CN102259848B - Nanographite sheet with conducting performance and manufacturing method thereof - Google Patents
Nanographite sheet with conducting performance and manufacturing method thereof Download PDFInfo
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- CN102259848B CN102259848B CN201010193713.6A CN201010193713A CN102259848B CN 102259848 B CN102259848 B CN 102259848B CN 201010193713 A CN201010193713 A CN 201010193713A CN 102259848 B CN102259848 B CN 102259848B
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Abstract
The invention discloses a nanographite sheet which is subjected to organic perssad surface modification and a manufacturing method thereof. The nanographite sheet is manufactured by taking graphite as a raw material, taking an aqueous solution of a surface active agent as an electrolyte and adopting an electrolytic method. The diameter of the nanographite sheet is 0.2-5.0mu m and the thickness of the nanographite sheet is 0.34-50.00nm. The nanographite sheet can be uniformly and stably dispersed in a polar solvent. The conductivity can reach 10-1S/cm. The nanographite sheet can be applied to manufacturing a conducting polymer composite material directly without reduction and is low in cost as well as can be widely applied to the fields of conducting materials, antistatic materials, electromagnetic shielding materials, microwave absorption and the like.
Description
Technical field
The invention belongs to electrical-conductive nanometer graphite material field, be specifically related to a kind of prepare by electrolytic process taking water phase surfactant mixture as electrolytic solution there is nano graphite flakes of conductivity and preparation method thereof.
Background technology
The preparation method of nano-graphite sheet material mainly contains electrochemical process, chemistry redox stripping method, mechanically peel method, chemical Vapor deposition process, arc-over and crystal epitaxy method etc. at present.Feature and the cost of the equipment and technology of comprehensive above each method, the method that may realize at present scale operation is mainly electrochemical process and chemistry redox method.
Although chemistry redox method has the advantage that easily realizes scale operation, processing step is comparatively complicated, generally needs chemical oxidation, diafiltration and three processes of reduction, and preparation cycle is longer.In prepared graphite flake, easily there is the residual of the impurity such as reductive agent.The standby nano-graphite sheet material of chemistry redox legal system has its limitation in nature simultaneously.The dispersed variation of graphite oxide after most reduction in solvent, is unfavorable for its application in preparation field of compound material.In addition, be subject to the impact of method of reducing, graphite oxide can only be realized partial reduction, so the conductivity of the nano graphite flakes that the method makes can be lost.
The nano graphite flakes kind of electrochemical production is various, in opposed polarity solvent, have can uniform and stable dispersion kind, can dissolve each other with most high molecular polymers, and there is good electroconductibility, without reduction, therefore can directly be used for the good conducing composite material of processability.This method is mainly used ionic liquid as electrolytic solution (number of patent application: 200810050291.X) at present, prepared nano graphite flakes good dispersity in aprotic polar solvent, but in water, ethanol isopolarity solvent, there is sedimentation, limited its application in conducing composite material field.In addition, expensive due to ionic liquid, particularly, in the time using fluoride ion liquid as ionogen, electrolytic process may produce corrosives, all will limit the application of electrochemical process.
Summary of the invention
In order to solve the problems of the prior art, that the present invention has developed is cheap using price, be easy to buy and water phase surfactant mixture wide in variety as electrolytic solution, with the method for electrochemical production nano graphite flakes.The object of this invention is to provide a kind of nano-graphite sheet material with electroconductibility of preparing taking tensio-active agent as raw material, it is good that this material possesses conductivity, and extent of exfoliation is high, the feature of can stable and uniform in polar solvent disperseing.Therefore this material and most high molecular polymer have good consistency, can be applicable to prepare the polymer composites field with electroconductibility.
Another object of the present invention is to provide a kind of preparation method of above-mentioned electrical-conductive nanometer graphite sheet material.
Object of the present invention can reach by following measures:
Have a nano graphite flakes for conductivity, the raw material of preparing this material comprises graphite, tensio-active agent and water.
The nano graphite flakes with conductivity in the present invention, its surface is with the contained organic group of tensio-active agent.Because organic group has improved the dispersiveness of nano graphite flakes in polar solvent, prepare conducting polymer composite material thereby be beneficial to.Nano graphite flakes of the present invention can stable and uniform disperse in aprotic polar solvent and/or proton polar solvent.Wherein, aprotic polar solvent can be DMF (DMF), N-Methyl pyrrolidone (NMP), N,N-dimethylacetamide (DMAC), acetone etc.; Proton polar solvent can be ethanol, water etc.
Above-mentioned organic group is specially one or more in alkyl carboxyl, alkylsulphonic acid base, alkyl sulfide acidic group, benzene sulfonamide acidic group, alkyl phosphate monoester base, fatty ammonium, aromatic series ammonium, alkyl imidazoline ammonium, Alkylpyridyl, fatty alcohol-polyoxyethylene ether base, alkylphenol polyoxyethylene base, aliphatic amine polyoxyethylene ether base, polyoxyethylene carboxylate base, beet base, amino acid based or amphoteric imidazoline class group.
In the raw material of the nano graphite flakes with conductivity in the present invention, tensio-active agent is selected from one or more in anion surfactant, cats product, nonionogenic tenside or amphoterics.
Because the electrical-conductive nanometer graphite flake in the present invention is prepared taking water as reaction medium, the therefore preferred good tensio-active agent of solvability in water.Wherein, anion surfactant is preferably one or more in alkyl carboxylate, alkylsulfonate, alkyl-sulphate, alkylbenzene sulfonate or alkyl phosphate monoester salt;
Cats product is preferably one or more in aliphatic quaternary ammonium salt, aromatic series quaternary ammonium salt, alkyl imidazoline quaternary ammonium salt or Fixanol;
Nonionogenic tenside is preferably one or more in fatty alcohol-polyoxyethylene ether, alkylphenol polyoxyethylene, aliphatic amine polyoxyethylene ether or polyoxyethylene carboxylate;
Amphoterics is preferably one or more in betaines, amino acids or amphoteric imidazoline class;
Above-mentioned tensio-active agent with the carbonatoms of moieties be 1-18.
When tensio-active agent with the carbonatoms of moieties be when more than 18, the solvability possible deviation of tensio-active agent in water, thus may cause the poorly conductive of solution, reaction may be difficult to cause and speed of reaction reduces.
Consider the factor of the aspects such as the complexity of solvability in water, electrolytic reaction and speed, price, above-mentioned tensio-active agent more preferably: one or more in more preferably benzene sulfonamide acid potassium salt, alkyl benzene sulphonate (ABS) sodium salt, benzene sulfonamide acid ammonium salt, alkylsulphonic acid sylvite, mersolates, alkylsulphonic acid ammonium salt, alkylsurfuric acid sylvite, alkylsurfuric acid sodium salt, alkylsurfuric acid ammonium salt, alkyl carboxylic acid sylvite, alkyl carboxylic acid sodium salt or the alkyl carboxylic acid ammonium salt of anion surfactant;
One or more in more preferably alkyl trimethyl ammonium bromide, alkyl triethyl brometo de amonio, alkyl trimethyl ammonium chloride, alkyl triethyl ammonium chloride, phenyl or benzyl trimethyl ammonium chloride, phenyl or benzyltrimethylammonium bromide, alkyl imidazoline quaternary ammonium salt, alkyl-pyridiniums chloride or the cetylpyridinium bromide salt of cats product;
More preferably alkyl alcohol polyoxyethylene (2-20) ether of nonionogenic tenside, polyoxyethylene (2-30) C
8-15one or more in base phenolic ether, alkylamine polyoxyethylene (2-20) ether or alkyl acid polyoxyethylene (2-20) ester;
Amphoterics is selected from alkyl dimethyl betaine, alkyl amido betaine, alkylamide L-Ala, alkylamide glycine, alkylamide L-glutamic acid, alkylamide Methionin, alkylamide proline(Pro), alkyl L-Ala, alkyl glycine, alkyl-glutamic acid, alkyl Methionin, alkyl proline(Pro), alkylamino L-Ala, alkylamino glycine, alkylamino L-glutamic acid, alkylamino Methionin, alkylamino proline(Pro), or one or more in alkyl sodium carboxymethyl tetrahydroglyoxaline,
Wherein, the carbonatoms of described moieties is 1-18.
The diameter of the nano graphite flakes with conductivity in the present invention is 0.2-5.0 μ m, and thickness is 0.34-50.00nm.
In order to obtain a kind of above-mentioned nano graphite flakes with conductivity, its preparation method is:
(1) electrolysis
Taking graphite as electrode, put into the aqueous solution electrolysis 2-40 hour of tensio-active agent, voltage control is 5-60V, and electric current is 0.01-2A, and wherein the concentration of tensio-active agent in water is 0.5mg/mL-100mg/mL, obtains nano graphite flakes A;
(2) diafiltration
The nano graphite flakes A of step (1) gained is residual to surfactant-free with deionized water diafiltration, obtain the residual nano graphite flakes of surfactant-free;
(3) dry
Gained nano graphite flakes, 100 DEG C of following abundant being dried, is obtained to the above-mentioned nano graphite flakes with conductivity.
In above-mentioned steps (2), for the effect of strengthening diafiltration can be carried out diafiltration with ethanol again.
In above-mentioned steps (3), dry can be forced air drying or vacuum-drying, and drying conditions is preferably 80 DEG C of following vacuum-dryings.
In order to ensure high purity and the high conductivity of prepared nano graphite flakes, the graphite in described raw material is preferably high purity graphite, i.e. more than 99.9% graphite of content of graphite.
The tensio-active agent using in described preparation method is selected from one or more in anion surfactant, cats product, nonionogenic tenside or amphoterics.
Above-mentioned, the description of anion surfactant, cats product, nonionogenic tenside or amphoterics as previously described.
Can ensure the dissolving of tensio-active agent in water by the method for heating.
Can be in the aqueous solution salt adding, as NaCl etc., to improve the electroconductibility of electrolytic solution, or cause the generation of electrolytic reaction.
The diameter of the nano graphite flakes with conductivity of being prepared by above-mentioned method is 0.2-5.0 μ m, and thickness is 0.34-50.00nm.
Meanwhile, the nano graphite flakes with conductivity of being prepared by above-mentioned method can stable and uniform disperse in aprotic polar solvent and/or proton polar solvent.Wherein, aprotic polar solvent can be DMF (DMF), N-Methyl pyrrolidone (NMP), N,N-dimethylacetamide (DMAC), acetone etc.; Proton polar solvent can be ethanol, water etc.
Nano graphite flakes in the present invention is good dispersity in more polar solvent, therefore can be good with most soluble high molecular polymers consistencies.There is good electroconductibility, without reduction, therefore can directly be used for the good conducing composite material of processability.Can be widely used in the fields such as electro-conductive material, antistatic material, electromagnetic shielding material, microwave absorbing.
Brief description of the drawings
Fig. 1 is the infrared spectrum of the nano graphite flakes prepared of Sodium dodecylbenzene sulfonate (DBS, embodiment 1) and ionic liquid (IL, comparative example 1).
In figure, can be observed the peak with S=O and phenyl ring, the nano graphite flakes surface of preparing taking DBS as raw material, the nano graphite flakes obvious difference of preparing with IL.
Embodiment
Related concrete pharmaceutical chemicals in the present invention:
Graphite Electrodes: the municipal neolite China ink factory in Changzhou (spectroscopically pure);
Sodium dodecylbenzene sulfonate, sodium laurylsulfonate, sodium lauryl sulphate, sodium stearate, cetyl trimethylammonium bromide, phenyl trimethyl ammonium chloride, polyoxyethylene (20) octylphenol ether (being commonly called as polyoxyethylene nonylphenol ether-20), Methionin, L-PROLINE.Traditional Chinese medicines reagent.
1-octyl group-3-Methylimidazole hexafluorophosphate ([omim]
+[PF6]
-).Become prompt chemistry.
The method of calculation of raw materials cost: the unit price that is multiplied by tensio-active agent or ionic liquid to prepare tensio-active agent that every gram of nano graphite flakes consumed or ionic liquid consumption.
Prepared product is pressed into after super-dry in tabletting machine to the print of the about 1mm of thickness, measures the conductivity of product with broadband dielectric spectroscopy instrument (Novocontrol BDS40).The said products is scattered in solvent, disperses through 30 minutes ultrasonic wave, leave standstill and judge its dispersiveness after 15 days.
Embodiment 1
Taking bar-shaped graphite as electrode, put into the aqueous solution electrolysis 1.5 hours of Sodium dodecylbenzene sulfonate, voltage control is 30V, and electric current is no more than 2A, and wherein the concentration of tensio-active agent in water is 20mg/mL; Residual to surfactant-free through the abundant diafiltration of deionized water; Fully dry under 80 DEG C of conditions.Obtain 0.15g nano graphite flakes, its specific conductivity is 4.8 × 10
-2s/cm.Product is good dispersity in DMF, DMAC, NMP and ethanol.0.27 yuan/gram of the raw materials cost of this nano graphite flakes.Infrared spectrum is shown in Fig. 1.
Embodiment 2
Taking bar-shaped graphite as electrode, put into the aqueous solution electrolysis 27 hours of sodium laurylsulfonate, voltage control is 30V, and electric current is 0.28A, and wherein the concentration of tensio-active agent in water is 30mg/mL; Residual to surfactant-free through the abundant diafiltration of deionized water; Fully dry under 80 DEG C of conditions.Obtain 2.2g nano graphite flakes, its specific conductivity is 4.0 × 10
-7s/cm.Product is good dispersity in DMF, DMAC, NMP, acetone and ethanol.0.44 yuan/gram of the raw materials cost of this nano graphite flakes.
Embodiment 3
Taking bar-shaped graphite as electrode, put into the aqueous solution electrolysis 14 hours of sodium lauryl sulphate, voltage control is 30V, and electric current is 0.43A, and wherein the concentration of tensio-active agent in water is 40mg/mL; Residual to surfactant-free through the abundant diafiltration of deionized water; Fully dry under 50 DEG C of vacuum conditions.Obtain 1.8g nano graphite flakes, its specific conductivity is 1.1 × 10
-3s/cm.Product is good dispersity in DMF, DMAC, NMP, acetone and ethanol.0.07 yuan/gram of the raw materials cost of this nano graphite flakes.
Embodiment 4
Taking bar-shaped graphite as electrode, put into the aqueous solution electrolysis 18 hours of sodium stearate, voltage control is 30V, and electric current is 0.40A, and wherein the concentration of tensio-active agent in water is 30mg/mL; Residual to surfactant-free through the abundant diafiltration of deionized water; Fully dry under 40 DEG C of vacuum conditions.Obtain 0.65g nano graphite flakes, its specific conductivity is 3.7 × 10
-3s/cm.Product is good dispersity in DMF, DMAC, NMP.0.52 yuan/gram of the raw materials cost of this nano graphite flakes.
Embodiment 5
Taking bar-shaped graphite as electrode, put into the aqueous solution electrolysis 25 hours of cetyl trimethylammonium bromide, voltage control is 25V, and electric current is 0.1A, and wherein the concentration of tensio-active agent in water is 20mg/mL; Residual to surfactant-free through the abundant diafiltration of deionized water; Fully dry under room temperature vacuum condition.Obtain 0.69g nano graphite flakes, its specific conductivity is 3.3 × 10
-3s/cm.Product is good dispersity in DMF, DMAC, NMP, acetone and ethanol.1.61 yuan/gram of the raw materials cost of this nano graphite flakes.
Embodiment 6
Taking bar-shaped graphite as electrode, put into the aqueous solution electrolysis 25 hours of phenyl trimethyl ammonium chloride, voltage control is 15V, and electric current is 0.2A, and wherein the concentration of tensio-active agent in water is 20mg/mL; Residual to surfactant-free through the abundant diafiltration of deionized water; Fully dry under room temperature vacuum condition.Obtain 1.0g nano graphite flakes, its specific conductivity is 4.0 × 10
-1s/cm.Product is good dispersity in water.The raw materials cost 0.19-2.51 unit of this nano graphite flakes/gram.
Embodiment 7
Taking bar-shaped graphite as electrode, put into the aqueous solution electrolysis 40 hours of polyoxyethylene nonylphenol ether-20, voltage control is 30V, and electric current is 0.03A, and wherein the concentration of tensio-active agent in water is 5mg/mL; Residual to surfactant-free through the abundant diafiltration of deionized water; Fully dry under 50 DEG C of vacuum conditions.Obtain 1.4g nano graphite flakes, its specific conductivity is 7.1 × 10
-2s/cm.Product is good dispersity in DMF, DMAC, NMP.0.01 yuan/gram of the raw materials cost of this nano graphite flakes.
Embodiment 8
Taking bar-shaped graphite as electrode, put into the aqueous solution electrolysis 30 hours of L-PROLINE, voltage control is 30V, and electric current is 0.5A, and wherein the concentration of tensio-active agent in water is 5mg/mL; Residual to surfactant-free through the abundant diafiltration of deionized water; Fully dry under 50 DEG C of vacuum conditions.Obtain 1.2g nano graphite flakes, its specific conductivity is 6.0 × 10
-3s/cm.Product is good dispersity in DMF, DMAC, NMP and water.The raw materials cost 0.07-2.80 unit of this nano graphite flakes/gram.
Comparative example 1
Taking bar-shaped graphite as electrode, put into ionic liquid [omim]
+[PF6]
-middle electrolysis 24 hours, voltage control is 30V, electric current is 2A; Residual to surfactant-free through deionized water and the abundant diafiltration of ethanol; Fully dry under 50 DEG C of vacuum conditions.Obtain 1.6g nano graphite flakes, its specific conductivity is 5.7 × 10
-2s/cm.Product is good dispersity in DMF, DMAC, NMP.100 yuan/gram of the raw materials cost of this nano graphite flakes.Infrared spectrum is shown in Fig. 1.
Claims (2)
1. a method of preparing the nano graphite flakes with conductivity, is characterized in that: the method comprises the following steps:
(1) electrolysis:
Taking graphite as electrode, put into the aqueous solution electrolysis 2-40 hour of tensio-active agent, voltage control is 5-60V, and electric current is 0.01-2A, and wherein the concentration of tensio-active agent in water is 0.5mg/mL-100mg/mL, obtains nano graphite flakes A;
(2) diafiltration:
Gained nano graphite flakes A in step (1) is residual to surfactant-free with deionized water diafiltration, obtain the residual nano graphite flakes of surfactant-free;
(3) dry:
Nano graphite flakes residual gained surfactant-free in step (2), 100 DEG C of following abundant being dried, is obtained having the nano graphite flakes of conductivity;
Described tensio-active agent is selected from one or more in anion surfactant, cats product, nonionogenic tenside or amphoterics,
Wherein anion surfactant is selected from one or more in alkyl carboxylic salt, alkylsulfonate, alkyl-sulphate, alkylbenzene sulfonate or alkyl phosphate monoester salt; Cats product is selected from one or more in aliphatic quaternary ammonium salt, aromatic series quaternary ammonium salt, alkyl imidazoline quaternary ammonium salt or Fixanol; Nonionogenic tenside is selected from one or more in fatty alcohol-polyoxyethylene ether, alkylphenol polyoxyethylene, aliphatic amine polyoxyethylene ether or polyoxyethylene carboxylate; Amphoterics is selected from one or more in betaines, amino acids or amphoteric imidazoline class; Wherein, described tensio-active agent with the carbonatoms of moieties be 1-18.
2. the preparation method of the nano graphite flakes with conductivity according to claim 1, is characterized in that: described anion surfactant is selected from one or more in benzene sulfonamide acid potassium salt, alkyl benzene sulphonate (ABS) sodium salt, benzene sulfonamide acid ammonium salt, alkylsulphonic acid sylvite, mersolates, alkylsulphonic acid ammonium salt, alkylsurfuric acid sylvite, alkylsurfuric acid sodium salt, alkylsurfuric acid ammonium salt, alkyl carboxylic acid sylvite, alkyl carboxylic acid sodium salt or alkyl carboxylic acid ammonium salt;
Cats product is selected from one or more in alkyl trimethyl ammonium bromide, alkyl triethyl brometo de amonio, alkyl trimethyl ammonium chloride, alkyl triethyl ammonium chloride, phenyl or benzyl trimethyl ammonium chloride, phenyl or benzyltrimethylammonium bromide, alkyl imidazoline quaternary ammonium salt, alkyl-pyridiniums chloride or cetylpyridinium bromide salt;
Nonionogenic tenside is selected from one or more in alkyl alcohol polyoxyethylene (2-20) ether, polyoxyethylene (2-30) C8-15 base phenolic ether, alkylamine polyoxyethylene (2-20) ether or alkyl acid polyoxyethylene (2-20) ester;
Amphoterics is selected from alkyl dimethyl betaine, alkyl amido betaine, alkylamide L-Ala, alkylamide glycine, alkylamide L-glutamic acid, alkylamide Methionin, alkylamide proline(Pro), alkyl L-Ala, alkyl glycine, alkyl-glutamic acid, alkyl Methionin, alkyl proline(Pro), alkylamino L-Ala, alkylamino glycine, alkylamino L-glutamic acid, alkylamino Methionin, alkylamino proline(Pro), or one or more in alkyl sodium carboxymethyl tetrahydroglyoxaline,
Wherein, the carbonatoms of described moieties is 1-18.
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| CN103213970A (en) * | 2012-01-18 | 2013-07-24 | 中国科学院上海硅酸盐研究所 | Method for preparing graphene powder and graphene transparent conductive film by oxyhydrogen flame method |
| CN102593454B (en) * | 2012-03-02 | 2014-12-03 | 合肥工业大学 | Preparation method for headspace iron trioxide and polypyrrole composite electrode material |
| CN104264178B (en) * | 2014-09-17 | 2016-11-30 | 中国科学院青海盐湖研究所 | A kind of electrocatalytic oxidation prepares the method for graphene oxide |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1175268A (en) * | 1994-12-15 | 1998-03-04 | 卡伯特公司 | Carbon materials reacted with diazonium salts |
| CN101186808A (en) * | 2007-12-14 | 2008-05-28 | 华南理工大学 | Method for preparing graphite series nano fluid |
| US20100055458A1 (en) * | 2008-09-03 | 2010-03-04 | Jang Bor Z | Dispersible and conductive Nano Graphene Platelets |
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2010
- 2010-05-26 CN CN201010193713.6A patent/CN102259848B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1175268A (en) * | 1994-12-15 | 1998-03-04 | 卡伯特公司 | Carbon materials reacted with diazonium salts |
| CN101186808A (en) * | 2007-12-14 | 2008-05-28 | 华南理工大学 | Method for preparing graphite series nano fluid |
| US20100055458A1 (en) * | 2008-09-03 | 2010-03-04 | Jang Bor Z | Dispersible and conductive Nano Graphene Platelets |
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Effective date of registration: 20170607 Address after: Japan Tokyo central Nihonbashi Muromachi 1-1-2 Patentee after: Toray Inc. Address before: 226009 Nantong Province Economic and Technological Development Zone, the New South Road, No. 58, No. Patentee before: Toray Fiber Research Institute (China) Co., Ltd. Effective date of registration: 20170607 Address after: Japan Tokyo central Nihonbashi Muromachi 1-1-2 Patentee after: Toray Industries, Inc. Address before: 226009 Nantong Province Economic and Technological Development Zone, the New South Road, No. 58, No. Patentee before: Toray Fiber Research Institute (China) Co., Ltd. |
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