CN103383898A - Preparing method of graphene paper current collector - Google Patents
Preparing method of graphene paper current collector Download PDFInfo
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- CN103383898A CN103383898A CN2012101372341A CN201210137234A CN103383898A CN 103383898 A CN103383898 A CN 103383898A CN 2012101372341 A CN2012101372341 A CN 2012101372341A CN 201210137234 A CN201210137234 A CN 201210137234A CN 103383898 A CN103383898 A CN 103383898A
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Abstract
The invention discloses a preparing method of a graphene paper current collector. The method comprises the steps that graphite, potassium permanganate and concentrated sulfuric acid are mixed for oxidizing reaction to obtain graphite oxide; the graphite oxide is added to a solvent to prepare graphite oxide solution; ultrasonic agitation is carried out on the graphite oxide solution to obtain evenly dispersed graphene oxide suspension liquid; the graphene oxide suspension liquid is placed in a reaction still for reaction to obtain graphene suspension liquid; the graphene suspension liquid is filtered in a vacuum mode with a micro-filtration membrane, oven-dried and peeled from the micro-filtration membrane to obtain graphene paper; reducing atmosphere is introduced to the graphene paper under the atmosphere of inert gases at the temperature of 500-1000 DEG C for reduction reaction, and then temperature is reduced to the indoor temperature to obtain the graphene paper current collector. The graphene paper current collector prepared with the method is quite high in electric conductivity.
Description
Technical field
The present invention relates to collector, particularly relate to a kind of preparation method of Graphene paper collector.
Background technology
Ultracapacitor is a kind of novel energy storage device, have the advantages such as high power density (for more than 10 times of common batteries), high cycle life (cycle-index can reach more than 100,000 times), fast charging and discharging performance are good, be widely used in the AC-battery power source of military field, device for mobile communication, computer and electric automobile etc.Usually ultracapacitor is mainly assembled by electrode active material layer, electrolyte, barrier film, collector, shell etc.The energy density of existing ultracapacitor is generally lower, the factor that affects energy density mainly contains the electric capacity of electrode material, the voltage of system, electrode material accounts for proportion of the total weight that electrode active material layer, collector, sheathing material form etc., therefore, increase the energy-storage property of electrode material and the weight of each composition material of reduction device and can effectively improve performance of devices.Wherein, the quality of reduction collector is a method that effectively improves energy density.
Collector is a kind of structure or part that collects electric current, and major function is that the electric current that cell active materials produces is collected, and electron channel is provided, and accelerates electric charge and shifts, and improves to discharge and recharge coulombic efficiency.Need to satisfy the characteristics such as conductivity is high, good mechanical property, quality is light, internal resistance is little as collector.
At present, in most document or in industry, anodal aluminium foil, the negative pole of adopting of general collector adopts Copper Foil, because the density of metal collector is larger, quality is heavier, the weight of general collector accounts for the 20-25% of whole battery, and the electrode material proportion that accounts for whole battery greatly reduces, and finally causes the energy density of ultracapacitor lower.
Since the strong K of the peace moral of Univ Manchester UK sea nurse (Andre K.Geim) etc. was prepared grapheme material in 2004, because being subject to people, its unique structure and photoelectric property pay attention to widely.Mono-layer graphite is due to its large specific area, good conduction, heat conductivility and low thermal coefficient of expansion and be considered to desirable material.As: 1. high strength, the Young mole, (1,100GPa), hot strength: (150-180GPa); 2. high conductivity (108S/m); 3. high specific area, (calculated value: 2,630m2/g).Graphene can be prepared into by certain method graphene film or Graphene paper, because the specific area of Graphene is larger, its density is lower, the lighter weight of Graphene paper, its high mechanical performance and high conductivity also can satisfy the key property index that collector is used simultaneously, therefore can serve as collector based on the prepared Graphene paper of Graphene and use, and can reduce the quality of collector.
Yet when traditional method of passing through the direct filtration of graphene suspension prepared Graphene paper, the Graphene paper of preparation often caused conductivity lower because there being a large amount of defectives.
Summary of the invention
Based on this, be necessary to provide the preparation method of the higher Graphene paper collector of a kind of conductivity.
A kind of preparation method of Graphene paper collector comprises the steps:
Graphite, potassium permanganate and the concentrated sulfuric acid are carried out obtaining graphite oxide after oxidation reaction;
Described graphite oxide is added in solvent, be mixed with graphite oxide solution;
With described graphite oxide solution ultrasonic agitation, obtain homodisperse graphene oxide suspension;
Described graphene oxide suspension is put into reactor react, obtain graphene suspension;
Adopt the described graphene suspension of miillpore filter vacuum filtration, then oven dry obtains Graphene paper after filter membrane is peeled off; And
Described Graphene paper under the atmosphere of inert gas, is passed into reducing atmosphere under 500 ~ 1000 ℃, carry out reduction reaction, cool to room temperature obtains described Graphene paper collector.
In embodiment, described graphite oxide adopts following method to make: graphite is added in the concentrated sulfuric acid, then add potassium permanganate therein, remain on below 10 ℃, stir 2h, after room-temperature water bath stirs, slowly add deionized water under condition of ice bath, graphite is carried out oxidation, add at last hydrogen peroxide to remove potassium permanganate, suction filtration carries out cyclic washing with watery hydrochloric acid and deionized water to solids, drying obtains graphite oxide.
In embodiment, described solvent is the aqueous solution of DMF or NMP therein, and wherein, the volume ratio of described DMF or NMP and water is 9:1 ~ 5:5.
In embodiment, the concentration of described graphite oxide solution is 0.25 ~ 1mg/ml therein.
In embodiment, the time of described ultrasonic agitation is 0.5 ~ 1 hour therein.
Therein in embodiment, 150 ~ 200 ℃ of the reaction temperature of described graphene oxide suspension in reactor, the reaction time is 5 ~ 12 hours.
In embodiment, under the atmosphere of inert gas, first the speed with 1 ~ 5 ℃/min is warming up to 200 ℃, is incubated 5 minutes, then is warming up to 500 ~ 1000 ℃ with the speed of 5 ~ 10 ℃/min with described Graphene paper therein.
In embodiment, the time of described reduction reaction is 0.5 ~ 2 hour therein.
In embodiment, described inert gas is argon gas therein, and the flow of described argon gas is 50 ~ 70ml/ minute.
Therein in embodiment, described reducing atmosphere is by 90 ~ 95% argon gas and 5 ~ 10% hydrogen form by volume.
Said method reduces epoxide group by solvent-thermal method, mist by hydrogen and nitrogen reduces other functional groups again, reduce comparatively thorough, and avoided in the process of thermal reduction, there is the existence of epoxide group can cause a large amount of defectives and the loss of carbon atom, therefore can improves the conductivity of Graphene paper collector.
Description of drawings
Fig. 1 is preparation method's the flow chart of the Graphene collector of an execution mode.
Embodiment
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.A lot of details have been set forth in the following description so that fully understand the present invention.But the present invention can implement much to be different from alternate manner described here, and those skilled in the art can be in the situation that do similar improvement without prejudice to intension of the present invention, so the present invention is not subjected to the restriction of following public concrete enforcement.
When traditional method of passing through the direct filtration of graphene suspension prepares Graphene paper, often the Graphene paper of preparation is even not, perhaps more difficult film forming, sum up its reason and be mainly and be more difficult to get stable graphene suspension, often the graphite oxide aqueous solution obtains by the hydrazine hydrate direct-reduction can producing in the process of graphene suspension and reunites.
Based on this, see also Fig. 1, the preparation method of the Graphene collector of an execution mode provided by the invention comprises the steps:
Step S101, graphite, potassium permanganate and the concentrated sulfuric acid are carried out obtaining graphite oxide after oxidation reaction.
For example, graphite can be added in the concentrated sulfuric acid, then add potassium permanganate, keep the temperature of mixture below 10 ℃, stir 2h, after room-temperature water bath stirs, slowly add deionized water under condition of ice bath, graphite is carried out oxidation, add at last hydrogen peroxide to remove potassium permanganate, suction filtration carries out cyclic washing with watery hydrochloric acid and deionized water to solids, drying obtains graphite oxide.
Step S102, graphite oxide is added in solvent, be mixed with graphite oxide solution.
Preferably, described solvent is DMF(N, the N dimethyl formamide) or the NMP(N-methyl pyrrolidone) the aqueous solution, wherein, the volume ratio of described DMF or NMP and water is 9:1 ~ 5:5.
Preferably, the concentration of graphite oxide solution is 0.25 ~ 1mg/ml.
Step S103, with the graphite oxide solution ultrasonic agitation, obtain homodisperse graphene oxide suspension.
Preferably, the time of ultrasonic agitation is 0.5 ~ 1 hour.
Graphite oxide is due to the existence that more hydrophilic radical is arranged, so its dispersiveness in water better, and after being reduced to Graphene, hydrophilic functional groups disappears, and causes its dispersive property in water relatively poor.Therefore can find suitable solvent, make graphene oxide and Graphene that dispersion effect preferably all be arranged therein, have certain reduction effect simultaneously in ultrasonic dispersion.
S104, graphene oxide suspension is put into reactor react, obtain graphene suspension.
Preferably, can adopt the quartz reaction still.Reaction temperature is 150 ~ 200 ℃, and the reaction time is 5 ~ 12 hours.
Step S105, employing miillpore filter vacuum filtration graphene suspension, then oven dry obtains Graphene paper after filter membrane is peeled off.
Can control by the thickness of the suspension that adds the thickness of Graphene paper.The temperature of oven dry is preferably 40 ℃.
Step S106, with Graphene paper under the atmosphere of inert gas, pass into reducing atmosphere under 500 ~ 1000 ℃, carry out reduction reaction, cool to room temperature obtains described Graphene paper collector.
Preferably, first the speed with 1 ~ 5 ℃/min is warming up to 200 ℃, is incubated 5 minutes, then is warming up to 500 ~ 1000 ℃ with the speed of 5 ~ 10 ℃/min.
Described inert gas is preferably argon gas, and the flow of described argon gas is preferably 50 ~ 70ml/ minute kind.
Described reducing atmosphere is preferably by 90 ~ 95% argon gas and 5 ~ 10% hydrogen form by volume.
The time of reduction reaction is preferably 0.5 ~ 2 hour.
The preparation method of above-mentioned Graphene collector has following advantage:
Owing to solvent being elected as DMF or NMP, make graphene oxide and Graphene all can disperse in this solvent, the reunion of the Graphene after avoiding reducing can be easier to obtain uniform Graphene paper; Reduce epoxide group by solvent-thermal method, mist by hydrogen and nitrogen reduces other functional groups again, reduce comparatively thorough, and avoided in the process of thermal reduction, there is the existence of epoxide group can cause a large amount of defectives and the loss of carbon atom, therefore can improves the conductivity of Graphene paper collector.
Further illustrate below in conjunction with specific embodiment.
Embodiment 1
Preparation technology's flow process of the synthetic Graphene collector of the present embodiment is as follows:
Natural flake graphite → graphite oxide → graphene oxide suspension → graphene suspension → Graphene paper → Graphene paper collector
(1) natural flake graphite: order is counted the 100-500 order;
(2) graphite oxide: 0.5g 500 purpose graphite powders are added in 0 ℃, the concentrated sulfuric acid of 11.5mL, add again 1.5g potassium permanganate, keep the temperature of mixture to remain on below 10 ℃, stir 2h, then after room-temperature water bath stirs 24h, slowly add the 46mL deionized water under condition of ice bath.After 15min, add again 140mL deionized water (wherein contain 2.5mL concentration be 30% hydrogen peroxide), the mixture color becomes glassy yellow afterwards, suction filtration, then be that 10% hydrochloric acid washs, suction filtration, namely obtain graphite oxide at 60 ℃ of vacuumize 48h with 250ml concentration.
(3) graphene oxide suspension: graphite oxide is added in the aqueous solution of DMF, (wherein the ratio of DMF and water is: 9:1), being configured to concentration is the ultrasonic 0.5h of graphite oxide solution of 0.25mg/ml, obtains homodisperse graphene oxide suspension.
(4) graphene suspension: with putting into the quartz reaction still in resulting graphene oxide suspension, react 5h at the temperature of 150 ℃.
(5) Graphene paper: adopt the graphene suspension in miillpore filter vacuum filtration (4), control the thickness of graphene oxide paper by the volume that adds suspension.After filtration, filter cake is placed in baking oven in 40 ℃ of oven dry, then Graphene paper is taken off from filter membrane.
(6) Graphene paper collector: with the Graphene paper of (5) gained, put into tube furnace, pass into argon gas and drive the interior air of stove away, then control the flow of argon gas at the air-flow of 50ml/min, first the heating rate with 1 ℃/min is warming up to 200 ℃, be incubated 5 minutes, then with the heating rate of 5 ℃/min, slowly be warming up to 500 ℃, pass into the mist of argon gas (90vol%) and hydrogen (10vol%) this moment, reduce 0.5h at this temperature, cool to room temperature obtains Graphene paper collector.
The mensuration of conductivity: the sample of embodiment 1 is cut into the rectangular pieces of 5cm*3cm, uses the two electrical measurement four point probe tester testing conductivities of D41-11D/ZM type under room temperature.Result shows that the conductivity of embodiment 1 is 1.2 * 10
4S/m illustrates that the Graphene conductivity after reduction is higher, reduction comparatively thorough.
Embodiment 2
Preparation technology's flow process of the synthetic Graphene collector of the present embodiment is as follows:
Natural flake graphite → graphite oxide → graphene oxide suspension → graphene suspension → Graphene paper → Graphene paper collector
(1) natural flake graphite: order is counted the 100-500 order;
(2) graphite oxide: 0.5g 500 purpose graphite powders are added in 0 ℃, the concentrated sulfuric acid of 11.5mL, add again 1.5g potassium permanganate, keep the temperature of mixture to remain on below 10 ℃, stir 2h, then after room-temperature water bath stirs 24h, slowly add the 46mL deionized water under condition of ice bath.After 15min, add again 140mL deionized water (wherein contain 2.5mL concentration be 30% hydrogen peroxide), the mixture color becomes glassy yellow afterwards, suction filtration, then be that 10% hydrochloric acid washs, suction filtration, namely obtain graphite oxide at 60 ℃ of vacuumize 48h with 250ml concentration.
(3) graphene oxide suspension: graphite oxide is added in the aqueous solution of NMP, (wherein the ratio of NMP and water is: 5:5), being configured to concentration is the ultrasonic 1h of graphite oxide solution of 0.25mg/ml, obtains homodisperse graphene oxide suspension.
(4) graphene suspension: with putting into the quartz reaction still in resulting graphene oxide suspension, react 12h at the temperature of 150 ℃.
(5) Graphene paper: adopt the graphene suspension in miillpore filter vacuum filtration (4), control the thickness of graphene oxide paper by the volume that adds suspension.After filtration, filter cake is placed in baking oven in 40 ℃ of oven dry, then Graphene paper is taken off from filter membrane.
(6) Graphene paper collector: with the Graphene paper of (5) gained, put into tube furnace, pass into argon gas and drive the interior air of stove away, then control the flow of argon gas at the air-flow of 50ml/min, first the heating rate with 5 ℃/min is warming up to 200 ℃, be incubated 5 minutes, then with the heating rate of 10 ℃/min, slowly be warming up to 1000 ℃, pass into the mist of argon gas (90vol%) and hydrogen (10vol%) this moment, reductase 12 h at this temperature, cool to room temperature obtains the Graphene collector.
Embodiment 3
Preparation technology's flow process of the synthetic Graphene collector of the present embodiment is as follows:
Natural flake graphite → graphite oxide → graphene oxide suspension → graphene suspension → Graphene paper → Graphene paper collector
(1) natural flake graphite: order is counted the 100-500 order;
(2) graphite oxide: 0.5g 500 purpose graphite powders are added in 0 ℃, the concentrated sulfuric acid of 11.5mL, add again 1.5g potassium permanganate, keep the temperature of mixture to remain on below 10 ℃, stir 2h, then after room-temperature water bath stirs 24h, slowly add the 46mL deionized water under condition of ice bath.After 15min, add again 140mL deionized water (wherein contain 2.5mL concentration be 30% hydrogen peroxide), the mixture color becomes glassy yellow afterwards, suction filtration, then be that 10% hydrochloric acid washs, suction filtration, namely obtain graphite oxide at 60 ℃ of vacuumize 48h with 250ml concentration.
(3) graphene oxide suspension: graphite oxide is added in the aqueous solution of DMF, (wherein the ratio of DMF and water is: 7:3), being configured to concentration is the ultrasonic 1h of graphite oxide solution of 1mg/ml, obtains homodisperse graphene oxide suspension.
(4) graphene suspension: with putting into the quartz reaction still in resulting graphene oxide suspension, react 12h at the temperature of 200 ℃.
(5) Graphene paper: adopt the graphene suspension in miillpore filter vacuum filtration (4), control the thickness of graphene oxide paper by the volume that adds suspension.After filtration, filter cake is placed in baking oven in 40 ℃ of oven dry, then Graphene paper is taken off from filter membrane.
(6) Graphene paper collector: with the Graphene paper of (5) gained, put into tube furnace, pass into argon gas and drive the interior air of stove away, then control the flow of argon gas at the air-flow of 70ml/min, first the heating rate with 3 ℃/min is warming up to 200 ℃, be incubated 5 minutes, then with the heating rate of 10 ℃/min, slowly be warming up to 500 ℃, pass into the mist of argon gas (95vol%) and hydrogen (5vol%) this moment, reduce 0.5h at this temperature, cool to room temperature obtains Graphene paper collector.
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.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. the preparation method of a Graphene paper collector, is characterized in that, comprises the steps:
Graphite, potassium permanganate and the concentrated sulfuric acid are carried out obtaining graphite oxide after oxidation reaction;
Described graphite oxide is added in solvent, be mixed with graphite oxide solution;
With described graphite oxide solution ultrasonic agitation, obtain homodisperse graphene oxide suspension;
Described graphene oxide suspension is put into reactor react, obtain graphene suspension;
Adopt the described graphene suspension of miillpore filter vacuum filtration, then oven dry obtains Graphene paper after filter membrane is peeled off; And
Described Graphene paper under the atmosphere of inert gas, is passed into reducing atmosphere under 500 ~ 1000 ℃, carry out reduction reaction, cool to room temperature obtains described Graphene paper collector.
2. the preparation method of Graphene paper collector according to claim 1, it is characterized in that, described graphite oxide adopts following method to make: graphite is added in the concentrated sulfuric acid, then add potassium permanganate, remain on below 10 ℃, stir 2h, after room-temperature water bath stirs, slowly add deionized water under condition of ice bath, graphite is carried out oxidation, add at last hydrogen peroxide to remove potassium permanganate, suction filtration, with watery hydrochloric acid and deionized water, solids is carried out cyclic washing, drying obtains graphite oxide.
3. the preparation method of Graphene paper collector according to claim 1, is characterized in that, described solvent is N, the aqueous solution of dinethylformamide or 1-METHYLPYRROLIDONE, wherein, the volume ratio of described DMF or 1-METHYLPYRROLIDONE and water is 9:1 ~ 5:5.
4. the preparation method of Graphene collector according to claim 1, is characterized in that, the concentration of described graphite oxide solution is 0.25 ~ 1mg/ml.
5. the preparation method of Graphene collector according to claim 1, is characterized in that, the time of described ultrasonic agitation is 0.5 ~ 1 hour.
6. the preparation method of Graphene collector according to claim 1, is characterized in that, 150 ~ 200 ℃ of the reaction temperature of described graphene oxide suspension in reactor, and the reaction time is 5 ~ 12 hours.
7. the preparation method of Graphene collector according to claim 1, it is characterized in that, under the atmosphere of inert gas, first the speed with 1 ~ 5 ℃/min is warming up to 200 ℃ with described Graphene paper, be incubated 5 minutes, then be warming up to 500 ~ 1000 ℃ with the speed of 5 ~ 10 ℃/min.
8. the preparation method of Graphene collector according to claim 1, is characterized in that, the time of described reduction reaction is 0.5 ~ 2 hour.
9. the preparation method of Graphene collector according to claim 1, is characterized in that, described inert gas is argon gas, and the flow of described argon gas is 50 ~ 70ml/ minute.
10. the preparation method of Graphene collector according to claim 1, is characterized in that, described reducing atmosphere is by 90 ~ 95% argon gas and 5 ~ 10% hydrogen form by volume.
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| CN103607795A (en) * | 2013-11-29 | 2014-02-26 | 中国科学院金属研究所 | Preparation method for graphene heating film |
| CN105938907A (en) * | 2016-05-26 | 2016-09-14 | 江苏深苏电子科技有限公司 | Preparation method of high-conductivity graphene current collector |
| CN107754786A (en) * | 2017-10-16 | 2018-03-06 | 广西大学 | One kind utilizes KMnO4The method that electrocatalytic oxidation is improved on direct oxidation graphite paper |
| CN105977495B (en) * | 2016-05-11 | 2018-09-04 | 中国东方电气集团有限公司 | A kind of preparation method of affluxion body in lithium ion batteries graphite paper |
| CN110350201A (en) * | 2019-06-29 | 2019-10-18 | 华南理工大学 | A kind of highly conductive graphene collector of water system battery lightweight and preparation method thereof |
| CN112151809A (en) * | 2020-10-30 | 2020-12-29 | 蜂巢能源科技有限公司 | Flexible current collector, preparation method thereof and lithium ion battery |
| CN115180619A (en) * | 2022-07-04 | 2022-10-14 | 中南林业科技大学 | Preparation method of high-stretchability high-fold graphene oxide paper |
| CN115448299A (en) * | 2022-08-30 | 2022-12-09 | 深圳市米韵科技有限公司 | High-conductivity graphene film and preparation method thereof |
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| CN103607795A (en) * | 2013-11-29 | 2014-02-26 | 中国科学院金属研究所 | Preparation method for graphene heating film |
| CN103607795B (en) * | 2013-11-29 | 2016-01-20 | 中国科学院金属研究所 | A kind of preparation method of Graphene heating film |
| CN105977495B (en) * | 2016-05-11 | 2018-09-04 | 中国东方电气集团有限公司 | A kind of preparation method of affluxion body in lithium ion batteries graphite paper |
| CN105938907A (en) * | 2016-05-26 | 2016-09-14 | 江苏深苏电子科技有限公司 | Preparation method of high-conductivity graphene current collector |
| CN107754786A (en) * | 2017-10-16 | 2018-03-06 | 广西大学 | One kind utilizes KMnO4The method that electrocatalytic oxidation is improved on direct oxidation graphite paper |
| CN107754786B (en) * | 2017-10-16 | 2020-06-16 | 广西大学 | By using KMnO4Method for improving electrocatalytic oxidation on direct oxidized graphite paper |
| CN110350201A (en) * | 2019-06-29 | 2019-10-18 | 华南理工大学 | A kind of highly conductive graphene collector of water system battery lightweight and preparation method thereof |
| CN112151809A (en) * | 2020-10-30 | 2020-12-29 | 蜂巢能源科技有限公司 | Flexible current collector, preparation method thereof and lithium ion battery |
| CN112151809B (en) * | 2020-10-30 | 2022-02-22 | 蜂巢能源科技有限公司 | Flexible current collector, preparation method thereof and lithium ion battery |
| CN115180619A (en) * | 2022-07-04 | 2022-10-14 | 中南林业科技大学 | Preparation method of high-stretchability high-fold graphene oxide paper |
| CN115180619B (en) * | 2022-07-04 | 2023-09-22 | 中南林业科技大学 | Preparation method of high-stretchability high-fold graphene oxide paper |
| CN115448299A (en) * | 2022-08-30 | 2022-12-09 | 深圳市米韵科技有限公司 | High-conductivity graphene film and preparation method thereof |
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