WO2013019101A1 - Composite electrode with in-situ polymerized polyaniline and preparation method thereof - Google Patents

Composite electrode with in-situ polymerized polyaniline and preparation method thereof Download PDF

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WO2013019101A1
WO2013019101A1 PCT/MY2012/000144 MY2012000144W WO2013019101A1 WO 2013019101 A1 WO2013019101 A1 WO 2013019101A1 MY 2012000144 W MY2012000144 W MY 2012000144W WO 2013019101 A1 WO2013019101 A1 WO 2013019101A1
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polyaniline
composite electrode
polysaccharide
weight
polyaniline composite
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PCT/MY2012/000144
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French (fr)
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Mohd Rais Ahmad
Sagir Alva
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Mimos Berhad
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/137—Electrodes based on electro-active polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3445—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/10—Esters of organic acids, i.e. acylates
    • C08L1/12—Cellulose acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/02—Polyamines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/0464—Electro organic synthesis
    • H01M4/0466—Electrochemical polymerisation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1399—Processes of manufacture of electrodes based on electro-active polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • H01M4/606—Polymers containing aromatic main chain polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/48—Conductive polymers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/125—Deposition of organic active material using liquid deposition, e.g. spin coating using electrolytic deposition e.g. in-situ electropolymerisation
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Definitions

  • the present invention relates generally to a composite electrode with in situ polymerized polyaniline comprising a composition of polyaniline, organic sulfonate, polysaccharide, imidazolium buffer and organic chemicals whereby said composite electrode can be used in various applications such as gas sensor, chemical sensor, electrochemical transducer, solar cell, super capacitor, corrosion protection layer etc. 2. BACKGROUND OF THE INVENTION
  • Conductive polymers such as polypyrrole, polyaniline and polythiophene have been used in a wide variety of electrochemical applications. The widespread use of these conducting polymers is due to some reasons such as ease of preparation, reproducible electrochemical characteristics, manufacturability for in volume production and low cost.
  • Polyaniline is one of the most important intrinsically conducting polymers due to the advantages of simple preparation, good chemical stability and high conductivity.
  • PANI and its composites are widely used as gas sensing materials for the detection of a number of chemicals.
  • Polymerization of aniline is often catalyzed by oxidizing agent such as ammonium persulfate.
  • the resulting polyaniline materials can appear in a number of forms depending on the charge at the nitrogen atoms.
  • different forms of polyaniline materials exhibit different degree of conductivity but invariably the polyaniline powder has no natural adhesion on electrode surface and only slightly soluble in most solvents.
  • the low solubility of polyaniline in common organic solvents causes difficulty in preparing polyaniline for casting or printing applications.
  • the electrodes are close to each other and electrical contacts are often inaccessible for electro-polymerization. Electrical contacts in miniaturized cells may liable to electrical shorting when the device is immersed in monomer solution. Therefore, other methods such as drop coating, solvent casting, screen printing or inkjet printing is more appropriate for applying polyaniline materials on electrode surface when electro-polymerization of the aniline monomer is not possible due to miniature size of the electrode.
  • the paste can be dispensed or printed onto the working electrode surface for a variety of applications such as in chemical sensors, amperometric cell and conductometric electrodes.
  • the ink or paste composition comprises binding component which is able to hold the polyaniline materials together while maintaining the conductive characteristic and electrochemical properties of polyaniline composite.
  • curing at near ambient temperature within short period of time is preferred because it will be convenient in manufacturing process as well as afford high throughput.
  • adhesion of the polyaniline materials on the electrode surface is the most important requirement in the preparation of polyaniline composite electrode.
  • the dispensed or printed polyaniline layer must exhibit strong adhesion to a wide range of electrode surface such as platinum, carbon, silver, silicon nitride, silicon, polysilicon, silicon oxide, polyester, FR4 or glass.
  • the polyaniline composite electrode is to be used as transducers in chemical sensors, the polyaniline composite layer must also able to provide good adhesion with a variety of polymeric sensing membranes such as PVC, acrylate, urethane or silicone rubber acting a sensing top layer.
  • Yet another object of the present invention is to provide a composite electrode with in situ polymerized polyaniline whereby the polyaniline is soluble in common organic solvent.
  • Yet another object of the present invention is to provide a composite electrode with in situ polymerized polyaniline which can be drop coated to afford homogenous phase of low impedance polymeric networks.
  • a polyaniline composite electrode comprising: an electrically-conductive substrate; a composition supported on said substrate; characterized in that said composition comprising: polyaniline; organic sulfonate; polysaccharide; imidazolium buffer; organic chemicals functioning as diluents in adjusting the viscosity of polyaniline ink; wherein in situ polymerized polyaniline is carried out to prepare said polyaniline composite electrode.
  • a method of preparing polyaniline composite electrode comprising steps of: i. mixing polysaccharide and organic sulfonic acid to produce positively charged polysaccharide and organic sulfonate salt solution; ii. mixing said polysaccharide-sulfonate salt solution with aniline to form doped monomer solution; iii. adding imidazolium buffer to said doped aniline monomer solution; iv. performing electropolymerization towards said doped aniline monomer solution to form doped polyaniline ink; v. applying said polyaniline ink on electrode surface; vi. curing said applied polyaniline ink under inert environment 4.
  • FIG. 1 is a polyaniline composite electrode of the present invention which is prepared via in situ polymerization of polyaniline.
  • FIG. 2 is a flow chart of preparation method for polyaniline composite electrode.
  • FIG. 3 is the aniline monomer solution in cellulose acetate-camphor sulfonate-methyl imidazolium dopant.
  • FIG. 4 is the polyaniline composite ink doped with camphor sulfonate which appears as dark colour solution.
  • FIG. 5 is the doped polyaniline composite electrode with camphor sulfonate dopant.
  • FIG. 6 is an exemplary of cyclic voltammetry graph of in situ polymerized polyaniline in cellulose acetate-camphor sulfonate.
  • polyaniline (PANI) composite electrode of the present invention which is prepared via in situ polymerization of polyaniline.
  • Said polyaniline composite electrode comprises of an electrically- conductive substrate and a composition supported on said substrate, wherein said composition comprising conductive polyaniline, organic sulfonate dopant, polysaccharide, imidazolium buffer and organic chemicals functioning as diluents in adjusting the viscosity of the doped polyaniline or polyaniline ink.
  • polysaccharide-sulfonate salt solution is prepared by mixing polysaccharide and organic sulfonic acid to produce positively charged polysaccharide and organic sulfonate salt solution.
  • polysaccharide-sulfonate salt solution is prepared by mixing polysaccharide and organic sulfonic acid to produce positively charged polysaccharide and organic sulfonate salt solution.
  • at least 1 % by weight to 10 % by weight of polysaccharide and at least 1 % by weight to 30 % by weight of organic sulfonic acid is used in the preparation of polysaccharide-sulfonate salt solution.
  • a solution of polysaccharide such as cellulose acetate and organic sulfonic acid such as camphor sulfonic acid is prepared by mixing the reagents in polar solvent such as tetrahydrofuran.
  • polar solvent such as tetrahydrofuran.
  • other polysaccharides low impedance polymeric materials such as ethyl cellulose, cellulose, chitosan, starch, dextrin, maltodextrin, beta-glucan, chitin, mannan, galactan, fructan or combination thereof can be used in place of cellulose acetate.
  • organic sulfonic acid such as dodecyl benzene sulfonic acid, polystyrene sulfonic acid, toluene sulfonic acid, Nafion, apolate or combination thereof can be used in place of camphor sulfonic acid.
  • Other solvent such as ethanol, 2-methoxyethanol, 2- propanol, acetone, 2-butanone, cyclohexanone, diethyl ether, methanol, trifluoroethanol, N-methyl pyrrolidone or combination thereof can be used in place of tetrahydrofuran.
  • polysaccharide-sulfonate white solid salt is precipitated out from the solution.
  • ethanol is added to re-dissolve the salt precipitate.
  • Said organic sulfonate functions as dopant for positively charged conductive polyaniline.
  • Said positively charged polysaccharide is used as polymeric cation counterion for organic sulfonate dopant and to provide electrical path during electropolymerization.
  • Uncharged polysaccharide is used to form low impedance polymeric networks as binder for polyaniline and other components.
  • aniline monomer solution is prepared by adding approximately 5 % by weight to 30 % weight of aniline to the polysaccharide- sulfonate salt solution, for example cellulose acetate-camphor sulfonate doped electrolyte. Positively charged polysaccharide is formed along with camphor sulfonate dopant.
  • polysaccharide- sulfonate salt solution for example cellulose acetate-camphor sulfonate doped electrolyte.
  • Positively charged polysaccharide is formed along with camphor sulfonate dopant.
  • imidazolium buffer such as methyl imidazole-methyl imidazolium solution, dodecyl imidazole, decyl imidazole or other polymeric imidazolium ion such as poly(4-vinyl imidazole) or combination thereof is added to said aniline monomer solution to increase the conductivity of the mixture as well as to provide stable electrical current path during electropolymerization in a potentiostat setup and assists oxidation of aniline.
  • imidazolium buffer such as methyl imidazole-methyl imidazolium solution, dodecyl imidazole, decyl imidazole or other polymeric imidazolium ion such as poly(4-vinyl imidazole) or combination thereof is added to said aniline monomer solution to increase the conductivity of the mixture as well as to provide stable electrical current path during electropolymerization in a potentiostat setup and assists oxidation of aniline.
  • reference electrode such as silver-silver chloride reference electrode
  • counter electrode such as platinum counter electrode
  • inert working electrode such as glassy carbon working electrodes
  • in situ electropolymerization occurs towards said aniline monomer solution to form doped polyaniline.
  • aniline monomer is polymerized by controlling the current density across the solution. The solution turns into dark in colour as doped polyaniline is formed.
  • the doped polyaniline or the polyaniline ink can be applied on said electrically-conductive substrate or electrode surface using the preferred coating technique such as screen printing, stencil printing, inkjet printing, solution casting and spin coating.
  • the conductive polyaniline function as active sensing agent or as electrochemical transducer.
  • Approximately 25 % by weight to 85 % by weight of organic chemical or solvent is added as diluents in each mixing to adjust the viscosity of the polyaniline ink.
  • Said organic chemicals comprises of the chemicals such as 2-methoxyethanol, n-methyl pyrrolidone, carbitol, butyl glycol, acrylic acid, pyruvic acid, ethyl acetate, tetrahydrofuran, toluene, xylene, propanol or combination thereof. Therefore, the concentration of said doped polyaniline can be controlled by the volume of organic chemicals to be added.
  • the applied polyaniline ink is cured under inert environment to evaporate off the solvents under continuous flow of nitrogen gas.
  • the deposited doped conductive polyaniline is characterized by performing cyclic voltammetry between -1V to 1V in potassium chloride solution. The example of the CV plot is described in FIG. 6. Exemplary embodiment of the method of the invention is described hereinafter and should not be construed to limit the scope of the present invention.
  • Polysaccharide-sulfonate salt solution was prepared by mixing 500 mg cellulose acetate and 74.8 mg camphor sulfonic acid (0.322 mmol). 10 ml of tetrahydrofuran (THF) was added into the mixture to achieve homogenous colourless solutions. After that, said homogenous solutions were mixed with 0.3 g (3.22 mmol) aniline and 500 ⁇ _ methyl imidazole-methyl immidazolium buffer solution. The mixture was stirred continuously until colourless viscous aniline monomer solution is obtained as illustrated in FIG. 3. The material was then electrochemically polymerized by using potentiostat such as Autolab PGSTAT Model 128N for 600 seconds.
  • potentiostat such as Autolab PGSTAT Model 128N for 600 seconds.
  • FIG. 5 shows the polyaniline composite electrode prepared by in situ polymerization of aniline monomer in cellulose-camphor sulfonate solution.
  • SPE Screen printed carbon electrodes
  • 30 ⁇ _ of PANI-CSA ink composition was dropped onto the cleaned carbon surface and dried over an hour under continuous flow of nitrogen gas.
  • the Electrode was characterized with cyclic voltammetric using potentiostat such as Autolab PGSTAT Model 128N with scan at -1V to +1V and scan rate at 0.1V/s in 0.1 M KCI solution.
  • the cyclic voltammetry graph is shown in FIG. 6.
  • polyaniline conducting polymers is applied for chemical sensor in the aforementioned embodiment, the present invention is not restricted to this but may alternatively be applied to other applications such as a gas sensor, electrochemical transducer, solar cell, super capacitor, electrode in lithium battery, corrosion protection layer etc.

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Abstract

The present invention relates generally to a composite electrode with in situ polymerized polyaniline comprising a composition of polyaniline, organic sulfonate, polysaccharide, imidazolium buffer and organic chemicals whereby said composite electrode can be used in various applications such as gas sensor, chemical sensor, electrochemical transducer, solar cell, super capacitor, corrosion protection layer etc.

Description

COMPOSITE ELECTRODE WITH IN-SITU POLYMERIZED POLYANILINE AND PREPARATION METHOD THEREOF
1. TECHNICAL FIELD OF THE INVENTION
The present invention relates generally to a composite electrode with in situ polymerized polyaniline comprising a composition of polyaniline, organic sulfonate, polysaccharide, imidazolium buffer and organic chemicals whereby said composite electrode can be used in various applications such as gas sensor, chemical sensor, electrochemical transducer, solar cell, super capacitor, corrosion protection layer etc. 2. BACKGROUND OF THE INVENTION
Conductive polymers such as polypyrrole, polyaniline and polythiophene have been used in a wide variety of electrochemical applications. The widespread use of these conducting polymers is due to some reasons such as ease of preparation, reproducible electrochemical characteristics, manufacturability for in volume production and low cost.
Polyaniline (PANI) is one of the most important intrinsically conducting polymers due to the advantages of simple preparation, good chemical stability and high conductivity. For example, PANI and its composites are widely used as gas sensing materials for the detection of a number of chemicals. Polymerization of aniline is often catalyzed by oxidizing agent such as ammonium persulfate. The resulting polyaniline materials can appear in a number of forms depending on the charge at the nitrogen atoms. Typically different forms of polyaniline materials exhibit different degree of conductivity but invariably the polyaniline powder has no natural adhesion on electrode surface and only slightly soluble in most solvents. The low solubility of polyaniline in common organic solvents causes difficulty in preparing polyaniline for casting or printing applications.
In miniaturized sensing devices, the electrodes are close to each other and electrical contacts are often inaccessible for electro-polymerization. Electrical contacts in miniaturized cells may liable to electrical shorting when the device is immersed in monomer solution. Therefore, other methods such as drop coating, solvent casting, screen printing or inkjet printing is more appropriate for applying polyaniline materials on electrode surface when electro-polymerization of the aniline monomer is not possible due to miniature size of the electrode.
If polyaniline composite paste is to be prepared, the paste can be dispensed or printed onto the working electrode surface for a variety of applications such as in chemical sensors, amperometric cell and conductometric electrodes. Moreover, it is important that the ink or paste composition comprises binding component which is able to hold the polyaniline materials together while maintaining the conductive characteristic and electrochemical properties of polyaniline composite. In addition to this, curing at near ambient temperature within short period of time is preferred because it will be convenient in manufacturing process as well as afford high throughput.
Therefore, adhesion of the polyaniline materials on the electrode surface is the most important requirement in the preparation of polyaniline composite electrode. Furthermore, the dispensed or printed polyaniline layer must exhibit strong adhesion to a wide range of electrode surface such as platinum, carbon, silver, silicon nitride, silicon, polysilicon, silicon oxide, polyester, FR4 or glass. Likewise if the polyaniline composite electrode is to be used as transducers in chemical sensors, the polyaniline composite layer must also able to provide good adhesion with a variety of polymeric sensing membranes such as PVC, acrylate, urethane or silicone rubber acting a sensing top layer.
It would hence be extremely advantageous to develop a method for preparing of polyaniline composite electrode through depositing homogenous phase of polyaniline conductive polymer on electrode surface by a coating technique such as solution casting method. In situ polymerized doped polyaniline which comprises of polyaniline, polysaccharide, organic sulfonate dopant and imidazolium buffer are drop coated to generate homogenous phase of low impedance polymeric networks. The obtained polyaniline composite not only exhibits good adhesion to electrode surface and but also affords reproducible electrochemical characteristics. 3. SUMMARY OF THE INVENTION
Accordingly, it is the primary aim of the present invention to provide a composite electrode with in situ polymerized polyaniline whereby the polyaniline composite exhibits good adhesion to a wide range of electrode surface. It is another object of the present invention to provide a composite electrode with in situ polymerized polyaniline whereby the polyaniline ink can be prepared for casting or printing application.
It is another object of the present invention to provide a composite electrode with in situ polymerized polyaniline which can be prepared within the binding matrix to produce homogenous solution of doped polyaniline.
Yet another object of the present invention is to provide a composite electrode with in situ polymerized polyaniline whereby the polyaniline is soluble in common organic solvent.
Yet another object of the present invention is to provide a composite electrode with in situ polymerized polyaniline which can be drop coated to afford homogenous phase of low impedance polymeric networks.
Other and further objects of the invention will become apparent with an understanding of the following detailed description of the invention or upon employment of the invention in practice. According to a preferred embodiment of the present invention there is provided,
A polyaniline composite electrode comprising: an electrically-conductive substrate; a composition supported on said substrate; characterized in that said composition comprising: polyaniline; organic sulfonate; polysaccharide; imidazolium buffer; organic chemicals functioning as diluents in adjusting the viscosity of polyaniline ink; wherein in situ polymerized polyaniline is carried out to prepare said polyaniline composite electrode.
In another aspect there is provided, A method of preparing polyaniline composite electrode comprising steps of: i. mixing polysaccharide and organic sulfonic acid to produce positively charged polysaccharide and organic sulfonate salt solution; ii. mixing said polysaccharide-sulfonate salt solution with aniline to form doped monomer solution; iii. adding imidazolium buffer to said doped aniline monomer solution; iv. performing electropolymerization towards said doped aniline monomer solution to form doped polyaniline ink; v. applying said polyaniline ink on electrode surface; vi. curing said applied polyaniline ink under inert environment 4. BRIEF DESCRIPTION OF THE DRAWINGS
Other aspect of the present invention and their advantages will be discerned after studying the Detailed Description in conjunction with the accompanying drawings in which: FIG. 1 is a polyaniline composite electrode of the present invention which is prepared via in situ polymerization of polyaniline.
FIG. 2 is a flow chart of preparation method for polyaniline composite electrode. FIG. 3 is the aniline monomer solution in cellulose acetate-camphor sulfonate-methyl imidazolium dopant.
FIG. 4 is the polyaniline composite ink doped with camphor sulfonate which appears as dark colour solution.
FIG. 5 is the doped polyaniline composite electrode with camphor sulfonate dopant.
FIG. 6 is an exemplary of cyclic voltammetry graph of in situ polymerized polyaniline in cellulose acetate-camphor sulfonate.
5. DETAILED DESCRIPTION OF THE DRAWINGS
In the following detailed description, numerous specific details are set forth in order to provide a thorough understanding of the invention. However, it will be understood by those or ordinary skill in the art that the invention may be practised without these specific details. In other instances, well known methods, procedures and/or components have not been described in detail so as not to obscure the invention. The invention will be more clearly understood from the following description of the embodiments thereof, given by way of example only with reference to the accompanying drawings which are not drawn to scale.
Referring to FIG. 1 , there is shown the polyaniline (PANI) composite electrode of the present invention which is prepared via in situ polymerization of polyaniline. Said polyaniline composite electrode comprises of an electrically- conductive substrate and a composition supported on said substrate, wherein said composition comprising conductive polyaniline, organic sulfonate dopant, polysaccharide, imidazolium buffer and organic chemicals functioning as diluents in adjusting the viscosity of the doped polyaniline or polyaniline ink.
Referring to FIG. 2, there is shown a flow chart of preparation method for polyaniline composite electrode. Said preparation method for polyaniline composite electrode typically comprises of six steps, whereby said preparation method can be carried at room temperature without heat requirement. In the first step, polysaccharide-sulfonate salt solution is prepared by mixing polysaccharide and organic sulfonic acid to produce positively charged polysaccharide and organic sulfonate salt solution. Preferably, at least 1 % by weight to 10 % by weight of polysaccharide and at least 1 % by weight to 30 % by weight of organic sulfonic acid is used in the preparation of polysaccharide-sulfonate salt solution. For example, a solution of polysaccharide such as cellulose acetate and organic sulfonic acid such as camphor sulfonic acid is prepared by mixing the reagents in polar solvent such as tetrahydrofuran. Alternatively other polysaccharides low impedance polymeric materials such as ethyl cellulose, cellulose, chitosan, starch, dextrin, maltodextrin, beta-glucan, chitin, mannan, galactan, fructan or combination thereof can be used in place of cellulose acetate. Other organic sulfonic acid such as dodecyl benzene sulfonic acid, polystyrene sulfonic acid, toluene sulfonic acid, Nafion, apolate or combination thereof can be used in place of camphor sulfonic acid. Other solvent such as ethanol, 2-methoxyethanol, 2- propanol, acetone, 2-butanone, cyclohexanone, diethyl ether, methanol, trifluoroethanol, N-methyl pyrrolidone or combination thereof can be used in place of tetrahydrofuran. Depending on the ratio of polysaccharide to organic sulfonic acid, polysaccharide-sulfonate white solid salt is precipitated out from the solution. In this case ethanol is added to re-dissolve the salt precipitate. Said organic sulfonate functions as dopant for positively charged conductive polyaniline. Said positively charged polysaccharide is used as polymeric cation counterion for organic sulfonate dopant and to provide electrical path during electropolymerization. Uncharged polysaccharide is used to form low impedance polymeric networks as binder for polyaniline and other components.
In the second step aniline monomer solution is prepared by adding approximately 5 % by weight to 30 % weight of aniline to the polysaccharide- sulfonate salt solution, for example cellulose acetate-camphor sulfonate doped electrolyte. Positively charged polysaccharide is formed along with camphor sulfonate dopant. In the third step approximately 1 % by weight to 5 % by weight of imidazolium buffer such as methyl imidazole-methyl imidazolium solution, dodecyl imidazole, decyl imidazole or other polymeric imidazolium ion such as poly(4-vinyl imidazole) or combination thereof is added to said aniline monomer solution to increase the conductivity of the mixture as well as to provide stable electrical current path during electropolymerization in a potentiostat setup and assists oxidation of aniline.
In the fourth step reference electrode such as silver-silver chloride reference electrode, counter electrode such as platinum counter electrode and inert working electrode such as glassy carbon working electrodes are immersed into the buffered aniline monomer solution. In situ electropolymerization occurs towards said aniline monomer solution to form doped polyaniline. In a potentiostat setup the aniline monomer is polymerized by controlling the current density across the solution. The solution turns into dark in colour as doped polyaniline is formed.
In the fifth step, the doped polyaniline or the polyaniline ink can be applied on said electrically-conductive substrate or electrode surface using the preferred coating technique such as screen printing, stencil printing, inkjet printing, solution casting and spin coating. The conductive polyaniline function as active sensing agent or as electrochemical transducer. Approximately 25 % by weight to 85 % by weight of organic chemical or solvent is added as diluents in each mixing to adjust the viscosity of the polyaniline ink. Said organic chemicals comprises of the chemicals such as 2-methoxyethanol, n-methyl pyrrolidone, carbitol, butyl glycol, acrylic acid, pyruvic acid, ethyl acetate, tetrahydrofuran, toluene, xylene, propanol or combination thereof. Therefore, the concentration of said doped polyaniline can be controlled by the volume of organic chemicals to be added. In the sixth step, the applied polyaniline ink is cured under inert environment to evaporate off the solvents under continuous flow of nitrogen gas. The deposited doped conductive polyaniline is characterized by performing cyclic voltammetry between -1V to 1V in potassium chloride solution. The example of the CV plot is described in FIG. 6. Exemplary embodiment of the method of the invention is described hereinafter and should not be construed to limit the scope of the present invention.
Example 1
Preparation of polyaniline-cellulose acetate-camphor sulfonate composite solution:
Polysaccharide-sulfonate salt solution was prepared by mixing 500 mg cellulose acetate and 74.8 mg camphor sulfonic acid (0.322 mmol). 10 ml of tetrahydrofuran (THF) was added into the mixture to achieve homogenous colourless solutions. After that, said homogenous solutions were mixed with 0.3 g (3.22 mmol) aniline and 500 μΙ_ methyl imidazole-methyl immidazolium buffer solution. The mixture was stirred continuously until colourless viscous aniline monomer solution is obtained as illustrated in FIG. 3. The material was then electrochemically polymerized by using potentiostat such as Autolab PGSTAT Model 128N for 600 seconds. The polymerization cycles were repeated for 10 times at 2 mA cm"2 current density in a three-electrode cell, whereby platinum stick as counter electrode, silver-silver chloride (Ag/AgCI) wire as reference electrode and glassy carbon stick as working electrode. The polyaniline composite ink doped with camphor sulfonate is obtained which appears as dark solution as shown in FIG. 4. FIG. 5 shows the polyaniline composite electrode prepared by in situ polymerization of aniline monomer in cellulose-camphor sulfonate solution.
Example 2
Preparation of PANI-CSA Nano Composite Electrode
Screen printed carbon electrodes (SPE) with 4 mm diameter were cleaned ultrasonically with deionized water for 1 minute. 30 μΙ_ of PANI-CSA ink composition was dropped onto the cleaned carbon surface and dried over an hour under continuous flow of nitrogen gas. The Electrode was characterized with cyclic voltammetric using potentiostat such as Autolab PGSTAT Model 128N with scan at -1V to +1V and scan rate at 0.1V/s in 0.1 M KCI solution. The cyclic voltammetry graph is shown in FIG. 6. While the polyaniline conducting polymers is applied for chemical sensor in the aforementioned embodiment, the present invention is not restricted to this but may alternatively be applied to other applications such as a gas sensor, electrochemical transducer, solar cell, super capacitor, electrode in lithium battery, corrosion protection layer etc.
While the preferred embodiment of the present invention and its advantages has been disclosed in the above Detailed Description, the invention is not limited thereto but only by the scope of the appended claim.

Claims

WHAT IS CLAIMED IS:
1. A polyaniline composite electrode comprising: an electrically-conductive substrate; a composition supported on said substrate; characterized in that said composition comprising: polyaniline; organic sulfonate; polysaccharide; imidazolium buffer; organic chemicals functioning as diluents in adjusting the viscosity of said polyaniline solution; wherein in situ polymerized polyaniline is carried out to prepare said polyaniline composite electrode.
2. A polyaniline composite electrode as claimed in Claim 1 wherein said organic sulfonate is camphor sulfonate, dodecyl benzene sulfonate, polystyrene sulfonate, toluene sulfonate, Nafion, apolate or combination thereof with a range of 1 % by weight to 30 % by weight of organic sulfonic acid is used.
3. A polyaniline composite electrode as claimed in Claim 1 wherein said polysaccharide is cellulose acetate, ethyl cellulose, cellulose, chitosan, starch, dextrin, maltodextrin, beta-glucan, chitin, mannan, galactan, fructan or combination thereof with a range of 1 % by weight to 10 % by weight of polysaccharide is used.
4. A polyaniline composite electrode as claimed in Claim 1 wherein approximately 5 % by weight to 30 % weight of aniline is added to prepare aniline monomer solution.
5. A polyaniline composite electrode as claimed in Claim 1 wherein said imidazolium buffer is methyl imidazole-methyl imidazolium solution, dodecyl imidazole, decyl imidazole, poly(4-vinyl imidazole) or combination thereof with a range of 1 % by weight to 5 % by weight of imidazolium buffer is used.
6. A polyaniline composite electrode as claimed in Claim 1 wherein said organic chemicals is 2-methoxyethanol, n-methyl pyrrolidone, carbitol, butyl glycol, acrylic acid, pyruvic acid, ethyl acetate, tetrahydrofuran, toluene, xylene, propanol or combination thereof with a range of 25 % by weight to 85 % by weight of organic chemicals is used.
7. A polyaniline composite electrode as claimed in Claim 1 wherein said polyaniline composite electrode can be used as a chemical sensor, gas sensor, electrochemical transducer, solar cell, super capacitor, electrode in lithium battery and corrosion protection layer.
8. A method of preparing polyaniline composite electrode comprising steps of: i. mixing polysaccharide and organic sulfonic acid to produce positively charged polysaccharide and organic sulfonate salt solution; ii. mixing said polysaccharide-sulfonate salt solution with aniline to form doped aniline monomer solution; iii. adding imidazolium buffer to said doped aniline monomer solution; iv. performing electropolymerization towards said doped aniline monomer solution to form doped polyaniline; v. applying said polyaniline on electrically-conductive substrate; vi. curing said applied polyaniline under inert environment.
9. A method of preparing polyaniline composite electrode as claimed in Claim 8 wherein solvent comprising of ethanol, tetrahydrofuran, 2-methoxyethanol, 2-propanol, acetone, 2-butanone, cyclohexanone, diethyl ether, methanol, trifluoroethanol, N-methyl pyrrolidone or combination thereof is added after said step of mixing polysaccharide and organic sulfonic acid to obtain homogeneous solution of said polysaccharide-sulfonate salt solution.
10. A method of preparing polyaniline composite electrode as claimed in Claim 8 wherein said method of preparing polyaniline composite electrode is carried out at room temperature without heat requirement.
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