CN104051160A - Graphene for electrical double-layer capacitor and preparation method thereof - Google Patents
Graphene for electrical double-layer capacitor and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a graphene for an electrical double-layer capacitor and a preparation method of the graphene. The preparation method of the graphene includes the steps that (1) graphite, potassium nitrate and potassium permanganate are weighted, mixed evenly and put into a reaction kettle, and concentrated sulfuric acid is weighed and added to the reaction kettle; (2) the reaction kettle in the step (1) is placed in a thermostat and is subjected to low temperature constant temperature oxidizing reaction, medium temperature constant temperature oxidizing reaction and high temperature constant temperature oxidizing reaction; (3) oxidizing agents are added to products obtained after reaction in the step (2) is finished, oxidizing reaction is conducted, and then products are subjected to acid pickling, washing and drying; (4) the products obtained in the step (3) are subjected to puffing and reduction in the air atmosphere, or are subjected to puffing and reduction in the high temperature inert atmosphere, and end products are obtained. The graphene can be used as electrode materials of the electrical double-layer capacitor or conductive additives of a lithium ion battery, the amount of layers of the graphene is less, the crystal structure is complete, the size is large, bend and drape exist in the microstructure, the agglomerated degree is small, the specific capacitance value is high, the process is simple, and the graphene is suitable for large scale production.
Description
Technical field
The present invention relates to a kind of Graphene using as super capacitance cell electrode material and preparation method thereof, belong to capacitor and field of new thereof.
Background technology
Graphene is a kind of two dimensional crystal, and carbon atom is arranged, interconnected according to hexagon, forms a carbon molecule, and its structure is highly stable.It is all faster than known conductor that Graphene at room temperature transmits the speed of electronics, and its structure on atomic scale is very special, must just can describe with relativity quantum physics (Relativistic quantum physics).Graphene-structured is highly stable, and up to now, researcher does not find to have in Graphene the situation of carbon atom disappearance yet.Connection in Graphene between each carbon atom is very pliable and tough, and in the time applying external mechanical force, carbon atom face is with regard to flexural deformation, thereby makes carbon atom needn't rearrange to adapt to external force, also just kept Stability Analysis of Structures.This stable lattice structure makes carbon atom have outstanding conductivity.When electronics in Graphene moves in track, can or not introduce foreign atom because of lattice defect scattering occurs.Because active force between atom is very strong, at normal temperatures, even if around carbon atom telescopes, the interference that in Graphene, electronics is subject to is also very little.It is the material that mankind's known strength is the highest, toughness is best, weight is the lightest, light transmittance is the highest, conductivity is best.
Before Graphene is found, material with carbon element has been a kind of important capacitor electrode material, and by successful commercialization.But when material with carbon element uses as capacitor electrode material, specific area utilance is low, reason is that it contains a large amount of micropores, can not effectively form electric double layer and these apertures are less than the micropore of 2nm.In addition also there is the problem of poorly conductive in material with carbon element, as capacitor electrode material.Compared with material with carbon element, Graphene has the advantage of highly significant as capacitor electrode material: the plane layer laminated structure of (1) Graphene is conducive to the infiltration of electrolyte and the absorption/desorption of ion, contribute to improve energy storage density and the power characteristic of capacitor, can not have the low problem of specific area utilance of similar material with carbon element; (2) Graphene has large specific area, and the specific area theoretical value of single-layer graphene is 2630cm
2/ g (Stoller M D, Park S J, Zhu Y W, et al.Graphene-Based Ultracapacitors.Nano Lett, 2008,8 (10): 3498～3502), the ratio capacitance of the single-layer graphene that experiment records is 21 μ F/cm
2(Wang H L, Casalongue H S, Liang Y Y, et al.Ni (OH)
2nanoplates Grown on Graphene as Advanced Electrochemical Pseudocapacitor Materials.J Am Chem Soc, 2010,132 (21): 7472～7477), calculate thus, graphene-based specific capacity of double-layer capacitor is up to 550F/g, even due to stacking, reunion between graphene sheet layer, it also can reach 100～230F/g, the double electric layer capacitor of making higher than material with carbon element than capacitance; (3) Graphene has excellent conduction and heat conductivility, can effectively reduce the internal resistance value of capacitor, and improves its heat dispersion.
Super capacitance cell is the novel energy-storing device that one has secondary cell (high energy density) and ultracapacitor (high power density) characteristic concurrently.In order to meet the characteristic that possesses secondary cell and ultracapacitor simultaneously, super capacitance cell electrode material need to have high ratio capacitance.Obviously be, the desirable super capacitance cell electrode material of a class through the grapheme material of processing and modify and have high specific capacitance value.
Summary of the invention
The object of the invention is to overcome the deficiency that prior art exists, a kind of Graphene for super capacitance cell and preparation method thereof is provided.
A kind of Graphene for super capacitance cell that the present invention proposes and preparation method thereof, first from crystalline flake graphite or high-temperature expansion graphite, by three sections of constant temperature oxidation processes of basic, normal, high temperature, make that graphite is fully oxidized, layering, and make the surface of graphite flake layer and edge carry oxy radical by the modification of oxidant, thereby prepare graphene oxide; Then, the graphene oxide of preparation is carried out to expanded, reduction and processes, release surface energy, accept or reject oxy radical, increase dispersed, final obtain have specific area large, conduct electricity very well, the Graphene higher than capacitance.
A kind of Graphene for super capacitance cell that the present invention proposes and preparation method thereof, concrete steps are as follows:
(1) taking weight ratio is that graphite 5g～150g, potassium nitrate 2.5g～75g and the potassium permanganate 15g～450g of 1: 0.5: 3 mixes, and is placed in reactor, measures 115～3450mL98% concentrated sulfuric acid and adds in reactor.
(2) reactor in step 1 is placed in to insulating box and carries out three stage constant temperature oxidation reactions of low temperature, gentle high temperature, it is the low-temperature zone constant temperature oxidation reaction of 0 DEG C～4 DEG C in temperature, then being the middle-temperature section constant temperature oxidation reaction of 35 DEG C～45 DEG C in temperature, is finally the high temperature section constant temperature oxidation reaction of 80 DEG C～100 DEG C in temperature.
(3) after step (2) has been reacted, add the oxidant of 75mL～2250mL to carry out oxidation reaction, then oxidation product is carried out to pickling and washing, finally dry.
(4) step (3) product is carried out expanded, reduction reaction a period of time in the air atmosphere of 200 DEG C～500 DEG C, or carry out expanded, reduction reaction a period of time in the high temperature inert atmosphere of 1000 DEG C～1200 DEG C, obtain a kind of Graphene for super capacitance cell.
In the present invention, the graphite described in step (1) be in crystalline flake graphite or high-temperature expansion graphite any.
In the present invention, the reaction time of the oxidation of low-temperature zone constant temperature described in step (2) is 3h～40h, and the reaction time of described middle-temperature section constant temperature oxidation is 2h～6h, and the reaction time of described high temperature section constant temperature oxidation is 5min～15min.
In the present invention, described in step (3), oxidant is hydrogen peroxide.
In the present invention, the time expanded, that reduction is processed of air atmosphere described in step (4) is 5min～40min, and described high temperature inert gas is expanded, the time of reduction-oxidation processing is 5min～40min.
Beneficial effect of the present invention:
(1) preparing the graphene oxide stage, owing to having adopted low temperature, middle temperature and three sections of constant temperature oxidation processes of high temperature and strong oxidizer oxidation, graphite raw material fully can be oxidized to graphene oxide, the graphite oxide of preparation surface and the contained functional group in edge are mainly the oxygen-containing functional groups such as hydroxyl, carbonyl and quinonyl simultaneously, contribute to improve ratio capacitance prepared by the present invention;
(2) the present invention adopts Cryogenic air atmosphere or high temperature inert atmosphere to carry out expanded, reduction processing to graphene oxide, makes the specific area of the final Graphene of preparing at 400m
2/ g to 1000m
2/ g, the number of plies, in 10 layers, improves crystal structural stability and the purity of Graphene simultaneously.
(3) microstructure of the Graphene that prepared by the present invention has bending and fold to a certain degree, discharge to the full extent surperficial energy, good dispersion, the difficult trend that sheet ply recurrence lamellar graphite occurs, be conducive to electrolyte and enter formation electric double layer, improve it and compare capacitance;
(4) the ratio capacitance of the Graphene that prepared by the present invention in aqueous electrolyte can reach 260F/g, has capacitance characteristic and secondary cell characteristic, is suitable as super capacitance cell electrode material and uses, and also can be used as lithium ion battery conductive additive and uses;
(5) preparation technology of the present invention is easy, and cost is low, is applicable to large-scale production.
Brief description of the drawings
Fig. 1 is ESEM picture (SEM) under the low power of the Graphene prepared of the present invention, as can be observed from Figure shown in Graphene reunion degree compared with little, size is large, crystal structure is complete.
Fig. 2 is ESEM (SEM) picture under the high power of the Graphene prepared of the present invention, as can be observed from Figure shown in the microstructure of Graphene there is bending and fold, can infer that from its tulle, transparent pattern its number of plies is less in addition.
Fig. 3 is Raman (Raman) spectrum of the Graphene prepared of the present invention, can observe Graphene of the present invention and have the features such as crystal structure is stable, purity is high from spectrogram.
Fig. 4 is infrared spectrum (FR-IR) figure of the Graphene prepared of the present invention, and described 300 DEG C of air atmospheres Graphene expanded, that reduction is processed contains more functional group (hydroxyl, carbonyl etc.) as can be observed from Figure; From figure, can also observe described 1000 DEG C of inert atmospheres Graphene expanded, that reduction is processed and contain relatively less functional group.
Fig. 5 is the constant current charge-discharge test that Graphene prepared by the present invention carries out, according to single electrode than the computing formula (C of capacitance
g=2I Δ t/m Δ V), can find that through calculating Graphene of the present invention has larger ratio capacitance.
Fig. 6 is cyclic voltammetric (CV) test that Graphene prepared by the present invention carries out, and the CV curve under different scanning rates all keeps approximate rectangular shape as can be observed from Figure, illustrates that the internal resistance of black alkene electrode is less, capacitor power is functional.
Embodiment
Hereinafter with reference to example, the present invention is described in further detail, but the invention is not restricted to these instantiations.
Below in conjunction with embodiment, the present invention is further described:
Example 1:
Take 5.0g crystalline flake graphite, 2.5g potassium nitrate, 15.0g potassium permanganate and evenly mix, be placed in special reactor, then add the 115mL concentrated sulfuric acid, 4 DEG C of reaction 24h of experience low temperature, 40 DEG C of reaction 4h of middle temperature, 90 DEG C of reaction 30min three phases of high temperature.Then in above-mentioned reaction unit, add 75mL hydrogen peroxide, after fully reacting, after pickling, washing, oven dry, obtain graphite oxide.Graphite oxide is expanded in 450 DEG C of air, obtain Graphene product of the present invention after reduction 30min.The specific area of prepared Graphene is about 456m
2/ g.Above-mentioned Graphene is evenly mixed with binding agent, conductive black (each constituent mass was than 90: 5: 5), be coated in nickel foam, dry, be cut into the disk that diameter is 1.0cm, use as electrode to be measured, wherein the load capacity of active material is greater than 4.0mg.Taking the KOH of 6mol/L as electrolyte, utilize above-mentioned electrode assembling to be measured to become CR2032 type button cell, utilize constant current charge-discharge instrument to test it and compare capacitance, voltage window (0.0～0.9V), charging and discharging currents scope (1.0～50mA), single electrode than capacitance according to (C
g=2I Δ t/m Δ V) calculate.Result of calculation shows, the ratio capacitance of corresponding Graphene be 262F/g.
Example 2:
Take 20.0g crystalline flake graphite, 10.0g potassium nitrate, 60.0g potassium permanganate and evenly mix, be placed in special reactor, then add the 460mL concentrated sulfuric acid, 4 DEG C of reaction 24h of experience low temperature, 40 DEG C of reaction 4h of middle temperature, 90 DEG C of reaction 30min three phases of high temperature.Then in above-mentioned reaction unit, add 300mL hydrogen peroxide, after fully reacting, after pickling, washing, oven dry, obtain graphite oxide.Graphite oxide is expanded in 300 DEG C of air, obtain Graphene product of the present invention after reduction 30min.The specific area of prepared Graphene is about 440m
2/ g.Above-mentioned Graphene is evenly mixed with binding agent, conductive black (each constituent mass was than 90: 5: 5), be coated in nickel foam, dry, be cut into the disk that diameter is 1.0cm, use as electrode to be measured, wherein the load capacity of active material is greater than 4.0mg.Taking the KOH of 6mol/L as electrolyte, utilize above-mentioned electrode assembling to be measured to become CR2032 type button cell, utilize constant current charge-discharge instrument to test it and compare capacitance, voltage window (0.0～0.9V), charging and discharging currents scope (1.0～50mA), single electrode than capacitance according to (C
g=2I Δ t/m Δ V) calculate.Result of calculation shows, the ratio capacitance of corresponding Graphene be 253F/g.
Example 3:
Take 150.0g crystalline flake graphite, 75.0g potassium nitrate, 450.0g potassium permanganate and evenly mix, be placed in special reactor, then add the 3450mL concentrated sulfuric acid, 4 DEG C of reaction 24h of experience low temperature, 40 DEG C of reaction 4h of middle temperature, 90 DEG C of reaction 30min three phases of high temperature.Then in above-mentioned reaction unit, add 2250mL hydrogen peroxide, after fully reacting, after pickling, washing, oven dry, obtain graphite oxide.Graphite oxide is expanded in 350 DEG C of air, obtain Graphene product of the present invention after reduction 30min.The specific area of prepared Graphene is about 432m
2/ g.Above-mentioned Graphene is evenly mixed with binding agent, conductive black (each constituent mass was than 90: 5: 5), be coated in nickel foam, dry, be cut into the disk that diameter is 1.0cm, use as electrode to be measured, wherein the load capacity of active material is greater than 4.0mg.Taking the KOH of 6mol/L as electrolyte, utilize above-mentioned electrode assembling to be measured to become CR2032 type button cell, utilize constant current charge-discharge instrument to test it and compare capacitance, voltage window (0.0～0.9V), charging and discharging currents scope (1.0～50mA), single electrode than capacitance according to (C
g=2I Δ t/m Δ V) calculate.Result of calculation shows, the ratio capacitance of corresponding Graphene be 256F/g.
Example 4:
Take 20.0g crystalline flake graphite, 10.0g potassium nitrate, 60.0g potassium permanganate and evenly mix, be placed in special reactor, then add the 460mL concentrated sulfuric acid, 4 DEG C of reaction 24h of experience low temperature, 40 DEG C of reaction 4h of middle temperature, 90 DEG C of reaction 30min three phases of high temperature.Then in above-mentioned reaction unit, add 300mL hydrogen peroxide, after fully reacting, after pickling, washing, oven dry, obtain graphite oxide.Graphite oxide is expanded in 1100 DEG C of inert atmospheres, obtain Graphene product of the present invention after reduction 10min.The specific area of prepared Graphene is about 560m
2/ g.Above-mentioned Graphene is evenly mixed with binding agent, conductive black (each constituent mass was than 90: 5: 5), be coated in nickel foam, dry, be cut into the disk that diameter is 1.0cm, use as electrode to be measured, wherein the load capacity of active material is greater than 4.0mg.Taking the KOH of 6mol/L as electrolyte, utilize above-mentioned electrode assembling to be measured to become CR2032 type button cell, utilize constant current charge-discharge instrument to test it and compare capacitance, voltage window (0.0～0.9V), charging and discharging currents scope (1.0～50mA), single electrode than capacitance according to (C
g=2I Δ t/m Δ V) calculate.Result of calculation shows, the ratio capacitance of corresponding Graphene be 192F/g.
Example 5:
Take 150.0g crystalline flake graphite, 75.0g potassium nitrate, 450.0g potassium permanganate and evenly mix, be placed in special reactor, then add the 3450mL concentrated sulfuric acid, 4 DEG C of reaction 24h of experience low temperature, 40 DEG C of reaction 4h of middle temperature, 90 DEG C of reaction 30min three phases of high temperature.Then in above-mentioned reaction unit, add 2250mL hydrogen peroxide, after fully reacting, after pickling, washing, oven dry, obtain graphite oxide.Graphite oxide is expanded in 1100 DEG C of inert atmospheres, obtain Graphene product of the present invention after reduction 15min.The specific area of prepared Graphene is about 576m
2/ g.Above-mentioned Graphene is evenly mixed with binding agent, conductive black (each constituent mass was than 90: 5: 5), be coated in nickel foam, dry, be cut into the disk that diameter is 1.0cm, use as electrode to be measured, wherein the load capacity of active material is greater than 4.0mg.Taking the KOH of 6mol/L as electrolyte, utilize above-mentioned electrode assembling to be measured to become CR2032 type button cell, utilize constant current charge-discharge instrument to test it and compare capacitance, voltage window (0.0～0.9V), charging and discharging currents scope (1.0～50mA), single electrode than capacitance according to (C
g=2I Δ t/m Δ V) calculate.Result of calculation shows, the ratio capacitance of corresponding Graphene be 186F/g.
Example 6:
Take 5.0g crystalline flake graphite, 2.5g potassium nitrate, 15.0g potassium permanganate and evenly mix, be placed in special reactor, then add the 115mL concentrated sulfuric acid, 4 DEG C of reaction 24h of experience low temperature, 40 DEG C of reaction 4h of middle temperature, 90 DEG C of reaction 30min three phases of high temperature.Then in above-mentioned reaction unit, add 75mL hydrogen peroxide, after fully reacting, after pickling, washing, oven dry, obtain graphite oxide.Graphite oxide is expanded in 1050 DEG C of inert atmospheres, obtain Graphene product of the present invention after reduction 12min.The specific area of prepared Graphene is about 532m
2/ g.Above-mentioned Graphene is evenly mixed with binding agent, conductive black (each constituent mass was than 90: 5: 5), be coated in nickel foam, dry, be cut into the disk that diameter is 1.0cm, use as electrode to be measured, wherein the load capacity of active material is greater than 4.0mg.Taking the KOH of 6mol/L as electrolyte, utilize above-mentioned electrode assembling to be measured to become CR2032 type button cell, utilize constant current charge-discharge instrument to test it and compare capacitance, voltage window (0.0～0.9V), charging and discharging currents scope (1.0～50mA), single electrode than capacitance according to (C
g=2I Δ t/m Δ V) calculate.Result of calculation shows, the ratio capacitance of corresponding Graphene be 202F/g.
Example 7:
Take 5.0g high-temperature expansion graphite, 2.5g potassium nitrate, 15.0g potassium permanganate and evenly mix, be placed in special reactor, then add the 115mL concentrated sulfuric acid, 4 DEG C of reaction 24h of experience low temperature, 40 DEG C of reaction 4h of middle temperature, 90 DEG C of reaction 30min three phases of high temperature.Then in above-mentioned reaction unit, add 75mL hydrogen peroxide, after fully reacting, after pickling, washing, oven dry, obtain graphite oxide.Graphite oxide is expanded in 1050 DEG C of inert atmospheres, obtain Graphene product of the present invention after reduction 12min.The specific area of prepared Graphene is about 432m
2/ g.Above-mentioned Graphene is evenly mixed with binding agent, conductive black (each constituent mass was than 90: 5: 5), be coated in nickel foam, dry, be cut into the disk that diameter is 1.0cm, use as electrode to be measured, wherein the load capacity of active material is greater than 4.0mg.Taking the KOH of 6mol/L as electrolyte, utilize above-mentioned electrode assembling to be measured to become CR2032 type button cell, utilize constant current charge-discharge instrument to test it and compare capacitance, voltage window (0.0～0.9V), charging and discharging currents scope (1.0～50mA), single electrode than capacitance according to (C
g=2I Δ t/m Δ V) calculate.Result of calculation shows, the ratio capacitance of corresponding Graphene be 172F/g.
Example 8:
Take 20.0g high-temperature expansion graphite, 10.0g potassium nitrate, 60.0g potassium permanganate and evenly mix, be placed in special reactor, then add the 460mL concentrated sulfuric acid, 4 DEG C of reaction 24h of experience low temperature, 40 DEG C of reaction 4h of middle temperature, 90 DEG C of reaction 30min three phases of high temperature.Then in above-mentioned reaction unit, add 300mL hydrogen peroxide, after fully reacting, after pickling, washing, oven dry, obtain graphite oxide.Graphite oxide is expanded in 1100 DEG C of inert atmospheres, obtain Graphene product of the present invention after reduction 10min.The specific area of prepared Graphene is about 480m
2/ g.Above-mentioned Graphene is evenly mixed with binding agent, conductive black (each constituent mass was than 90: 5: 5), be coated in nickel foam, dry, be cut into the disk that diameter is 1.0cm, use as electrode to be measured, wherein the load capacity of active material is greater than 4.0mg.Taking the KOH of 6mol/L as electrolyte, utilize above-mentioned electrode assembling to be measured to become CR2032 type button cell, utilize constant current charge-discharge instrument to test it and compare capacitance, voltage window (0.0～0.9V), charging and discharging currents scope (1.0～50mA), single electrode than capacitance according to (C
g=2I Δ t/m Δ V) calculate.Result of calculation shows, the ratio capacitance of corresponding Graphene be 183F/g.
Example 9:
Taking 150.0g high-temperature expansion graphite, 75.0g potassium nitrate, 450.0g potassium permanganate evenly mixes, be placed in special reactor, then add the 3450mL concentrated sulfuric acid, 4 DEG C of reaction 24h of experience low temperature, 40 DEG C of reaction 4h of middle temperature, 90 DEG C of reaction 30min three phases of high temperature.Then in above-mentioned reaction unit, add 2250mL hydrogen peroxide, after fully reacting, after pickling, water Shen, oven dry, obtain graphite oxide.Graphite oxide is expanded in 1100 DEG C of inert atmospheres, obtain Graphene product of the present invention after reduction 15min.The specific area of prepared Graphene is about 476m
2/ g.Above-mentioned Graphene is evenly mixed with binding agent, conductive black (each constituent mass was than 90: 5: 5), be coated in nickel foam, dry, be cut into the disk that diameter is 1.0cm, use as electrode to be measured, wherein the load capacity of active material is greater than 4.0mg.Taking the KOH of 6mol/L as electrolyte, utilize above-mentioned electrode assembling to be measured to become CR2032 type button cell, utilize constant current charge-discharge instrument to test it and compare capacitance, voltage window (0.0～0.9V), charging and discharging currents scope (1.0～50mA), single electrode than capacitance according to (C
g=2I Δ t/m Δ V) calculate.Result of calculation shows, the ratio capacitance of corresponding Graphene be 176F/g.
Claims (5)
1. Graphene for super capacitance cell and preparation method thereof, is characterized in that comprising the following steps:
(1) taking weight ratio is graphite, potassium nitrate and the potassium permanganate of 1: 0.5: 3, mixes and is placed in reactor, then measure 98% concentrated sulfuric acid and add in reactor;
(2) reactor in step (1) is placed in to insulating box and carries out the three stages constant temperature oxidation of low temperature, gentle high temperature, it is the low-temperature zone constant temperature oxidation of 0 DEG C～4 DEG C in temperature, then being the middle-temperature section constant temperature oxidation of 35 DEG C～45 DEG C in temperature, is finally the high temperature section constant temperature oxidation of 80 DEG C～100 DEG C in temperature;
(3) after step (2) has been reacted, the oxidant adding is oxidized, and then oxidation product is carried out to pickling and washing, finally dries;
(4) step (3) product is carried out to expanded, reduction reaction in the air atmosphere of 200 DEG C～500 DEG C, or in the high temperature inert atmosphere of 1000 DEG C～1200 DEG C, carry out expanded, reduction, obtain a kind of Graphene for super capacitance cell.
2. according to claim 1 for Graphene of super capacitance cell and preparation method thereof, it is characterized in that: the graphite described in step (1) be in crystalline flake graphite or high-temperature expansion graphite any.
3. according to claim 1 for Graphene of super capacitance cell and preparation method thereof, it is characterized in that: the reaction time of the oxidation of low-temperature zone constant temperature described in step (2) is 3h～40h, the reaction time of described middle-temperature section constant temperature oxidation is 2h～6h, and the reaction time of described high temperature section constant temperature oxidation is 5min～15min.
4. according to claim 1 for graphene oxide of super capacitance cell and preparation method thereof, it is characterized in that: described in step (3), oxidant is hydrogen peroxide.
5. according to claim 1 for Graphene of super capacitance cell and preparation method thereof, it is characterized in that: the reaction time expanded, reduction of air atmosphere described in step (4) is 5min～40min; The described high temperature inert gas reaction time expanded, reduction is 5min～40min.
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| CN105036108A (en) * | 2015-06-23 | 2015-11-11 | 苏州大学 | Method for preparing sodium-ion battery electrode carbon material from corn leaves |
| CN105036108B (en) * | 2015-06-23 | 2017-03-08 | 苏州大学 | A kind of method that utilization maize leaves prepare sodium-ion battery electrode material with carbon element |
| CN105977039A (en) * | 2016-06-29 | 2016-09-28 | 陈小刚 | Graphene activity composite electrode super-capacitor cell |
| CN106486295A (en) * | 2016-10-29 | 2017-03-08 | 大英聚能科技发展有限公司 | The preparation method of the Graphene of high specific capacitance/high surface carbon composite |
| CN107195879A (en) * | 2017-05-09 | 2017-09-22 | 东南大学 | A kind of preparation method of the graphite oxide negative material of high performance lithium ion battery |
| CN110739158A (en) * | 2019-09-23 | 2020-01-31 | 青岛大学 | surface-modified oxygen-containing functional group-containing graphene for super capacitor |
| CN110739158B (en) * | 2019-09-23 | 2022-06-24 | 青岛大学 | Surface-modified oxygen-containing functional group-containing graphene for supercapacitor |
| CN114956061A (en) * | 2022-06-01 | 2022-08-30 | 安徽理工大学环境友好材料与职业健康研究院(芜湖) | Improved preparation and application of graphene negative electrode material of sodium-ion battery |
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