CN104495826A - Single-layer graphene dispersion liquid and preparation method thereof - Google Patents
Single-layer graphene dispersion liquid and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 207
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 129
- 239000006185 dispersion Substances 0.000 title claims abstract description 108
- 239000007788 liquid Substances 0.000 title claims abstract description 52
- 239000002356 single layer Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 78
- 239000010439 graphite Substances 0.000 claims abstract description 78
- 238000010008 shearing Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims description 36
- 239000003795 chemical substances by application Substances 0.000 claims description 28
- 230000008569 process Effects 0.000 claims description 25
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- -1 NOP Chemical compound 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 230000009467 reduction Effects 0.000 claims description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 12
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 12
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 12
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- NRHMKIHPTBHXPF-TUJRSCDTSA-M sodium cholate Chemical compound [Na+].C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC([O-])=O)C)[C@@]2(C)[C@@H](O)C1 NRHMKIHPTBHXPF-TUJRSCDTSA-M 0.000 claims description 10
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 9
- 239000004793 Polystyrene Substances 0.000 claims description 9
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 9
- 229920002223 polystyrene Polymers 0.000 claims description 9
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 9
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 claims description 9
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 9
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 7
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 claims description 7
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 6
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 6
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 claims description 6
- NJPQAIBZIHNJDO-UHFFFAOYSA-N 1-dodecylpyrrolidin-2-one Chemical compound CCCCCCCCCCCCN1CCCC1=O NJPQAIBZIHNJDO-UHFFFAOYSA-N 0.000 claims description 6
- AFPHTEQTJZKQAQ-UHFFFAOYSA-N 3-nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC([N+]([O-])=O)=C1 AFPHTEQTJZKQAQ-UHFFFAOYSA-N 0.000 claims description 6
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 6
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 claims description 6
- 229940117389 dichlorobenzene Drugs 0.000 claims description 6
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 claims description 6
- 229960001826 dimethylphthalate Drugs 0.000 claims description 6
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- PZYDAVFRVJXFHS-UHFFFAOYSA-N n-cyclohexyl-2-pyrrolidone Chemical compound O=C1CCCN1C1CCCCC1 PZYDAVFRVJXFHS-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 6
- 239000012286 potassium permanganate Substances 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 239000002270 dispersing agent Substances 0.000 abstract 3
- 239000002994 raw material Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 26
- 239000010410 layer Substances 0.000 description 12
- 238000001035 drying Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 5
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- 230000003287 optical effect Effects 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
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- 239000004094 surface-active agent Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical compound CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
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- DHKQQCXJDHXTOV-UHFFFAOYSA-M [NH4+].[Br-].[Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C Chemical compound [NH4+].[Br-].[Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C DHKQQCXJDHXTOV-UHFFFAOYSA-M 0.000 description 1
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- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
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- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to the field of nanomaterial processing, and particularly relates to a single-layer graphene dispersion liquid and a preparation method thereof. The dispersion liquid comprises the following raw materials in percentage by weight: 1wt%-10wt% of graphene and 0.01wt%-5wt% of a dispersing agent, wherein the concentration of the graphene dispersion liquid is 10-60mg mL<-1>; the diameter of graphene is 200nm-10mn; and the preparation method comprises the following steps: preparing secondary expansion graphite from graphite; mixing secondary expansion graphite with the dispersing agent to obtain a mixed dispersing system; and carrying out mechanical shearing and peeling on the mixed dispersing system, so as to obtain the single-layer graphene dispersion liquid. According to the single-layer graphene dispersion liquid, flakes of secondary expansion graphite can be subjected to mechanical separating, so as to obtain single-layer graphene; and by virtue of the dispersion action of the dispersing agent, the obtained graphene dispersion liquid is relatively good in dispersity, and exists in a single layer.
Description
Technical field
The present invention relates to nano material manufacture field, in particular to single-layer graphene dispersion liquid and preparation method thereof.
Background technology
2004, Univ Manchester UK physicist An Deliehaimu and Constantine Nuo Woxiaoluofu, successfully from graphite, isolate Graphene in an experiment, and confirm that it can Individual existence, because two people are in " the initiative experiment of two-dimensional graphene material ", common acquisition Nobel Prize in physics in 2010, has pulled open prelude prepared by Graphene.Graphene is another important carbon material after soccerballene and carbon nanotube.Graphene is the cellular hexaplanar two dimensional crystal formed by monolayer carbon atomic arrangement, and carbon atom is with sp
2form hydridization.The surface-area of Graphene is up to 2630m
2/ g is the twice of Single Walled Carbon Nanotube; Under normal temperature, electronic mobility is more than 200000cm
2/ Vs is higher than silicon single crystal; Thermal conductivity up to 5300W/mK, higher than diamond; Resistivity only has 10
-6Ω cm, similar with silver; Single-layer graphene is almost completely transparent, the light of every layer absorption 2.3%; Graphene is the thinnest in the world at present, and the strongest nano material, and its intensity can reach 1000GPa, is 200 times of steel.The characteristic of these excellences of Graphene makes it have huge potential application in gas sensor, opto-electronic device, chemical energy source (solar cell, lithium ion battery), catalyzer, the field such as antistatic.
In the application of reality, graphene sheet layer is easily assembled, affect the performance of Graphene performance, therefore usual by graphene dispersion in organic solvent or water phase surfactant mixture, solvent molecule or surfactant molecule are adsorbed on the surface of Graphene, rely on Intermolecular Forces or electrostatic repulsion forces, realize the Monolayer Dispersion of Graphene.Homogeneous, stable dispersion liquid is the essential condition of Graphene at various fields application and research, but the concentration of the graphene dispersing solution of report is all lower at present, limits the industrialized development of Graphene.
At present, the main method of graphene dispersing solution has: directly by Graphene or Graphene and surface-active mixed solution ultrasonic disperse under hyperacoustic water bath condition.Such as, Jonathan N.Coleman (Umar Khan, Arlene O ' Neill, Mustafa Lotya, Sukanta De, Jonathan N.Coleman.High-Concentration Solvent Exfoliation of Graphene, Small, 2010,6,864-871.) etc. investigator by the graphite dispersion of sheet in solvent nitrogen methyl-2-pyrrolidone (NMP), utilize ultrasonic echography 460h, obtain graphene dispersing solution, its concentration is 3.3mg mL
-1.The graphene dispersing solution concentration that this method obtains is low, and is that multi-layer graphene sheet, treatment time are long, seriously limits the actual demand of Graphene.Dan Li (Dan Li, Marc B.M ü ller, Scott Gilje, Richard B.Kaner, Gordon G.Wallace.Processable Aqueous Dispersions of Graphene Nanosheets, Nature Nanotechnology, 2008,3,101-105.) etc. investigator by graphene oxide water solution with a certain amount of hydrazine hydrate and ammonia soln 95 DEG C reduction 1h, obtaining concentration is 0.5mg mL
-1graphene dispersing solution, the graphene dispersing solution concentration that this method obtains is low, poor stability, can not meet industry various demands.On the whole, the preparation cost of existing graphene dispersing solution is higher, constrains the industrialization process of Graphene.In addition, due to the congregation of graphene sheet layer, in existing business-like graphene dispersing solution, graphene sheet layer is multilayer existence, is difficult to the graphene dispersing solution obtaining individual layer.
CN104151582 provides the preparation method of a kind of Graphene-polyimide conduction black film, first reexpansion is carried out to expanded graphite and obtain reexpansion graphite, by reexpansion graphite and the mixing of black fillers dispersed liquid, the dispersion liquid that ultrasonic stripping obtains Graphene and black filler is carried out to it, this dispersion liquid add the preparation such as diamine monomer can curtain coating material on a glass.Have employed reexpansion preparing graphite alkene in the method, but the graphene dispersing solution mobility adopting the mode of ultrasonic stripping to produce is better, and alternatively concentration is lower, and cannot proves that Graphene is that individual layer exists.
CN102942177 provides a kind of preparation method of graphene film, and expansible black lead is carried out thermal expansion and is processed into quasiflake graphite by (1), then is placed in solvent with basic solution immersion, suction filtration, washing and carries out ultrasonic disperse and obtain micro-nano graphene film; (2) the micro-nano graphene film prepared in step (1) is distributed in inorganic strong protonic acid soaks, after suction filtration, proceed to H
2o
2soak in solution, then suction filtration, washing, drying; (3) transferred in solvent by the micro-nano graphene film processed through step (2) and disperse, constant temperature leaves standstill, then carries out reexpansion after suction filtration or drying; (4) the micro-nano graphene film processed through step (3) is transferred in solvent carry out ultrasonic disperse, be transferred in the stove with reduction protection atmosphere after filtration drying, after carrying out High-Temperature Deoxygenation reduction, namely obtain graphene film.Can find out that graphene dispersion prepared by the method is poor by scanning electron microscopic picture, produce packing phenomenon.
Summary of the invention
The object of the present invention is to provide a kind of single-layer graphene dispersion liquid and preparation method thereof, to solve the problem that single-layer graphene is difficult to disperse.
One aspect of the invention provides a kind of preparation method of single-layer graphene dispersion liquid, comprising:
Step 1, is prepared into reexpansion graphite by graphite; Step 2, is mixed to get mixed dispersion in mass ratio by described reexpansion graphite, dispersion agent at 5: 1 ~ 1: 5; Step 3, carries out mechanical shearing stripping by described mixed dispersion; Step 4, obtains single-layer graphene dispersion liquid.
In certain embodiments, be preferably, in described step 2, described dispersion agent comprises: Sodium dodecylbenzene sulfonate, sodium laurylsulfonate, polyvinylpyrrolidone, Sodium cholic acid, polystyrene, cetyl trimethylammonium bromide one or more.
In certain embodiments, be preferably, in described step 2, described mixed dispersion also comprises: water or solvent, described solvent comprises: cyclopentanone, pimelinketone, piperidines-1-formaldehyde, vinyl pyrrolidone, 1, 3-dimethyl-2-tetrahydroglyoxaline, bromobenzene, benzonitrile, phenmethyl M-nitro benzoic acid, N, N-dimethyl propylene thiazolinyl urea ketone, N-ethyl-2-pyrrolidone, N-Methyl pyrrolidone, acetic acid dimethylamide, cyclohexyl pyrrolidone, benzyl oxide, Virahol, NOP, dioxolane, ethyl acetate, 1-quinoline, benzaldehyde, thanomin, Unimoll DA, N-dodecylpyrrolidone, pyridine, dimethyl phthalate, ethanol, acetone, vinyl-acetic ester, ethylene glycol, toluene, heptane, pentane, hexane, methane amide, dimethyl formamide, dimethyl sulfoxide (DMSO), dichlorobenzene, chloroform, one or more of tetrahydrofuran (THF).
In certain embodiments, be preferably, in described step 3, the equipment that described mechanical shearing adopts comprises: one or more in ball mill, mulser, dispersion machine, shredder, homogenizer, fluid collider.
In certain embodiments, be preferably, the speed of described mechanical shearing is 2000 ~ 15000 revs/min, and/or the time of described mechanical shearing is 1 ~ 30 hour.
In certain embodiments, be preferably, in described step 1, the preparation method of described reexpansion graphite comprises: described graphite is carried out oxide treatment by step a.; Graphite after step a process is carried out expansion process by step b.; Graphite after step b process is carried out oxide treatment by step c again; Steps d. the graphite after step c process is carried out high temperature reduction expansion and obtain reexpansion graphite.
In certain embodiments, be preferably, in described step a, in oxide treatment, the wherein mass ratio 25: 1 ~ 45: 1 of graphite and oxygenant, the oxygenant of employing comprises: one or more in sulfuric acid, nitric acid, potassium permanganate, Potcrate, hydrogen peroxide, nitrous acid, hypochlorous acid.
In certain embodiments, be preferably, in described steps d, the temperature that described high temperature reduction expands is 600 ~ 1800 DEG C.
Another aspect of the present invention additionally provides a kind of single-layer graphene dispersion liquid prepared by aforesaid method, it is characterized in that, comprising: the Graphene of 1 ~ 10wt%, 0.01 ~ 5wt% dispersion agent; The concentration of described graphene dispersing solution is 10 ~ 60mg mL
-1, Graphene diameter be 200 nanometer ~ 10 micron; Described dispersion agent be Sodium dodecylbenzene sulfonate, sodium laurylsulfonate, polyvinylpyrrolidone, Sodium cholic acid, polystyrene, cetyl trimethylammonium bromide one or more.
In certain embodiments, be preferably, single-layer graphene dispersion liquid also comprises: water or solvent, described solvent comprises: cyclopentanone, pimelinketone, piperidines-1-formaldehyde, vinyl pyrrolidone, 1, 3-dimethyl-2-tetrahydroglyoxaline, bromobenzene, benzonitrile, phenmethyl M-nitro benzoic acid, N, N-dimethyl propylene thiazolinyl urea ketone, N-ethyl-2-pyrrolidone, N-Methyl pyrrolidone, acetic acid dimethylamide, cyclohexyl pyrrolidone, benzyl oxide, Virahol, NOP, dioxolane, ethyl acetate, 1-quinoline, benzaldehyde, thanomin, Unimoll DA, N-dodecylpyrrolidone, pyridine, dimethyl phthalate, ethanol, acetone, vinyl-acetic ester, ethylene glycol, toluene, heptane, pentane, hexane, methane amide, dimethyl formamide, dimethyl sulfoxide (DMSO), dichlorobenzene, chloroform, one or more of tetrahydrofuran (THF).
Single-layer graphene dispersion liquid that the embodiment of the present invention provides and preparation method thereof, compared with prior art, is first prepared into reexpansion graphite by graphite, and destroy the Van der Waals force between graphitic molecules, reexpansion graphite presents lamella isolating construction; Adding dispersion agent agent on this basis increases dispersed; Mechanical shearing stripping is carried out to the mixed dispersion of reexpansion graphite and dispersion agent, the lamella of reexpansion graphite is separated and can obtains single-layer graphene, by the dissemination of dispersion agent, obtain better dispersed, the graphene dispersing solution existed with individual layer.
Accompanying drawing explanation
Fig. 1 is graphene dispersing solution optical photograph in the embodiment of the present invention 1;
Fig. 2 is graphene dispersing solution transmission electron microscope photo in the embodiment of the present invention 1;
Fig. 3 is Graphene Raman spectrum in the embodiment of the present invention 1;
Fig. 4 is that in the embodiment of the present invention 1, graphene dispersion uv-vis spectra proves good dispersity.
Embodiment
By reference to the accompanying drawings the present invention is described in further detail below by specific embodiment.
Consider that current single-layer graphene makes difficulty, and the problem of very easily assembling, the invention provides a kind of single-layer graphene dispersion liquid and preparation method thereof.
The preparation method of this kind of single-layer graphene dispersion liquid, comprising:
Step 1, is prepared into reexpansion graphite by graphite;
Step 2, is mixed to get mixed dispersion in mass ratio by reexpansion graphite, dispersion agent at 5: 1 ~ 1: 5;
Step 3, carries out mechanical shearing stripping by mixed dispersion;
Step 4, obtains single-layer graphene dispersion liquid.
By single-layer graphene dispersion liquid prepared by the preparation method of above-mentioned single-layer graphene dispersion liquid, comprising: the Graphene of 1 ~ 10wt%, 0.01 ~ 5wt% dispersion agent; The concentration of graphene dispersing solution is 10 ~ 60mg mL
-1; The diameter of Graphene is 200 nanometer ~ 10 micron; Dispersion agent be Sodium dodecylbenzene sulfonate, sodium laurylsulfonate, polyvinylpyrrolidone, Sodium cholic acid, polystyrene, cetyl trimethylammonium bromide one or more.
In the present embodiment, first graphite is prepared into reexpansion graphite, destroy the Van der Waals force between graphitic molecules, reexpansion graphite presents lamella isolating construction; Adding dispersion agent on this basis increases dispersed; Mechanical shearing is carried out to the mixed dispersion of reexpansion graphite and dispersion agent, the lamella of reexpansion graphite is separated and can obtains single-layer graphene, by the dissemination of dispersion agent, obtain better dispersed, the graphene dispersing solution existed with individual layer.
The standby layer graphite of reexpansion graphite is separated by mechanical shearing, discovery is studied through contriver, mechanical means such as ball mill, mulser, dispersion machine, shredder, homogenizer, fluid collider is adopted to carry out peeling off the Graphene that can obtain few layer, spherical, bar-shaped grinding medium is increased in these mechanical means, shear area can be increased, improve peeling effect further, can single-layer graphene be obtained.And the use of grinding medium is beneficial to the dispersed of dispersion liquid, improve the dispersion effect of dispersion liquid.
Next, explanation is specifically done to the preparation of this single-layer graphene dispersion liquid:
Embodiment 1
Preparation reexpansion graphite: 5g graphite is put in the there-necked flask of 500mL, there-necked flask is dipped in mixture of ice and water, then add the concentrated nitric acid of 45mL and the vitriol oil of 87.5mL, the Potcrate of 55g is added in there-necked flask slowly and (at least adds more than 15 minutes.Attention: can produce dioxide peroxide when adding Potcrate, can produce blast during concentration height), this process stir process 72 hours, washes into neutrality with a large amount of water by the graphite of process, obtains powder after drying; Then to oxidation after graphite in tube furnace, Bulking Time 30 seconds-5 minutes temperature are carried out high temperature reduction and are obtained an expanded graphite in 1000-1300 DEG C of situation, and expanding at 600-1500 DEG C of high temperature reduction after adopting above-mentioned same method process expanded graphite obtains reexpansion graphite.
Prepare single-layer graphene dispersion liquid: reexpansion graphite, polyvinylpyrrolidone are mixed to get mixed dispersion in mass ratio 3: 2; Carry out mechanical shearing by ball mill to mixed dispersion, velocity of shear is 2000 revs/min, and the time of described mechanical shearing is 20 hours, obtains single-layer graphene dispersion liquid, wherein contains: the Graphene of 6wt%, 4wt% dispersion agent; The diameter of described Graphene is 200 nanometer ~ 8 micron;
It should be noted that, in the present embodiment, oxygenant can also replace with in potassium permanganate, hydrogen peroxide, hypochlorous acid, nitrous acid one or more.
Dispersion agent can also be selected from: Sodium dodecylbenzene sulfonate, sodium laurylsulfonate, Sodium cholic acid, polystyrene, cetyl trimethylammonium bromide one or more.
The graphene dispersing solution this embodiment obtained carries out optical imagery, and as shown in Figure 1, this single-layer graphene dispersion liquid is the slurry of dark thick, is inverted by dispersion liquid, flows hardly, have good good dispersity, the feature of stability, high concentration.Take pictures under transmission electron microscope, as shown in Figure 2, dispersion liquid is all almost single-layer graphene film.The powder preparing dispersion liquid is carried out Raman sign, and by the shape at 2D peak, we judge to obtain single-layer graphene, as shown in Figure 3.After the graphene dispersing solution dilution this embodiment obtained, measure the absorption spectrum of the ultraviolet-visible of dilution different concns dispersion liquid, the linear good dispersity showing graphene dispersing solution of maximum absorption peak, as shown in Figure 4.Can see from these four figure, it relates to the high-content of graphene dispersing solution, good dispersiveness and individual layer characteristic.This graphene dispersing solution solves Graphene bad dispersibility, problem such as stability is low, concentration is lower in water and various organic solvent thereof.
Embodiment 2
Preparation reexpansion graphite: 5g graphite is put in the there-necked flask of 500mL, there-necked flask is dipped in mixture of ice and water, then add the concentrated nitric acid of 50mL and the hydrogen peroxide of 98mL, the Potcrate of 45g is added in there-necked flask slowly and (at least adds more than 15min.Attention: can produce dioxide peroxide when adding Potcrate, can produce blast during concentration height), this process stir process 72h, washes into neutrality with a large amount of water by the graphite of process, obtains powder after drying; Then to oxidation after graphite in tube furnace, Bulking Time 30S ~ 5min, temperature is carried out high temperature reduction and is obtained an expanded graphite in 1300 ~ 1500 DEG C of situations, and expanding at 800 ~ 1800 DEG C of high temperature reductions after adopting above-mentioned same method process expanded graphite obtains reexpansion graphite.
Prepare single-layer graphene dispersion liquid: by reexpansion graphite, polyvinylpyrrolidone mass ratio 1: 1, be mixed to get mixed dispersion; Carry out mechanical shearing by fluid collider to mixed dispersion, velocity of shear is 10500 revs/min, and the time of described mechanical shearing is 5 hours, obtains single-layer graphene dispersion liquid, its, the Graphene of 7wt%, 7wt% dispersion agent; The diameter of described Graphene is 500 nanometer ~ 10 micron;
It should be noted that, in the present embodiment, oxygenant can also in the present embodiment, oxygenant can also replace with in potassium permanganate, sulfuric acid, hypochlorous acid, nitrous acid one or more.
Dispersion agent can also be selected from: Sodium dodecylbenzene sulfonate, sodium laurylsulfonate, Sodium cholic acid, polystyrene, cetyl trimethylammonium bromide ammonium one or more.
Embodiment 3
Preparation reexpansion graphite: 5g graphite is put in the there-necked flask of 500mL, there-necked flask is dipped in mixture of ice and water, then add the nitrous acid of 45mL and the hydrogen peroxide of 87.5mL, the hypochlorous acid of 55g is added in there-necked flask slowly and (at least adds more than 15min.), this process stir process 72h, washes into neutrality with a large amount of water by the graphite of process, obtains powder after drying; Then to oxidation after graphite in tube furnace, Bulking Time 30S ~ 5min, temperature is carried out high temperature reduction and is obtained an expanded graphite in 1300 ~ 1500 DEG C of situations, and expanding at 1300 ~ 1500 DEG C of high temperature reductions after adopting above-mentioned same method process expanded graphite obtains reexpansion graphite.
Prepare single-layer graphene dispersion liquid: be 3: 1 in mass ratio by reexpansion graphite, Sodium cholic acid, be mixed to get mixed dispersion; Solvent NOP is added in mixed dispersion, in clarifixator (the spherical grinding medium of interior loading), mechanical shearing is carried out to mixing the solution finally obtained by fluid mulser, velocity of shear is 8000 revs/min, the time of mechanical shearing is 30 hours, obtain single-layer graphene dispersion liquid, wherein, Graphene, the 1.7wt% dispersion agent of 5wt%; The diameter of described Graphene is 200 nanometer ~ 8 micron;
It should be noted that, in the present embodiment, oxygenant can also one or more in the vitriol oil, concentrated nitric acid, potassium permanganate, Potcrate.
Dispersion agent can also be selected from: Sodium dodecylbenzene sulfonate, sodium laurylsulfonate, polyvinylpyrrolidone, polystyrene, cetyl trimethylammonium bromide one or more, or Sodium cholic acid and other alternative dispersion agents share.
Solvent can also be substituted by following material: cyclopentanone, pimelinketone, piperidines-1-formaldehyde, vinyl pyrrolidone, 1, 3-dimethyl-2-tetrahydroglyoxaline, bromobenzene, benzonitrile, phenmethyl M-nitro benzoic acid, N, N-dimethyl propylene thiazolinyl urea ketone, N-ethyl-2-pyrrolidone, N-Methyl pyrrolidone, acetic acid dimethylamide, cyclohexyl pyrrolidone, benzyl oxide, Virahol, dioxolane, ethyl acetate, 1-quinoline, benzaldehyde, thanomin, Unimoll DA, N-dodecylpyrrolidone, pyridine, dimethyl phthalate, ethanol, acetone, vinyl-acetic ester, ethylene glycol, toluene, heptane, pentane, hexane, methane amide, dimethyl formamide, dimethyl sulfoxide (DMSO), dichlorobenzene, chloroform, one or more of tetrahydrofuran (THF).
Embodiment 4:
Preparation reexpansion graphite: 5g graphite is put in the there-necked flask of 500mL, there-necked flask is dipped in mixture of ice and water, then add the potassium permanganate of 45mL and the nitrous acid of 87.5mL, the Potcrate of 55g is added in there-necked flask slowly and (at least adds more than 15min.Attention: can produce dioxide peroxide when adding Potcrate, can produce blast during concentration height), this process stir process 72h, washes into neutrality with a large amount of water by the graphite of process, obtains powder after drying; Then to oxidation after graphite in tube furnace, Bulking Time 30S ~ 5min, temperature is carried out high temperature reduction and is obtained an expanded graphite in 1300 ~ 1500 DEG C of situations, and after adopting above-mentioned same method process expanded graphite, high temperature reduction expands and obtains reexpansion graphite.
Prepare single-layer graphene dispersion liquid: reexpansion graphite, cetyl trimethylammonium bromide are mixed to get mixed dispersion in mass ratio at 5: 1; Add again solvent Unimoll DA; By dispersion machine (including bar-shaped grinding medium), mechanical shearing is carried out to mixed dispersion, velocity of shear is 13500 revs/min, and the time of described mechanical shearing is 4 hours, obtains single-layer graphene dispersion liquid, wherein, Graphene, the 0.2wt% dispersion agent of 1wt%; The diameter of described Graphene is 800 nanometer ~ 5 micron;
It should be noted that, in the present embodiment, oxygenant can also one or more in concentrated nitric acid, the vitriol oil, hypochlorous acid, hydrogen peroxide.
Dispersion agent can also be selected from: Sodium dodecylbenzene sulfonate, sodium laurylsulfonate, polyvinylpyrrolidone, Sodium cholic acid, polystyrene one or more, or cetyl trimethylammonium bromide and other alternative dispersion agents share.
Solvent can also be substituted by following material: cyclopentanone, pimelinketone, piperidines-1-formaldehyde, vinyl pyrrolidone, 1, 3-dimethyl-2-tetrahydroglyoxaline, bromobenzene, benzonitrile, phenmethyl M-nitro benzoic acid, N, N-dimethyl propylene thiazolinyl urea ketone, N-ethyl-2-pyrrolidone, N-Methyl pyrrolidone, acetic acid dimethylamide, cyclohexyl pyrrolidone, benzyl oxide, Virahol, NOP, dioxolane, ethyl acetate, 1-quinoline, benzaldehyde, thanomin, N-dodecylpyrrolidone, pyridine, dimethyl phthalate, ethanol, acetone, vinyl-acetic ester, ethylene glycol, toluene, heptane, pentane, hexane, methane amide, dimethyl formamide, dimethyl sulfoxide (DMSO), dichlorobenzene, chloroform, one or more of tetrahydrofuran (THF), or Unimoll DA shares with other alternative solvents.
The graphene dispersing solution concentration that the method obtains is high, stability is strong and be single-layer graphene film.In addition, preparation technology is simple, cost is low, and is conducive to the advantages such as industrialization production.The graphene dispersing solution of this acquisition has potential actual application value in fields such as optical, electrical materials.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a preparation method for single-layer graphene dispersion liquid, is characterized in that, comprising:
Step 1, is prepared into reexpansion graphite by graphite;
Step 2, is mixed to get mixed dispersion in mass ratio by described reexpansion graphite, dispersion agent at 5: 1 ~ 1: 5;
Step 3, carries out mechanical shearing stripping by described mixed dispersion;
Step 4, obtains single-layer graphene dispersion liquid.
2. the preparation method of single-layer graphene dispersion liquid as claimed in claim 1, it is characterized in that, in described step 2, described dispersion agent comprises: Sodium dodecylbenzene sulfonate, sodium laurylsulfonate, polyvinylpyrrolidone, Sodium cholic acid, polystyrene, cetyl trimethylammonium bromide one or more.
3. the preparation method of single-layer graphene dispersion liquid as claimed in claim 1, it is characterized in that, in described step 2, described mixed dispersion also comprises: water or solvent;
Described solvent comprises: cyclopentanone, pimelinketone, piperidines-1-formaldehyde, vinyl pyrrolidone, 1, 3-dimethyl-2-tetrahydroglyoxaline, bromobenzene, benzonitrile, phenmethyl M-nitro benzoic acid, N, N-dimethyl propylene thiazolinyl urea ketone, N-ethyl-2-pyrrolidone, N-Methyl pyrrolidone, acetic acid dimethylamide, cyclohexyl pyrrolidone, benzyl oxide, Virahol, NOP, dioxolane, ethyl acetate, 1-quinoline, benzaldehyde, thanomin, Unimoll DA, N-dodecylpyrrolidone, pyridine, dimethyl phthalate, ethanol, acetone, vinyl-acetic ester, ethylene glycol, toluene, heptane, pentane, hexane, methane amide, dimethyl formamide, dimethyl sulfoxide (DMSO), dichlorobenzene, chloroform, one or more of tetrahydrofuran (THF).
4. the preparation method of single-layer graphene dispersion liquid as claimed in claim 1, it is characterized in that, in described step 3, the equipment that described mechanical shearing adopts comprises: one or more in ball mill, mulser, dispersion machine, shredder, homogenizer, fluid collider.
5. the preparation method of single-layer graphene dispersion liquid as claimed in claim 4, it is characterized in that, the speed of described mechanical shearing is 2000 ~ 15000 revs/min, and/or the time of described mechanical shearing is 1 ~ 30 hour.
6. the preparation method of the single-layer graphene dispersion liquid as described in any one of claim 1-5, is characterized in that, in described step 1, the preparation method of described reexpansion graphite comprises:
Described graphite is carried out oxide treatment by step a.;
Graphite after step a process is carried out expansion process by step b.;
Graphite after step b process is carried out oxide treatment by step c again;
Steps d. the graphite after step c process is carried out high temperature reduction expansion and obtain reexpansion graphite.
7. the preparation method of single-layer graphene dispersion liquid as claimed in claim 6, it is characterized in that, in described step a, in oxide treatment, the wherein mass ratio 25: 1 ~ 45: 1 of graphite and oxygenant, the oxygenant of employing comprises: one or more in sulfuric acid, nitric acid, potassium permanganate, Potcrate, hydrogen peroxide, hypochlorous acid, nitrous acid.
8. the preparation method of single-layer graphene dispersion liquid as claimed in claim 6, is characterized in that, in described steps d, the temperature that described high temperature reduction expands is 600 ~ 1800 DEG C.
9. by a single-layer graphene dispersion liquid prepared by the preparation method of single-layer graphene dispersion liquid described in any one of claim 1-8, it is characterized in that, comprising: the Graphene of 1 ~ 10wt%, 0.01 ~ 5wt% dispersion agent; The concentration of described graphene dispersing solution is 10 ~ 60mg mL
-1, Graphene diameter be 200 nanometer ~ 10 micron; Described dispersion agent be Sodium dodecylbenzene sulfonate, sodium laurylsulfonate, polyvinylpyrrolidone, Sodium cholic acid, polystyrene, cetyl trimethylammonium bromide one or more.
10. single-layer graphene dispersion liquid as claimed in claim 9, it is characterized in that, also comprise: water or solvent, described solvent comprises: cyclopentanone, pimelinketone, piperidines-1-formaldehyde, vinyl pyrrolidone, 1, 3-dimethyl-2-tetrahydroglyoxaline, bromobenzene, benzonitrile, phenmethyl M-nitro benzoic acid, N, N-dimethyl propylene thiazolinyl urea ketone, N-ethyl-2-pyrrolidone, N-Methyl pyrrolidone, acetic acid dimethylamide, cyclohexyl pyrrolidone, benzyl oxide, Virahol, NOP, dioxolane, ethyl acetate, 1-quinoline, benzaldehyde, thanomin, Unimoll DA, N-dodecylpyrrolidone, pyridine, dimethyl phthalate, ethanol, acetone, vinyl-acetic ester, ethylene glycol, toluene, heptane, pentane, hexane, methane amide, dimethyl formamide, dimethyl sulfoxide (DMSO), dichlorobenzene, chloroform, one or more of tetrahydrofuran (THF).
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104959050A (en) * | 2015-04-29 | 2015-10-07 | 北京天恒盛通科技发展有限公司 | Highly dispersed highly stable high concentration and high yield graphene dispersion liquid and preparation method thereof |
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| CN107381643A (en) * | 2016-12-12 | 2017-11-24 | 广东纳路纳米科技有限公司 | A kind of mechanical stripping Van der Waals stratified material prepares the universal method of two-dimensional material |
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| CN107922764A (en) * | 2015-07-22 | 2018-04-17 | 剑桥企业有限公司 | Nanometer sheet dispersion, its production method and application thereof |
| CN108084583A (en) * | 2017-11-29 | 2018-05-29 | 吉林云亭石墨烯技术股份有限公司 | A kind of preparation method of graphene and its preparation of sound insulation graphene EPS |
| CN108439390A (en) * | 2018-05-29 | 2018-08-24 | 武汉科技大学 | Based on the method for isolating and purifying graphene from Pintsch process charcoal |
| CN108802111A (en) * | 2018-03-21 | 2018-11-13 | 北京旭碳新材料科技有限公司 | Miniature gas-sensitive sensor and preparation method thereof |
| CN109019576A (en) * | 2018-09-05 | 2018-12-18 | 七台河宝泰隆石墨烯新材料有限公司 | A kind of technique of physical method production graphene |
| CN109368629A (en) * | 2018-12-03 | 2019-02-22 | 广东电网有限责任公司 | A kind of graphene dispersion system and preparation method thereof |
| CN109879276A (en) * | 2019-03-15 | 2019-06-14 | 山东华冠智能卡有限公司 | A kind of dispersing method of graphene |
| CN111813156A (en) * | 2020-08-10 | 2020-10-23 | 宁夏墨工科技有限公司 | Self-adaptive system for graphene slurry concentration control |
| CN113800505A (en) * | 2021-08-02 | 2021-12-17 | 江苏杉元科技有限公司 | Graphene aqueous slurry and preparation method thereof |
| CN114671429A (en) * | 2022-04-27 | 2022-06-28 | 深圳材启新材料有限公司 | Preparation method of high-quality graphene dispersion liquid |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101993061A (en) * | 2009-08-19 | 2011-03-30 | 中国科学院金属研究所 | Method for preparing high-quality graphene with controllable layer number |
| CN103935997A (en) * | 2014-05-10 | 2014-07-23 | 由伟 | Method for producing graphene based on sodium dodecylbenzene sulfonate |
| CN104151582A (en) * | 2014-07-17 | 2014-11-19 | 哈尔滨工业大学 | Method for preparing graphene-polyimide conductive black film |
-
2014
- 2014-12-25 CN CN201410817919.XA patent/CN104495826B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101993061A (en) * | 2009-08-19 | 2011-03-30 | 中国科学院金属研究所 | Method for preparing high-quality graphene with controllable layer number |
| CN103935997A (en) * | 2014-05-10 | 2014-07-23 | 由伟 | Method for producing graphene based on sodium dodecylbenzene sulfonate |
| CN104151582A (en) * | 2014-07-17 | 2014-11-19 | 哈尔滨工业大学 | Method for preparing graphene-polyimide conductive black film |
Non-Patent Citations (4)
| Title |
|---|
| CATHARINA KNIEKE等: "Scalable production of graphene sheets by mechanical delamination", 《CARBON》 * |
| 艾书伦等: "石墨烯制备方法的研究进展", 《粘接》 * |
| 郭晓琴等: "石墨烯纳米片的制备和表征", 《化工新型材料》 * |
| 郭晓琴等: "超声剥离二次膨胀石墨制备石墨烯纳米片", 《功能材料》 * |
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