoric acid, stir 12 hours, vacuum filtration, by deionized water repetitive scrubbing solid matter to pH value, be neutral, finally solid matter is placed in to 60 ℃ of vacuum drying ovens and dries 12 hours, make Graphene.
Embodiment bis-
A preparation method for Graphene, comprises the following steps:
(1) taking purity is that 99.5% graphite 5g adds in the mix acid liquor being comprised of the 475ml vitriol oil (massfraction is 98%) and 120ml concentrated nitric acid (massfraction is 65%), be placed under frozen water mixing bath environment and stir 20 minutes, in mixing solutions, add 20g potassium permanganate at leisure again, stir 1 hour, then mixing solutions is heated to 85 ℃ and keep 30 minutes, add afterwards 92ml deionized water to continue at 85 ℃, to keep 30 minutes, finally add 30ml superoxol (massfraction is 30%), stir 10 minutes, mixing solutions is carried out to suction filtration, with 300ml dilute hydrochloric acid and 450ml deionized water, solids is washed respectively successively again, wash altogether three times, last solid matter is the dry graphite oxide that makes for 12 hours in 60 ℃ of vacuum drying ovens,
The graphite oxide making is added in deionized water, carry out ultrasonicly, ultrasonic power is 500W, and after ultrasonic 2 hours, making concentration is the graphene oxide solution of 0.8mg/ml; Graphene oxide solution is divided into two parts, in a solution, adds sodium bicarbonate, the pH value of solution is adjusted to 6, make electronegative graphene oxide solution; Toward adding dimethylaminopropyl ethyl carboxamide (EDC) to final concentration in other a solution, be that 0.6mg/ml and quadrol to final concentration are 4mg/ml, stirring at room 1 hour, makes positively charged graphene oxide solution after reaction;
(2) get the silica nanometer bead aqueous solution that 50ml concentration is 20mg/ml, the particle diameter of described silica nanometer bead is 60nm, add positively charged graphene oxide solution described in 8ml, mix, stir 30 minutes, centrifugal three times, after being dissolved in to deionized water, centrifugal sediment makes the silica nanometer bead aqueous solution that 50ml is coated with positively charged graphene oxide; Add subsequently electronegative graphene oxide solution described in 8ml, mix, stir 30 minutes, centrifugal three times, make the silica nanometer bead aqueous solution that is coated with electronegative graphene oxide after centrifugal sediment is dissolved in to deionized water;
The above-mentioned operation 3 times that adds positively charged graphene oxide solution and add electronegative graphene oxide solution repeatedly, finally makes graphene oxide/silica nanometer bead matrix material after centrifugal;
(3) described graphene oxide/silica nanometer bead matrix material is placed under inert atmosphere, with the temperature rise rates of 25 ℃/min, rise to 900 ℃, keep 0.5 hour, after being down to room temperature, make the silica nanometer bead that is coated with Graphene, the ratio that is finally 1g: 2ml in solid-to-liquid ratio adds to the described silica nanometer bead that is coated with Graphene in hydrofluoric acid, stir 12 hours, vacuum filtration, by deionized water repetitive scrubbing solid matter to pH value, be neutral, finally solid matter is placed in to 60 ℃ of vacuum drying ovens and dries 12 hours, make Graphene.
Embodiment tri-
A preparation method for Graphene, comprises the following steps:
(1) taking purity is that 99.5% graphite 2g adds in the mix acid liquor being comprised of the 170ml vitriol oil (massfraction is 98%) and 48ml concentrated nitric acid (massfraction is 65%), be placed under frozen water mixing bath environment and stir 20 minutes, in mixing solutions, add 8g potassium permanganate at leisure again, stir 1 hour, then mixing solutions is heated to 85 ℃ and keep 30 minutes, add afterwards 92ml deionized water to continue at 85 ℃, to keep 30 minutes, finally add 16ml superoxol (massfraction is 30%), stir 10 minutes, mixing solutions is carried out to suction filtration, with 250ml dilute hydrochloric acid and 300ml deionized water, solids is washed respectively successively again, wash altogether three times, last solid matter is the dry graphite oxide that makes for 12 hours in 60 ℃ of vacuum drying ovens,
The graphite oxide making is added in deionized water, carry out ultrasonicly, ultrasonic power is 800W, and after ultrasonic 2 hours, making concentration is the graphene oxide solution of 1mg/ml; Graphene oxide solution is divided into two parts, in a solution, adds sodium bicarbonate, the pH value of solution is adjusted to 3, make electronegative graphene oxide solution; Toward adding dimethylaminopropyl ethyl carboxamide (EDC) to final concentration in other a solution, be that 1mg/ml and quadrol to final concentration are 6mg/ml, stirring at room 1 hour, makes positively charged graphene oxide solution after reaction;
(2) get the silica nanometer bead aqueous solution that 50ml concentration is 30mg/ml, the particle diameter of described silica nanometer bead is 70nm, add positively charged graphene oxide solution described in 10ml, mix, stir 30 minutes, centrifugal three times, after being dissolved in to deionized water, centrifugal sediment makes the silica nanometer bead aqueous solution that 50ml is coated with positively charged graphene oxide; Add subsequently electronegative graphene oxide solution described in 10ml, mix, stir 30 minutes, centrifugal three times, make the silica nanometer bead aqueous solution that is coated with electronegative graphene oxide after centrifugal sediment is dissolved in to deionized water;
The above-mentioned operation 10 times that adds positively charged graphene oxide solution and add electronegative graphene oxide solution repeatedly, finally makes graphene oxide/silica nanometer bead matrix material after centrifugal;
(3) described graphene oxide/silica nanometer bead matrix material is placed under inert atmosphere, with the temperature rise rates of 15 ℃/min, rise to 700 ℃, keep 2 hours, after being down to room temperature, make the silica nanometer bead that is coated with Graphene, the ratio that is finally 1g: 2ml in solid-to-liquid ratio adds to the described silica nanometer bead that is coated with Graphene in hydrofluoric acid, stir 12 hours, vacuum filtration, by deionized water repetitive scrubbing solid matter to pH value, be neutral, finally solid matter is placed in to 60 ℃ of vacuum drying ovens and dries 12 hours, make Graphene.
Embodiment tetra-
A preparation method for Graphene, comprises the following steps:
(1) taking purity is that 99.5% graphite 1g adds in the mix acid liquor being comprised of the 90ml vitriol oil (massfraction is 98%) and 25ml concentrated nitric acid (massfraction is 65%), be placed under frozen water mixing bath environment and stir 20 minutes, in mixing solutions, add 4g potassium permanganate at leisure again, stir 1 hour, then mixing solutions is heated to 85 ℃ and keep 30 minutes, add afterwards 92ml deionized water to continue at 85 ℃, to keep 30 minutes, finally add 9ml superoxol (massfraction is 30%), stir 10 minutes, mixing solutions is carried out to suction filtration, with 100ml dilute hydrochloric acid and 150ml deionized water, solids is washed respectively successively again, wash altogether three times, last solid matter is the dry graphite oxide that makes for 12 hours in 60 ℃ of vacuum drying ovens,
The graphite oxide making is added in deionized water, carry out ultrasonicly, ultrasonic power is 500W, and after ultrasonic 0.5 hour, making concentration is the graphene oxide solution of 0.5mg/ml; Graphene oxide solution is divided into two parts, in a solution, adds sodium bicarbonate, the pH value of solution is adjusted to 4, make electronegative graphene oxide solution; Toward adding dimethylaminopropyl ethyl carboxamide (EDC) to final concentration in other a solution, be that 1mg/ml and quadrol to final concentration are 5mg/ml, stirring at room 1 hour, makes positively charged graphene oxide solution after reaction;
(2) get the silica nanometer bead aqueous solution that 50ml concentration is 20mg/ml, the particle diameter of described silica nanometer bead is 50nm, add positively charged graphene oxide solution described in 5ml, mix, stir 30 minutes, centrifugal three times, after being dissolved in to deionized water, centrifugal sediment makes the silica nanometer bead aqueous solution that 50ml is coated with positively charged graphene oxide; Add subsequently electronegative graphene oxide solution described in 5ml, mix, stir 30 minutes, centrifugal three times, make the silica nanometer bead aqueous solution that is coated with electronegative graphene oxide after centrifugal sediment is dissolved in to deionized water;
The above-mentioned operation 5 times that adds positively charged graphene oxide solution and add electronegative graphene oxide solution repeatedly, finally makes graphene oxide/silica nanometer bead matrix material after centrifugal;
(3) described graphene oxide/silica nanometer bead matrix material is placed under inert atmosphere, with the temperature rise rates of 30 ℃/min, rise to 850 ℃, keep 2 hours, after being down to room temperature, make the silica nanometer bead that is coated with Graphene, the ratio that is finally 0.5g: 2ml in solid-to-liquid ratio adds to the described silica nanometer bead that is coated with Graphene in hydrofluoric acid, stir 12 hours, vacuum filtration, by deionized water repetitive scrubbing solid matter to pH value, be neutral, finally solid matter is placed in to 60 ℃ of vacuum drying ovens and dries 12 hours, make Graphene.
Effect embodiment
For effectively illustrating, provide the performance test results of embodiment mono-～tetra-as follows by beneficial effect of the present invention.
The preparation method of electrochemical capacitor
First, the ratio that is 85: 5: 10 according to mass ratio, mixes the obtained Graphene of the embodiment of the present invention, polyvinylidene difluoride (PVDF) binding agent and conductive agent acetylene black respectively, makes slurry;
Secondly, slurry is coated on aluminium foil, drying, slicing treatment, make electrochemical capacitor electrode sheet;
Finally, by Graphene electrodes sheet, barrier film, Graphene electrodes sheet in order stack of laminations dress up battery core, use again battery housing seal battery core, toward the spout being arranged on battery container, in battery container, inject electrolytic solution subsequently, the ionogen in described electrolytic solution adopts organic electrolyte tetraethyl ammonium a tetrafluoro borate/propylene carbonate (1mol/L Et
4nBF
4/ PC), sealing spout, makes electrochemical capacitor, and electrochemical capacitor is carried out to electro-chemical test.
The prepared Graphene of embodiment mono-～tetra-is respectively used to prepare four electrochemical capacitors, and it is as shown in table 1 that electrochemical capacitor carries out the specific storage test result of charge-discharge test under 0.5A/g and 100A/g current density.
Table 1. electrochemical capacitor carries out the specific storage of charge-discharge test under 0.5A/g and 100A/g current density
As can be seen from Table 1, use the specific storage of the prepared electrochemical capacitor of the embodiment of the present invention one～tetra-Graphene under 0.5A/g current density to can reach 286F/g.Compare the specific storage of using the electrochemical capacitor 160F/g left and right that commercial gac makes, use the prepared electrochemical capacitor of the embodiment of the present invention one～tetra-Graphene to there is very high specific storage, thereby can judge, the Graphene that the embodiment of the present invention one～tetra-provides has large specific surface area.In addition, while using the prepared electrochemical capacitor of the embodiment of the present invention one～tetra-Graphene to rise to 100A/g from 0.5A/g, capability retention, all more than 81%, is up to 85%, has excellent high rate performance.
To sum up, the preparation method of a kind of Graphene provided by the invention be take silica nanometer bead as carrier, and the mode by self-assembly layer by layer makes Graphene, has avoided graphene sheet layer to be stacked and the agglomeration traits that causes.The Graphene being made by this preparation method has large specific surface area and stored energy capacitance.Used the electrochemical capacitor electrode material of this Graphene to there is higher stored energy capacitance and excellent high rate performance.
Claims (9)
1. a preparation method for Graphene, is characterized in that, comprises the following steps:
(1) get graphite oxide and be scattered in deionized water, ultrasonic, making concentration is the graphene oxide solution of 0.5～1mg/ml; Get the described graphene oxide solution of part, regulate pH value to 3～6, make electronegative graphene oxide solution; Separately get the described graphene oxide solution of part, in described graphene oxide solution, add dimethylaminopropyl ethyl carboxamide and quadrol, after reaction, make positively charged graphene oxide solution;
(2) get the silica nanometer bead aqueous solution that concentration is 20～30mg/ml, add described positively charged graphene oxide solution, mix, stir, centrifugal, after being dissolved in to deionized water, centrifugal sediment makes the silica nanometer bead aqueous solution that is coated with positively charged graphene oxide; Add subsequently described electronegative graphene oxide solution, mix, stir, centrifugal, after being dissolved in to deionized water, centrifugal sediment makes the silica nanometer bead aqueous solution that is coated with electronegative graphene oxide;
The above-mentioned operation 3～10 times that adds positively charged graphene oxide solution and add electronegative graphene oxide solution repeatedly, finally makes graphene oxide/silica nanometer bead matrix material after centrifugal;
(3) described graphene oxide/silica nanometer bead matrix material is placed under inert atmosphere, with the temperature rise rates of 15～30 ℃/min, rise to 700～900 ℃, keep 0.5～2 hour, after being down to subsequently room temperature, make the silica nanometer bead that is coated with Graphene, the ratio that is finally 1g: 0.5～2ml in solid-to-liquid ratio adds to the described silica nanometer bead that is coated with Graphene in hydrofluoric acid, stir, vacuum filtration, by deionized water washed solid to pH value, be neutral, vacuum-drying, makes Graphene.
2. the preparation method of a kind of Graphene as claimed in claim 1, is characterized in that, in described step (1), ultrasonic power is 500～800w, and ultrasonic time is 0.5～2 hour.
3. the preparation method of a kind of Graphene as claimed in claim 1, it is characterized in that, graphite oxide makes as follows in described step (1): get purity and be 99.5% graphite, adding massfraction is in the mix acid liquor of 98% the vitriol oil and the massfraction concentrated nitric acid that is 65%, at frozen water, mix in bath and stir, then add potassium permanganate, stir 1～2 hour, subsequently mixing solutions being heated to 85～95 ℃ keeps 30～60 minutes, finally adding massfraction is that 30% hydrogen peroxide is removed potassium permanganate, suction filtration, with dilute hydrochloric acid and deionized water, solids is carried out to repetitive scrubbing, vacuum-drying, make graphite oxide.
4. the preparation method of a kind of Graphene as claimed in claim 3, is characterized in that, graphite in described step (1): the vitriol oil: concentrated nitric acid: potassium permanganate: the ratio of hydrogen peroxide is 1g: 85～95ml: 24～25ml: 4～6g: 6～10ml.
5. the preparation method of a kind of Graphene as claimed in claim 1, is characterized in that, in described step (1), adding dimethylaminopropyl ethyl carboxamide to final concentration is 0.6～1mg/ml, and adding quadrol to final concentration is 4～6mg/ml.
6. the preparation method of a kind of Graphene as claimed in claim 1, is characterized in that, described in described step (2), the particle diameter of silica nanometer bead is 50～70nm.
7. the preparation method of a kind of Graphene as claimed in claim 1, it is characterized in that, the ratio that described in described step (2), positively charged graphene oxide solution is 1: 150～400 in graphene oxide with the mass ratio of silica nanometer bead with the described silica nanometer bead aqueous solution is mixed, and described electronegative graphene oxide solution mixes with the ratio that the described silica nanometer bead aqueous solution is 1: 150～400 in graphene oxide with the mass ratio of silica nanometer bead.
8. a Graphene, is characterized in that, described Graphene is the preparation method as described in arbitrary claim in claim 1～7 make.
9. the application of Graphene as claimed in claim 8 in electrochemical capacitor.
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Cited By (3)
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| CN104030276A (en) * | 2014-06-09 | 2014-09-10 | 中南大学 | Method for preparing few-layer graphene |
| CN104999088A (en) * | 2015-07-03 | 2015-10-28 | 中国地质大学（北京） | Method for preparing gold nanoparticles based on quick reduction of graphene self-assembly multilayer films |
| CN109081334A (en) * | 2018-10-31 | 2018-12-25 | 山东大学 | A kind of amidation modified graphene oxide and the preparation method and application thereof |
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| CN101894682B (en) * | 2010-02-26 | 2012-07-04 | 上海奥威科技开发有限公司 | High-energy ultracapacitor |
| CN102145305A (en) * | 2011-04-08 | 2011-08-10 | 南京航空航天大学 | Method for preparing graphene-loaded nano alloy catalyst |
| CN102208598B (en) * | 2011-05-12 | 2014-03-12 | 中国科学院宁波材料技术与工程研究所 | Electrode plate of graphene coating modified lithium secondary battery and manufacturing method thereof |
| CN102502609A (en) * | 2011-11-10 | 2012-06-20 | 东华大学 | Method for preparing graphene hollow microspheres for anisotropic conductive materials |
| CN102515148B (en) * | 2011-11-25 | 2013-12-25 | 东南大学 | Method for casting graphene cast body |
| CN102515152B (en) * | 2011-12-23 | 2013-04-24 | 深圳市贝特瑞纳米科技有限公司 | Method for preparing spheroidal graphene |
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| CN104030276A (en) * | 2014-06-09 | 2014-09-10 | 中南大学 | Method for preparing few-layer graphene |
| CN104030276B (en) * | 2014-06-09 | 2016-06-08 | 中南大学 | The preparation method of a kind of few layer graphene |
| CN104999088A (en) * | 2015-07-03 | 2015-10-28 | 中国地质大学（北京） | Method for preparing gold nanoparticles based on quick reduction of graphene self-assembly multilayer films |
| CN104999088B (en) * | 2015-07-03 | 2017-03-29 | 中国地质大学（北京） | A kind of golden nanometer particle redox graphene multilamellar film composite material and preparation method thereof |
| CN109081334A (en) * | 2018-10-31 | 2018-12-25 | 山东大学 | A kind of amidation modified graphene oxide and the preparation method and application thereof |
| CN109081334B (en) * | 2018-10-31 | 2022-01-04 | 山东大学 | Amidation modified graphene oxide and preparation method and application thereof |
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