CN103665405A - Method for preparing ionic liquid modified graphene/polyaniline composite film - Google Patents
Method for preparing ionic liquid modified graphene/polyaniline composite film Download PDFInfo
- Publication number
- CN103665405A CN103665405A CN201310643616.6A CN201310643616A CN103665405A CN 103665405 A CN103665405 A CN 103665405A CN 201310643616 A CN201310643616 A CN 201310643616A CN 103665405 A CN103665405 A CN 103665405A
- Authority
- CN
- China
- Prior art keywords
- polyaniline
- graphene
- ion liquid
- modified graphene
- laminated film
- 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.)
- Pending
Links
Images
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a method for preparing an ionic liquid modified graphene/polyaniline conductive composite film by utilizing a self-assembly technology layer upon layer, belonging to a photoelectric composite material preparation technology field. The method comprises: immersing a treated substrate in a polyaniline aqueous solution surface-modified with sulfonyl or carboxyl for some time, immersing in the deionized water for some time after taking it out, immersing in an ionic liquid modified graphene aqueous dispersion liquid for some time after drying, drying after immersing in the deionized water for some time, and repeating the said process, to obtain the graphene-polyaniline uniform film with a regular layered structure. The graphene/polyaniline conductive composite film prepared by the method has advantages of regularity, uniformity, ultrathin thickness, and controllable structure and performance, and has a good application prospect in the sensor and super capacitor fields because the ionic liquid modified graphene does not affect conductivity of the grapheme.
Description
Technical field
The invention belongs to photoelectricity composite material preparation field, particularly relate to a kind of preparation method of ion liquid modified graphene/polyaniline laminated film.
Background technology
Graphene has had the performances such as unique structure and excellent electricity, calorifics, mechanics, the focus that studied person studies always since coming out.Compound having obtained of Graphene and conducting polymer paid close attention to widely, the long-range conjugated structure of polyaniline has been given its unique electricity and optical property, by Graphene and the compound graphene-polyaniline composite material obtaining of polyaniline comprehensively Graphene and polyaniline performance characteristics and advantage separately, in many application scenarios such as energy storage device, sensor, diode, electrochromic devices, there is prospect widely.At present, the methods such as chemistry polymerizing in situ method, electrochemical polymerization method, direct blend are often taked in the preparation of graphene-polyaniline composite material both at home and abroad, these methods are prepared graphene-polyaniline composite material, are all difficult to the component concentration of Graphene in matrix material and polyaniline, arrangement mode and Compound Degree to control.
It is simple that the technology of self-assembly layer by layer has preparation method, without complicated plant and instrument, film forming is not subject to the restriction of substrate sizes and shape, filmogen is abundant, the having good stability of film, and construction unit can be assembled in a certain order, with composition structure, arrangement mode and the thickness of the horizontal controlling diaphragm of supramolecule, thereby the performance of resulting laminated film is controlled etc. to advantage.In recent years, document Langmuir2012,12637-12646 etc. have reported by self-assembling method layer by layer and have prepared grapheme/polyaniline composite material, mainly to obtain laminated film by graphene oxide and the self-assembly layer by layer of polyaniline static, then laminated film is reduced under hydrazine hydrate or sodium borohydride solution, obtain graphene/polyaniline laminated film, when this can make graphene oxide reduce, also by polyaniline reduction, will affect conduction and the chemical property of polyaniline.In order to address this problem, there is at present document RSC Adv, 2013, 17866-17873 report is prepared the method for graphene/polyaniline laminated film by polymkeric substance as the modified graphenes such as sodium polystyrene sulfonate (PSS) and polyaniline self-assembly layer by layer, the laminated film that this method prepares has stronger detection performance to hydrogen peroxide, but because the polymkeric substance such as PSS are non-conductive, when having solved Graphene dispersiveness, also reduced the electronic transmission performance of Graphene, reduced the application performance of Graphene, especially reduced at sensor, the application of the field of electronic devices such as ultracapacitor.
Ionic liquid has low volatility, good chemical stability and thermostability, and the excellent advantages such as ionic conductivity have good application prospect in fields such as catalysis, synthetic, electrochemistry.At present, the preparation of ion liquid modified Graphene has been reported, and modified graphene prepared by this method has not only improved the dispersing property of Graphene, has also increased the electroconductibility of Graphene simultaneously.Due to ion liquid modified Graphene positively charged, the polyaniline of sulfonic group or carboxyl finishing is electronegative, take them as assembled unit, utilize static layer-by-layer to prepare ion liquid modified graphene/polyaniline laminated film, by overcoming the problem of existing existence, greatly improve its performance and using value.
Summary of the invention
Problem to be solved by this invention is to provide a kind of preparation method of ion liquid modified graphene/polyaniline laminated film, it is assembled unit that the method directly be take ion liquid modified Graphene and polyaniline, being assembled into Graphene with polyaniline together with, dependence electrostatic interaction forms graphene/polyaniline laminated film, preparation method is simple, the thickness of the graphene/polyaniline composite membrane of gained and properity etc. can be controlled effectively, be expected to be used widely aspect sensor, electrode and ultracapacitor.
The preparation method who the present invention relates to liquid modifying graphene/polyaniline laminated film, comprising:
(1) configure the polyaniline aqueous solution of ion liquid modified Graphene aqueous dispersions and process sulfonic group or carboxyl modified;
(2) substrate surface band positive electricity after treatment, is immersed in sulfonic group or the carboxy-modified polyaniline aqueous solution and is soaked 5～60min, then in deionized water, soaks 5～20min, and nitrogen or airflow dry up;
(3) substrate again second step being obtained is immersed in ion liquid modified Graphene aqueous dispersions and soaks 5～60min, then in deionized water, soaks 5～20min, and nitrogen or airflow dry up;
(4) repeat above-mentioned step (2) and (3) 2～100 times, obtain the ion liquid modified graphene/polyaniline laminated film of the different numbers of plies.
In above-mentioned steps (1), use ion liquid modified Graphene, make Graphene surface band positive electricity, and energy stable dispersion is in solvent; And modified polyaniline is electronegative under alkalescence condition, thereby Graphene and polyaniline assembled unit can rely on electrostatic interaction to mutually combine layer assembly to together.Wherein the pH value of ion liquid modified Graphene aqueous dispersions is 1～14, and the polyaniline pH value of water solution of sulfonic group or carboxyl modified is 7～14, and their concentration is all between 0.01～100mg/mL.
The present invention compares with art methods, its remarkable advantage: (1) has overcome the resulting graphene-polyaniline composite material of existing other technologies and do not can be uniformly dispersed, and can not effectively control matrix material Compound Degree, is difficult for the problem of machine-shaping.(2) overcome existing by the problem of graphene oxide and polyaniline self-assembly skill layer by layer p-poly-phenyl amine performance impact.(3) overcome the existing problem that affects graphene conductive performance by polymer modification graphene dispersing solution and polyaniline self-assembly layer by layer.(4) laminated film that prepared by this technology has good application prospect in fields such as sensor, ultracapacitor, photodiodes.
Accompanying drawing explanation
The SEM figure of the ion liquid modified graphene/polyaniline laminated film of Fig. 1.
SEM picture can observe the variation of the front and back of self-assembly layer by layer plate electrode surface topography and the variation of different layers number form looks.Due to electrostatic adsorption, electronegative modified polyaniline is deposited on the electrode surface of modification, and the ion liquid modified Graphene of positively charged electricity is adsorbed on the modified polyaniline surface of positively charged.Bare electrode (A) can be observed smooth surface, without any material; During deposition five layers (B), can observe the Graphene of obvious sheet structure and be adsorbed on fibrous polyaniline structure; Deposit ten layers (C) and can see that ionic liquid Graphene and modified polyaniline are combined with each other uniformly, also illustrated that increase Graphene and the polyaniline self-assembly layer by layer along with the number of plies obtained more uniform laminated film.
Embodiment
Below in conjunction with specific examples, further set forth the present invention.These examples are only not used in and limit the scope of the invention for the present invention is described.
Embodiment 1
The preparation of the ion liquid modified Graphene of the first step: 10mg glyoxaline ion liquid is joined in 10mg graphene oxide (0.5mg/L) uniform dispersion, add again 10mg KOH, ultrasonic dispersion 10min, mixing solutions is reacted to 24h 80 ℃ of stirred in water bath, centrifugal and with ethanol, deionized water wash, dry.
The preparation of the sulfonic group modified polyaniline of second step: the cyan acid of 0.5g is mixed to polyaniline and join in 40mL oleum and stir 2h, with methyl alcohol and acetone, product is precipitated out, with the deionized water that contains part methyl alcohol, product cleaning is extremely neutral again, vacuum-drying 24h, obtains dark cyan sulfonic acid modified polyaniline.0.5g sulfonic acid modified polyaniline is joined in 20mL0.1M NaOH solution, remove after most of water, vacuum-drying 24h, obtains the sulfonic acid modified polyaniline of intense violet color.
The 3rd step substrate is cleaned 10min successively in suds, acetone, ethanol, deionized water, substrate after cleaning is placed on and in PDDA solution, soaks 30min (wherein PDDA be 1wt%, the aqueous solution that contains 0.5M NaCl), use a large amount of washed with de-ionized water, dry up, make substrate surface positively charged.
The 4th step is made into by the sulfonic group modified polyaniline preparing the aqueous solution that concentration is 0.5mg/mL, then the electronegative substrate after modifying is soaked to 30min in its aqueous solution and makes its surface band negative electricity, with dry after washed with de-ionized water.
The 5th step is made into by the ion liquid modified Graphene preparing the aqueous dispersions that concentration is 0.5mg/mL, then the electronegative substrate after modifying is soaked to 30min therein and makes its surface band positive electricity, with dry after washed with de-ionized water.
The 6th step repeats the 4th above-mentioned step and and the 5th step 10 times.
The first step is with the first step in embodiment 1
Second step is with the second step in embodiment 1
The 3rd step is with the 3rd step in embodiment 1
It is that concentration is the aqueous solution of 1.0mg/mL that the 4th step is made into concentration by the sulfonic group modified polyaniline preparing, and then the electronegative substrate after modifying is soaked to 15min in its aqueous solution and makes its surface band negative electricity, with dry after washed with de-ionized water.
The 5th step is made into by the ion liquid modified Graphene preparing the aqueous dispersions that concentration is 0.5mg/mL, then the electronegative substrate after modifying is soaked to 30min therein and makes its surface band positive electricity, with dry after washed with de-ionized water.
The 6th step repeats the 4th above-mentioned step and and the 5th step 10 times.
Embodiment 3
The first step is with the first step in embodiment 1
Second step is with the second step in embodiment 1
The 3rd step is with the 3rd step in embodiment 1
It is that concentration is the aqueous solution of 0.5mg/mL that the 4th step is made into concentration by the sulfonic group modified polyaniline preparing, and then the electronegative substrate after modifying is soaked to 30min in its aqueous solution and makes its surface band negative electricity, with dry after washed with de-ionized water.
The 5th step is made into by the ion liquid modified Graphene preparing the aqueous dispersions that concentration is 1.0mg/mL, then the electronegative substrate after modifying is soaked to 15min therein and makes its surface band positive electricity, with dry after washed with de-ionized water.
The 6th step repeats the 4th above-mentioned step and the 5th step 15 times.
Claims (7)
1. a preparation method for ion liquid modified graphene/polyaniline laminated film, is characterized in that being prepared and being obtained by following steps:
(1) configure the polyaniline aqueous solution of ion liquid modified Graphene aqueous dispersions and process sulfonic group or carboxyl modified;
(2) substrate surface band positive electricity after treatment, is immersed in sulfonic group or the carboxy-modified polyaniline aqueous solution and is soaked 5～60min, then in deionized water, soaks 5～20min, and nitrogen or airflow dry up;
(3) substrate again second step being obtained is immersed in ion liquid modified Graphene aqueous dispersions and soaks 5～60min, then in deionized water, soaks 5～20min, and nitrogen or airflow dry up;
(4) repeat above-mentioned step (2) and (3) 2～100 times, obtain the ion liquid modified graphene/polyaniline laminated film of the different numbers of plies.
2. the preparation method of a kind of ion liquid modified graphene/polyaniline laminated film according to claim 1, it is characterized in that step (1) intermediate ion liquid modifying Graphene aqueous dispersions concentration is 0.05～100mg/mL, is 0.1～100mg/mL through the concentration of sulfonic group or the carboxy-modified polyaniline aqueous solution.
3. the preparation method of a kind of ion liquid modified graphene/polyaniline laminated film according to claim 1, the pH value that it is characterized in that step (1) intermediate ion liquid modifying Graphene aqueous dispersions is 1～14, and sulfonic group or carboxy-modified polyaniline pH value of water solution are 7～14.
4. the preparation method of a kind of ion liquid modified graphene/polyaniline laminated film according to claim 1, it is characterized in that in the middle polyaniline dispersion liquid of step (2), polyaniline makes surface with negative charge through sulfonic group or carboxyl finishing, step (3) intermediate ion liquid modifying Graphene surface is with positive charge.
5. the preparation method of a kind of ion liquid modified graphene/polyaniline laminated film according to claim 1, it is characterized in that in step (3) ionic liquid kind for modified graphene have imidazole salt, pyridine salt, quaternary ammonium salt and season phosphonium salt class etc.
6. the preparation method of a kind of ion liquid modified graphene/polyaniline laminated film according to claim 1, the preparation method who it is characterized in that step (3) intermediate ion liquid modifying Graphene is: 10～100mg ionic liquid (as imidazoles) is joined in 10～100mg graphene oxide (0.5～5mg/L) uniform dispersion, add again 10～100mg KOH, ultrasonic dispersion 10～60min, mixing solutions is reacted to 12～48h 50～100 ℃ of stirred in water bath, centrifugal and with ethanol, deionized water wash, dry.
7. according to the preparation method of a kind of ion liquid modified graphene/polyaniline laminated film claimed in claim 1, it is characterized in that substrate is opticglass, quartz, silicon single crystal, metal, Calcium Fluoride (Fluorspan) or plastics.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310643616.6A CN103665405A (en) | 2013-12-03 | 2013-12-03 | Method for preparing ionic liquid modified graphene/polyaniline composite film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310643616.6A CN103665405A (en) | 2013-12-03 | 2013-12-03 | Method for preparing ionic liquid modified graphene/polyaniline composite film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103665405A true CN103665405A (en) | 2014-03-26 |
Family
ID=50304250
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310643616.6A Pending CN103665405A (en) | 2013-12-03 | 2013-12-03 | Method for preparing ionic liquid modified graphene/polyaniline composite film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103665405A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103966594A (en) * | 2014-05-07 | 2014-08-06 | 哈尔滨工业大学 | Preparation method for polyaniline/sulfonated graphene composite film with gold surface |
| CN105601914A (en) * | 2015-12-29 | 2016-05-25 | 上海第二工业大学 | Preparing method of ionic liquid functionalized graphene/conductive polyaniline nanowire composition material |
| CN105932287A (en) * | 2016-05-24 | 2016-09-07 | 宁波墨西科技有限公司 | Graphene composite conductive agent and preparation method thereof |
| CN106442666A (en) * | 2016-08-11 | 2017-02-22 | 青岛科技大学 | Ionic liquid functional carbon nitride nanosheet modified electrode as well as preparation and application of electrode in chlorphenol detection |
| CN108275678A (en) * | 2017-12-28 | 2018-07-13 | 青岛科技大学 | A kind of graphene oxide/ionic liquid nanocomposite and preparation method thereof |
| CN109337671A (en) * | 2018-11-16 | 2019-02-15 | 北京航空航天大学 | Laminated photochromic film and preparation method thereof |
| CN109935727A (en) * | 2017-12-15 | 2019-06-25 | 京东方科技集团股份有限公司 | A kind of preparation method of substrate, display device and conductive film |
| CN114950169A (en) * | 2021-12-30 | 2022-08-30 | 昆明理工大学 | Ionic liquid-based high-performance conductive composite membrane and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102786705A (en) * | 2012-09-04 | 2012-11-21 | 江南大学 | Method for preparing graphene/polyaniline laminated films on basis of layer-by-layer self-assembly technique |
-
2013
- 2013-12-03 CN CN201310643616.6A patent/CN103665405A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102786705A (en) * | 2012-09-04 | 2012-11-21 | 江南大学 | Method for preparing graphene/polyaniline laminated films on basis of layer-by-layer self-assembly technique |
Non-Patent Citations (1)
| Title |
|---|
| CHENGZHOU ZHU ET AL.: ""Layer-by-Layer Self-Assembly for Constructing a Graphene/Platinum Nanoparticle Three-Dimensional Hybrid Nanostructure Using Ionic Liquid as a Linker"", 《LANGMUIR》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103966594A (en) * | 2014-05-07 | 2014-08-06 | 哈尔滨工业大学 | Preparation method for polyaniline/sulfonated graphene composite film with gold surface |
| CN105601914A (en) * | 2015-12-29 | 2016-05-25 | 上海第二工业大学 | Preparing method of ionic liquid functionalized graphene/conductive polyaniline nanowire composition material |
| CN105932287A (en) * | 2016-05-24 | 2016-09-07 | 宁波墨西科技有限公司 | Graphene composite conductive agent and preparation method thereof |
| CN106442666A (en) * | 2016-08-11 | 2017-02-22 | 青岛科技大学 | Ionic liquid functional carbon nitride nanosheet modified electrode as well as preparation and application of electrode in chlorphenol detection |
| CN106442666B (en) * | 2016-08-11 | 2019-01-18 | 青岛科技大学 | Ion liquid functionalization azotized carbon nano sheet modified electrode and its preparation and the application for detecting chlorophenol |
| CN109935727A (en) * | 2017-12-15 | 2019-06-25 | 京东方科技集团股份有限公司 | A kind of preparation method of substrate, display device and conductive film |
| US10892417B2 (en) | 2017-12-15 | 2021-01-12 | Boe Technology Group Co., Ltd. | Substrate, display device, conductive film with dopant and method for fabricating the same |
| CN108275678A (en) * | 2017-12-28 | 2018-07-13 | 青岛科技大学 | A kind of graphene oxide/ionic liquid nanocomposite and preparation method thereof |
| CN109337671A (en) * | 2018-11-16 | 2019-02-15 | 北京航空航天大学 | Laminated photochromic film and preparation method thereof |
| CN114950169A (en) * | 2021-12-30 | 2022-08-30 | 昆明理工大学 | Ionic liquid-based high-performance conductive composite membrane and preparation method and application thereof |
| CN114950169B (en) * | 2021-12-30 | 2023-06-09 | 昆明理工大学 | Ionic liquid-based high-performance conductive composite film and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103665405A (en) | Method for preparing ionic liquid modified graphene/polyaniline composite film | |
| Rajesh et al. | A high performance PEDOT/PEDOT symmetric supercapacitor by facile in-situ hydrothermal polymerization of PEDOT nanostructures on flexible carbon fibre cloth electrodes | |
| Boriboon et al. | Cellulose ultrafine fibers embedded with titania particles as a high performance and eco-friendly separator for lithium-ion batteries | |
| Du et al. | Rational-design of polyaniline cathode using proton doping strategy by graphene oxide for enhanced aqueous zinc-ion batteries | |
| Moon et al. | Three-dimensional porous stretchable supercapacitor with wavy structured PEDOT: PSS/graphene electrode | |
| Liu et al. | Facile preparation of graphene/polyaniline composite hydrogel film by electrodeposition for binder-free all-solid-state supercapacitor | |
| Xia et al. | A novel hierarchically structured and highly hydrophilic poly (vinyl alcohol-co-ethylene)/poly (ethylene terephthalate) nanoporous membrane for lithium-ion battery separator | |
| CN102250324B (en) | Preparation method of poly(3,4-ethylenedioxythiophene) (PEDOT)-coated carbon nanotube composite material | |
| CN104992853A (en) | Method of preparing flexible bendable thin film electrode of supercapacitor | |
| CN102543464B (en) | ZnO/reduced graphene oxide/polypyrrole ternary composite material preparation method, and application of the ternary composite material | |
| Ye et al. | A knittable fibriform supercapacitor based on natural cotton thread coated with graphene and carbon nanoparticles | |
| CN102786705A (en) | Method for preparing graphene/polyaniline laminated films on basis of layer-by-layer self-assembly technique | |
| CN103854878A (en) | Supercapacitor based on polypyrrole / manganese dioxide / carbon cloth and manufacturing method thereof | |
| Su et al. | Annealing-assisted dip-coating synthesis of ultrafine Fe3O4 nanoparticles/graphene on carbon cloth for flexible quasi-solid-state symmetric supercapacitors | |
| Zhuang et al. | Polyaniline-mediated coupling of Mn3O4 nanoparticles on activated carbon for high-performance asymmetric supercapacitors | |
| Liu et al. | Synchronous-ultrahigh conductive-reactive N-atoms doping strategy of carbon nanofibers networks for high‐performance flexible energy storage | |
| CN106283659A (en) | A kind of preparation method of electric-conducting polyimide fiber material | |
| CN105140042B (en) | A kind of preparation method and applications of bacteria cellulose/activated carbon fiber/CNT membrane material | |
| Wang et al. | Comparative study on polyvinyl chloride film as flexible substrate for preparing free-standing polyaniline-based composite electrodes for supercapacitors | |
| Sun et al. | Polypyrrole/SnCl2 modified bacterial cellulose electrodes with high areal capacitance for flexible supercapacitors | |
| CN103400701A (en) | Manganese dioxide/carbon nanotube composite material and preparation method thereof | |
| Xu et al. | Membrane-based symmetric supercapacitors composed of cellulose solution-derived polydopamine-modified separators and polypyrrole/graphene-doped polydopamine-modified electrodes | |
| Faraji et al. | 2.0-V flexible all-solid-state symmetric supercapacitor device with high electrochemical performance composed of MWCNTs-WO 3-graphite sheet | |
| Chen et al. | Recent advances in flexible supercapacitors | |
| Zhang et al. | Swelling-reconstructed chitosan-viscose nonwoven fabric for high-performance quasi-solid-state supercapacitors |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140326 |