CN102534730A - Preparation method for flexibly transparent high-conductivity graphene thin film - Google Patents
Preparation method for flexibly transparent high-conductivity graphene thin film Download PDFInfo
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- CN102534730A CN102534730A CN2012100422818A CN201210042281A CN102534730A CN 102534730 A CN102534730 A CN 102534730A CN 2012100422818 A CN2012100422818 A CN 2012100422818A CN 201210042281 A CN201210042281 A CN 201210042281A CN 102534730 A CN102534730 A CN 102534730A
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Abstract
The invention discloses a preparation method for a flexibly transparent high-conductivity graphene thin film, belonging to the field of an electronic information material. The preparation method provided by the invention comprises the following steps of: (1) by using low-temperature expandable graphite as a raw material, preparing a graphene solution by using a liquid phase for carrying out high-speed shearing emulsion and centrifugal seperation; (2) preparing a flexible graphene thin film from the graphene solution by using electrophoretic deposition; and (3) carrying out thermal treatment on the graphene thin film under an ammonia/nitrogen mixing atmosphere to prepare the flexibly transparent high-conductivity graphene thin film. The preparation method provided by the invention has the advantages of simple technology, non-pollution, low cost, adjustable size and the like; and the thin film can be widely applied to fields such as transparent conducting electrodes, anti-static anti-electromagnetic radiation thin films, super-capacitors, catalyst carriers and the like.
Description
Technical field
The present invention relates to a kind of transparent conductive graphene membrane preparation method, relate in particular to the high conductive graphene membrane preparation method of a kind of flexible and transparent.
Background technology
Transparent conductive film has been widely used in fields such as liquid crystal display (touch-screen), electromagnetic shielding door and window, freezer door glass, thermal reflecting coating, solar cell; Transparent conductive film commonly used at present is indium tin oxide (ITO); Has high transparent and high conduction performance; But raw material and equipment price are expensive, and production cost is higher.There are problems such as the big and conductivity less stable of rete fragility at aspect of performance ITO film.Compare with the ITO film; Graphene film not only possesses excellent light transmission and electroconductibility; And, have excellent chemicalstability again because it possesses good snappiness, be expected to aspect touch-screen and flexible transparency electrode, replace the ITO film; And aspect thermal reflecting coating, anti-electrostatic and electromagnetic shielding transparent window, obtain the application of high performance-price ratio, so one of emphasis direction that transparent conductive film is a Graphene to be used.
Graphene film mainly contains three kinds of preparing methods [M J Allen; V C Tung; R B Kaner. Honeycomb carbon:a review of graphene. Chem Rev 110 (2010) 132 – 145.]: vacuum filtration process, liquid phase coating method and chemical Vapor deposition process (CVD); Vacuum filtration process uses multiaperture pellumina under vacuum, to filter graphene oxide (or Graphene) solution; Carry out the gas chemistry reduction then and obtain graphene film, this method shifts through film can obtain single graphene film, loaded down with trivial details but the film shifting process is complicated.The liquid phase coating method can utilize spin coating, dip-coating or self-assembly to form film at substrate surface, heat-treats then to obtain graphene film (CN201010611061.3), and this method technology is easy, and specimen size is not limited.Vacuum filtration process and liquid phase coating method often need carry out chemical reduction reaction to graphene oxide film, and the oxygen-containing functional group of Graphene remained on surface influences its electroconductibility, so film conductivity is lower, square resistance is generally 10
3More than Ω/.Chemical Vapor deposition process uses can gasify the pyrolysated carbon source as raw material, and the pyrolytic carbon atom is dissolved in the transition metal substrate under the high temperature, separates out carbon atom after the cooling; Growth graphene film (CN201110092763.X, CN101760724B, 201010218410.5); Its transparency and electroconductibility are higher; Transparency is higher than 90%, and square resistance is tens ohms, but film thickness is difficult to control; And transition metal Cu, Ni paillon foil size as catalyzer in the experimentation are limited, are difficult to obtain the large size sample.
Electrophoretic deposition (EPD) is when counter electrode applies certain voltage in colloidal solution; Colloidal particle is shifted to electrode surface and is formed settled layer; Advantage such as this film (or coating) has thickness evenness height, good planeness, sedimentation velocity is fast and product size is adjustable has been successfully applied to Production of Ceramics [M Verde, A C Caballero; Y Iglesias; M Villegas, B Ferrari, Electrophoretic deposition of flake-shaped ZnO nanoparticles. J Electrochem Soc 157 (2010) H55 – H59.].Because there are a large amount of oxygen-containing functional groups in the graphene oxide surface of liquid phase oxidation preparation; Like hydroxyl, carbonyl, carboxyl, epoxide etc.; Effect of electric field will make electronegative graphene oxide move toward anode in the electrophoretic deposition process, and deposit and form film.Meanwhile, oxygen-containing functional group produces electrochemical reducting reaction at anode surface, thereby is decomposed elimination, makes graphene oxide be transformed into Graphene, has increased substantially the conductivity of film.The deposition and the electrochemical reduction of charged colloidal particle in the electrophoretic deposition process (graphene oxide) carry out simultaneously; The severe toxicity that has used when having avoided the graphene oxide liquid-phase reduction, explosive reductive agent (like Hydrazine Hydrate 80, dimethylhydrazine, sodium borohydride etc.) are a kind of easy, the quick and environment-friendly preparation method thereofs of Graphene and film thereof.With the graphite oxide aqueous solution is raw material, utilizes electrophoretic deposition on (anode) at the bottom of the stainless steel lining, to prepare specific conductivity up to 1.43 * 10
4Sm
-1Graphene film (S J An; Y W Zhu; S H Lee, et al. Thin Film Fabrication and Simultaneous Anodic Reduction of Deposited Graphene Oxide Platelets by Electrophoretic Deposition, J. Phys. Chem. Lett. 2010; 1,1259 – 1263).Ultimate analysis shows, anode surface generation oxidizing reaction in the electrophoretic deposition process is deposited on the oxidized decomposition of hydroxy-acid group in the graphene oxide of anode surface, thereby reduces oxygen-containing functional group quantity significantly, makes graphene oxide be transformed into the Graphene of conduction.Present electrophoretic deposition prepares graphene film and uses graphene oxide to be raw material (CN201110004775.2) usually; Because the graphene oxide preparation not only relates to strong acid (nitric acid, sulfuric acid) and strong oxidizer (potassium permanganate, ydrogen peroxide 50); When producing in batches, has certain dangerous and pollution; And a large amount of oxygen-containing functional groups is contained on the graphene oxide surface; These nonconducting functional groups are difficult to thorough oxidized decomposition at anode surface, especially when film thickness is big, thereby influence the electroconductibility of film.The graphene film electroconductibility of selecting other better conductivity Graphene raw materials to be paired in further raising electrophoretic deposition is significant.
Summary of the invention
The object of the invention is to provide the preparation method of the high conductive graphene membrane of a kind of flexible and transparent; This method synthesis has been considered material choice, thin film preparation process and film aftertreatment technology, improves the controllability of thin film preparation process, pollution-free, the transparency and high conductivity.Specifically comprise the following aspects:
(1) guaranteeing that Graphene has under the situation of certain productive rate, selecting better conductivity Graphene raw material, promptly reducing (non-conductive) oxygen-containing functional group density on Graphene raw material surface;
(2) graphene film of electrophoretic deposition preparation is heat-treated, further reduce the oxygen-containing functional group density on surface, improve film conductivity;
(3) thermal treatment process is combined with the doping of film, improve the electronic carrier concentration of film, significantly improve its electroconductibility.
The objective of the invention is to realize like this, it is characterized in that method steps is:
(1) is raw material with the expandable graphite at low-temperature, utilize the high speed shear mulser in liquid phase, to carry out emulsification pretreatment, and through spinning, the upper solution of acquisition is Graphene solution;
(2) with the stainless steel substrates being negative electrode, is anode with the stainless steel substrates that applies FM, prepares graphene film through electrophoretic deposition at anode surface by Graphene solution;
The graphene film that (3) will contain FM floods in acetone solvent, dissolves to remove FM, obtains soft graphite alkene film;
(4) soft graphite alkene film is heat-treated under the ammonia/nitrogen mixed atmosphere, prepare the high conductive graphene membrane of flexible and transparent.
The concentration of described expandable graphite at low-temperature is 0.1-10 mg/mL;
Described liquid phase is a kind of solvent in methane amide, N or the N,N-DIMETHYLACETAMIDE;
Described high speed shear emulsive mechanical rotor rotating speed is 5000-10000 rpm, and emulsification times is 10-120 min;
Described centrifugal rotational speed is 6000-10000 rpm, and centrifugation time is 0.2-1 h;
Described Graphene strength of solution is 0.01-1.0 mg/mL;
Described electrophoretic deposition carries out under constant-current mode, galvanic current 0.1-1.0 mA, and interelectrode distance is 0.2-10 mm, depositing time 0.5-15 min;
NH in the described graphene film thermal treatment mixed atmosphere
3/ N
2The ratio of gas flow is 1:9, and thermal treatment temp is 400-600 ℃, and heat treatment time is 0.5-2 h.
The invention has the advantages that: the raw material that use (1) is industrial goods expansible black lead alkene, prepares in the process of Graphene solution and does not use strong acid and strong oxidizer carrying out high speed shear emulsification, avoids occurring pollutant emission; (2) because expansible black lead is mainly the Graphene of atomic layers thick and the intercalation sulfate ion of interlayer thereof; So what high speed shear emulsification was prepared is that the surface contains a small amount of oxygen-containing functional group Graphene; Its non-conductive functional group densities is far below graphene oxide, and galvanic deposit has very high conductivity in the film of anode surface; (3) film thermal treatment is combined with the nitrogen ion doping, further eliminate the Graphene surface functional group, increase electronic carrier concentration, obtain the high conductive graphene membrane of flexible and transparent.
Embodiment
Embodiment 1
(1) with the expandable graphite at low-temperature is raw material; The preparation solid content is the dimethyl formamide solution of 0.5 mg/mL, in the high speed shear mulser, carries out emulsification pretreatment and spinning, and the upper solution of acquisition is Graphene solution; Wherein emulsification rotor speed is 10000 rpm; Emulsification times is 60 min, and centrifugal rotational speed is 10000 rpm, centrifugation time 1 h.
(2) be that the Graphene solution of 0.1 mg/mL is the electrophoretic deposition raw material with concentration; With the stainless steel substrates is negative electrode; Stainless steel substrates to apply FM is an anode, under constant-current mode, prepares graphene film through electrophoretic deposition at anode surface, and galvanic current is 0.5 mA; Interelectrode distance is 5 mm, depositing time 0.5 min.
The graphene film that (3) will contain FM floods in acetone solvent, dissolves to remove FM, obtains soft graphite alkene film.
(4) soft graphite alkene film (throughput ratio is 1:9) under the ammonia/nitrogen mixed atmosphere is heat-treated, thermal treatment temp is 500 ℃, and heat treatment time is 1 h, prepares the high conductive graphene membrane of flexible and transparent.
Using ellipsometer to measure soft graphite alkene film thickness is 120 nm, and the film clarity of ultraviolet-visible pectrophotometer test is 91% (550 nm), and it is 240 W/ that the four point probe tester is measured film rectangular resistance.
Embodiment 2
(1) with the expandable graphite at low-temperature is raw material; The preparation solid content is the dimethyl formamide solution of 5 mg/mL, in the high speed shear mulser, carries out emulsification pretreatment and spinning, and the upper solution of acquisition is Graphene solution; Wherein emulsification rotor speed is 10000 rpm; Emulsification times is 60 min, and the high speed centrifugation rotating speed is 6000 rpm, centrifugation time 0.2 h.
(2) be that the Graphene solution of 0.1 mg/mL is the electrophoretic deposition raw material with concentration; With the stainless steel substrates is negative electrode; Stainless steel substrates to apply FM is an anode, under constant-current mode, prepares graphene film through electrophoretic deposition at anode surface, and galvanic current is 1.0 mA; Interelectrode distance is 5 mm, depositing time 4 min.
The graphene film that (3) will contain FM floods in acetone solvent, dissolves to remove FM, obtains soft graphite alkene film.
(4) soft graphite alkene film (throughput ratio is 1:9) under the ammonia/nitrogen mixed atmosphere is heat-treated, thermal treatment temp is 500 ℃, and heat treatment time is 1 h, prepares the high conductive graphene membrane of flexible and transparent.
Using ellipsometer to measure soft graphite alkene film thickness is 470 nm, and the film clarity of ultraviolet-visible pectrophotometer test is 82 % (550 nm), and it is 90 W/ that the four point probe tester is measured film rectangular resistance.
Claims (5)
1. high conductive graphene membrane preparation method of flexible and transparent is characterized in that the graphene film step of preparation process is:
(1) is raw material with the expandable graphite at low-temperature, utilize the high speed shear mulser in liquid phase, to carry out emulsification pretreatment, and through spinning, the upper solution of acquisition is Graphene solution;
(2) with the stainless steel substrates being negative electrode, is anode with the stainless steel substrates that applies FM, prepares graphene film through electrophoretic deposition at anode surface by Graphene solution;
The graphene film that (3) will contain FM floods in acetone, dissolves to remove FM, obtains soft graphite alkene film;
(4) soft graphite alkene film is heat-treated under the ammonia/nitrogen mixed atmosphere, prepare the high conductive graphene membrane of flexible and transparent.
2. the high conductive graphene membrane preparation method of a kind of flexible and transparent according to claim 1, the concentration that it is characterized in that expandable graphite at low-temperature is 0.1-10 mg/mL; Used liquid phase is a kind of solvent in methane amide, N or the N,N-DIMETHYLACETAMIDE; High speed shear emulsive mechanical rotor rotating speed is 5000-10000 rpm, and emulsification times is 10-120 min; Centrifugal rotational speed is 6000-10000 rpm, centrifugation time 0.2-1 h.
3. the high conductive graphene membrane preparation method of a kind of flexible and transparent according to claim 1 is characterized in that the Graphene strength of solution is 0.01-1.0 mg/mL.
4. the high conductive graphene membrane preparation method of a kind of flexible and transparent according to claim 1 is characterized in that electrophoretic deposition carries out under constant-current mode, galvanic current 0.1-1.0 mA, interelectrode distance 0.2-10 mm, depositing time 0.5-15 min.
5. the high conductive graphene membrane preparation method of a kind of flexible and transparent according to claim 1 is characterized in that NH in the thermal treatment mixed atmosphere of graphene film
3/ N
2The ratio of gas flow is 1:9, and thermal treatment temp is 400-600 ℃, and heat treatment time is 0.5-2 h.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102701199A (en) * | 2012-07-15 | 2012-10-03 | 桂林理工大学 | Method for preparing graphene oxide by dispersed emulsion assisted with Hummers method |
| CN102877109A (en) * | 2012-09-19 | 2013-01-16 | 四川大学 | Method for preparing grapheme transparent conducting films by electrophoretic deposition |
| CN103924239A (en) * | 2013-01-16 | 2014-07-16 | 中国科学院上海硅酸盐研究所 | Preparation method for graphene-anodised aluminium composite conductive material |
| CN104058388A (en) * | 2013-03-18 | 2014-09-24 | 海洋王照明科技股份有限公司 | Nitrogen-doped graphene film and preparation method thereof and capacitor |
| CN104362326A (en) * | 2014-10-29 | 2015-02-18 | 华南师范大学 | Preparation method of flexible electrode material |
| CN106211732A (en) * | 2016-09-08 | 2016-12-07 | 河南民生特种装备有限公司 | Graphene film makees the electromagnetic shielding chamber of window |
| CN106531820A (en) * | 2016-09-14 | 2017-03-22 | 中国电子科技集团公司第四十八研究所 | Preparation method of graphene electrode suitable for HIT cell, graphene electrode and HIT cell |
| CN106652820A (en) * | 2016-12-28 | 2017-05-10 | 歌尔股份有限公司 | LED micro-display screen and preparing method thereof |
| CN106637923A (en) * | 2016-10-17 | 2017-05-10 | 哈尔滨工业大学 | Method of quickly and continuously depositing graphene on surface of electric-conductive fibers |
| CN107256809A (en) * | 2017-06-29 | 2017-10-17 | 河北工业大学 | A kind of preparation method of transparent flexible ultracapacitor |
| CN111653399A (en) * | 2020-07-13 | 2020-09-11 | 诸暨初升新材料科技有限公司 | Method for preparing transparent conductive film from carboxyl functionalized graphene |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102701199A (en) * | 2012-07-15 | 2012-10-03 | 桂林理工大学 | Method for preparing graphene oxide by dispersed emulsion assisted with Hummers method |
| CN102877109A (en) * | 2012-09-19 | 2013-01-16 | 四川大学 | Method for preparing grapheme transparent conducting films by electrophoretic deposition |
| CN103924239A (en) * | 2013-01-16 | 2014-07-16 | 中国科学院上海硅酸盐研究所 | Preparation method for graphene-anodised aluminium composite conductive material |
| CN104058388A (en) * | 2013-03-18 | 2014-09-24 | 海洋王照明科技股份有限公司 | Nitrogen-doped graphene film and preparation method thereof and capacitor |
| CN104362326A (en) * | 2014-10-29 | 2015-02-18 | 华南师范大学 | Preparation method of flexible electrode material |
| CN106211732A (en) * | 2016-09-08 | 2016-12-07 | 河南民生特种装备有限公司 | Graphene film makees the electromagnetic shielding chamber of window |
| CN106531820A (en) * | 2016-09-14 | 2017-03-22 | 中国电子科技集团公司第四十八研究所 | Preparation method of graphene electrode suitable for HIT cell, graphene electrode and HIT cell |
| CN106531820B (en) * | 2016-09-14 | 2019-01-25 | 中国电子科技集团公司第四十八研究所 | Graphene electrodes preparation method, Graphene electrodes and HIT battery suitable for HIT battery |
| CN106637923A (en) * | 2016-10-17 | 2017-05-10 | 哈尔滨工业大学 | Method of quickly and continuously depositing graphene on surface of electric-conductive fibers |
| CN106652820A (en) * | 2016-12-28 | 2017-05-10 | 歌尔股份有限公司 | LED micro-display screen and preparing method thereof |
| CN106652820B (en) * | 2016-12-28 | 2019-12-06 | 歌尔股份有限公司 | LED micro display screen and preparation method thereof |
| CN107256809A (en) * | 2017-06-29 | 2017-10-17 | 河北工业大学 | A kind of preparation method of transparent flexible ultracapacitor |
| CN111653399A (en) * | 2020-07-13 | 2020-09-11 | 诸暨初升新材料科技有限公司 | Method for preparing transparent conductive film from carboxyl functionalized graphene |
| CN111653399B (en) * | 2020-07-13 | 2021-08-06 | 诸暨初升新材料科技有限公司 | Method for preparing transparent conductive film from carboxyl functionalized graphene |
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Application publication date: 20120704 |