CN102491317A - Preparation method of reduced graphene oxide - Google Patents
Preparation method of reduced graphene oxide Download PDFInfo
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Abstract
The invention provides a preparation method of reduced graphene oxide, which includes dispersing graphite oxide into water under the condition of ultrasonic oscillation to obtain colloid; restoring the graphite oxide with zinc as the reducing agent to obtain reduced graphene oxide under acid or alkaline condition with the weight ratio of the graphite oxide to the zinc as 1: (5.5-6.5). The preparation method utilizes the zinc as the reducing agent, and the zinc has good reducing performance to the graphite oxide, is low in cost and non-toxic, cannot damage health of operators and is high in environment-protection performance. No other functional groups need to be introduced if the zinc serves as the reducing agent, so that good electric performance of the reduced graphene oxide can be favorably maintained. More importantly, the zinc is metalloid, so that the preparation method can be used for preparing the reduced graphene oxide under both the acid condition and the alkaline condition. Therefore, preparation conditions can be flexibly selected according to requirements by means of the preparation method.
Description
Technical field
The present invention relates to the Graphene field, particularly a kind of preparation method of graphene.
Background technology
Graphene is a kind of new carbon of the tightly packed one-tenth bi-dimensional cellular of monolayer carbon atom shape structure, and it is other dimension blackings of member, like the elementary cell of zero dimension soccerballene, one-dimensional nano carbon pipe, three-dimensional graphite etc.
Graphene also has many peculiar properties except having particular structural, significantly be thermal conductivity and physical strength.Graphene is a kind of good conductor, can very fast distribute heat, and passing Graphene, electronics almost has no resistance, and the heat that is produced is also considerably less.Graphene is rigid very, and its hardness is higher than diamond, and intensity is superior to iron and steel, and ideal tensile strength can reach 110～130GPa.Simultaneously, Graphene is again a kind of very excellent semiconductor material, has than the high a lot of carrier mobility of silicon.The still present classic material of known conductivity at normal temperatures of Graphene, electronics movement velocity therein is higher than general conductor, and this characteristic makes it in nanoelectronic element, transmitter, transistor and field of batteries, great application prospect arranged.Graphene also has good light transmittance, is conventional I TO film potential substitute products.
Preparation method of graphene mainly contains chemical reduction method, and micromechanics is peeled off method and chemical gaseous phase deposition method, and back two kinds of method output are lower, and are higher to processing requirement.Therefore the main at present chemical reduction method that adopts.Chemical reduction method is raw material with the graphite oxide, uses dimethylhydrazine, Resorcinol and Peng Qinghuana etc. to obtain Graphene as reductive agent reduction-oxidation graphite usually.But these reductive agent toxicity are big or inflammable, are unfavorable for operator's health, and operation is comparatively inconvenience also, and can introduce the electric property that other functional groups influence Graphene.
Summary of the invention
The technical problem that the present invention solves is to provide a kind of preparation method of graphene, and this method is not used poisonous raw material, and the feature of environmental protection is higher, and can not introduce the electric property that other functional groups influence Graphene.
In view of this, the present invention provides a kind of preparation method of graphene, comprising:
A), under the condition of ultra-sonic oscillation, graphite oxide is scattered in the water, obtain colloid;
B), under acid or alkaline condition, be that reductive agent reduces said graphite oxide with zinc, obtain Graphene; The weight ratio of said graphite oxide and zinc is 1: (5.5～6.5).
Preferably, said step b) is carried out under alkaline condition, is specially:
B1), in said colloid, adding mol ratio successively is 1: the zinc of (10～15) and alkali obtain Graphene; Said alkali is sodium hydroxide or Pottasium Hydroxide, and the weight ratio of said graphite oxide and zinc is 1: (5.5～6.5).
Preferably, the weight ratio of said sodium hydroxide or Pottasium Hydroxide and graphite oxide is (15～30): 1.
Preferably, the reaction times of said step b1 is 5h～8h.
Preferably, the temperature of reaction of said step b1 is 80 ℃～100 ℃.
Preferably, said step b) is carried out under acidic conditions, is specially:
B2), in said colloid, add zinc and acid solution successively, obtain Graphene; Said acid solution is that concentration is hydrochloric acid or the sulphuric acid soln of 0.5mol/L～2mol/L, and the weight ratio of said graphite oxide and zinc is 1: (5.5～6.5).
7, preparation method according to claim 6 is characterized in that, the weight ratio of HCl in the said hydrochloric acid or sulfuric acid and graphite oxide is (15～50): 1.
8, preparation method according to claim 6 is characterized in that, the reaction times of said step b2 is 5h～8h.
9, preparation method according to claim 1 is characterized in that, the concentration of graphite oxide is 0.8g/L 1.2g/L in the said colloid.
The present invention provides a kind of preparation method of graphene, and it is graphite oxide to be scattered in to obtain the graphite oxide colloid in the water earlier, is reductive agent then with zinc, and reduction-oxidation graphite makes under acidity or alkaline condition.The present invention uses zinc as reductive agent, and zinc has reducing property preferably to graphite oxide, and its non-toxic inexpensive; Can not damage health of operators; Environmental-protecting performance is higher, also can not introduce other functional groups with zinc as reductive agent, helps the electric property that keeps Graphene good.What is more important, zinc are a kind of amphoteric metals, make aforesaid method not only can but also can under alkaline condition, prepare Graphene under acidic conditions, and under acidic conditions, product purity is higher, and purification step is simple, and aftertreatment is easy; Preparation under alkaline condition, reducing degree is higher, and realizes the modification to Graphene when can realize reduction-oxidation graphite.Therefore, adopt aforesaid method to select preparation condition flexibly according to demand.
Description of drawings
Fig. 1 is the ultraviolet-visible spectrum of graphite oxide solution;
Fig. 2 is the XRD figure of a, b, c, d;
Fig. 3 is the XRD figure of e, f, g, h;
Fig. 4 is the infrared spectrogram of a, b, c, d;
Fig. 5 is the infrared spectrogram of e, f, g, h.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiment of the invention is described, describe just to further specifying feature and advantage of the present invention but should be appreciated that these, rather than to the restriction of claim of the present invention.
The embodiment of the invention discloses a kind of preparation method of graphene, comprise the steps:
A), under the condition of ultra-sonic oscillation, graphite oxide is scattered in the water, obtain colloid;
B), under acidity or alkaline condition, be that reductive agent reduces said graphite oxide with zinc, obtain Graphene; The weight ratio of said graphite oxide and zinc is 1: (5.5～6.5).
Aforesaid method is to adopt ultra-sonic oscillation that graphite oxide is scattered in the water earlier; Obtain colloid; Come reduction-oxidation graphite with zinc as reductive agent then; Because zinc is a kind of amphoteric metal, all can bring into play reductive action at acidic conditions or alkaline condition, makes this reduction reaction under acidic conditions and alkaline condition, all can carry out.The advantage of preparation Graphene is that product purity is higher under acidic conditions, and purification step is simple, and aftertreatment is easy; The advantage of preparation Graphene is that reducing degree is higher under alkaline condition, and realizes when can realize redox graphene Graphene is modified.Therefore, adopt aforesaid method to select preparation condition flexibly according to demand.And the zinc reductive agent that adopts is nontoxic, uses comparatively environmental protection, and can not introduce the electric property that other functional groups influence Graphene.
Step a is the process that Graphene is dispersed in water medium among the above-mentioned preparation method, and graphene oxide can be according to the preparation of Hummer method, and in order to guarantee the abundant oxidation of graphite, graphite oxide is preferably according to following method preparation:
S1), graphite is mixed with the vitriol oil to be placed on stir 15min～20min in the ice bath;
S2), in the mixture that step S1 obtains, add potassium permanganate, at 30 ℃～40 ℃ insulation 25min～40min;
S3), in the mixture that step S2 obtains, add distilled water diluting, place 95 ℃～100 ℃ oil bath to be incubated 10～20min, add superoxol again;
S4), with the product spinning, behind the salt acid elution, again with washed with de-ionized water to pH value to 5, drying.
For the reduction reaction that makes step b is more abundant, the concentration that the present invention preferably controls graphite oxide in the colloid is 0.8g/L 1.2g/L.
Step b is to be that reductive agent carries out the reductive operation with graphite oxide with zinc; The present invention selects zinc to be as the reason of reductive agent: at first; Zinc is a kind of reductive agent of non-toxic inexpensive, use its as reductive agent can operator health constitute injury, good environmental protection; Secondly, zinc is a kind of amphoteric metal, and no matter still it all can reduce to graphite oxide under alkaline condition at acidic conditions, and preparation condition can be selected flexibly; With respect to other amphoteric metals, gallium, germanium and indium simple substance price are comparatively expensive, and production cost is too high; The electrode potential of tin is lower, and reductibility is not as good as zinc, if be that reductive agent can cause reaction conditions too harsh with tin, or the product reduction is insufficient, and product purity is low; Though the electrode potential of aluminium is higher, the inventor finds after deliberation: be applied to the reduction of graphite oxide, its reducing property is not as good as zinc.For this reason, the present invention selects with zinc as reductive agent, with the environmental-protecting performance that improves reaction, the flexible selectivity and the product purity of preparation condition.
In the process of reduction-oxidation graphite, in order to guarantee to make graphite oxide by fully reduction, the weight ratio of controlled oxidation graphite of the present invention and zinc is 1: (5.5～6.5) are preferably 1: (5.6～6.0), more preferably 1: (5.7～5.8).
Zinc can be realized the reduction to graphite oxide again under alkaline condition under acidic conditions, carry out if be reflected under the alkaline condition, and then step b preferably carries out according to following mode:
B1), at 60 ℃～100 ℃, in above-mentioned colloid, add zinc and alkali successively, said alkali is NaOH or KOH, the weight ratio of graphite oxide and zinc is 1: (5.5～6.5) obtain Graphene.
In the above-mentioned steps, in order to improve degree of purity of production, it is 80 ℃～100 ℃ that temperature of reaction preferably is set, and the time of reduction reaction preferably is set to 5h～8h.Alkali is used for and zinc reaction on the one hand, is used for dispersoid on the other hand, and the alkali add-on is crossed and lowly is prone to cause speed of reaction slow excessively, reduces fully inadequately, need prolong the reaction times thus; The alkali add-on is too high then can to cause too much alkali residual, has increased the follow-up number of times that product is washed.For this reason, the present invention's mol ratio of preferably controlling alkali and zinc is (11～13): 1.The weight ratio of graphite oxide and sodium hydroxide or Pottasium Hydroxide is preferably 1: (15～30).
The advantage of reduction-oxidation graphite is under the alkaline condition: reducing degree is higher, and is convenient to Graphene is modified.Under alkaline condition, graphite oxide is peeled off more easily and is obtained stable electronegative colloid, can carry out the static assembling with the sheet molecule of positively charged, and the assembling of this molecular level is more effective than existing physical mixed.Therefore, adopt aforesaid method to realize that through in the reduction reaction process, introducing guest molecule one goes on foot the Graphene of preparing the modification effect excellence.
Guest molecule stable existence under alkaline condition of introducing, and can with the graphite oxide surface-OH ,-O-,-compound of reactions such as COOH, can be MOX, like Fe
3O
4Magnetic nano-particle, ZnO or TiO
2Deng; Biological micromolecule is like oligonucleotide etc.; Organic molecule is like pyridine etc.; Lamellar compound is like layered double hydroxide etc.If guest molecule is MOX or oxyhydroxide, behind the high-temperature vacuum calcining reduction, obtain the matrix material of MOX and Graphene.
In addition, under alkaline condition and 80 ℃～100 ℃ TR, prepare the reducing degree that Graphene can also improve graphene oxide, product purity is higher.
If reduction reaction is carried out under acidic conditions, then step b preferably carries out according to following mode:
B2), in above-mentioned colloid, add zinc and acid solution successively, obtain Graphene, said acid solution is that concentration is hydrochloric acid or the sulphuric acid soln of 0.5mol/L～2mol/L, the weight ratio of graphite oxide and zinc is 1: (5.5～6.5).
The acidic conditions advantage of preparation Graphene down is: product purity is higher, and purification step is simple, and aftertreatment is easy.In the above-mentioned steps, in order to make the graphite oxide reduction fully, the temperature of reduction reaction preferably is set to 60 ℃～100 ℃, and the time preferably is set to 5h～8h.Acid strength is crossed and low is prone to cause speed of reaction slow excessively, reduces fully inadequately, need prolong the reaction times thus; Acid strength is too high then can be caused too much sour residually, has increased the follow-up number of times that product is washed.For this reason, preferably to control the concentration of acid solution be 0.5mol/L～2mol/L in the present invention.The weight ratio of HCl in the hydrochloric acid or sulfuric acid and graphite oxide is preferably (15～50): 1.
With behind the reacting liquid filtering, remove unreacted zinc with the salt acid elution according to the method described above, be attached to the zinc salt on product surface again with water washing, drying promptly gets Graphene.
Can be known by The above results, adopt method provided by the invention to prepare Graphene, its zinc that adopts non-toxic inexpensive is as reductive agent, good environmental protection; Can not introduce other functional groups and influence the Graphene electric property; Simultaneously, it not only can but also can prepare Graphene under acidic conditions under alkaline condition, and product purity is higher under acidic conditions, and purification step is simple, and aftertreatment is easy; Under alkaline condition, can realize realizing Graphene is modified in the reduction-oxidation graphite.Therefore, adopt aforesaid method to select preparation condition flexibly according to demand.
In order further to understand the present invention, below in conjunction with embodiment preparation method of graphene provided by the invention to be described, protection scope of the present invention is not limited by the following examples.
Embodiment 1 preparation graphite oxide
1, distilled water flushing powdered graphite, the upper strata suspended substance that inclines filters drying;
2, get dried graphite 5g, 98% vitriol oil 230mL and mix and place ice bath, stir 15min, make its thorough mixing. take by weighing 30g KMnO
4Add after above-mentioned mixed solution continues to stir 2h, continue stirring 30min in the warm water bath in moving into 35 ℃, 460ml zero(ppm) water is slowly added in the reaction system, place 98 ℃ of oil baths to be incubated 15min then, add 1400ml warm water afterwards, add 100ml 30%H again
2O
2, product is centrifugal, and with 2L 5%HCl solution washing, water is washed till PH ≈ 5 again, and drying obtains graphite oxide.
Adopt ultra-sonic oscillation that the 120mg graphite oxide is scattered in the 150ml water; Be illustrated in figure 1 as the ultraviolet-visible spectrum of this graphite oxide solution; Graphite oxide solution has a characteristic peak at wavelength 230nm place, and a characteristic peak is arranged about 300nm, and hence one can see that, and graphite oxide successfully prepares.
The employed graphite oxide of following examples prepares by present embodiment.
Embodiment 2
1, adopts ultra-sonic oscillation that the 120mg graphite oxide is scattered in the 120ml water, obtain colloid;
2, in the colloid that step 1 obtains, add 655mg zinc powder and 30ml 2.0mol/L hydrochloric acid successively, room temperature reaction finishes reaction after 6 hours, and the mixture that reaction is obtained filters, washing, and drying obtains Graphene.
1, adopts ultra-sonic oscillation that the 120mg graphite oxide is scattered in the 120ml water, obtain colloid;
2, in the colloid that step 1 obtains, add 658mg zinc powder and 30ml 2.0mol/L hydrochloric acid successively, finish reaction after 6 hours 60 ℃ of reactions, the mixture that reaction is obtained filters, washing, and drying obtains Graphene.
Embodiment 4
1, adopts ultra-sonic oscillation that the 120mg graphite oxide is scattered in the 120ml water, obtain colloid;
2, in the colloid that step 1 obtains, add 662mg zinc powder and 30ml 2.0mol/L hydrochloric acid successively, finish reaction after 6 hours 80 ℃ of reactions, the mixture that reaction is obtained filters, washing, and drying obtains Graphene.
Embodiment 5
1, adopts ultra-sonic oscillation that the 120mg graphite oxide is scattered in the 120ml water, obtain colloid;
2, in the colloid that step 1 obtains, add 658mg zinc powder and 30ml 2.0mol/L hydrochloric acid successively, 100 ℃ of reactions finish reaction after 6 hours, and the mixture that reaction is obtained filters, washing, and drying obtains Graphene.
Embodiment 6
1, adopts ultra-sonic oscillation that the 120mg graphite oxide is scattered in the 150ml water, obtain colloid;
2, in the colloid that step 1 obtains, add 654mg zinc powder and 4.8g NaOH successively, finish reaction after 6 hours in the room temperature isothermal reaction, the mixture that reaction is obtained filters, and washs with hydrochloric acid and water successively, and drying obtains Graphene.
Embodiment 7
1, adopts ultra-sonic oscillation that the 120mg graphite oxide is scattered in the 150ml water, obtain colloid;
2, in the colloid that step 1 obtains, add 655mg zinc powder and 4.8g NaOH successively, finish reaction after 6 hours 60 ℃ of isothermal reactions, the mixture that reaction is obtained filters, and washs with hydrochloric acid and water successively, and drying obtains Graphene.
Embodiment 8
1, adopts ultra-sonic oscillation that the 120mg graphite oxide is scattered in the 150ml water, obtain colloid;
2, in the colloid that step 1 obtains, add 655mg zinc powder and 4.8g NaOH successively, finish reaction after 6 hours 80 ℃ of isothermal reactions, the mixture that reaction is obtained filters, and washs with hydrochloric acid and water successively, and drying obtains Graphene.
Embodiment 9
1, adopts ultra-sonic oscillation that the 120mg graphite oxide is scattered in the 150ml water, obtain colloid;
2, in the colloid that step 1 obtains, add 655mg zinc powder and 4.8g NaOH successively, finish reaction after 6 hours 100 ℃ of isothermal reactions, the mixture that reaction is obtained filters, and washs with hydrochloric acid and water successively, and drying obtains Graphene.
Get the graphene powder of embodiment 2～5 preparations respectively, numbering is followed successively by a, b, c, d, gets the graphene powder of embodiment 6～9 preparations, and numbering is followed successively by e, f, g, h; Above-mentioned materials is carried out X-ray powder diffraction analysis, IR spectroscopy and quantitative elemental analysis successively, and analytical results is following:
[XRD powder diffraction analysis]
Like Fig. 2 is the XRD figure of a, b, c, d, from figure, can see, along with the rising of temperature, the 2 θ=11.8 ° diffraction peak that (corresponding d=0.75nm) locates dies down completely dissolve when temperature is 100 ℃ gradually; And ° diffraction peak that (corresponding d=0.38nm) locates strengthens gradually in 2 θ=23.5, when temperature is 100 ℃, arrives extreme value.Fig. 3 is e, f, and g, the XRD figure of h, temperature is increased to by room temperature in 100 ℃ the process, and diffraction peak ° is located all not have in 2 θ=11.8, has only unimodal that 2 θ=23.5 ° locate.Because the interlayer of graphite oxide contains functional groups such as carbonyl, epoxy group(ing), interlamellar spacing can reach 0.60～0.90nm, be reduced into Graphene after, interlayer functional group disappears, interlamellar spacing is reduced into about 0.30nm.Can explain in conjunction with XRD figure, under acidic conditions, with the rising of temperature of reaction; The reducing degree of graphite oxide increases, fullest in the time of 100 ℃, and the decidable graphite oxide is reduced to Graphene; And under alkaline condition, room temperature can reach good reduction effect.
[IR spectroscopy]
Fig. 4 is the infrared spectrogram of a, b, c, d, and Fig. 5 is the infrared spectrogram of e, f, g, h.Can find out by a, b, c, d contrast, reduction GO under acidic conditions, temperature is bigger to the influence of reducing degree, and under the room temperature, wave number is at 3430cm
-1, 1614cm
-1The flexible of representation hydroxy almost do not reduce with flexural vibration respectively, and wave number is at 1727cm
-1, 1384cm
-1, 1226cm
-1, 1064cm
-1Represent the C-O stretching vibration of C=O, C-O, C-O-C, alcohol still obviously to exist respectively, the GO reduction not exclusively when room temperature was described; And along with the rising of temperature, in the time of 80 ℃, 3430cm
-1, 1614cm
-1Place's weakened, the flexible and flexural vibration of representation hydroxy reduce respectively, and water-absorbent weakens, and wave number is at 1727cm
-1, 1384cm
-1, 1226cm
-1, 1064cm
-1Absorption peak obviously disappear or reduce; In the time of 100 ℃, absorption intensity continues to weaken, and shows that reducing degree further increases; Through Zn-NaOH and Zn-HCl reduction GO contrast, can find out when Zn-HCl reductive extreme value appears at 100 ℃, and Zn-NaOH can well reduce at normal temperatures, the most thorough 100 ℃ of reduction.
[quantitative elemental analysis]
Test result is listed in table 1:
Table 1 ultimate analysis test result
The result of ultimate analysis shows, shows than raw material GO, a, b, c, d data, under acidic conditions; With the rising of temperature, the GO reduction is more and more abundant, e, f, g, h explanation; Reduction normal temperature just has reduction effect preferably under alkaline condition, and is the most thorough 100 ℃ of reduction.
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be conspicuous concerning those skilled in the art, and defined General Principle can realize under the situation that does not break away from the spirit or scope of the present invention in other embodiments among this paper.Therefore, the present invention will can not be restricted to these embodiment shown in this paper, but will meet and principle disclosed herein and features of novelty the wideest corresponding to scope.
Claims (9)
1. preparation method of graphene comprises:
A), under the condition of ultra-sonic oscillation, graphite oxide is scattered in the water, obtain colloid;
B), under acid or alkaline condition, be that reductive agent reduces said graphite oxide with zinc, obtain Graphene; The weight ratio of said graphite oxide and zinc is 1: (5.5～6.5).
2. preparation method according to claim 1 is characterized in that, said step b) is carried out under alkaline condition, is specially:
B1), in said colloid, adding mol ratio successively is 1: the zinc of (10～15) and alkali obtain Graphene; Said alkali is sodium hydroxide or Pottasium Hydroxide, and the weight ratio of said graphite oxide and zinc is 1: (5.5～6.5).
3. preparation method according to claim 2 is characterized in that, the weight ratio of said sodium hydroxide or Pottasium Hydroxide and graphite oxide is (15～30): 1.
4. preparation method according to claim 2 is characterized in that, the reaction times of said step b1 is 5h～8h.
5. preparation method according to claim 2 is characterized in that, the temperature of reaction of said step b1 is 80 ℃～100 ℃.
6. preparation method according to claim 1 is characterized in that, said step b) is carried out under acidic conditions, is specially:
B2), in said colloid, add zinc and acid solution successively, obtain Graphene; Said acid solution is that concentration is hydrochloric acid or the sulphuric acid soln of 0.5mol/L～2mol/L, and the weight ratio of said graphite oxide and zinc is 1: (5.5～6.5).
7. preparation method according to claim 6 is characterized in that, the weight ratio of HCl in the said hydrochloric acid or sulfuric acid and graphite oxide is (15～50): 1.
8. preparation method according to claim 6 is characterized in that, the reaction times of said step b2 is 5h～8h.
9. preparation method according to claim 1 is characterized in that, the concentration of graphite oxide is 0.8g/L～1.2g/L in the said colloid.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102826540A (en) * | 2012-08-06 | 2012-12-19 | 常州第六元素材料科技股份有限公司 | Preparation method for reduced graphene or graphene film |
| CN103578796A (en) * | 2013-11-15 | 2014-02-12 | 复旦大学 | Preparation method of super-capacitor electrode without adhesives |
| CN103896257A (en) * | 2012-12-26 | 2014-07-02 | 海洋王照明科技股份有限公司 | Preparation method for graphene |
| CN107611392A (en) * | 2017-09-07 | 2018-01-19 | 南京汉尔斯生物科技有限公司 | A kind of graphene composite material for improving lithium polymer battery mechanical strength |
| WO2018084694A1 (en) * | 2016-11-03 | 2018-05-11 | Karex Holdings Sdn Bhd. | Polyisoprene latex graphene composites and methods of making them |
| CN115650214A (en) * | 2022-10-15 | 2023-01-31 | 四川大学 | Low-energy-consumption extremely-fast efficient graphene oxide reduction method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006320853A (en) * | 2005-05-20 | 2006-11-30 | Hitachi Powdered Metals Co Ltd | Graphite-based hydrogen storage material and its manufacturing method |
| CN101857222A (en) * | 2010-05-28 | 2010-10-13 | 常州大学 | Preparation method of large-area and continuous graphen/zinc oxide composite structure |
| CN101864098A (en) * | 2010-06-03 | 2010-10-20 | 四川大学 | Preparation method of polymer/graphene composite material through in situ reduction |
| CN102040217A (en) * | 2009-10-26 | 2011-05-04 | 国家纳米科学中心 | Method for preparing graphene |
| JP2011105569A (en) * | 2009-11-20 | 2011-06-02 | Fuji Electric Holdings Co Ltd | Method for manufacturing graphene thin film |
-
2011
- 2011-12-12 CN CN201110412972.8A patent/CN102491317B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006320853A (en) * | 2005-05-20 | 2006-11-30 | Hitachi Powdered Metals Co Ltd | Graphite-based hydrogen storage material and its manufacturing method |
| CN102040217A (en) * | 2009-10-26 | 2011-05-04 | 国家纳米科学中心 | Method for preparing graphene |
| JP2011105569A (en) * | 2009-11-20 | 2011-06-02 | Fuji Electric Holdings Co Ltd | Method for manufacturing graphene thin film |
| CN101857222A (en) * | 2010-05-28 | 2010-10-13 | 常州大学 | Preparation method of large-area and continuous graphen/zinc oxide composite structure |
| CN101864098A (en) * | 2010-06-03 | 2010-10-20 | 四川大学 | Preparation method of polymer/graphene composite material through in situ reduction |
Non-Patent Citations (1)
| Title |
|---|
| XIAOGUANG MEI ET. AL.: "Ultrasonication-assisted ultrafast reduction of graphene oxide by zinc powder at room temperature", 《CARBON》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102826540A (en) * | 2012-08-06 | 2012-12-19 | 常州第六元素材料科技股份有限公司 | Preparation method for reduced graphene or graphene film |
| CN102826540B (en) * | 2012-08-06 | 2016-01-13 | 常州第六元素材料科技股份有限公司 | A kind of method preparing reduced graphene or graphene film |
| CN103896257A (en) * | 2012-12-26 | 2014-07-02 | 海洋王照明科技股份有限公司 | Preparation method for graphene |
| CN103578796A (en) * | 2013-11-15 | 2014-02-12 | 复旦大学 | Preparation method of super-capacitor electrode without adhesives |
| WO2018084694A1 (en) * | 2016-11-03 | 2018-05-11 | Karex Holdings Sdn Bhd. | Polyisoprene latex graphene composites and methods of making them |
| US11214664B2 (en) | 2016-11-03 | 2022-01-04 | Karex Holdings Sdn Bhd. | Polyisoprene latex graphene composites and methods of making them |
| US11827765B2 (en) | 2016-11-03 | 2023-11-28 | Karex Holdings Sdn Bhd. | Polyisoprene latex graphene composites and methods of making them |
| CN107611392A (en) * | 2017-09-07 | 2018-01-19 | 南京汉尔斯生物科技有限公司 | A kind of graphene composite material for improving lithium polymer battery mechanical strength |
| CN115650214A (en) * | 2022-10-15 | 2023-01-31 | 四川大学 | Low-energy-consumption extremely-fast efficient graphene oxide reduction method |
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