CN102275896A - Intercalation method for preparing graphite oxide - Google Patents
Intercalation method for preparing graphite oxide Download PDFInfo
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- CN102275896A CN102275896A CN2011101427918A CN201110142791A CN102275896A CN 102275896 A CN102275896 A CN 102275896A CN 2011101427918 A CN2011101427918 A CN 2011101427918A CN 201110142791 A CN201110142791 A CN 201110142791A CN 102275896 A CN102275896 A CN 102275896A
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Abstract
The invention relates to an intercalation method for preparing graphite oxide. The method comprises the following steps of: firstly placing graphite powder in a reaction vessel, and then adding concentrated sulfuric acid and stirring; adding potassium permanganate and stirring; placing the reaction vessel in a water bath of 30-40 DEG C; placing the reaction vessel subjected to water-bath heating reaction into an ice bath, adding deionized water into the reaction vessel and stirring; after ice-bath cooling reaction, continuously adding deionized water into the reaction vessel and stirring; continuously stirring, dropwise adding hydrogen peroxide into the reaction vessel till no bubbles are generated; filtering out insoluble substances in a suspending liquid, washing several times respectively by using diluted hydrochloric acid and deionized water; and leaching the insoluble substances, placing the leached insoluble substances in a vacuum drying oven, and drying for 1-2 days at the room temperature to obtain the graphite oxide. The intercalation method provided by the invention has the advantages of shorter reaction time, higher oxygen intercalation degree, safer synthetic process, suitability for large-scale production and the like.
Description
Technical field
The invention belongs to the graphite oxide preparing technical field, especially a kind of graft process prepares the method for graphite oxide.
Background technology
Prepare the strategic starting point that graphite oxide is considered to extensive synthesizing graphite alkene from graphite, graphite oxide can further be used mechanical means, as ultra-sonic dispersion in pyrolysis expansion or the solvent, the graphene oxide suspension of the accurate two dimension of preparation, increase its mechanical property by surface modification then, and form Graphene through reduction reaction.The method for preparing graphite oxide comparatively commonly used at present mainly contains following several.
Brodie method: at first with the HNO of being fuming
3Handle natural micro powder graphite, use KClO then
3Or KClO
4Be to insert the oxygen agent, the temperature of reaction system need maintain 0 ℃ and then be warming up to 60～80 ℃ earlier, constantly stirring reaction 20～24h.Subsequently reactant is had high input in the water gaging, filters, be washed to filtrate near neutrality after, drying obtains graphite oxide.The degree of graphitization of the graphite oxide that the washing back obtains is lower, need carry out repeatedly oxide treatment to improve degree of oxidation, and the reaction times is longer relatively, and can obtain chemical constitution after continuous three oxide treatment is C
8O
2.13H
1.60Graphite oxide.The advantage of this method is that its degree can utilize oxidization time to control, and synthetic graphite oxide texture ratio is more regular.But because of adopting KClO
3Or KClO
4Make oxygenant, danger is bigger, and can produce ClO in reaction process
2Deng toxic gas, these gases are blasted under high density easily.
Staudemaier method: at first adopt dense H
2SO
4With the HNO of being fuming
3Mixed system is handled Graphite Powder 99, equally also is with KClO then
3Or KClO
4For inserting the oxygen agent, the temperature of reaction system maintains 0 ℃ always, and degree of oxidation increases with the increase in reaction times, can control the final degree of oxidation of graphite by controlling reaction time.The GO carbon-coating that these class methods obtain destroys serious, its end face also can be introduced a large amount of oxygen-containing functional groups such as carboxyl, and the time of fully reacting is longer, and degree of oxidation is lower, repeatedly oxide treatment need be carried out, just graphite peaks can be do not occurred in the XRD figure of resultant product behind the general oxidation 56h.Also can produce more toxic gas in the reaction process in addition, as Cl
2, ClO
2Deng.
Hummers method: at first with Graphite Powder 99 and anhydrous Na NO
3Join the dense H that places in the ice bath
2SO
4In, powerful then the stirring adds KMnO down
4, reaction process is divided low temperature (below 4 ℃), middle temperature (about 35 ℃) and high temperature (below 98 ℃) reaction three phases.Be 30% H then with volumetric concentration
2O
2Reduce remaining KMnO
4And MnO
2, make its soluble MnSO that becomes colorless
4, under the processing of hydrogen peroxide, suspension becomes glassy yellow.Filter, wash 3 times, vacuum hydro-extraction obtains graphite oxide then.Though this method KMnO
4Replaced KClO
3And KClO
4, improved the security of testing relatively, reduced the generation of toxic gas, but KMnO
4At NaNO
3Enriching H
2SO
4System in improper still being easy to of temperature control blast, and need the technological factor of control more in the reaction process.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, the method that a kind of reaction times is short, graft process that insert that the oxygen degree is higher, synthesis technique is comparatively safe and be suitable for scale operation prepares graphite oxide is provided.
According to technical scheme provided by the invention, the method that described graft process prepares graphite oxide comprises the steps:
A, get Graphite Powder 99 earlier and place reaction vessel, to add weight percentage again in reaction vessel be 98% the vitriol oil and stir, and Graphite Powder 99 satisfies with the add-on of the vitriol oil: the vitriol oil of the corresponding 40～50ml of adding of per 1 gram Graphite Powder 99;
B, adding potassium permanganate and stirring in the reaction vessel of step a, the add-on of potassium permanganate satisfies: per 1 gram Graphite Powder 99 correspondence adds 3～4 potassium permanganate that restrain;
C, the reaction vessel of step b placed 30～40 ℃ water-bath reacting by heating 1～3 hour;
Reaction vessel after d, the heating in water bath for reaction places ice bath, carry out the ice bath hypothermic response, in reaction vessel, add deionized water and stirring, mixing speed is 600～800 rev/mins, carried out hypothermic response 20～40 minutes, the add-on of deionized water satisfies: the corresponding deionized water that adds 40～50ml of per 1 gram Graphite Powder 99;
Behind e, the ice bath hypothermic response, continue to add deionized water and stir in reaction vessel, at this moment, the deionized water add-on satisfies: the corresponding deionized water that adds 80～100ml of per 1 gram Graphite Powder 99;
F, continue to stir, hydrogen peroxide is dropwise joined answering in the container up to there not being bubble to produce of step e, at this moment, the reactant in the reaction vessel can become suspension;
G, the insolubles in the suspension is filtered out by glass core vacuum apparatus, the insolubles that filters out earlier with dilute hydrochloric acid wash some all over after, wash some times with deionized water;
Insolubles after the washing of h, suction filtration deionization behind the suction filtration placed insolubles under the vacuum drying oven room temperature dry 1～2 day, obtained graphite oxide after the vacuum-drying.
The adding speed of potassium permanganate was for evenly adding potassium permanganate among the step b at 15～20 minutes.
The speed control that adds deionized water in the steps d in the reaction vessel makes temperature of reaction system remain on 0～10 ℃.
Method of the present invention have the reaction times short, insert that the oxygen degree is higher, synthesis technique is comparatively safe and be suitable for advantage such as scale operation.
Description of drawings:
Fig. 1 is a process flow sheet of the present invention.
Embodiment
The invention will be further described below in conjunction with specific embodiment.
Embodiment 1
Utilize the sea to reach the method that 100 order crystalline graphite powder graft process prepare graphite oxide and comprise following preparation process:
1, take by weighing the 2g sea and reach 100 order crystalline graphite powders, pour round-bottomed flask into funnel, getting the 100ml weight percentage is that 98% vitriol oil is slowly poured round-bottomed flask into, puts into one then and stirs magneton;
2, setting stirring velocity is 200 rev/mins, takes by weighing 7g potassium permanganate and evenly joins in the clock time in the vitriol oil Graphite Powder 99 solution at 18～20 minutes;
3, round-bottomed flask is dipped in the water bath, bath temperature rises to 35 ℃ of reactions 2 hours, and mixing speed is made as 500 rev/mins;
4, after two hours, round-bottomed flask is changed in the ice bath groove, carried out the ice bath hypothermic response, slowly the 100ml deionized water is joined in the round-bottomed flask, with the dilution vitriol oil, mixing speed is 600～800 rev/mins.
5, temperature no longer rises in flask, can add the 200ml deionized water fast, and at this moment solution colour becomes brown.
6, continue to stir, 30% hydrogen peroxide that with weight percentage is dropwise joins in the round-bottomed flask up to there not being bubble to produce, and at this moment solution can become glassy yellow suspension.
7, by glass core vacuum apparatus the insolubles in the glassy yellow suspension is filtered out, then with earlier being 10% dilute hydrochloric acid, respectively washing the insolubles that filters out twice with the 100ml deionized water again with the 100ml weight percentage.
8, the insolubles after the suction filtration deionization washing was placed the insolubles behind the suction filtration in the vacuum drying oven under the room temperature dry 1～2 day again, obtained 4.1 gram graphite oxides after the vacuum-drying, was C through characterizing the graphite oxide chemical constitution that method with this embodiment prepares gained
8O
3.02H
2.05
Embodiment 2
Utilize the sea to reach the method that 500 order crystalline graphite powder graft process prepare graphite oxide and comprise following preparation process:
1, take by weighing the 2g sea and reach 500 order crystalline graphite powders, pour round-bottomed flask into funnel, getting the 100ml weight percentage is that 98% vitriol oil is slowly poured round-bottomed flask into, puts into one then and stirs magneton;
2, setting stirring velocity is 200 rev/mins, takes by weighing 7g potassium permanganate and evenly joins in 15～16 minutes in the vitriol oil Graphite Powder 99 solution;
3, round-bottomed flask is dipped in the water bath, bath temperature rises to 35 ℃ of reactions 2 hours, and mixing speed is made as 500 rev/mins;
4, after two hours, round-bottomed flask is changed in the ice bath groove, carried out the ice bath hypothermic response, slowly the 100ml deionized water is joined in the round-bottomed flask, with the dilution vitriol oil, mixing speed is 600～800 rev/mins.
5, temperature no longer rises in flask, can add the 200ml deionized water fast, and at this moment solution colour becomes brown.
6, continue stirring, is that 30% hydrogen peroxide dropwise joins in the round-bottomed flask up to there not being bubble to produce with weight percentage, and at this moment solution can become glassy yellow suspension.
7, by glass core vacuum apparatus the insolubles in the glassy yellow suspension is filtered out, then earlier with the 100ml weight percentage be 10% dilute hydrochloric acid wash twice, wash twice with the 100ml deionization again.
8, the insolubles after the suction filtration deionization washing was placed the insolubles behind the suction filtration in the vacuum drying oven under the room temperature dry 1～2 day again, obtained 4.2 gram graphite oxides after the vacuum-drying, was C through characterizing the graphite oxide chemical constitution that method with this embodiment prepares gained
8O
3.05H
2.20
Embodiment 3
Utilize the sea to reach the method that 100 order crystalline graphite powder intercalations obtain graphite oxide, comprise following preparation process:
1, take by weighing the 25g sea and reach 100 order crystalline graphite powders, pour round-bottomed flask into funnel, getting the 1000ml weight percentage is that 98% vitriol oil is slowly poured round-bottomed flask into, puts into one then and stirs magneton;
2, setting stirring velocity is 200 rev/mins, takes by weighing 87.5g potassium permanganate and evenly joins in 16～18 minutes in the vitriol oil Graphite Powder 99 solution;
3, round-bottomed flask is dipped in the water bath, bath temperature rises to 35 ℃ of reactions 2 hours, and mixing speed is made as 500 rev/mins;
4, after two hours, round-bottomed flask is changed in the ice bath groove, carried out the ice bath hypothermic response, slowly the 1000ml deionized water is joined in the round-bottomed flask, with the dilution vitriol oil, mixing speed is 600-800 rev/min.
5, temperature no longer rises in flask, can add the 2000ml deionized water fast, and at this moment solution colour becomes brown.
6, continue stirring, is that 30% hydrogen peroxide dropwise joins in the round-bottomed flask up to there not being bubble to produce with weight percentage, and at this moment solution can become glassy yellow suspension.
7, by glass core vacuum apparatus the graphite oxide in the glassy yellow suspension is filtered out, then earlier with the 3000ml weight percentage be 10% dilute hydrochloric acid wash twice, wash twice with the 3000ml deionization again.
8, the insolubles after the suction filtration deionization washing was placed the insolubles behind the suction filtration in the vacuum drying oven under the room temperature dry 1～2 day again, obtained 49.6 gram graphite oxides after the vacuum-drying, was C through characterizing the graphite oxide chemical constitution that method with this embodiment prepares gained
8O
2.89H
2.0
Embodiment 4
Utilize the sea to reach the method that 500 order crystalline graphite powder intercalations obtain graphite oxide and comprise following preparation process:
1, take by weighing the 25g sea and reach 500 order crystalline graphite powders, pour round-bottomed flask into funnel, getting the 1000ml weight percentage is that 98% vitriol oil is slowly poured round-bottomed flask into, puts into one then and stirs magneton;
2, setting stirring velocity is 200 rev/mins, takes by weighing 87.5g potassium permanganate, progressively joins in 20 minutes in the vitriol oil Graphite Powder 99 solution;
3, round-bottomed flask is dipped in the water bath, bath temperature rises to 35 ℃ of reactions 2 hours, and mixing speed is made as 500 rev/mins;
4, after two hours, round-bottomed flask is changed in the ice bath groove, carry out the ice bath hypothermic response, slowly the 1000ml deionized water is joined in the round-bottomed flask, with the dilution vitriol oil, the speed control that adds deionized water makes temperature of reaction system remain on 5～6 ℃, and mixing speed is 600～800 rev/mins.
5, temperature no longer rises in flask, can add the 2000ml deionized water fast, and at this moment solution colour becomes brown.
6, continue stirring, is that 30% hydrogen peroxide dropwise joins in the round-bottomed flask up to there not being bubble to produce with weight percentage, and at this moment solution can become glassy yellow suspension.
7, by glass core vacuum apparatus the graphite oxide in the glassy yellow suspension is filtered out, then earlier with the 3000ml weight percentage be 10% dilute hydrochloric acid wash twice, wash twice with the 3000ml deionization again.
8, the insolubles after the suction filtration deionization washing was placed the insolubles behind the suction filtration in the vacuum drying oven under the room temperature dry 1～2 day again, obtained 50.3 gram graphite oxides after the vacuum-drying, was C through characterizing the graphite oxide chemical constitution that method with this embodiment prepares gained
8O
3.08H
2.18
Embodiment 5
Utilize the sea to reach the method that 100 order crystalline graphite powder graft process prepare graphite oxide and comprise following preparation process:
1, gets Graphite Powder 99 2 gram earlier and place round-bottomed flask, in round-bottomed flask, add the 90ml weight percentage again and be 98% the vitriol oil, put into one then and stir magneton and stir;
2, setting stirring velocity is 200 rev/mins, takes by weighing 6 gram potassium permanganate, progressively joins in 20 minutes in the vitriol oil Graphite Powder 99 solution;
3, round-bottomed flask is dipped in the water bath, bath temperature rises to 40 ℃ of reactions 1 hour, and mixing speed is made as 500 rev/mins;
4, round-bottomed flask is changed in the ice bath groove, carry out the ice bath hypothermic response, slowly the 90ml deionized water is joined in the round-bottomed flask, with the dilution vitriol oil, the speed control that adds deionized water makes temperature of reaction system remain on 0～2 ℃, and mixing speed is 600～800 rev/mins, hypothermic response 20～40 minutes, temperature no longer rises in the hypothermic response, round-bottomed flask;
5, continue in round-bottomed flask, to add the deionized water of 180ml and stir;
6, continue stirring, is that 30% hydrogen peroxide dropwise joins in the round-bottomed flask up to there not being bubble to produce with weight percentage, and at this moment solution can become glassy yellow suspension;
7, by glass core vacuum apparatus the insolubles in the suspension is filtered out, the insolubles that filters out is washed 2 times with dilute hydrochloric acid earlier, after dilute hydrochloric acid is washed, washes 2 times with deionized water;
8, the insolubles after the suction filtration deionization washing behind the suction filtration placed insolubles under the vacuum drying oven room temperature dry 1～2 day, obtained 4.08 gram graphite oxides after the vacuum-drying, was C through characterizing the graphite oxide chemical constitution that method with this embodiment prepares gained
8O
3.0H
2.15
Embodiment 6
Utilize the sea to reach the method that 100 order crystalline graphite powder graft process prepare graphite oxide and comprise following preparation process:
1, gets Graphite Powder 99 2 gram earlier and place round-bottomed flask, in round-bottomed flask, add the 90ml weight percentage again and be 98% the vitriol oil, put into one then and stir magneton and stir;
2, setting stirring velocity is 200 rev/mins, takes by weighing 8 gram potassium permanganate, progressively joins in 20 minutes in the vitriol oil Graphite Powder 99 solution;
3, round-bottomed flask is dipped in the water bath, bath temperature rises to 30 ℃ of reactions 3 hours, and mixing speed is made as 500 rev/mins;
4, round-bottomed flask is changed in the ice bath groove, carry out the ice bath hypothermic response, slowly the 90ml deionized water is joined in the round-bottomed flask, with the dilution vitriol oil, the speed control that adds deionized water makes temperature of reaction system remain on 8～10 ℃, and mixing speed is 600～800 rev/mins, hypothermic response 20～40 minutes, temperature no longer rises in the hypothermic response, round-bottomed flask;
5, continue in round-bottomed flask, to add the deionized water of 180ml and stir;
6, continue stirring, is that 30% hydrogen peroxide dropwise joins in the round-bottomed flask up to there not being bubble to produce with weight percentage, and at this moment solution can become glassy yellow suspension;
7, by glass core vacuum apparatus the insolubles in the suspension is filtered out, the insolubles that filters out is washed 2 times with dilute hydrochloric acid earlier, after dilute hydrochloric acid is washed, washes 2 times with deionized water;
8, the insolubles after the suction filtration deionization washing behind the suction filtration placed insolubles under the vacuum drying oven room temperature dry 1～2 day, obtained 4.15 gram graphite oxides after the vacuum-drying, was C through characterizing the graphite oxide chemical constitution that method with this embodiment prepares gained
8O
2.98H
2.07
As can be seen from the above embodiments, the graphite oxide weight that obtains is about the twice of Graphite Powder 99 raw material weight, is C through sign with the graphite oxide chemical constitution that this method prepares gained
8O
2.98～3.05H
2.05～2.20, illustrated that it is higher that method of the present invention is inserted the oxygen degree.
Claims (3)
1. a graft process prepares the method for graphite oxide, it is characterized in that this method comprises the steps:
A, get Graphite Powder 99 earlier and place reaction vessel, to add weight percentage again in reaction vessel be 98% the vitriol oil and stir, and Graphite Powder 99 satisfies with the add-on of the vitriol oil: the vitriol oil of the corresponding 40～50ml of adding of per 1 gram Graphite Powder 99;
B, adding potassium permanganate and stirring in the reaction vessel of step a, the add-on of potassium permanganate satisfies: per 1 gram Graphite Powder 99 correspondence adds 3～4 potassium permanganate that restrain;
C, the reaction vessel of step b placed 30～40 ℃ water-bath reacting by heating 1～3 hour;
Reaction vessel after d, the heating in water bath for reaction places ice bath, carry out the ice bath hypothermic response, in reaction vessel, add deionized water and stirring, mixing speed is 600～800 rev/mins, hypothermic response 20～40 minutes, the add-on of deionized water satisfies: the corresponding deionized water that adds 40～50ml of per 1 gram Graphite Powder 99;
Behind e, the ice bath hypothermic response, continue to add deionized water and stir in reaction vessel, at this moment, the deionized water add-on satisfies: the corresponding deionized water that adds 80～100ml of per 1 gram Graphite Powder 99;
F, continue to stir, hydrogen peroxide is dropwise joined in the reaction vessel of step e up to there not being bubble to produce, at this moment, the reactant in the reaction vessel can become suspension;
G, the insolubles in the suspension is filtered out by glass core vacuum apparatus, the insolubles that filters out earlier with dilute hydrochloric acid wash some all over after, respectively wash some times with deionized water;
Insolubles after the washing of h, suction filtration deionization behind the suction filtration placed insolubles under the vacuum drying oven room temperature dry 1～2 day, obtained graphite oxide after the vacuum-drying.
2. graft process as claimed in claim 1 prepares the method for graphite oxide, it is characterized in that: the adding speed of potassium permanganate was for evenly adding potassium permanganate among the step b at 15～20 minutes.
3. graft process as claimed in claim 1 prepares the method for graphite oxide, it is characterized in that: the speed control that adds deionized water in the steps d in the reaction vessel makes temperature of reaction system remain on 0～10 ℃.
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| CN102581295A (en) * | 2012-01-10 | 2012-07-18 | 黑龙江大学 | Method of using liquid-phase reduction method to prepare nano copper powder loaded graphene |
| CN102745684A (en) * | 2012-07-24 | 2012-10-24 | 南京理工大学 | Biologic graphite oxide obtained by nutrifying bacteria and preparation method for biologic graphite oxide |
| CN102745683A (en) * | 2012-07-24 | 2012-10-24 | 南京理工大学 | Biological oxidation graphite and preparation method thereof |
| CN102974838A (en) * | 2012-11-30 | 2013-03-20 | 黑龙江大学 | Method for preparing graphene loaded nano nickel composite powder material by hydrothermal method |
| CN104773721A (en) * | 2015-04-01 | 2015-07-15 | 广东烛光新能源科技有限公司 | Preparation method of graphene |
| CN107603480A (en) * | 2017-07-31 | 2018-01-19 | 常州建轩纺织品有限公司 | A kind of preparation method of Salt And Alkali Tolerance anticorrosion high polymer material |
| CN109476487A (en) * | 2016-06-24 | 2019-03-15 | 加利福尼亚大学董事会 | Carbon-based oxides and the large-scale production for restoring carbon-based oxides |
| US11397173B2 (en) | 2011-12-21 | 2022-07-26 | The Regents Of The University Of California | Interconnected corrugated carbon-based network |
| US11569538B2 (en) | 2014-06-16 | 2023-01-31 | The Regents Of The University Of California | Hybrid electrochemical cell |
| US11791453B2 (en) | 2016-08-31 | 2023-10-17 | The Regents Of The University Of California | Devices comprising carbon-based material and fabrication thereof |
| US11810716B2 (en) | 2014-11-18 | 2023-11-07 | The Regents Of The University Of California | Porous interconnected corrugated carbon-based network (ICCN) composite |
| US11842850B2 (en) | 2016-01-22 | 2023-12-12 | The Regents Of The University Of California | High-voltage devices |
| US11891539B2 (en) | 2015-12-22 | 2024-02-06 | The Regents Of The University Of California | Cellular graphene films |
| US11915870B2 (en) | 2012-03-05 | 2024-02-27 | The Regents Of The University Of California | Capacitor with electrodes made of an interconnected corrugated carbon-based network |
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| CN102581295A (en) * | 2012-01-10 | 2012-07-18 | 黑龙江大学 | Method of using liquid-phase reduction method to prepare nano copper powder loaded graphene |
| US11915870B2 (en) | 2012-03-05 | 2024-02-27 | The Regents Of The University Of California | Capacitor with electrodes made of an interconnected corrugated carbon-based network |
| CN102745684B (en) * | 2012-07-24 | 2013-09-11 | 南京理工大学 | Biologic graphite oxide obtained by nutrifying bacteria and preparation method for biologic graphite oxide |
| CN102745683B (en) * | 2012-07-24 | 2013-09-25 | 南京理工大学 | Biological oxidation graphite and preparation method thereof |
| CN102745683A (en) * | 2012-07-24 | 2012-10-24 | 南京理工大学 | Biological oxidation graphite and preparation method thereof |
| CN102745684A (en) * | 2012-07-24 | 2012-10-24 | 南京理工大学 | Biologic graphite oxide obtained by nutrifying bacteria and preparation method for biologic graphite oxide |
| CN102974838A (en) * | 2012-11-30 | 2013-03-20 | 黑龙江大学 | Method for preparing graphene loaded nano nickel composite powder material by hydrothermal method |
| CN102974838B (en) * | 2012-11-30 | 2015-06-10 | 黑龙江大学 | Method for preparing graphene loaded nano nickel composite powder material by hydrothermal method |
| US11569538B2 (en) | 2014-06-16 | 2023-01-31 | The Regents Of The University Of California | Hybrid electrochemical cell |
| US11810716B2 (en) | 2014-11-18 | 2023-11-07 | The Regents Of The University Of California | Porous interconnected corrugated carbon-based network (ICCN) composite |
| CN104773721A (en) * | 2015-04-01 | 2015-07-15 | 广东烛光新能源科技有限公司 | Preparation method of graphene |
| US11891539B2 (en) | 2015-12-22 | 2024-02-06 | The Regents Of The University Of California | Cellular graphene films |
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| CN109476487A (en) * | 2016-06-24 | 2019-03-15 | 加利福尼亚大学董事会 | Carbon-based oxides and the large-scale production for restoring carbon-based oxides |
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