WO2013028061A1 - Polyaniline composite electrode and method of preparing the polyaniline composite electrode - Google Patents

Polyaniline composite electrode and method of preparing the polyaniline composite electrode Download PDF

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Publication number
WO2013028061A1
WO2013028061A1 PCT/MY2012/000190 MY2012000190W WO2013028061A1 WO 2013028061 A1 WO2013028061 A1 WO 2013028061A1 MY 2012000190 W MY2012000190 W MY 2012000190W WO 2013028061 A1 WO2013028061 A1 WO 2013028061A1
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electrode
polyaniline
polyaniline composite
low impedance
weight percent
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PCT/MY2012/000190
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French (fr)
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Mohd. Rais Ahmad
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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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • 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
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0414—Methods of deposition of the material by screen printing
    • 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
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • 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

Definitions

  • the present invention relates to polyaniline composite electrode and method of preparing the polyaniline composite electrode.
  • polymerization of aniline is often catalyzed by oxidizing agent such as ammonium persulfate as shown in Scheme 1.
  • oxidizing agent such as ammonium persulfate
  • the resulting polyaniline materials can appear in a number of forms depending on charge at nitrogen atoms. Different forms of polyaniline materials exhibit different degree of conductivity but polyaniline powder has no natural adhesion on electrode surface and slightly soluble in most solvents.
  • the dispensed or printed polyaniline composite paste must exhibit strong adhesion with a wide range of electrode surface such as platinum, carbon, silver, silicon nitride, silicon, polysilicon, silicon oxide, polyester, Flame Retardant Class 4 or glass.
  • electrode surface such as platinum, carbon, silver, silicon nitride, silicon, polysilicon, silicon oxide, polyester, Flame Retardant Class 4 or glass.
  • the polyaniline composite layer must give good adhesion with a variety of polymeric sensing membranes such as PVC, acrylate, urethane or silicone rubber acting a sensing top layer.
  • the present invention relates to polyaniline composite electrode and method of preparing the polyaniline composite electrode.
  • the polyaniline composite electrode is prepared without any electrochemical process.
  • An electrode having an outer surface is covered by polyaniline composite layer wherein the polyaniline composite layer includes 30 to 60 weight percent of polyaniline, 5 to 30 weight percent of lipophilic salt, 2 to 10 weight percent of low impedance polymeric matrix, 1 to 5 weight percent of cross linker and 10 to 50 weight percent of organic solvent.
  • the electrode having reproducible oxidation and reduction peaks on cyclic voltammetry scan between -1 V to 1 V.
  • the method of preparing the polyaniline composite electrode includes the steps of:
  • step (iii) applying the composite paste obtained from step (iii) on a surface of a conductive substrate;
  • step (iv) heating the electrode obtained from step (iv) at temperature between 50°C to 150°C for a period between 10 minutes to 60 minutes.
  • the low impedance polymer is (glycidyl methacrylate-tetrahydrofurfuryl acrylate) copolymer, (methyl methacrylate-glycidyl methacrylate- tetrahydrofurfuryl acrylate) copolymer, cellulose acetate, ethyl cellulose, poly (methyl methacrylate) or any combination thereof.
  • the crosslinker is meta-xylylenediamine, para-xylylenediamine, para- phenylenediamine, 1 ,3-diaminopropane, 1 ,4-diaminobutane or any combination thereof.
  • the electrode is a conductive substrate such as screen printed carbon, compacted graphite, silver, platinum and gold.
  • the lipophilic salt is para-dodecylsulfonate, toluene sulfonate, polyanethol sulfonate, nation or any combination thereof.
  • the organic solvent is 2-methoxyethanol, n-methyl pyrrolidone, carbitol, butyl glycol, acrylic acid, pyruvic acid, ethyl acetate, tetrahydrofuran, toluene, xylene, dimethylsulfoxide, propanol or any combination thereof.
  • the mixture of organic chemicals is selected from 2-methoxyethanol, n- methyl pyrrolidone, carbitoi, butyl glycol, acrylic acid, pyruvic acid, ethyl acetate, tetrahydrofuran, toluene, xylene, dimethylsulfoxide and propanol.
  • the polyaniline composite paste is applied on a surface of an electrode by using screen printing, stencil printing, ink jet printing, solution casting, spin coating or any combination thereof.
  • Figure 1 shows the steps involved in preparing the polyaniline composite electrode
  • Figure 2 shows the cyclic voltammetry measurement of polyaniline composite electrode with acrylate copolymer matrix, in 0.1 M potassium chloride
  • Figure 3 shows the cyclic voltammetry measurement of polyaniline composite electrode with acrylate copolymer-cellulose acetate blend matrix, in 0.1 M potassium chloride.
  • the present invention relates to polyaniline composite electrode and method of preparing the polyaniline composite electrode.
  • the polyaniline composite electrode is fabricated without any electrochemical process.
  • a novel polyaniline composite paste comprises polyaniline and lipophilic salt intermingled in homogenous phase of low impedance polymeric networks is prepared.
  • the paste is applied on outer surface of an electrode to produce the polyaniline composite electrode.
  • electrode contacts are inaccessible for electro- polymerization and thus coating method is a technique of choice for applying polyaniline materials on electrode surface.
  • binding component i.e. low impedance polymeric network and the crosslinker able to hold the polyaniline materials together while maintaining conductive characteristic and electrochemical properties of polyaniline composite.
  • near ambient temperature curing within short time is preferred because it will be convenient to manufacture and afford high throughput of the polyaniline composite electrode.
  • conductive substrate such as carbon, silver, platinum or gold
  • sensing membrane such as Polyvinyl chloride (PVC), acrylate, urethane and silicone rubber
  • the polyaniline composite electrode having an outer surface which is covered by polyaniline composite layer wherein the polyaniline composite layer includes 30 to 60 weight percent of polyaniline, 5 to 30 weight percent of lipophilic salt, 2 to 10 weight percent of low impedance polymeric matrix, 1 to 5 weight percent of cross linker and 10 to 50 weight percent of organic solvent.
  • the polyaniline composite electrode having reproducible oxidation and reduction peaks on cyclic voltammetry scan between -1 V to 1 V which is critical for use as a ransducer or sensor.
  • the polyaniline composite layer has a chemical structure
  • a method of preparing the polyaniline composite electrode is described herein.
  • the method includes five main steps as illustrated in Figure 1 and described in examples 1 and 2.
  • a solution of low impedance polymeric materials such as acrylate copolymer and diamine crosslinker in polar organic solvent is prepared.
  • the low impedance polymeric solution is prepared by mixing low impedance polymer and crosslinker in organic solvent, wherein the ratio is 1 part of crosslinker and at least 1 part of low impedance polymer, by weight.
  • the crosslinker is used to present link between strands of polymeric networks and to improve adhesion with electrode surface.
  • the crosslinker is meta- xylylenediamine, para-xylylenediamine, para-phenylenediamine, 1 ,3- diaminopropane, 1 ,4-diaminobutane or any combination thereof.
  • the low impedance polymeric matrix is (glycidyl methacrylate-tetrahydrofurfuryl acrylate) copolymer, (methyl methacrylate-glycidyl methacrylate-tetrahydrofurfuryl acrylate) copolymer, cellulose acetate, ethyl cellulose, poly (methyl methacrylate) or any combination thereof.
  • Copolymer of methyl methacrylate, glycidyl methacrylate and tetrahydrofurfuryl acrylate contains oxirane moiety that react with primary alkyl or aromatic diamine upon heat treatment.
  • Advantages of using diamine include its availability in liquid form, ease of purification and mild curing temperature. Moreover, the diamine gives sufficient room to accommodate polyaniline strands.
  • Other low impedance polymeric materials such as cellulose, cellulose acetate and ethyl cellulose can also provide homogenous phase for polyaniline strands. However, the polysaccharide matrix lacks cross-linkable groups.
  • polyaniline material and lipophilic salt in polar organic solvent is also prepared.
  • the polyaniline solution is prepared by mixing polyaniline and lipophilic salt in organic solvent, wherein the ratio is 1 part of lipophilic salt and at least 1 part of polyaniline, by weight.
  • Lipophilic anion such as long-chain aryl sulfonate increases solubility of polyaniline in organic solvents.
  • the lipophilic salt is para-dodecylsulfonate, toluene sulfonate, polyanethol sulfonate, nation or any combination thereof.
  • polyaniline composite paste is prepared by mixing the low impedance polymeric solution and conductive polyaniline solution in a mixture of organic chemicals.
  • the mixture of organic chemicals is selected from 2-methoxyethanol, n-methyl pyrroiidone, carbitol, butyl glycol, acrylic acid, pyruvic acid, ethyl acetate, tetrahydrofuran, toluene, xylene, dimethylsulfoxide and propanol.
  • the polyaniline composite paste is applied on an outer surface of a conductive substrate.
  • the conductive substrate is an electrode such as screen printed carbon, compacted graphite, silver, platinum and gold.
  • a number of methods such as screen printing, stencil printing, ink jet printing, solution casting, spin coating or any combination thereof can be used to coat the polyaniline composite paste onto the conducting substrate.
  • the heat treatment is performed at a temperature between 50°C to 150°C for a period between 10 minutes to 60 minutes.
  • the polar organic solvent used for preparing the low impedance polymeric solution and the polyaniline solution is 2-methoxyethanol, n-methyl pyrroiidone, carbitol, butyl glycol, acrylic acid, pyruvic acid, ethyl acetate, tetrahydrofuran, toluene, xylene, dimethylsulfoxide, propanol or any combination thereof.
  • Example 1 Preparation of Polyaniline Composite Paste with (methyl methacrylate- glycidyl methacrylate-tetrahydrofurfuryl acrylate) Copolymer Matrix
  • m-Xylylene diamine is purified by following steps: (i) diluting with diethyl ether; (ii) washing with saturated sodium bicarbonate and brine solutions, (iii) drying with sodium sulfate followed by magnesium sulfate; (iv) stirring over barium oxide, phosphorus pentoxide or calcium hydride for 3 to 12 hours and (v) followed by distillation under reduced pressure.
  • Copolymer of methyl methacrylate, glycidyl methacrylate-tetrahydrofurfuryl acrylate (100 mg) is transferred into a glass vial and 50 ⁇ _ of purified m-xylylene diamine crosslinker is added into the acrylate copolymer. Thereafter mixture of the acrylate copolymer and crosslinker is diluted with tetrahydrofuran to give 5 weight percent solution of the acrylate copolymer. The vial is tightly capped and sonicated at 40 °C for 30 minutes.
  • Conductive polyaniline 300 mg and 50 mg sodium p-toluene sulfonate are added into a glass vial and the resultant mixture is dissolved with 1 -methyl-2- pyrrolidone to give 3 weight percent of conductive polyaniline solution.
  • the vial was tightly capped and sonicated at 40 °C for 30 minutes.
  • the conductive polyaniline solution (30 ⁇ _) and 20 ⁇ _ of the acrylate copolymer-diamine solution are combined in a glass vial.
  • the vial was tightly capped and sonicated at 40 °C for 30 minutes.
  • Polyaniline composite solution (5 ⁇ _) obtained from sonication is coated onto screen-printed carbon electrode. Solvent is evaporated under nitrogen atmosphere for 1 hour and the electrode is treated via heating at 100 e C for 15 minutes. Cyclic voltammetry of polyaniline composite electrode is performed between -1 V and 1 V with different scan rates using Metrohm Autolab system in 0.1 M potassium chloride solution with silver-silver chloride double-junction reference electrode and platinum counter electrode. Results of the cyclic voltamemetry is shown in Figure 2.
  • Example 2 Preparation of Polyaniline Composite with Acrylate Copolymer- Cellulose Acetate Blend Matrix
  • Conductive polyaniline solution is prepared by forming homogenous mixture of polyaniline and lipophilic sulfonate salt as described in Example 1.
  • Solution of cellulose acetate is prepared by adding 1 gram of cellulose acetate in tetrahydrofuran to afford a solution of 3 weight percent.
  • One part of cellulose acetate solution is added to five parts of conductive polyaniline solution and the combined portions are sonicated in a capped glass vial for 30 minutes. Additional portions of tetrahydrofuran or butyl carbitol is added to adjust viscosity of resulting composite ink and to avoid precipitation of cellulose acetate.

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Abstract

The present invention relates to a polyaniline composite electrode and method of preparing the polyaniline composite electrode. The polyaniline composite electrode is prepared without any electrochemical process. Firstly, a polyaniline composite paste comprises polyaniline and lipophilic salt intermingled in homogenous phase of low impedance polymeric networks is prepared. Then the paste is applied on electrode surface to produce the polyaniline composite electrode. The polyaniline composite electrode having an outer surface which is covered by polyaniline composite layer wherein the polyaniline composite layer includes 30 to 60 weight percent of polyaniline, 5 to 30 weight percent of lipophilic salt, 2 to 10 weight percent of low impedance polymeric matrix, 1 to 5 weight percent of cross linker and 10 to 50 weight percent of organic solvent. The 1 method of preparing polyaniline composite electrode includes the steps of (i) mixing low impedance polymer and crosslinker in organic solvent to produce low impedance polymeric solution; (ii) mixing polyaniline and lipophilic salt in organic solvent to produce polyaniline solution; (iii) mixing the low impedance polymeric solution and polyaniline solution in a mixture of organic chemicals to form 20 polyaniline composite paste (iv) applying the composite paste obtained from step (iii) on a surface of a electrode; and (v) heating the electrode obtained from step (iv) at temperature between 50°C to 150°C for a period between 10 minutes to 60 minutes.

Description

POLYANILINE COMPOSITE ELECTRODE AND METHOD OF PREPARING THE POLYANILINE COMPOSITE ELECTRODE
FIELD OF INVENTION
The present invention relates to polyaniline composite electrode and method of preparing the polyaniline composite electrode.
BACKGROUND ART OF THE INVENTION
Polymerization of aniline is often catalyzed by oxidizing agent such as ammonium persulfate as shown in Scheme 1. The resulting polyaniline materials can appear in a number of forms depending on charge at nitrogen atoms. Different forms of polyaniline materials exhibit different degree of conductivity but polyaniline powder has no natural adhesion on electrode surface and slightly soluble in most solvents.
Scheme 1 : Polymerization of aniline
In miniaturized sensing devices, electrodes are close together to each other and electrical contacts are difficult to achieve. Therefore electro- polymerization of aniline is difficult to perform on these cell windows. Moreover electrical contacts in miniaturized cells are prone to electrical shorting when immersed in monomer electrolyte.
Solution casting or printing of polyaniline ink onto electrode surface is preferred when electro-polymerization of aniline monomer is not possible due to miniature size of electrode, inaccessibility of electrical contacts or electrical shorting of contact pads in monomer electrolyte solution. Adhesion of polyaniline materials on the electrode surface is the most important requirement for polyaniline composite electrode. If polyaniline composite paste can be prepared, the paste can be dispensed or printed onto working electrode surface for a variety of applications such as in chemical sensors, Amperometric cell and Conductometric electrodes. The dispensed or printed polyaniline composite paste must exhibit strong adhesion with a wide range of electrode surface such as platinum, carbon, silver, silicon nitride, silicon, polysilicon, silicon oxide, polyester, Flame Retardant Class 4 or glass. Likewise when used as transducers in chemical sensors, the polyaniline composite layer must give good adhesion with a variety of polymeric sensing membranes such as PVC, acrylate, urethane or silicone rubber acting a sensing top layer.
SUMMARY OF THE INVENTION
The present invention relates to polyaniline composite electrode and method of preparing the polyaniline composite electrode. The polyaniline composite electrode is prepared without any electrochemical process. An electrode having an outer surface is covered by polyaniline composite layer wherein the polyaniline composite layer includes 30 to 60 weight percent of polyaniline, 5 to 30 weight percent of lipophilic salt, 2 to 10 weight percent of low impedance polymeric matrix, 1 to 5 weight percent of cross linker and 10 to 50 weight percent of organic solvent. The electrode having reproducible oxidation and reduction peaks on cyclic voltammetry scan between -1 V to 1 V. The method of preparing the polyaniline composite electrode includes the steps of:
i) mixing low impedance polymer and crosslinker in organic solvent to produce low impedance polymeric solution with a ratio of 1 part of crosslinker and at least 1 part of low impedance polymer, by weight; ii) mixing polyaniline and lipophilic salt in organic solvent to produce polyaniline solution with a ratio of 1 part of lipophilic salt and at least 1 part of polyaniline, by weight;
iii) mixing low impedance polymeric solution and polyaniline solution in a mixture of organic chemicals to form polyaniline composite paste;
iv) applying the composite paste obtained from step (iii) on a surface of a conductive substrate; and
v) heating the electrode obtained from step (iv) at temperature between 50°C to 150°C for a period between 10 minutes to 60 minutes.
The low impedance polymer is (glycidyl methacrylate-tetrahydrofurfuryl acrylate) copolymer, (methyl methacrylate-glycidyl methacrylate- tetrahydrofurfuryl acrylate) copolymer, cellulose acetate, ethyl cellulose, poly (methyl methacrylate) or any combination thereof.
The crosslinker is meta-xylylenediamine, para-xylylenediamine, para- phenylenediamine, 1 ,3-diaminopropane, 1 ,4-diaminobutane or any combination thereof.
The electrode is a conductive substrate such as screen printed carbon, compacted graphite, silver, platinum and gold.
The lipophilic salt is para-dodecylsulfonate, toluene sulfonate, polyanethol sulfonate, nation or any combination thereof.
The organic solvent is 2-methoxyethanol, n-methyl pyrrolidone, carbitol, butyl glycol, acrylic acid, pyruvic acid, ethyl acetate, tetrahydrofuran, toluene, xylene, dimethylsulfoxide, propanol or any combination thereof. The mixture of organic chemicals is selected from 2-methoxyethanol, n- methyl pyrrolidone, carbitoi, butyl glycol, acrylic acid, pyruvic acid, ethyl acetate, tetrahydrofuran, toluene, xylene, dimethylsulfoxide and propanol. The polyaniline composite paste is applied on a surface of an electrode by using screen printing, stencil printing, ink jet printing, solution casting, spin coating or any combination thereof.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention will become more fully understood from the detailed description given herein below and accompanying drawings which are given by way of illustration only, and thus are not limitative of the present invention, wherein:
Figure 1 shows the steps involved in preparing the polyaniline composite electrode;
Figure 2 shows the cyclic voltammetry measurement of polyaniline composite electrode with acrylate copolymer matrix, in 0.1 M potassium chloride; and Figure 3 shows the cyclic voltammetry measurement of polyaniline composite electrode with acrylate copolymer-cellulose acetate blend matrix, in 0.1 M potassium chloride.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to polyaniline composite electrode and method of preparing the polyaniline composite electrode. The polyaniline composite electrode is fabricated without any electrochemical process. Firstly, a novel polyaniline composite paste comprises polyaniline and lipophilic salt intermingled in homogenous phase of low impedance polymeric networks is prepared. Then the paste is applied on outer surface of an electrode to produce the polyaniline composite electrode. A detailed description of preferred embodiments of the invention is disclosed herein. It should be understood, however, that the disclosed preferred embodiments are merely exemplary of the invention, which may be embodied in various forms. Therefore, the details disclosed herein are not to be interpreted as limiting, but merely as the basis for the claims and for teaching one skilled in the art of the invention.
In miniaturized devices, electrode contacts are inaccessible for electro- polymerization and thus coating method is a technique of choice for applying polyaniline materials on electrode surface. Moreover, it is important that binding component, i.e. low impedance polymeric network and the crosslinker able to hold the polyaniline materials together while maintaining conductive characteristic and electrochemical properties of polyaniline composite. Furthermore, near ambient temperature curing within short time is preferred because it will be convenient to manufacture and afford high throughput of the polyaniline composite electrode. For sensing applications, adhesion of the cured polyaniline composite on a wide range of conductive substrate such as carbon, silver, platinum or gold, as well as, binding of a wide variety of sensing membrane such as Polyvinyl chloride (PVC), acrylate, urethane and silicone rubber, is a critical criterion for polyaniline composite electrode.
The polyaniline composite electrode having an outer surface which is covered by polyaniline composite layer wherein the polyaniline composite layer includes 30 to 60 weight percent of polyaniline, 5 to 30 weight percent of lipophilic salt, 2 to 10 weight percent of low impedance polymeric matrix, 1 to 5 weight percent of cross linker and 10 to 50 weight percent of organic solvent. The polyaniline composite electrode having reproducible oxidation and reduction peaks on cyclic voltammetry scan between -1 V to 1 V which is critical for use as a ransducer or sensor. The polyaniline composite layer has a chemical structure
Figure imgf000007_0001
A method of preparing the polyaniline composite electrode is described herein. The method includes five main steps as illustrated in Figure 1 and described in examples 1 and 2. Firstly, a solution of low impedance polymeric materials such as acrylate copolymer and diamine crosslinker in polar organic solvent is prepared. The low impedance polymeric solution is prepared by mixing low impedance polymer and crosslinker in organic solvent, wherein the ratio is 1 part of crosslinker and at least 1 part of low impedance polymer, by weight. The crosslinker is used to present link between strands of polymeric networks and to improve adhesion with electrode surface. The crosslinker is meta- xylylenediamine, para-xylylenediamine, para-phenylenediamine, 1 ,3- diaminopropane, 1 ,4-diaminobutane or any combination thereof. The low impedance polymeric matrix is (glycidyl methacrylate-tetrahydrofurfuryl acrylate) copolymer, (methyl methacrylate-glycidyl methacrylate-tetrahydrofurfuryl acrylate) copolymer, cellulose acetate, ethyl cellulose, poly (methyl methacrylate) or any combination thereof. Copolymer of methyl methacrylate, glycidyl methacrylate and tetrahydrofurfuryl acrylate contains oxirane moiety that react with primary alkyl or aromatic diamine upon heat treatment. Advantages of using diamine include its availability in liquid form, ease of purification and mild curing temperature. Moreover, the diamine gives sufficient room to accommodate polyaniline strands. Other low impedance polymeric materials such as cellulose, cellulose acetate and ethyl cellulose can also provide homogenous phase for polyaniline strands. However, the polysaccharide matrix lacks cross-linkable groups.
Then a solution of polyaniline material and lipophilic salt in polar organic solvent is also prepared. The polyaniline solution is prepared by mixing polyaniline and lipophilic salt in organic solvent, wherein the ratio is 1 part of lipophilic salt and at least 1 part of polyaniline, by weight. Lipophilic anion such as long-chain aryl sulfonate increases solubility of polyaniline in organic solvents. The lipophilic salt is para-dodecylsulfonate, toluene sulfonate, polyanethol sulfonate, nation or any combination thereof. Then polyaniline composite paste is prepared by mixing the low impedance polymeric solution and conductive polyaniline solution in a mixture of organic chemicals. The mixture of organic chemicals is selected from 2-methoxyethanol, n-methyl pyrroiidone, carbitol, butyl glycol, acrylic acid, pyruvic acid, ethyl acetate, tetrahydrofuran, toluene, xylene, dimethylsulfoxide and propanol. Thereafter, the polyaniline composite paste is applied on an outer surface of a conductive substrate. The conductive substrate is an electrode such as screen printed carbon, compacted graphite, silver, platinum and gold. A number of methods such as screen printing, stencil printing, ink jet printing, solution casting, spin coating or any combination thereof can be used to coat the polyaniline composite paste onto the conducting substrate. This is followed by heat treatment to induce cross linking process to take place. The heat treatment is performed at a temperature between 50°C to 150°C for a period between 10 minutes to 60 minutes. The polar organic solvent used for preparing the low impedance polymeric solution and the polyaniline solution is 2-methoxyethanol, n-methyl pyrroiidone, carbitol, butyl glycol, acrylic acid, pyruvic acid, ethyl acetate, tetrahydrofuran, toluene, xylene, dimethylsulfoxide, propanol or any combination thereof. The present invention is further described in the following examples:
Example 1 : Preparation of Polyaniline Composite Paste with (methyl methacrylate- glycidyl methacrylate-tetrahydrofurfuryl acrylate) Copolymer Matrix
Firstly, m-Xylylene diamine is purified by following steps: (i) diluting with diethyl ether; (ii) washing with saturated sodium bicarbonate and brine solutions, (iii) drying with sodium sulfate followed by magnesium sulfate; (iv) stirring over barium oxide, phosphorus pentoxide or calcium hydride for 3 to 12 hours and (v) followed by distillation under reduced pressure.
Copolymer of methyl methacrylate, glycidyl methacrylate-tetrahydrofurfuryl acrylate (100 mg) is transferred into a glass vial and 50 μΙ_ of purified m-xylylene diamine crosslinker is added into the acrylate copolymer. Thereafter mixture of the acrylate copolymer and crosslinker is diluted with tetrahydrofuran to give 5 weight percent solution of the acrylate copolymer. The vial is tightly capped and sonicated at 40 °C for 30 minutes.
Conductive polyaniline (300 mg) and 50 mg sodium p-toluene sulfonate are added into a glass vial and the resultant mixture is dissolved with 1 -methyl-2- pyrrolidone to give 3 weight percent of conductive polyaniline solution. The vial was tightly capped and sonicated at 40 °C for 30 minutes. The conductive polyaniline solution (30 μΙ_) and 20 μΙ_ of the acrylate copolymer-diamine solution are combined in a glass vial. The vial was tightly capped and sonicated at 40 °C for 30 minutes.
Polyaniline composite solution (5 μΙ_) obtained from sonication is coated onto screen-printed carbon electrode. Solvent is evaporated under nitrogen atmosphere for 1 hour and the electrode is treated via heating at 100 eC for 15 minutes. Cyclic voltammetry of polyaniline composite electrode is performed between -1 V and 1 V with different scan rates using Metrohm Autolab system in 0.1 M potassium chloride solution with silver-silver chloride double-junction reference electrode and platinum counter electrode. Results of the cyclic voltamemetry is shown in Figure 2. Example 2: Preparation of Polyaniline Composite with Acrylate Copolymer- Cellulose Acetate Blend Matrix
Conductive polyaniline solution is prepared by forming homogenous mixture of polyaniline and lipophilic sulfonate salt as described in Example 1. Solution of cellulose acetate is prepared by adding 1 gram of cellulose acetate in tetrahydrofuran to afford a solution of 3 weight percent. One part of cellulose acetate solution is added to five parts of conductive polyaniline solution and the combined portions are sonicated in a capped glass vial for 30 minutes. Additional portions of tetrahydrofuran or butyl carbitol is added to adjust viscosity of resulting composite ink and to avoid precipitation of cellulose acetate.
Final composite ink is coated on screen-printed carbon electrode. Solvent is evaporated under continous flow of nitrogen gas for one hour prior to heat treatment in an oven at 100 eC for 15 minutes. Cyclic voltammetry of polyaniline composite electrode is performed between -1 V and 1 V with different scan rates using Metrohm Autolab system in 0.1 M potassium chloride solution with silver- silver chloride double-junction reference electrode and platinum counter electrode. Results of the cyclic voltamemetry is shown in Figure 3.

Claims

1. An electrode having an outer surface which is covered by polyaniline composite layer wherein the polyaniline composite layer includes 30 to 60 weight percent of polyaniline, 5 to 30 weight percent of lipophilic salt, 2 to 10 weight percent of low impedance polymeric matrix, 1 to 5 weight percent of cross linker and 10 to 50 weight percent of organic solvent.
2. The electrode as claimed in claim 1 wherein the electrode is a conductive substrate such as screen printed carbon, compacted graphite, silver, platinum and gold.
3. The electrode as claimed in claim 1 wherein the polyaniline composite la er has a chemical structure of:
Figure imgf000011_0001
4. The electrode as claimed in claim 1 wherein the low impedance polymeric matrix is (glycidyl methacrylate-tetrahydrofurfuryl acrylate) copolymer, (methyl methacrylate-glycidyl methacrylate-tetrahydrofurfuryl acrylate) copolymer, cellulose acetate, ethyl cellulose, poly (methyl methacrylate) or any combination thereof.
5. The electrode as claimed in claim 1 wherein the crosslinker is meta- xylylenediamine, para-xylylenediamine, para-phenylenediamine, 1 ,3- diaminopropane, 1 ,4-diaminobutane or any combination thereof.
6. The electrode as claimed in claim 1 wherein the organic solvent is 2- methoxyethanol, n-methyl pyrrolidone, carbitol, butyl glycol, acrylic acid, pyruvic acid, ethyl acetate, tetrahydrofuran, toluene, xylene, dimethylsulfoxide, propanol or any combination thereof.
7. The electrode as claimed in claim 1 wherein the lipophilic salt is para- dodecylsulfonate, toluene sulfonate, polyanethol sulfonate, nafion or any combination thereof.
8. The electrode as claimed in claim 1 wherein the electrode having reproducible oxidation and reduction peaks on cyclic voltammetry scan between -1 V to 1 V.
9. A method of preparing polyaniline composite electrode, the method includes steps of:
i) mixing low impedance polymer and crosslinker in organic solvent to produce low impedance polymeric solution with a ratio of 1 part of crosslinker and at least 1 part of low impedance polymer, by weight; ii) mixing polyaniline and lipophilic salt in organic solvent to produce polyaniline solution with a ratio of 1 part of lipophilic salt and at least 1 part of polyaniline, by weight;
iii) mixing low impedance polymeric solution and polyaniline solution in a mixture of organic chemicals to form polyaniline composite paste;
iv) applying the composite paste obtained from step (iii) on a surface of a conductive substrate; and
v) heating the electrode obtained from step (iv) at temperature between 50°C to 150°C for a period between 10 minutes to 60 minutes.
10. The method of preparing polyaniline composite electrode as claimed in claim 9 wherein the low impedance polymer is (glycidyl methacrylate- tetrahydrofurfuryl acrylate) copolymer, (methyl methacrylate-glycidyl methacrylate-tetrahydrofurfuryl acrylate) copolymer, cellulose acetate, ethyl cellulose, poly (methyl methacrylate) or any combination thereof.
1 1 . The method of preparing polyaniline composite electrode as claimed in claim 9 wherein the crosslinker is mefa-xylylenediamine, para- xylylenediamine, para-phenylenediamine, 1 ,3-diaminopropane, 1 ,4- diaminobutane or any combination thereof.
12. The method of preparing polyaniline composite electrode as claimed in claim 9 wherein the electrode is a conductive substrate such as screen printed carbon, compacted graphite, silver, platinum and gold.
13. The electrode as claimed in claim 9 wherein the lipophilic salt is para- dodecylsulfonate, toluene sulfonate, polyanethol sulfonate, nation or any combination thereof.
14. The method of preparing polyaniline composite electrode as claimed in claim 9 wherein the organic solvent is 2-methoxyethanol, n-methyl pyrrolidone, carbitol, butyl glycol, acrylic acid, pyruvic acid, ethyl acetate, tetrahydrofuran, toluene, xylene, dimethylsulfoxide, propanol or any combination thereof.
15. The method preparing polyaniline composite electrode as claimed in claim 9 wherein the mixture of organic chemicals is selected from 2- methoxyethanol, n-methyl pyrrolidone, carbitol, butyl glycol, acrylic acid, pyruvic acid, ethyl acetate, tetrahydrofuran, toluene, xylene, dimethylsulfoxide and propanol.
16. The method of preparing polyaniline composite electrode as claimed in claim 9 wherein the polyaniline composite paste is applied on a surface of an electrode by using screen printing, stencil printing, ink jet printing, solution casting, spin coating or any combination thereof.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11034796B1 (en) 2015-08-06 2021-06-15 Cornell University Poly(arylamine)s and uses thereof
CN115020705A (en) * 2022-04-25 2022-09-06 合肥国轩科宏新能源科技有限公司 Polyurethane elastic fiber positive electrode material and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0398286A2 (en) * 1989-05-18 1990-11-22 Nisshinbo Industries, Inc. Ammonia sensor
US5869007A (en) * 1996-08-22 1999-02-09 Gumbs Associates, Inc. Conducting polymer based acid/base sensors
WO2011053118A2 (en) * 2009-10-30 2011-05-05 Mimos Berhad Composition of low impedance bulk polymeric membrane

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0398286A2 (en) * 1989-05-18 1990-11-22 Nisshinbo Industries, Inc. Ammonia sensor
US5869007A (en) * 1996-08-22 1999-02-09 Gumbs Associates, Inc. Conducting polymer based acid/base sensors
WO2011053118A2 (en) * 2009-10-30 2011-05-05 Mimos Berhad Composition of low impedance bulk polymeric membrane

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11034796B1 (en) 2015-08-06 2021-06-15 Cornell University Poly(arylamine)s and uses thereof
CN115020705A (en) * 2022-04-25 2022-09-06 合肥国轩科宏新能源科技有限公司 Polyurethane elastic fiber positive electrode material and preparation method and application thereof
CN115020705B (en) * 2022-04-25 2024-05-14 合肥国轩科宏新能源科技有限公司 Polyurethane elastic fiber positive electrode material and preparation method and application thereof

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