CN105001420A - Preparing method for polypyrrole nanofiber conductive electrode material - Google Patents
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Abstract
The invention relates to a preparing method for a polypyrrole nanofiber conductive electrode material, and belongs to the field of conductive nanomaterials. The preparing method includes the steps that an electrode base material is fully infiltrated in an aqueous surfactant solution with dispersed pyrrole monomers; a neutral or acid aqueous solution containing an oxidizing agent is added dropwise into the mixed system and reacts for 2-24 h at the temperature of 0 DEG C-30 DEG C; the obtained product containing electrode bases is washed many times and dried in a vacuum mode to obtain the polypyrrole nanofiber conductive electrode material. The preparing method is simple in technology, low in cost and suitable for large-scale industrial production. The polypyrrole nanofiber conductive electrode material can be widely applied to the fields of supercapacitors, microorganism fuel cells, lithium ion cells, transistors, sensors and the like.
Description
Technical field
The present invention relates to a kind of preparation method of polypyrrole nanofibers conductive electrode material, in particular to the method preparing polypyrrole nanofibers conductive electrode material with sulfonate type anion surfactant assistant chemical oxidation in-situ polymerization, belong to electrical-conductive nanometer Material Field.
Background technology
Polypyrrole, as modal conductive polymers, namely becomes a kind of desirable electrode materials with the redox reaction of the biocompatibility of its excellence, Rapid reversible, high conductivity and larger energy loads and is widely used in ultracapacitor, microbiological fuel cell, lithium ion battery, transistor and sensor aspect.But the polypyrrole prepared under usual conditions all presents with particulate state and there is the problem being difficult to dissolving and melting, and then constrains its forming process and application.Because nanometer sized materials has excellent surface effects and volume effect, and the electrode materials that polypyrrole nanofibers is modified all has and significantly promotes in mass transfer characteristic and specific conductivity etc., therefore, in the preparation process of polypyrrole, directly form nanofiber pattern and then seem particularly important.
The preparation method of polypyrrole nanofibers mainly concentrates on template, electrochemical process and chemical oxidization method.Template prepares the most frequently used method of polypyrrole nanofibers, such as: China Patent Publication No. CN102675877B, publication date is on September 4th, 2013, disclose polypyrrole nano line and its production and use, this invention obtains nanohole alumine template by two-step electrochemical anodizing method, then gold-plated for this template rear immersion is contained in the ethanolic soln of 2-guanidine pyridine benzoglyoxaline and carry out electrodeposition process, namely obtain polypyrrole nano line finally by after physico-chemical processes removing template.China Patent Publication No. CN102924718A, publication date is on February 13rd, 2013, disclose a kind of preparation method with the polypyrrole of nanostructure, this invention using the Manganse Dioxide of nanostructure as template, by carrying out with pyrrole monomer being in an acidic solution obtained by reacting the nanostructure polypyrrole identical with Manganse Dioxide pattern.More than citing adopts template synthesis polypyrrole nanofibers comparatively loaded down with trivial details, and there is the difficulty that the shortcoming removing and can destroy polypyrrole nanofibers structure in template procedure and template be difficult to remove.Electrochemical production polypyrrole nanofibers is adopted also to have more report.Such as: China Patent Publication No. CN1465748A, publication date is on January 7th, 2004, disclose the method for directly forming polypyrrole nano line on electrode surface, this invention, by controlling the concentration of pyrrole monomer, doping agent in electrolytic solution, directly generates the polypyrrole nano line of different lengths and diameter with potentiostatic method or cyclic voltammetry at electrode surface.China Patent Publication No. CN102544501A, publication date is on July 4th, 2012, disclose a kind of method preparing polypyrrole nanometer wire-graphene composite material, this invention adopts three-electrode system to carry out electrochemical polymerization in the Sodium phosphate dibasic containing pyrrole monomer and Graphene powder and the lithium perchlorate aqueous solution and obtains polypyrrole nano line.Although adopt electrochemical production polypyrrole nanofibers to have the short feature of polymerization time, be limited by the output of electrochemical synthesis own less, be thus difficult to scale operation.
Chemical oxidization method is the conventional approach being easy to the polypyrrole nanofibers obtaining high yield, and equipment cost is low and simple to operate.Such as: China Patent Publication No. CN1597732, publication date is on March 23rd, 2005, discloses the preparation method of electric conductive polypyrrole nanometer wire, and this invention adopts quaternary ammonium cation tensio-active agent assistant chemical oxidation style to prepare polypyrrole nano line.China Patent Publication No. CN103343394A, publication date is on October 9th, 2013, disclose a kind of preparation method of polypyrrole nanofibers, this invention is with diazosulfide class fluorescent agent for doping agent, and oxypolymerization obtains the polypyrrole nanofibers having fluorescence and electroconductibility concurrently in a nitrogen atmosphere.But the polypyrrole nanofibers more than adopting the case of chemical oxidization method to obtain all exists with the form of insoluble powder precipitation of not melting in resulting solution, cannot, directly as materials'use, need to carry out follow-up purification, shaping or modification during practical application.
Summary of the invention
For above-mentioned Problems existing, the object of the present invention is to provide a kind of technique simple, with low cost, the method preparing polypyrrole nanofibers conductive electrode that suitability for industrialized is produced, the method overcome technological process and the electrochemical process high cost of template synthesis polypyrrole nanofibers relative complex, the shortcomings such as low yield, utilize the chemical oxidative polymerization that tensio-active agent is auxiliary, the material system of polypyrrole nanofibers and polytype body material In-situ reaction can be obtained, the form of polypyrrole nanofibers can be kept, directly solve again the formation problems that polypyrrole nanofibers is applied to energy electrode materials, possess and settle at one go, with low cost, the simple advantage of technique.
For achieving the above object, the technical solution used in the present invention is:
A preparation method for polypyrrole nanofibers conductive electrode material, described preparation method carries out according to following steps:
A. be in the water phase surfactant mixture of 1mmol/L-3mol/L in concentration, add pyrrole monomer and the electrode base material of 0.5g/L-50g/L successively, make electrode base material fully be infiltrated on the water phase surfactant mixture being dispersed with pyrrole monomer with the stir speed (S.S.) of 50r/min-400r/min;
B. above-mentioned mixed system temperature is adjusted to 0-30 DEG C, dropwise add under the stir speed (S.S.) of 50r/min-400r/min with pyrrole monomer mol ratio be the oxygenant neutral aqueous solution of 10:1-1:10 or concentration is the acidic aqueous solution of 2mmol/L-4mol/L, 2-24 hour is reacted under said temperature and stir speed (S.S.), obtain containing the product of electrode base material, successively through deionized water, absolute ethanol washing and be polypyrrole nanofibers conductive electrode material after drying under 60 DEG C of vacuum conditions.
Described tensio-active agent is sulfonate type anion surfactant RSO
3m, wherein, R is anthraquinone or naphthoquinones, and M is basic metal.
Described electrode base material is the one in conducting metal sill or carbon-based material or flexible fabric or polymer fiber film or polymer yarn or natural cellulose silk.
Described acidic aqueous solution adopts the one preparation in a water tosic acid or two hydration 5-sulphosalicylic acids or phosphoric acid or hydrochloric acid.
Described oxygenant is the one in hydrogen peroxide or ammonium persulphate or nine water iron nitrates or Anhydrous Ferric Chloride or potassium bichromate.
Owing to have employed above technical scheme, the present invention has the following advantages:
1) the inventive method prepares polypyrrole nanofibers on a large scale by the regulation and control of Surfactant, and can directly obtain polypyrrole nanofibers conductive electrode material without the need to carrying out following process process to polypyrrole nanofibers;
2) the polypyrrole nanofibers conductive electrode material prepared of the present invention has different specific conductivity, biocompatibility and the three-dimensional space net structure interweaved depending on the difference of its electrode base material, can meet the demand of different application field to conductive electrode material structure and performance.
Preparation method's technique of the present invention is simple, with low cost, suitability for industrialized scale operation.Ultracapacitor, microbiological fuel cell, lithium ion battery, transistor and sensor field can be widely used in.
Embodiment
below in conjunction with specific embodiment, the present invention is described in further detail.
A preparation method for polypyrrole nanofibers conductive electrode material, described preparation method carries out according to following steps:
A. be in the water phase surfactant mixture of 1mmol/L-3mol/L in concentration, add pyrrole monomer and the electrode base material of 0.5g/L-50g/L successively, make electrode base material fully be infiltrated on the water phase surfactant mixture being dispersed with pyrrole monomer with the stir speed (S.S.) of 50r/min-400r/min.
Described tensio-active agent is sulfonate type anion surfactant RSO
3m, wherein, R is anthraquinone or naphthoquinones, and M is basic metal.
Described electrode base material is the one in conducting metal sill or carbon-based material or flexible fabric or polymer fiber film or polymer yarn or natural cellulose silk.
B. above-mentioned mixed system temperature is adjusted to 0-30 DEG C, dropwise add under the stir speed (S.S.) of 50r/min-400r/min with pyrrole monomer mol ratio be the oxygenant neutral aqueous solution of 10:1-1:10 or concentration is the acidic aqueous solution of 2mmol/L-4mol/L, 2-24 hour is reacted under said temperature and stir speed (S.S.), obtain containing the product of electrode base material, successively through deionized water, absolute ethanol washing and be polypyrrole nanofibers conductive electrode material after drying under 60 DEG C of vacuum conditions.
Described acidic aqueous solution adopts the one preparation in a water tosic acid or two hydration 5-sulphosalicylic acids or phosphoric acid or hydrochloric acid.
Described oxygenant is the one in hydrogen peroxide or ammonium persulphate or nine water iron nitrates or Anhydrous Ferric Chloride or potassium bichromate.
Specific embodiment
Embodiment 1
A. getting area is 3.14cm
2conducting metal sill circular shaped foam nickel be electrode base material; The anthraquinone-2-sulfonic acid sodium salt weighing 0.0621g is dissolved in the deionized water of 200ml, adding 0.1g pyrrole monomer is placed in the ice bath of 0 DEG C, be that 50r/min stirs 2min with stir speed (S.S.), pyrrole monomer is made to be dispersed in the aqueous solution of tensio-active agent, then add foam nickel electrode matrix material, continue to be stirred to nickel foam and be fully infiltrated on above-mentioned mixed system;
B. the water tosic acid weighing 0.0761g is dissolved in 200ml deionized water, adds 0.5069g hydrogen peroxide, treats that it dissolves in the ice bath being placed on 0 DEG C completely for subsequent use; Acid for the above-mentioned hydrogen peroxide aqueous solution is dropwise joined above-mentioned containing in the mixed system of nickel foam, pyrrole monomer and tensio-active agent, continue in the ice bath of 0 DEG C, to react 2h with the stir speed (S.S.) of 50r/min; React the black product of rear taking-up containing nickel foam, after using deionized water, absolute ethanol washing colourless to washings successively, under being placed in 60 DEG C of vacuum conditions, after dry lower drying, namely obtain polypyrrole nanofibers conductive electrode material;
C. get the Ni-based polypyrrole nanofibers conductive electrode material of above-mentioned gained foam as positive electrode material, using metal lithium sheet as negative material, assemble button-shaped lithium ion battery; With 0.2C current density to this button-shaped lithium ion battery carry out constant current charge-discharge test its specific storage for 187mAh/g.
Embodiment 2
A. to get area be the square carbon-based material conduction carbon cloth of 2cm × 2cm is electrode base material; Weigh 1 of 0.7806g, 2-naphthoquinones-4-sulfonate sodium is dissolved in the deionized water of 150ml, adding 1.5g pyrrole monomer is placed in the water-bath of 10 DEG C, be that 100r/min stirs 2min with stir speed (S.S.), pyrrole monomer is made to be dispersed in the aqueous solution of tensio-active agent, then add conduction carbon cloth electrode base material, continue to be stirred to conduction carbon cloth and be fully infiltrated on above-mentioned mixed system;
B. the two hydration 5-sulphosalicylic acids weighing 0.7626g are dissolved in 150ml deionized water, add 0.1118g ammonium persulphate, treat that it dissolves in the environment being placed on 10 DEG C completely for subsequent use; Above-mentioned ammonium persulphate acidic aqueous solution is dropwise joined in the above-mentioned mixed system containing conduction carbon cloth, pyrrole monomer and tensio-active agent, continue in the water-bath of 10 DEG C, to react 4h with the stir speed (S.S.) of 100r/min; React the black product of rear taking-up containing conduction carbon cloth, after using deionized water, absolute ethanol washing colourless to washings successively, be placed under 60 DEG C of vacuum conditions and namely obtain polypyrrole nanofibers conductive electrode material after drying;
C. above-mentioned gained conductive carbon fabricbase polypyrrole nanofibers conductive electrode material is got as anode material, to conduct electricity carbon cloth as cathode material, assembling double-chamber microbiological fuel cell system; Fix extrernal resistance with 1000 Ω and start double-chamber microbiological fuel cell system, test its maximum power density is 1492mW/m
2.
Embodiment 3
A. to get area be the rectangular-shaped flexible fabric of 1cm × 5cm is electrode base material; The anthraquinone-2-sulfonic acid sodium salt weighing 4.6539g is dissolved in the deionized water of 150ml, adding 1.8g pyrrole monomer is placed in the water-bath of 15 DEG C, be that 150r/min stirs 2min with stir speed (S.S.), pyrrole monomer is made to be dispersed in the aqueous solution of tensio-active agent, then add flexible fabric electrode base material, continue to be stirred to flexible fabric and be fully infiltrated on above-mentioned mixed system;
B. the phosphoric acid weighing 9.8g is dissolved in 100ml deionized water, adds 21.6782g nine water iron nitrate, treats that it dissolves in the environment being placed on 15 DEG C completely for subsequent use; Above-mentioned nine water iron nitrate acidic aqueous solutions are dropwise joined above-mentioned containing in the mixed system of flexible fabric, pyrrole monomer and tensio-active agent, continue in the water-bath of 15 DEG C, to react 6h with the stir speed (S.S.) of 150r/min; React rear taking-up containing the black product of flexible fabric, after using deionized water, absolute ethanol washing colourless to washings successively, be placed under 60 DEG C of vacuum conditions and namely obtain polypyrrole nanofibers conductive electrode material after drying;
C. two pieces of above-mentioned gained flexible fabric base polypyrrole nanofibers conductive electrode materials are got, with polyvinyl alcohol gel ionogen for solid electrolyte, assembling symmetric form flexible super capacitor; With 50mA/g current density, test gained specific storage is carried out for 126F/g to this ultracapacitor.
Embodiment 4
A. to get area be the square polymer fiber film of 20cm × 20cm is electrode base material; Weigh 1 of 93.672 g, 2-naphthoquinones-4-sulfonate sodium is dissolved in the deionized water of 180ml, adding 7.2g pyrrole monomer is placed in the water-bath of 20 DEG C, be that 200r/min stirs 2min with stir speed (S.S.), pyrrole monomer is made to be dispersed in the aqueous solution of tensio-active agent, then add polymer fiber membrane electrode body material, continue to be stirred to polymer fiber film and be fully infiltrated on above-mentioned mixed system;
B. the hydrochloric acid weighing 21.876g is dissolved in 200ml deionized water, adds 8.7037g Anhydrous Ferric Chloride, treats that it dissolves in the environment being placed on 20 DEG C completely for subsequent use; Above-mentioned Anhydrous Ferric Chloride acidic aqueous solution is dropwise joined above-mentioned containing in the mixed system of polymer fiber film, pyrrole monomer and tensio-active agent, continue in the water-bath of 0 DEG C, to react 8h with the stir speed (S.S.) of 200r/min; React rear taking-up containing the black product of polymer fiber film, after using deionized water, absolute ethanol washing colourless to washings successively, be placed under 60 DEG C of vacuum conditions and namely obtain polypyrrole nanofibers conductive electrode material after drying;
C. get two panels above-mentioned resulting polymers tunica fibrosa base polypyrrole nanofibers conductive electrode material, with porous height water-absorbing sponge for intermediate medium, assemble symmetrical capacitor type alcohol sensor; Test this symmetrical capacitor type alcohol sensor with the spirituous solution of different mass mark, can obtain it has higher sensitivity to the change of 1% alcohol quality mark.
Embodiment 5
A. to get length be the polymer yarn of 100cm is electrode base material; Weigh 1 of 78.06g, 2-naphthoquinones-4-sulfonate sodium is dissolved in the deionized water of 100ml, adding 5g pyrrole monomer is placed in the water-bath of 25 DEG C, be that 250r/min stirs 2min with stir speed (S.S.), pyrrole monomer is made to be dispersed in the aqueous solution of tensio-active agent, then add polymer yarn electrode base material, continue to be stirred to polymer yarn and be fully infiltrated on above-mentioned mixed system;
B. the two hydration 5-sulphosalicylic acids weighing 122.023g are dissolved in 120ml deionized water, add 2.1925g potassium bichromate, treat that it dissolves in the environment being placed on 25 DEG C completely for subsequent use; Above-mentioned potassium bichromate acidic aqueous solution is dropwise joined above-mentioned containing in the mixed system of polymer yarn, pyrrole monomer and tensio-active agent, continue in the water-bath of 0 DEG C, to react 12h with the stir speed (S.S.) of 250r/min; React rear taking-up containing the black product of polymer yarn, after using deionized water, absolute ethanol washing colourless to washings successively, be placed under 60 DEG C of vacuum conditions and namely obtain polypyrrole nanofibers conductive electrode material after drying;
C. get two above-mentioned resulting polymers yarn base polypyrrole nanofibers conductive electrode materials, with polyvinyl alcohol gel ionogen for solid electrolyte, assemble cross fibrous crystal pipe; With the scanning speed of 1mV/s to this cross fibrous crystal pipe carry out on-off ratio test its on-off ratio for 1000.
Embodiment 6
A. to get length be the natural cellulose silk of 50cm is electrode base material; The anthraquinone-2-sulfonic acid sodium salt weighing 4.6539g is dissolved in the deionized water of 100ml, adding 3g pyrrole monomer is placed in the water-bath of 30 DEG C, be that 300r/min stirs 2min with stir speed (S.S.), pyrrole monomer is made to be dispersed in the aqueous solution of tensio-active agent, then add natural cellulose silk electrode base material, continue to be stirred to natural cellulose silk and be fully infiltrated on above-mentioned mixed system;
B. the two hydration 5-sulphosalicylic acids weighing 6.1011g are dissolved in 120ml deionized water, add 18.0652g nine water iron nitrate, treat that it dissolves in the environment being placed on 30 DEG C completely for subsequent use; Above-mentioned nine water iron nitrate acidic aqueous solutions are dropwise joined above-mentioned containing in the mixed system of natural cellulose silk, pyrrole monomer and tensio-active agent, continue in the water-bath of 0 DEG C, to react 14h with the stir speed (S.S.) of 300r/min; React the black product of rear taking-up including natural fibers element silk, after using deionized water, absolute ethanol washing colourless to washings successively, be placed under 60 DEG C of vacuum conditions and namely obtain polypyrrole nanofibers conductive electrode material after drying;
C. get two above-mentioned gained natural cellulose silk base polypyrrole nanofibers conductive electrode materials, with polyvinyl alcohol gel ionogen for solid electrolyte, assemble cross fibrous crystal pipe; With the scanning speed of 1mV/s to this cross fibrous crystal pipe carry out on-off ratio test its on-off ratio for 1002.
Embodiment 7
A. to get area be the rectangular polymer tunica fibrosa of 5cm × 10cm is electrode base material; Weigh 1 of 26.02 g, 2-naphthoquinones-4-sulfonate sodium is dissolved in the deionized water of 200ml, adding 4.4g pyrrole monomer is placed in the water-bath of 5 DEG C, be that 350r/min stirs 2min with stir speed (S.S.), pyrrole monomer is made to be dispersed in the aqueous solution of tensio-active agent, then add polymer fiber membrane electrode body material, continue to be stirred to polymer fiber film and be fully infiltrated on above-mentioned mixed system;
B. the water tosic acid weighing 27.3917g is dissolved in 180ml deionized water, adds 4.0149g hydrogen peroxide, treats that it dissolves in the environment being placed on 5 DEG C completely for subsequent use; Acid for the above-mentioned hydrogen peroxide aqueous solution is dropwise joined above-mentioned containing in the mixed system of polymer fiber film, pyrrole monomer and tensio-active agent, continue in the water-bath of 5 DEG C, to react 18h with the stir speed (S.S.) of 350r/min; React rear taking-up containing the black product of polymer fiber film, after using deionized water, absolute ethanol washing colourless to washings successively, be placed under 60 DEG C of vacuum conditions and namely obtain polypyrrole nanofibers conductive electrode material after drying;
C. get two panels above-mentioned resulting polymers tunica fibrosa base polypyrrole nanofibers conductive electrode material, with porous height water-absorbing sponge for intermediate medium, assemble symmetrical capacitor type formaldehyde sensor; Test this symmetrical capacitor type formaldehyde sensor with the formaldehyde solution of different mass mark, can obtain it has higher sensitivity to the change of 0.1% formaldehyde massfraction.
Embodiment 8
A. getting area is 6.28cm
2conducting metal sill circular shaped foam nickel be electrode base material; The anthraquinone-2-sulfonic acid sodium salt weighing 58.1738g is dissolved in the deionized water of 250ml, adding 11g pyrrole monomer is placed in the ice bath of 0 DEG C, be that 400r/min stirs 2min with stir speed (S.S.), pyrrole monomer is made to be dispersed in the aqueous solution of tensio-active agent, then add foam nickel electrode matrix material, continue to be stirred to nickel foam and be fully infiltrated on above-mentioned mixed system;
B. the phosphoric acid weighing 21.56g is dissolved in 200ml deionized water, adds 85.1033g Anhydrous Ferric Chloride, treats that it dissolves in the ice bath being placed on 0 DEG C completely for subsequent use; Above-mentioned Anhydrous Ferric Chloride acidic aqueous solution is dropwise joined above-mentioned containing in the mixed system of nickel foam, pyrrole monomer and tensio-active agent, continue in the ice bath of 0 DEG C, to react 24h with the stir speed (S.S.) of 400r/min; React the black product of rear taking-up containing nickel foam, after using deionized water, absolute ethanol washing colourless to washings successively, under being placed in 60 DEG C of vacuum conditions, after dry lower drying, namely obtain polypyrrole nanofibers conductive electrode material;
C. get the Ni-based polypyrrole nanofibers conductive electrode material of above-mentioned gained foam as positive electrode material, using metal lithium sheet as negative material, assemble button-shaped lithium ion battery; With 0.2C current density to this button-shaped lithium ion battery carry out constant current charge-discharge test its specific storage for 206mAh/g.
Embodiment 9
A. to get area be the rectangular-shaped flexible fabric of 2cm × 10cm is electrode base material; Weigh 1 of 62.448g, 2-naphthoquinones-4-sulfonate sodium is dissolved in the deionized water of 150ml, adding 6g pyrrole monomer is placed in the water-bath of 0 DEG C, be that 250r/min stirs 2min with stir speed (S.S.), pyrrole monomer is made to be dispersed in the aqueous solution of tensio-active agent, then add flexible fabric electrode base material, continue to be stirred to flexible fabric and be fully infiltrated on above-mentioned mixed system;
B. the hydrochloric acid weighing 14.6g is dissolved in 100ml deionized water, adds 28.941g potassium bichromate, treats that it dissolves in the environment being placed on 0 DEG C completely for subsequent use; Above-mentioned nine water iron nitrate acidic aqueous solutions are dropwise joined above-mentioned containing in the mixed system of flexible fabric, pyrrole monomer and tensio-active agent, continue in the water-bath of 0 DEG C, to react 24h with the stir speed (S.S.) of 250r/min; React rear taking-up containing the black product of flexible fabric, after using deionized water, absolute ethanol washing colourless to washings successively, be placed under 60 DEG C of vacuum conditions and namely obtain polypyrrole nanofibers conductive electrode material after drying;
C. two pieces of above-mentioned gained flexible fabric base polypyrrole nanofibers conductive electrode materials are got, with polyvinyl alcohol gel ionogen for solid electrolyte, assembling symmetric form flexible super capacitor; With 50mA/g current density, test gained specific storage is carried out for 131F/g to this ultracapacitor.
Embodiment 10
A. to get area be the square carbon-based material conduction carbon cloth of 5cm × 5cm is electrode base material; The anthraquinone-2-sulfonic acid sodium salt weighing 23.2695g is dissolved in the deionized water of 150ml, adding 7.5g pyrrole monomer is placed in the water-bath of 0 DEG C, be that 300r/min stirs 2min with stir speed (S.S.), pyrrole monomer is made to be dispersed in the aqueous solution of tensio-active agent, then add conduction carbon cloth electrode base material, continue to be stirred to conduction carbon cloth and be fully infiltrated on above-mentioned mixed system;
B. the water tosic acid weighing 4.28g is dissolved in 150ml deionized water, adds 25.5106g ammonium persulphate, treats that it dissolves in the environment being placed on 0 DEG C completely for subsequent use; Above-mentioned ammonium persulphate acidic aqueous solution is dropwise joined in the above-mentioned mixed system containing conduction carbon cloth, pyrrole monomer and tensio-active agent, continue in the water-bath of 0 DEG C, to react 12h with the stir speed (S.S.) of 250r/min; React the black product of rear taking-up containing conduction carbon cloth, after using deionized water, absolute ethanol washing colourless to washings successively, be placed under 60 DEG C of vacuum conditions and namely obtain polypyrrole nanofibers conductive electrode material after drying;
C. above-mentioned gained conductive carbon fabricbase polypyrrole nanofibers conductive electrode material is got as anode material, to conduct electricity carbon cloth as cathode material, assembling double-chamber microbiological fuel cell system; Fix extrernal resistance with 1000 Ω and start double-chamber microbiological fuel cell system, test its maximum power density is 1612mW/m
2.
Embodiment 11
A. to get area be the square polymer fiber film of 15cm × 15cm is electrode base material; Weigh 1 of 42.1524 g, 2-naphthoquinones-4-sulfonate sodium is dissolved in the deionized water of 180ml, adding 9g pyrrole monomer is placed in the water-bath of 0 DEG C, be that 250r/min stirs 2min with stir speed (S.S.), pyrrole monomer is made to be dispersed in the aqueous solution of tensio-active agent, then add polymer fiber membrane electrode body material, continue to be stirred to polymer fiber film and be fully infiltrated on above-mentioned mixed system;
B. the Anhydrous Ferric Chloride weighing 25.7838g adds in 200ml deionized water, treats that it dissolves in the environment being placed on 0 DEG C completely for subsequent use; Above-mentioned anhydrous chlorides of rase water solution is dropwise joined above-mentioned containing in the mixed system of polymer fiber film, pyrrole monomer and tensio-active agent, continue in the water-bath of 0 DEG C, to react 20h with the stir speed (S.S.) of 250r/min; React rear taking-up containing the black product of polymer fiber film, after using deionized water, absolute ethanol washing colourless to washings successively, be placed under 60 DEG C of vacuum conditions and namely obtain polypyrrole nanofibers conductive electrode material after drying;
C. get two panels above-mentioned resulting polymers tunica fibrosa base polypyrrole nanofibers conductive electrode material, with porous height water-absorbing sponge for intermediate medium, assemble symmetrical capacitor type alcohol sensor; Test this symmetrical capacitor type alcohol sensor with the spirituous solution of different mass mark, can obtain it has higher sensitivity to the change of 1% alcohol quality mark.
Embodiment 12
A. to get area be the square carbon-based material conduction carbon cloth of 12cm × 12cm is electrode base material; Weigh 7.806 1,2-naphthoquinones-4-sulfonate sodium is dissolved in the deionized water of 150ml, adding 4.5g pyrrole monomer is placed in the water-bath of 0 DEG C, be that 100r/min stirs 2min with stir speed (S.S.), pyrrole monomer is made to be dispersed in the aqueous solution of tensio-active agent, then add conduction carbon cloth electrode base material, continue to be stirred to conduction carbon cloth and be fully infiltrated on above-mentioned mixed system;
B. the potassium bichromate weighing 8.4568g adds in 150ml deionized water, treats that it dissolves in the environment being placed on 0 DEG C completely for subsequent use; Above-mentioned potassium dichromate aqueous solution is dropwise joined in the above-mentioned mixed system containing conduction carbon cloth, pyrrole monomer and tensio-active agent, continue in the water-bath of 10 DEG C, to react 8h with the stir speed (S.S.) of 100r/min; React the black product of rear taking-up containing conduction carbon cloth, after using deionized water, absolute ethanol washing colourless to washings successively, be placed under 60 DEG C of vacuum conditions and namely obtain polypyrrole nanofibers conductive electrode material after drying;
C. above-mentioned gained conductive carbon fabricbase polypyrrole nanofibers conductive electrode material is got as anode material, to conduct electricity carbon cloth as cathode material, assembling double-chamber microbiological fuel cell system; Fix extrernal resistance with 1000 Ω and start double-chamber microbiological fuel cell system, test its maximum power density is 1465mW/m
2.
Embodiment 13
A. to get length be the polymer yarn of 60cm is electrode base material; The anthraquinone-2-sulfonic acid sodium salt weighing 4.6539g is dissolved in the deionized water of 100ml, adding 1g pyrrole monomer is placed in the water-bath of 10 DEG C, be that 250r/min stirs 2min with stir speed (S.S.), pyrrole monomer is made to be dispersed in the aqueous solution of tensio-active agent, then add polymer yarn electrode base material, continue to be stirred to polymer yarn and be fully infiltrated on above-mentioned mixed system;
B. the nine water iron nitrates weighing 1.0036g add in 120ml deionized water, treat that it dissolves in the environment being placed on 10 DEG C completely for subsequent use; Above-mentioned nine water iron nitrate aqueous solutions are dropwise joined above-mentioned containing in the mixed system of polymer yarn, pyrrole monomer and tensio-active agent, continue in the water-bath of 10 DEG C, to react 8h with the stir speed (S.S.) of 250r/min; React rear taking-up containing the black product of polymer yarn, after using deionized water, absolute ethanol washing colourless to washings successively, be placed under 60 DEG C of vacuum conditions and namely obtain polypyrrole nanofibers conductive electrode material after drying;
C. get two above-mentioned resulting polymers yarn base polypyrrole nanofibers conductive electrode materials, with polyvinyl alcohol gel ionogen for solid electrolyte, assemble cross fibrous crystal pipe; With the scanning speed of 1mV/s to this cross fibrous crystal pipe carry out on-off ratio test its on-off ratio for 998.
Claims (5)
1. a preparation method for polypyrrole nanofibers conductive electrode material, is characterized in that: described preparation method carries out according to following steps:
A. be in the water phase surfactant mixture of 1mmol/L-3mol/L in concentration, add pyrrole monomer and the electrode base material of 0.5g/L-50g/L successively, with the stir speed (S.S.) of 50r/min-400r/min, electrode base material is fully infiltrated on and is dispersed with in the water phase surfactant mixture of pyrrole monomer;
B. above-mentioned mixed system temperature is adjusted to 0-30 DEG C, dropwise add under the stir speed (S.S.) of 50r/min-400r/min with pyrrole monomer mol ratio be the oxygenant neutral aqueous solution of 10:1-1:10 or concentration is the acidic aqueous solution of 2mmol/L-4mol/L, 2-24 hour is reacted under said temperature and stir speed (S.S.), obtain containing the product of electrode base material, successively through deionized water, absolute ethanol washing and be polypyrrole nanofibers conductive electrode material after drying under 60 DEG C of vacuum conditions.
2. the preparation method of a kind of polypyrrole nanofibers conductive electrode material as claimed in claim 1, is characterized in that: described tensio-active agent is sulfonate type anion surfactant RSO
3m, wherein, R is anthraquinone or naphthoquinones, and M is basic metal.
3. the preparation method of a kind of polypyrrole nanofibers conductive electrode material as claimed in claim 1, is characterized in that: described electrode base material is the one in conducting metal sill or carbon-based material or flexible fabric or polymer fiber film or polymer yarn or natural cellulose silk.
4. the preparation method of a kind of polypyrrole nanofibers conductive electrode material as claimed in claim 1, is characterized in that: described acidic aqueous solution adopts the one preparation in a water tosic acid or two hydration 5-sulphosalicylic acids or phosphoric acid or hydrochloric acid.
5. the preparation method of a kind of polypyrrole nanofibers conductive electrode material as claimed in claim 1, is characterized in that: described oxygenant is the one in hydrogen peroxide or ammonium persulphate or nine water iron nitrates or Anhydrous Ferric Chloride or potassium bichromate.
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