CN101993065B - Method for preparing graphene powder - Google Patents
Method for preparing graphene powder Download PDFInfo
- Publication number
- CN101993065B CN101993065B CN201010593157A CN201010593157A CN101993065B CN 101993065 B CN101993065 B CN 101993065B CN 201010593157 A CN201010593157 A CN 201010593157A CN 201010593157 A CN201010593157 A CN 201010593157A CN 101993065 B CN101993065 B CN 101993065B
- Authority
- CN
- China
- Prior art keywords
- graphene
- powder
- graphene oxide
- spray
- drying
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 169
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 138
- 238000000034 method Methods 0.000 title claims abstract description 69
- 239000000843 powder Substances 0.000 title claims abstract description 65
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000010438 heat treatment Methods 0.000 claims abstract description 26
- 239000000725 suspension Substances 0.000 claims abstract description 19
- 238000004108 freeze drying Methods 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000007921 spray Substances 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 238000005054 agglomeration Methods 0.000 claims abstract description 11
- 230000002776 aggregation Effects 0.000 claims abstract description 11
- 238000005118 spray pyrolysis Methods 0.000 claims abstract description 9
- 238000005516 engineering process Methods 0.000 claims abstract description 8
- 238000001694 spray drying Methods 0.000 claims abstract description 7
- 230000001590 oxidative effect Effects 0.000 claims abstract description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 29
- 239000010439 graphite Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000011324 bead Substances 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 5
- 238000009830 intercalation Methods 0.000 claims description 5
- 230000002687 intercalation Effects 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000003595 mist Substances 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 17
- 238000002360 preparation method Methods 0.000 abstract description 16
- 239000002131 composite material Substances 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003063 flame retardant Substances 0.000 abstract description 2
- 239000013067 intermediate product Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 46
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000010410 layer Substances 0.000 description 6
- 239000002086 nanomaterial Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 238000001132 ultrasonic dispersion Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000007669 thermal treatment Methods 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000000859 sublimation Methods 0.000 description 3
- 230000008022 sublimation Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000013332 literature search Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- -1 sodium halide Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Images
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a method for preparing graphene powder in large scale, which is characterized by comprising the following steps of: firstly, uniformly peeling graphene oxide into a graphene oxide suspension solution; then, atomizing the graphene oxide solution by using the spray drying technology comprising spray pyrolysis drying and spray freeze drying, and removing a solvent to obtain graphene oxide powder; and finally, oxidizing grapheme by using the non-expansion heat treatment process to obtain non-agglomerative graphene powder. The continuous preparation process of the spray technology and the non-expansion heat treatment process ensure the large-scale preparation of the graphene powder. The prepared graphene powder comprising intermediate product graphene oxide powder does not have agglomeration and has good dispersivity in the solvent. The graphene powder is used as a filling material to prepare high strength composite materials, conductive composite materials, novel air-tight flame-retardant composite materials, novel nanodevices and the like.
Description
Technical Field
The invention relates to a method for preparing graphene powder on a large scale, and belongs to the technical field of novel nano materials.
Background
The graphene has excellent electric conduction and heat conduction performance, ultrahigh mechanical strength, unique gas resistance, high specific surface area and surface activity, so that the graphene can be a new-generation functional material beyond a carbon nano tube. The graphene powder can be used as a polymer filler to improve the conductivity of the composite material, so that the graphene powder can be used for antistatic polymers and can also be used for the important industries of the countries such as the electric shielding of wires and cables; the graphene powder as a polymer additive can improve the mechanical strength of a polymer system by hundreds of times, for example, graphene is uniformly dispersed in polyphenylene sulfide, and the polyphenylene sulfide can be used for aircraft manufacturing, so that a graphene powder material can be added into a large aircraft in the future. In view of the huge usage amount of polymer materials in industrial and civil applications, with the continuous development of graphene in different polymers, the demand of graphene will increase in the next few years.
Like other nano materials, the large-scale preparation of the nano material is a key factor for restricting the application and research of the nano material. At present, the price of high-quality graphene powder is $ 1000 per gram, which is more than ten times of the gold price, and the price is a fatal strike for the application research in the industry. The patent and literature search shows that the vast majority of related technologies at home and abroad are to prepare graphene solution, and then obtain blocks by centrifuging or filtering the dispersion in the solution. CN200910193873.8, a method for producing graphene, discloses a method for producing graphene, in which graphite powder is ball-milled by a wet method in an organic solvent; the surface of a grinding ball used for wet ball milling is wrapped with a soft polymer, and the friction force between the soft polymer and graphite is utilized to improve the grinding and stripping effect, but the method has long ball milling time and high energy consumption, and the ball milling product is required to be subjected to complex separation. CN201010179119.1 method for preparing graphene or graphene oxide by high efficiency and low cost mechanical stripping adopts a similar method. CN 200910077131.9 "preparation method of graphene" uses metal sodium and halogenated hydrocarbon as raw materials, and prepares graphene by reacting in a solvent under an inert environment, and there are also reports in literature that graphene is realized by reacting potassium with an organic solvent, and the greatest disadvantage of this preparation route is that chemical properties such as sodium halide and potassium are active, and there is a great risk in storage and preparation processes, and at the same time, the preparation process is difficult to control, so that it is difficult to realize high-yield single-layer graphene. CN200910052042.9 method for preparing graphene-based nanomaterial by electron beam irradiation reduces graphite oxide by using a certain dose of electron beam irradiation to obtain graphene nanomaterial, but graphene is agglomerated in the reduction process, and after drying, the graphene needs to be ground to be converted into powder, and the powder is also agglomerated microscopically. Other methods, such as patent 200910050318.X "a method for preparing single-layer graphene simply and without toxicity", 200910054919.8 "a method for preparing graphene based on ascorbic acid", 200910099595.X "a method for preparing solution phase of graphene", 200910017788.6 "a method for preparing functional nano-graphene", 200910070735.0 "a method for preparing single-layer graphene", and the like, obtain a graphene solution or aggregate, and it is very difficult to uniformly disperse the aggregated graphene flakes having a thickness of only one atomic layer. One of the more currently reported methods is the rapid thermal processing Graphene oxide method, which was published in 2010 on Small for a review of Graphene oxide, high purity reduced Graphene oxide, and Graphene: versatile building blocks for carbon-based materials only mentions that processing graphene oxide at 1050 ℃ at a heating rate of more than 2000 ℃/min is a main method for preparing graphene powder, and CN200880101275.7, a high-efficiency method for preparing layered exfoliated graphene, directly obtains graphene with a large specific surface area by exfoliating graphite oxide through rapid thermal treatment, but due to the defects of small treatment amount, uneven heating and the like in the rapid thermal treatment process, the finally prepared powder has a high specific surface area but serious agglomeration on a microscopic scale. Another disadvantage of this method is that the rapid expansion of 200 to 500 times the volume makes the process difficult to control and the product difficult to collect. CN201010179339.4 "a method for preparing dry graphene powder", firstly, graphene is prepared into a suspension, and then freeze-dried into a powder. This freeze-drying technique can produce dry powder, but it is time-consuming, and the graphene sheets are connected to each other during the freeze-drying process and need to be re-dispersed.
In conclusion, the existing method for preparing graphene in a micro-scale manner in a laboratory is generally realized by a centrifugation or suction filtration method, and the prepared product is difficult to be uniformly dispersed in a solvent again. There are also areas where improvements in rapid heat treatment processes and freeze drying processes are needed. At present, no simple method for preparing the non-agglomerated graphene powder in a large scale is reported.
Disclosure of Invention
The invention provides a method for preparing graphene powder on a large scale aiming at the defects of the prior art explained in the technical background, which thoroughly solves the agglomeration problem of the graphene powder prepared in the prior art, so that the prepared graphene powder is easily dispersed in a solvent, and the method can realize the large-scale preparation of the graphene powder.
A method for preparing graphene powder in a large scale comprises the following steps: firstly, uniformly stripping graphite oxide into a stable graphene oxide suspension solution; secondly, atomizing the graphene oxide solution prepared in the first step by using a spray drying technology including spray pyrolysis drying and spray freeze drying, and removing a solvent to obtain graphene oxide; and thirdly, under the protection of inert or reducing atmosphere, carrying out expansion-free heat treatment on the graphene oxide to obtain graphene powder.
The graphene oxide has a thickness of a single or several atomic layers, and a characteristic length or width dimension of 500 nanometers to 100 micrometers.
The non-expansion heat treatment refers to that the temperature is gradually increased to a set value, the temperature rise rate is less than 50 ℃/second, and the method is not a method for preparing graphene by rapidly processing graphene oxide reported at present. The problems of dust and difficulty in collection caused by the fact that the volume is rapidly expanded to 200-500 times in the rapid heat treatment process are solved.
In the first step of the preparation method, firstly, the graphite oxide is obtained by carrying out oxidation intercalation on crystalline flake graphite, highly oriented pyrolytic graphite and the like. The oxidative intercalation process may be a Brodie process, Staudenmaier process or Hummers process. Intercalation is realized between each atomic layer, namely first-order intercalation;
and secondly, the method is characterized in that the graphite oxide prepared in the first step is stripped into single or several atomic layers of graphene oxide, so that the prepared graphene oxide is uniformly dispersed and forms a stable suspension solution without any precipitate. The solvent can be water or organic solvent, such as ethanol, acetone, dimethylformamide, ethylene glycol, N-methylpyrrolidone, tetrahydrofuran, or dispersant, such as common surfactant, sodium p-styrene sulfonate, ammonia water, sodium chloride, sodium carbonate, potassium hydroxide, sodium hydroxide, ammonium carbonate, etc.;
③ the concentration of the formed stable graphene oxide suspension is 0.1mg/ml to 2 mg/ml.
In the second step of the preparation method, the spray drying technique includes spray pyrolysis drying and spray freeze drying;
the spray drying equipment comprises spray pyrolysis drying equipment and spray freeze drying equipment, or any similar equipment with the same working principle;
and thirdly, spray pyrolysis drying, namely spraying the graphene oxide suspension solution prepared in the step 1 into fine vaporous liquid beads, and drying the graphene oxide suspension solution into graphene oxide powder in a few seconds by contacting with hot air. Collecting the powder from the bottom of the drying tower and a cyclone separator; the typical air inlet temperature is 150 ℃ and 250 ℃;
and fourthly, spray freeze drying, namely spraying the graphene oxide suspension solution into fine mist liquid beads, contacting with cold air to form fine ice blocks containing graphene oxide sheets, and collecting powder through a freeze drying method. Typical inlet temperatures are-40 ℃ to-10 ℃.
The spraying rate can be 50ml to 5L per hour according to different equipment. The use of industrial equipment can reach 500L per hour or even higher.
In the third step of the preparation method, typical reducing atmosphere is hydrogen and ammonia, and typical inert atmosphere is nitrogen, argon and the like. But are not limited to these gases.
② the heat treatment temperature is 500-1200 ℃.
And the heat treatment time is 30 seconds to 2 hours.
According to the method for preparing the graphene powder, the obtained graphene is powder without agglomeration, and is not a block or a solution.
According to the method for preparing the graphene powder, the specific surface area of the obtained graphene is 300-2600 m2The specific surface area increases with the reduction in the number of graphene layers produced.
According to the method for preparing the graphene powder, the obtained graphene can be rapidly dispersed in the solvent, so that no dispersant is required to be added, and the dispersant can be added to ensure that the dispersion is more uniform.
According to the method for preparing the graphene powder, the obtained graphene can be directly compounded with polymers through an internal mixer or an extruder without being crushed or ground.
According to the method for preparing the graphene powder, the continuous production of the graphene oxide powder can be realized through a continuous spraying process.
According to the method for preparing the graphene powder, a large amount of graphene oxide can be subjected to heat treatment at one time to realize large-scale preparation of graphene, the requirement of rapid expansion stripping of the graphene oxide through rapid heat treatment is not met in the aspect of graphene oxide heat treatment, the problem that the powder is difficult to collect due to rapid expansion and dispersion is also solved, and the amount of heat treatment capable of being performed at one time is only limited by the size of heat treatment equipment.
The present invention solves two key problems: the first key problem is to realize the graphene powder without agglomeration, and the graphene powder also comprises an intermediate product graphene oxide powder. In the spray pyrolysis drying process, the rapid gasification of the solvent is utilized to effectively prevent the graphene oxide flakes from agglomerating. In the spray freeze drying process, the liquid drop containing the graphene oxide is rapidly frozen to form solid powder in a short time, and the graphene oxide powder is obtained along with sublimation of the solvent, compared with the method for preparing the powder by directly using a freeze-drying technology, the method has the advantages that macroscopic solution is firstly dispersed into fine particles, the possibility of agglomeration is greatly reduced, the sublimation speed of the solvent is high, the graphene oxide powder is converted into the graphene powder through treatment of reducing gas, and the agglomeration is avoided, see the comparison of experimental results of example 4 and comparative example 2.
The second key problem is that large-scale preparation is realized, the graphene oxide is treated by spray drying in a large amount, a continuous treatment process can be realized, the graphene oxide powder is uninterruptedly prepared, rapid heat treatment is not needed in the heat treatment process of converting the graphene oxide into the graphene, the problems of rapid volume expansion and difficult powder collection of the graphene oxide powder prepared by the conventional rapid heat treatment of the graphene oxide are avoided, 1 to hundreds of grams of graphene oxide powder is converted into the graphene only within a few minutes according to the size of an annealing furnace, and the test results of example 2 and comparative example 1 are compared. The graphene oxide and graphene powder can be directly compounded with a polymer through an internal mixer or an extruder without crushing or grinding to prepare a polymer composite material, can be dispersed in water or an organic solvent and then compounded with other materials, and can also be directly used for sensors, photocatalysis, adsorption, solar cells, nano devices and the like.
The method for preparing the graphene powder in a large scale is suitable for preparing high-strength composite materials, conductive composite materials, novel air-tightness and flame-retardant composite materials, novel nanometer devices and the like by using the graphene powder as a filler.
Drawings
Fig. 1 is a digital photograph of the graphene oxide powder obtained in example 1 dispersed in deionized water;
FIG. 2 is a scanning electron micrograph of the graphene powder obtained in example 1;
fig. 3 is a scanning electron micrograph of the graphene oxide powder obtained in example 2;
FIG. 4 is a scanning electron micrograph of the graphene powder obtained in example 2;
FIG. 5 is a scanning electron micrograph of the graphene oxide powder obtained in example 3;
fig. 6 is a digital photograph of the graphene powder obtained in example 4 dispersed in acetone;
fig. 7 is a scanning electron micrograph of graphene obtained by rapid thermal treatment of comparative example 1;
fig. 8 is a transmission electron micrograph of the graphene oxide powder obtained by freeze-drying in comparative example 2.
Detailed Description
The essential features and the significant advantages of the invention will be further elucidated below by means of specific examples, which are by no means limiting.
Example 1:
the first step is as follows:preparing a graphene oxide solution. By using an improved Hummer method, 69ml of 98% concentrated sulfuric acid is taken, and 1.5g of natural crystalline flake graphite and 1.5g of NaNO are respectively added into the mixture during stirring3Accurately controlling the temperature of the reaction solution at 0 +/-0.5 ℃, and slowly adding 9g of KMnO4Stirring the powder to react for 1 hour, adding 100ml of deionized water, raising the temperature of reactants to 95 +/-1 ℃, and reacting for 30 minutes. The reaction mixture was diluted with deionized water and 10ml of 30% H was added2O2Filtering while the solution is hot, and fully washing the solution by using ionized water until no SO is contained in the filtrate4 2-. Weighing 100mg of graphite oxide in a beaker, adding deionized water to prepare 1000ml of solution, and then carrying out ultrasonic dispersion on the solution for 5 minutes to obtain a stable 0.1mg/ml graphene oxide suspension solution.
The second step is that: using a conventional spray pyrolysis dryer or the like, the inlet temperature was set at 150 ℃, and the liquid ejection rate was 5000ml per hour. The graphene oxide powder can be dispersed in deionized water by stirring, the photograph is shown in fig. 1, and the transparent brown solution is the result of uniform dispersion of graphene oxide.
The third step: raising the temperature of the graphene oxide powder to 500 ℃ under the protection of nitrogen, and keeping the temperature for one minute to obtain the non-agglomerated graphene powder, as shown in fig. 2. The graphene flakes have a size of 0.5 to 10 microns and are naturally rolled into agglomerates due to only one atomic layer, each agglomerate having a size of about 0.5 to 5 microns, with no significant agglomeration between agglomerates.
Example 2:
firstly, preparing a graphene oxide solution. Adding natural crystalline flake graphite into a mixed solution of 98% concentrated sulfuric acid and nitric acid by using an improved Staudenmaier method, adding potassium nitrate by stirring, controlling the temperature of a reaction solution to be 0-10 ℃, stirring a reactant for 6 hours to obtain graphite oxide, filtering and drying to obtain the graphite oxide. Weighing 300mg of graphite oxide in a beaker, adding deionized water to prepare 500ml of solution, adding 2ml of KOH solution with the concentration of 1M, and then carrying out ultrasonic dispersion on the solution for 20 minutes to obtain the stable 0.6mg/ml graphene oxide suspension solution.
The second step is that: a conventional spray dryer or the like was used, the inlet temperature was set at 200 ℃, the liquid discharge rate was 2000ml per hour, and the nozzle diameter was 2 mm. The graphene oxide powder is collected, and a field emission scanning electron microscope test proves that the graphene oxide powder obtained by the preparation technology is free from agglomeration, as shown in fig. 3.
The third step: raising the temperature of the graphene oxide powder to 1000 ℃ under the protection of argon, and keeping the temperature for one minute to obtain the non-agglomerated graphene powder, as shown in fig. 4.
Example 3:
the first step is as follows: the graphene oxide solution was prepared as in case 2. Weighing 1g of graphite oxide in a beaker, adding deionized water to prepare 500ml of solution, adding 10ml of 1M NaOH solution, and then carrying out ultrasonic dispersion on the solution for 60 minutes to obtain a stable graphene oxide suspension solution with the concentration of 2 mg/ml.
The second step is that: using a conventional spray dryer or similar device, the inlet temperature was set at 300 ℃ and the liquid was sprayed out at a rate of 1000ml per hour. The collected graphene oxide powder is tested by a field emission scanning electron microscope to prove that the graphene oxide powder obtained by the preparation technology is not agglomerated, as shown in fig. 5.
The third step: and (3) raising the temperature of the graphene oxide powder to 600 ℃ under the protection of hydrogen gas, and keeping the temperature for one minute to obtain the non-agglomerated graphene powder, wherein the morphology of the non-agglomerated graphene powder is similar to that of the graphene oxide powder shown in the figure 4.
Example 4:
the first step is as follows: the graphene oxide solution was prepared as in case 2. Weighing 1000mg of graphite oxide in a beaker, adding deionized water to prepare 1L of solution, adding 2ml of ammonia water, and then carrying out ultrasonic dispersion on the solution for 1 minute to obtain a stable 0.1mg/ml graphene oxide suspension solution.
The second step is that: using a conventional spray dryer or similar device, the inlet temperature was set at-40 ℃ and the liquid was sprayed out at a rate of 2500ml per hour. And collecting the graphene oxide powder.
The third step: and (3) heating the oxidized graphene powder to 600 ℃ under the protection of ammonia gas, and preserving the heat for one minute to obtain non-agglomerated graphene powder, wherein the morphology of the obtained graphene powder is similar to that of the graphene powder shown in the figures 2 and 4. 1mg was taken and placed in 10ml acetone and dissolved rapidly to form a stable black solution, as shown in FIG. 6.
Example 5: the temperature of the air inlet is set to be minus 20 ℃, and other preparation processes are the same as those of the embodiment 4. The morphology of the obtained graphene powder is similar to that of the graphene powder shown in figures 2 and 3.
Comparative example 1: comparative experiment of graphene obtained by rapid thermal treatment of graphite oxide. Adding natural crystalline flake graphite into a mixed solution of 98% concentrated sulfuric acid and nitric acid by using an improved Staudenmaier method, adding potassium nitrate by stirring, controlling the temperature of a reaction solution to be 0-10 ℃, stirring a reactant for 6 hours to obtain graphite oxide, filtering and drying to obtain the graphite oxide. 300mg of graphite oxide is weighed into a ceramic boat and quickly pushed into a tube furnace at 1000 ℃, and the heat treatment is carried out for 30 seconds under the protection of nitrogen. The results of the sem examination are shown in fig. 7, where the vermicular graphite, i.e., the graphite flakes that were not exfoliated, were still connected together at some locations to form a porous expanded graphite structure.
Comparative example 2: comparative test of the obtained graphene oxide powder by freeze-drying. By using an improved Hummer method, 98% concentrated sulfuric acid is taken, cooled at low temperature, and a certain amount of natural crystalline flake graphite and NaNO are respectively added into the mixture during stirring3And KMnO4Controlling the temperature of the reaction solution to be 0-10 ℃, stirring for 5 hours, then carrying out high-temperature reaction, controlling the temperature of the reaction solution to be within 100 ℃, and continuing stirring for 30 minutes. Diluting the reaction solution with deionized water, and adding a proper amount of H2O2Filtering while the solution is hot, and fully washing the solution by using ionized water until no SO is contained in the filtrate4 2-. Weighing 500mg of graphite oxide in a beaker, adding deionized water to prepare 1000ml of solution, and then carrying out ultrasonic dispersion on the solution for 5 minutes to obtain a stable 0.5mg/ml graphene oxide solution. The solution was frozen in a refrigerator, and graphene oxide powder was obtained using a freeze dryer, and the transmission electron micrograph of the powder is shown in fig. 8. Sublimation of graphene oxide sheets in a monolayer in a freezing process and solventIn the process, partial agglomeration still exists, and the different appearances of the edge and the folds on the surface are proved by mutually overlapping a plurality of pieces of graphene oxide.
Claims (5)
1. A method for preparing graphene powder in a large scale is characterized by comprising the following steps:
a) uniformly stripping graphite oxide into a graphene oxide suspension solution;
b) b, atomizing the suspension solution prepared in the step a by using a spray drying technology, and removing the solvent to obtain graphene oxide powder;
c) under the protection of inert or reducing atmosphere, adopting a non-expansion heat treatment method to treat the graphene oxide powder prepared in the step b to finally prepare non-agglomeration graphene powder;
the spray drying comprises spray pyrolysis drying or spray freeze drying; wherein,
firstly, spray pyrolysis drying is to spray a graphene oxide suspension solution into fine vaporous liquid beads, the liquid beads are contacted with hot air and dried into graphene oxide powder within a few seconds, and the powder is collected by the bottom of a drying tower and a cyclone separator; the temperature of the air inlet is 150 ℃ and 250 ℃;
secondly, spray freeze drying is to spray the graphene oxide suspension solution into fine mist liquid beads, the fine mist liquid beads are contacted with cold air to form fine ice blocks containing graphene oxide sheets, then powder is collected by a freeze drying method, and the temperature of an air inlet is between 40 ℃ below zero and 10 ℃ below zero;
the heating rate of the non-expansion heat treatment is less than 50 ℃/second;
the reducing atmosphere in the non-expansion heat treatment is hydrogen or ammonia, and the inert atmosphere is nitrogen or argon; the temperature of the non-expansion heat treatment is 500-1200 ℃, and the time of the non-expansion heat treatment is 30 seconds to 2 hours.
2. The method of claim 1, wherein the graphite oxide is obtained by oxidative intercalation of crystalline flake graphite or highly oriented pyrolytic graphite.
3. The method of claim 1, wherein the solvent used to form the graphene oxide suspension is water or an organic solvent comprising ethanol, acetone, dimethylformamide, ethylene glycol, N-methylpyrrolidone, tetrahydrofuran.
4. The method of claim 3, wherein the suspension solution has a concentration of 0.1mg/ml to 2 mg/ml; a dispersant is added to the suspension solution.
5. The method of claim 4 wherein the dispersant is a surfactant, sodium p-styrene sulfonate, aqueous ammonia, sodium chloride, sodium carbonate, potassium hydroxide, sodium hydroxide, or ammonium carbonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010593157A CN101993065B (en) | 2010-12-17 | 2010-12-17 | Method for preparing graphene powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010593157A CN101993065B (en) | 2010-12-17 | 2010-12-17 | Method for preparing graphene powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101993065A CN101993065A (en) | 2011-03-30 |
| CN101993065B true CN101993065B (en) | 2012-09-05 |
Family
ID=43783903
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010593157A Active CN101993065B (en) | 2010-12-17 | 2010-12-17 | Method for preparing graphene powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101993065B (en) |
Families Citing this family (50)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102730667B (en) * | 2011-04-08 | 2014-04-09 | 安炬科技股份有限公司 | Method for preparing monolayer graphite |
| CN102757036B (en) * | 2011-04-26 | 2014-07-23 | 海洋王照明科技股份有限公司 | Preparation method of porous graphene |
| CN102305821A (en) * | 2011-05-30 | 2012-01-04 | 江南大学 | Electrochemical sensor electrode with integrated functions of enriching and detecting 1-hydroxypyrene, and preparation method of electrochemical sensor electrode |
| CN102431999B (en) * | 2011-09-22 | 2014-07-02 | 中国科学院金属研究所 | Method for preparing high-quality graphene |
| CN103159208A (en) * | 2011-12-14 | 2013-06-19 | 海洋王照明科技股份有限公司 | Preparation method of graphene |
| CN103387223A (en) * | 2012-05-07 | 2013-11-13 | 海洋王照明科技股份有限公司 | Preparation method of graphite |
| CN102701197A (en) * | 2012-06-27 | 2012-10-03 | 苏州大学 | Preparation method of soluble graphite oxide powder |
| CN102786045B (en) * | 2012-07-27 | 2014-04-09 | 中国航空工业集团公司北京航空材料研究院 | Method for preparing oxidized graphene |
| CN102850543B (en) * | 2012-09-28 | 2014-12-17 | 中国科学院宁波材料技术与工程研究所 | Graphene/conductive polymer composite material and preparation method thereof |
| CN103012953B (en) * | 2012-10-23 | 2015-06-17 | 台州学院 | Flame-retardant polypropylene/graphene/carbon nano tube nanocomposite material and preparation method thereof |
| CN103224229B (en) * | 2013-04-15 | 2015-07-15 | 中国科学院宁波材料技术与工程研究所 | Method for rapid preparation of graphene powder by freezing filtration |
| CN103224230B (en) * | 2013-04-16 | 2017-07-07 | 湖南元素密码石墨烯高科技有限公司 | A kind of preparation method of Graphene |
| CN103204497A (en) * | 2013-04-16 | 2013-07-17 | 中国科学院福建物质结构研究所 | Method for preparing graphene material and application thereof in chemical energy storage and/or conversion |
| CN103253661B (en) * | 2013-05-27 | 2014-10-22 | 中国科学院上海微系统与信息技术研究所 | Method for preparing graphene powder at large scale |
| CN103346022B (en) * | 2013-07-03 | 2016-03-02 | 中国科学院福建物质结构研究所 | A kind of preparation method of graphene/ nanocarbon particle composite |
| CN104356487B (en) * | 2014-11-27 | 2016-06-15 | 上海电缆研究所 | The preparation method of a kind of cable Graphene semi-conductive screen material |
| KR101975033B1 (en) * | 2015-02-13 | 2019-08-23 | 대주전자재료 주식회사 | Graphene having pores made by irregular and random, and Manufacturing method of the same |
| CN105195067B (en) * | 2015-09-15 | 2017-12-15 | 四川大学 | A kind of graphene aerogel microballoon and its production and use |
| CN105271189A (en) * | 2015-09-23 | 2016-01-27 | 东莞市迈科科技有限公司 | Nitrogen doped graphene particle and preparation method thereof |
| CN105742073A (en) * | 2015-12-17 | 2016-07-06 | 中国科学技术大学 | Graphene-based composite and preparation method thereof |
| CN105384164B (en) * | 2015-12-18 | 2018-01-09 | 上海理工大学 | High-specific surface area hierarchical porous structure fold graphene and preparation method thereof |
| CN105621400B (en) * | 2015-12-28 | 2018-03-20 | 成都新柯力化工科技有限公司 | A kind of method that graphene is prepared using carbonate as raw material |
| CN105540573B (en) * | 2016-01-27 | 2017-12-12 | 浙江碳谷上希材料科技有限公司 | A kind of more fold dry state graphene oxide microballoons of highly dissoluble and preparation method thereof |
| CN106082187B (en) * | 2016-06-13 | 2019-03-29 | 南京工业大学 | Functionalized graphene oxide and rapid preparation method for assembly of functionalized graphene oxide |
| CN105967179B (en) * | 2016-06-30 | 2018-11-20 | 常州第六元素材料科技股份有限公司 | A kind of easy dispersed graphite alkene raw powder's production technology and the graphene powder using this method preparation |
| CN106207094B (en) * | 2016-08-01 | 2018-07-03 | 上海银浆科技有限公司 | A kind of lithium battery graphene conductive slurry and preparation method thereof |
| CN106044763B (en) * | 2016-08-08 | 2019-01-01 | 华侨大学 | A method of preparing graphene powder at room temperature |
| CN108117913B (en) * | 2016-11-28 | 2021-05-18 | 中国科学院金属研究所 | Preparation method and application of spherical graphene lubricating additive |
| WO2018110776A1 (en) * | 2016-12-12 | 2018-06-21 | 한국지질자원연구원 | Method for manufacturing crumpled graphene composite, composite manufactured thereby, and supercapacitor including composite |
| CN106602063B (en) * | 2016-12-30 | 2020-08-11 | 长兴德烯科技有限公司 | Preparation method of graphene flower and application of graphene flower in lithium-sulfur battery |
| CN107057058B (en) * | 2017-05-03 | 2019-08-20 | 杭州高烯科技有限公司 | A kind of graphene/cast nylon composite material and preparation method thereof |
| CN107022121B (en) * | 2017-05-03 | 2018-09-21 | 杭州高烯科技有限公司 | A kind of compounded rubber and preparation method thereof microsphere modified based on spitball shape graphene |
| WO2018196474A1 (en) | 2017-04-28 | 2018-11-01 | 杭州高烯科技有限公司 | Paper ball-like graphene microsphere, composite material thereof, and preparation method therefor |
| CN106966383B (en) * | 2017-04-28 | 2019-08-09 | 杭州高烯科技有限公司 | A kind of spitball shape graphene microballoon and preparation method thereof |
| CN106977768B (en) * | 2017-05-03 | 2019-01-01 | 杭州高烯科技有限公司 | A kind of method that spitball shape graphene improves 6 impact strength of nylon |
| CN107353439B (en) * | 2017-06-21 | 2019-09-24 | 长兴德烯科技有限公司 | A kind of PPR composite material and preparation method of graphene toughening |
| CN107200992B (en) * | 2017-06-21 | 2019-10-15 | 长兴德烯科技有限公司 | A kind of ABS composite material and preparation method thereof of graphene toughening |
| CN107385563B (en) * | 2017-08-23 | 2020-02-04 | 山东圣泉新材料股份有限公司 | Graphene modified alginate fiber and preparation method and application thereof |
| CN107963625B (en) * | 2017-11-09 | 2020-09-01 | 温州大学 | Silicon-crosslinked three-dimensional porous graphene and preparation method thereof |
| CN108329050B (en) * | 2018-03-23 | 2020-08-28 | 中国科学技术大学 | Preparation method of silicon dioxide aerogel block |
| CN110577215B (en) * | 2018-06-07 | 2023-05-16 | 山东欧铂新材料有限公司 | High-dispersion graphene oxide powder and preparation method and application thereof |
| CN109289219A (en) * | 2018-09-05 | 2019-02-01 | 七台河宝泰隆石墨烯新材料有限公司 | The method of dry graphene powder |
| CN109233014A (en) * | 2018-09-21 | 2019-01-18 | 佛山市禅城区诺高环保科技有限公司 | A kind of preparation method of butadiene rubber-graphene oxide composite material |
| CN109455709A (en) * | 2018-12-25 | 2019-03-12 | 中国科学院电工研究所 | A kind of graphene powder material and preparation method thereof |
| CN111992202A (en) * | 2020-08-11 | 2020-11-27 | 浙江工业大学 | graphene-WO3/TiO2Preparation method of composite microspheres |
| CN112945997A (en) * | 2021-02-01 | 2021-06-11 | 天津艾克凯胜石墨烯科技有限公司 | Sample preparation method for aqueous graphene slurry before scanning electron microscope |
| CN113003569B (en) * | 2021-04-28 | 2021-10-29 | 南京工业大学 | Method for preparing reduced graphene oxide powder with high specific surface area |
| CN115650216B (en) * | 2022-07-20 | 2024-07-05 | 上海交通大学 | Method for preparing graphene nanosheets by graphite ball milling of negative electrode of waste lithium battery and application of graphene nanosheets |
| CN117247004B (en) * | 2023-01-04 | 2024-07-19 | 厦门凯纳石墨烯技术股份有限公司 | Purification method, purification device and preparation method of graphene powder |
| CN116022780B (en) * | 2023-02-01 | 2024-05-24 | 哈尔滨工程大学 | Oligolayer graphene with large interlayer spacing and low-temperature rapid preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101559944A (en) * | 2009-05-27 | 2009-10-21 | 天津大学 | Conductive graphene film and self-assembly preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8132746B2 (en) * | 2007-04-17 | 2012-03-13 | Nanotek Instruments, Inc. | Low-temperature method of producing nano-scaled graphene platelets and their nanocomposites |
-
2010
- 2010-12-17 CN CN201010593157A patent/CN101993065B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101559944A (en) * | 2009-05-27 | 2009-10-21 | 天津大学 | Conductive graphene film and self-assembly preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101993065A (en) | 2011-03-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101993065B (en) | Method for preparing graphene powder | |
| Li et al. | A facile one-step method to produce Ni/graphene nanocomposites and their application to the thermal decomposition of ammonium perchlorate | |
| Li et al. | Electrochemically active MnO2/RGO nanocomposites using Mn powder as the reducing agent of GO and the MnO2 precursor | |
| Tan et al. | Hierarchical zinc oxide/reduced graphene oxide composite: preparation route, mechanism study and lithium ion storage | |
| Ye et al. | Green fabrication of cellulose/graphene composite in ionic liquid and its electrochemical and photothermal properties | |
| Bao et al. | Scalable upcycling silicon from waste slicing sludge for high-performance lithium-ion battery anodes | |
| Wang et al. | Hydrothermal synthesis and electrochemical performance of NiO microspheres with different nanoscale building blocks | |
| US10985372B2 (en) | Pyrolytic carbon black composite and method of making the same | |
| TW201536676A (en) | Preparation method of graphene and dispersed composition of graphene | |
| CN105271170B (en) | Preparation method of nano carbon and composite material of nano carbon | |
| CN108565434B (en) | Preparation method of tungsten disulfide/nitrogen and sulfur co-doped graphene compound | |
| CN103145120A (en) | Preparation method of porous graphene | |
| El-Gendy et al. | Green, single-pot synthesis of functionalized Na/N/P co-doped graphene nanosheets for high-performance supercapacitors | |
| Salavati-Niasari et al. | Controlled synthesis of spherical α-Ni (OH) 2 hierarchical nanostructures via a simple hydrothermal process and their conversion to NiO | |
| US20180034055A1 (en) | Composite including porous graphene and carbon nanotube material | |
| CN106744894A (en) | A kind of preparation method of graphene powder | |
| Liu et al. | Solid-state mechanochemistry advancing two dimensional materials for lithium-ion storage applications: A mini review | |
| Jin et al. | Elaborate interface design of SnS2/SnO2@ C/rGO nanocomposite as a high-performance anode for lithium-ion batteries | |
| Liu et al. | Hierarchical dandelion-like copper oxide wrapped by reduced graphene oxide: Hydrothermal synthesis and their application in supercapacitors | |
| Wang et al. | Synthesis of partially graphitic nanoflake-like carbon/Fe 3 O 4 magnetic composites from chitosan as high-performance electrode materials in supercapacitors | |
| Lin-jun et al. | Synthesis of graphene/metal nanocomposite film with good dispersibility via solvothermal method | |
| Wan et al. | A novel sol-gel process to encapsulate micron silicon with a uniformly Ni-doped graphite carbon layer by coupling for use in lithium ion batteries | |
| Wang et al. | Effect of K2CO3 doping on CO2 sorption performance of silicate lithium-based sorbent prepared from citric acid treated sediment | |
| Wang et al. | Preparation and photocatalytic activity of cuprous oxide/carbon nanofibres composite films | |
| CN109095457A (en) | A method of quickly preparing reduced graphene and its composite material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20110330 Assignee: Shanghai Simbatt Energy Technology Co., Ltd. Assignor: Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences Contract record no.: 2013310000047 Denomination of invention: Method for preparing graphene powder Granted publication date: 20120905 License type: Exclusive License Record date: 20130516 |
|
| LICC | Enforcement, change and cancellation of record of contracts on the licence for exploitation of a patent or utility model |