CN105001420B - A kind of preparation method of polypyrrole nanofibers conductive electrode material - Google Patents
A kind of preparation method of polypyrrole nanofibers conductive electrode material Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of polypyrrole nanofibers conductive electrode material, belong to electrical-conductive nanometer Material Field.The present invention, which is used, first fully infiltrates electrode base material in the aqueous surfactant solution of pyrrole monomer is dispersed with, state then up and neutrality or acidic aqueous solution containing oxidant are added dropwise in mixed system, reacted 2-24 hours under the conditions of 0-30 DEG C, by product of the gained containing electrode matrix, vacuum drying produces polypyrrole nanofibers conductive electrode material after repeatedly washing.Preparation method technique of the present invention is simple, with low cost, suitable for large-scale industrialized production.It can be widely applied to the fields such as ultracapacitor, microbiological fuel cell, lithium ion battery, transistor and sensor.
Description
Technical field
The present invention relates to a kind of preparation method of polypyrrole nanofibers conductive electrode material, sulfonate type is more particularly to used
The method that anion surfactant assistant chemical oxidation in-situ polymerization prepares polypyrrole nanofibers conductive electrode material, belongs to
Electrical-conductive nanometer Material Field.
Background technology
Polypyrrole as most common conducting polymer, i.e., with its excellent biocompatibility, Rapid reversible oxidation also
Original reaction, high conductivity and larger energy loads and as a kind of preferable electrode material be widely used in ultracapacitor,
In terms of microbiological fuel cell, lithium ion battery, transistor and sensor.But the polypyrrole prepared under usual conditions with
It is granular to present and there is the problem of being difficult to dissolve and melt, and then constrain its processing and forming and application.Due to nanoscale material
Material has excellent skin effect and bulk effect, and the electrode material of polypyrrole nanofibers modification is in mass transfer characteristic and conductance
Have in terms of rate and significantly lifted, therefore, formation nanofiber pattern then seems outstanding directly in the preparation process of polypyrrole
To be important.
The preparation method of polypyrrole nanofibers is concentrated mainly on template, electrochemical process and chemical oxidization method.Template
It is to prepare polypyrrole nanofibers most common method, for example：China Patent Publication No. CN102675877B, publication date is
On September 4th, 2013, discloses polypyrrole nano line and its production and use, the invention is obtained by two-step electrochemical anodizing method
Nanohole alumine template is obtained, then electricity will be carried out in gold-plated rear ethanol solution of the immersion containing 2- guanidine pyridine benzimidazoles of the template
Deposition processes, polypyrrole nano line is obtained after most removing template through physical-chemical process afterwards.China Patent Publication No.
CN102924718A, publication date is on 2 13rd, 2013, discloses a kind of preparation side of the polypyrrole with nanostructured
Method, the invention is using the manganese dioxide of nanostructured as template, by being reacted in an acidic solution with pyrrole monomer
With manganese dioxide pattern identical nanostructured polypyrrole.Illustrating above, it is more numerous to prepare polypyrrole nanofibers using template
It is trivial, and have the shortcomings that to remove and can destroy polypyrrole nanofibers structure in template procedure and template is difficult to the difficulty that removes.Adopt
Polypyrrole nanofibers are prepared with electrochemical process also more report.For example：China Patent Publication No. CN1465748A, it is open
Date is on January 7th, 2004, and the method for disclosing directly forming polypyrrole nano line on electrode surface, the invention is electric by controlling
Pyrrole monomer, the concentration of dopant in liquid are solved, different length is directly generated in electrode surface with potentiostatic method or cyclic voltammetry
With the polypyrrole nano line of diameter.China Patent Publication No. CN102544501A, publication date is on July 4th, 2012, is disclosed
A kind of method for preparing polypyrrole nanometer wire-graphene composite material, the invention is containing pyrrole monomer using three-electrode system
Polypyrrole nano line is obtained with carrying out electrochemical polymerization in the disodium hydrogen phosphate and the lithium perchlorate aqueous solution of Graphene powder.Using electricity
Although chemical method prepare polypyrrole nanofibers with polymerization time it is short the characteristics of, be limited by electrochemistry formated yield itself compared with
It is small, thus be difficult to mass produce.
Chemical oxidization method is the conventional approach for the polypyrrole nanofibers for being easily obtained high yield, and equipment cost is low and operates
Simply.For example：China Patent Publication No. CN1597732, publication date is on March 23rd, 2005, discloses electric polypyrrole and receives
The preparation method of rice noodles, the invention prepares polypyrrole nanometer using quaternary ammonium cation surfactant assistant chemical oxidizing process
Line.China Patent Publication No. CN103343394A, publication date is on October 9th, 2013, discloses a kind of polypyrrole Nanowire
The preparation method of dimension, the invention is using diazosulfide class fluorescer as dopant, and oxidation polymerization in a nitrogen atmosphere is had concurrently
The polypyrrole nanofibers of fluorescence and electric conductivity.But the polypyrrole nanofibers obtained above using the case of chemical oxidization method are existed
Exist in synthetic solvent in the form of the insoluble powder precipitation do not melted, it is impossible to directly as materials'use, needed during practical application
Carry out follow-up purification, shaping or modification.
The content of the invention
For above-mentioned problem, it is an object of the invention to provide a kind of technique is simple, with low cost, suitable industry
The method for preparing polypyrrole nanofibers conductive electrode of metaplasia production, the method overcome template and prepares polypyrrole nanofibers
The shortcomings of relative complex high cost of technical process and electrochemical process, low yield, the chemical oxidation aided in using surfactant
Polymerization, can obtain the material system of polypyrrole nanofibers and polytype matrix material In-situ reaction, can keep poly-
The form of pyrroles's nanofiber, and the formation problems that polypyrrole nanofibers are applied to energy electrode material are directly solved, tool
It is standby settle at one go, the simple advantage of with low cost, technique.
To achieve the above object, the technical solution adopted by the present invention is：
A kind of preparation method of polypyrrole nanofibers conductive electrode material, the preparation method is entered according to following steps
OK：
A. in the aqueous surfactant solution that concentration is 1mmol/L-3mol/L, sequentially add 0.5g/L-50g/L's
Pyrrole monomer and electrode base material, make electrode base material fully be infiltrated on 50r/min-400r/min stir speed (S.S.)
It is dispersed with the aqueous surfactant solution of pyrrole monomer；
B. above-mentioned mixed system temperature is adjusted to 0-30 DEG C, added dropwise under 50r/min-400r/min stir speed (S.S.)
It is 10 to enter with pyrrole monomer mol ratio：1-1：10 oxidant neutral aqueous solution or concentration is 2mmol/L-4mol/L acid
Property the aqueous solution, under said temperature and stir speed (S.S.) react 2-24 hours, the obtained product containing electrode base material, according to
It is secondary through deionized water, absolute ethyl alcohol washing and under 60 DEG C of vacuum conditions dry after be polypyrrole nanofibers conductive electrode material
Material.
Described surfactant is sulfonate type anion surfactant RSO3M, wherein, R is anthraquinone or naphthoquinones, M
For alkali metal.
Described electrode base material is conducting metal sill or carbon-based material or flexible fabric or polymer fiber film
Or one kind in polymer yarn or native cellulose silk.
Described acidic aqueous solution is using in a water p-methyl benzenesulfonic acid or two hydration 5-sulphosalicylic acids or phosphoric acid or hydrochloric acid
A kind of preparation.
Described oxidant is in hydrogen peroxide or ammonium persulfate or nine water ferric nitrates or anhydrous ferric chloride or potassium bichromate
One kind.
As a result of above technical scheme, the present invention has advantages below：
1）The inventive method prepares polypyrrole nanofibers by the regulation and control of Surfactant on a large scale, and without right
Polypyrrole nanofibers, which carry out following process processing, can directly obtain polypyrrole nanofibers conductive electrode material；
2）The difference that polypyrrole nanofibers conductive electrode material prepared by the present invention regards its electrode base material has not
Same electrical conductivity, biocompatibility and the three-dimensional space net structure interweaved, can meet different application field to conductive electrode
The demand of material structure and performance.
Preparation method technique of the present invention is simple, with low cost, suitable for large-scale industrialized production.It can be widely applied to super
The fields such as capacitor, microbiological fuel cell, lithium ion battery, transistor and sensor.
Embodiment
The present invention is described in further detail with reference to specific embodiment.
A kind of preparation method of polypyrrole nanofibers conductive electrode material, the preparation method is entered according to following steps
OK：
A. in the aqueous surfactant solution that concentration is 1mmol/L-3mol/L, sequentially add 0.5g/L-50g/L's
Pyrrole monomer and electrode base material, make electrode base material fully be infiltrated on 50r/min-400r/min stir speed (S.S.)
It is dispersed with the aqueous surfactant solution of pyrrole monomer.
Described surfactant is sulfonate type anion surfactant RSO3M, wherein, R is anthraquinone or naphthoquinones, M
For alkali metal.
Described electrode base material is conducting metal sill or carbon-based material or flexible fabric or polymer fiber film
Or one kind in polymer yarn or native cellulose silk.
B. above-mentioned mixed system temperature is adjusted to 0-30 DEG C, added dropwise under 50r/min-400r/min stir speed (S.S.)
It is 10 to enter with pyrrole monomer mol ratio：1-1：10 oxidant neutral aqueous solution or concentration is 2mmol/L-4mol/L acid
Property the aqueous solution, under said temperature and stir speed (S.S.) react 2-24 hours, the obtained product containing electrode base material, according to
It is secondary through deionized water, absolute ethyl alcohol washing and under 60 DEG C of vacuum conditions dry after be polypyrrole nanofibers conductive electrode material
Material.
Described acidic aqueous solution is using in a water p-methyl benzenesulfonic acid or two hydration 5-sulphosalicylic acids or phosphoric acid or hydrochloric acid
A kind of preparation.
Described oxidant is in hydrogen peroxide or ammonium persulfate or nine water ferric nitrates or anhydrous ferric chloride or potassium bichromate
One kind.
Specific embodiment
Embodiment 1
A. it is 3.14cm to take area2Conducting metal sill circular shaped foam nickel be electrode base material；Weigh 0.0621g
Anthraquinone-2-sulfonic acid sodium salt be dissolved in 200ml deionized water, add 0.1g pyrrole monomers after be placed in 0 DEG C of ice bath, to stir
Mix speed and stir 2min for 50r/min, pyrrole monomer is dispersed in the aqueous solution of surfactant, then add foam
Nickel electrode matrix material, continues stirring and above-mentioned mixed system is fully infiltrated on to nickel foam；
B. the water p-methyl benzenesulfonic acid for weighing 0.0761g is dissolved in 200ml deionized waters, adds 0.5069g hydrogen peroxide,
It is placed in after it is completely dissolved standby in 0 DEG C of ice bath；By the acid aqueous solution of above-mentioned hydrogen peroxide be added dropwise to it is above-mentioned containing
In the mixed system of nickel foam, pyrrole monomer and surfactant, continue the stir speed (S.S.) with 50r/min in 0 DEG C of ice bath
React 2h；The black product containing nickel foam is taken out after the completion of reaction, washed successively with deionized water, absolute ethyl alcohol to cleaning solution without
After color, it is placed under 60 DEG C of vacuum conditions after drying lower dry and produces polypyrrole nanofibers conductive electrode material；
C. the Ni-based polypyrrole nanofibers conductive electrode material of above-mentioned gained foam is taken as positive electrode, with metal lithium sheet
As negative material, button-shaped lithium ion battery is assembled；Constant current is carried out to this button-shaped lithium ion battery with 0.2C current densities
Charge-discharge test obtains its specific capacity for 187mAh/g.
Embodiment 2
A. it is electrode base material to take the conductive carbon cloth of square carbon-based material that area is 2cm × 2cm；Weigh 0.7806g
1,2- naphthoquinones -4- sulfonate sodiums be dissolved in 150ml deionized water, add and 10 DEG C of water-bath be placed in after 1.5g pyrrole monomers
In, 2min is stirred by 100r/min of stir speed (S.S.), pyrrole monomer is dispersed in the aqueous solution of surfactant, then
Conductive carbon cloth electrode base material is added, continues stirring to conductive carbon cloth and is fully infiltrated on above-mentioned mixed system；
B. the two hydration 5-sulphosalicylic acids for weighing 0.7626g are dissolved in 150ml deionized waters, add 0.1118g over cures
Sour ammonium, is placed in standby in 10 DEG C of environment after it is completely dissolved；Above-mentioned ammonium persulfate acidic aqueous solution is added dropwise to
State in the mixed system containing conductive carbon cloth, pyrrole monomer and surfactant, continue the stir speed (S.S.) with 100r/min 10
DEG C water-bath in react 4h；The black product containing conductive carbon cloth is taken out after the completion of reaction, is washed successively with deionized water, absolute ethyl alcohol
Wash to cleaning solution it is colourless after, be placed under 60 DEG C of vacuum conditions dry after produce polypyrrole nanofibers conductive electrode material；
C. the conductive carbon cloth base polypyrrole nanofibers conductive electrode material of above-mentioned gained is taken as anode material, with conductive carbon
Cloth assembles double-chamber microbiological fuel cell system as cathode material；Extrernal resistance, which is fixed, with 1000 Ω starts two-chamber microbial fuel
Battery system, test its maximum power density be 1492mW/m2。
Embodiment 3
A. it is electrode base material to take the rectangular-shaped flexible fabric that area is 1cm × 5cm；Weigh 4.6539g anthraquinone -2-
Sulfonate sodium is dissolved in 150ml deionized water, add 1.8g pyrrole monomers after be placed in 15 DEG C of water-bath, using stir speed (S.S.) as
150r/min stirs 2min, pyrrole monomer is dispersed in the aqueous solution of surfactant, then adds flexible fabric electricity
Pole matrix material, continues stirring and above-mentioned mixed system is fully infiltrated on to flexible fabric；
B. the phosphoric acid for weighing 9.8g is dissolved in 100ml deionized waters, adds the water ferric nitrates of 21.6782g nine, treats that it is completely molten
It is placed in after solution standby in 15 DEG C of environment；Above-mentioned nine water ferric nitrate acidic aqueous solution is added dropwise to and above-mentioned knitted containing flexible
In the mixed system of thing, pyrrole monomer and surfactant, the lasting stir speed (S.S.) with 150r/min is anti-in 15 DEG C of water-bath
Answer 6h；The black product containing flexible fabric is taken out after the completion of reaction, washed successively with deionized water, absolute ethyl alcohol to cleaning solution without
After color, it is placed in after being dried under 60 DEG C of vacuum conditions and produces polypyrrole nanofibers conductive electrode material；
C. two pieces of above-mentioned gained flexible fabric base polypyrrole nanofibers conductive electrode materials are taken, with polyvinyl alcohol gel electricity
Solution matter is solid electrolyte, assembles symmetric form flexible super capacitor；This ultracapacitor is carried out with 50mA/g current densities
Test gained specific capacity is 126F/g.
Embodiment 4
A. the square polymer fiber film for taking area to be 20cm × 20cm is electrode base material；Weigh 93.672 g's
1,2- naphthoquinones -4- sulfonate sodiums are dissolved in 180ml deionized water, are placed in after adding 7.2g pyrrole monomers in 20 DEG C of water-bath,
2min is stirred by 200r/min of stir speed (S.S.), pyrrole monomer is dispersed in the aqueous solution of surfactant, Ran Houjia
Enter polymer fiber film electrode base material, continue stirring and above-mentioned mixed system is fully infiltrated on to polymer fiber film；
B. the hydrochloric acid for weighing 21.876g is dissolved in 200ml deionized waters, is added 8.7037g anhydrous ferric chlorides, is treated that its is complete
It is placed in after dissolving standby in 20 DEG C of environment；Above-mentioned anhydrous ferric chloride acidic aqueous solution is added dropwise to above-mentioned containing polymer
In the mixed system of tunica fibrosa, pyrrole monomer and surfactant, continue the stir speed (S.S.) with 200r/min in 0 DEG C of water-bath
React 8h；The black product containing polymer fiber film is taken out after the completion of reaction, is washed successively with deionized water, absolute ethyl alcohol to washing
Wash liquid it is colourless after, be placed under 60 DEG C of vacuum conditions dry after produce polypyrrole nanofibers conductive electrode material；
C. the above-mentioned resulting polymers tunica fibrosa base polypyrrole nanofibers conductive electrode material of two panels is taken, with porous high water absorption
Sponge is intermediate medium, assembles symmetrical capacitor type alcohol sensor；With the alcoholic solution of different quality containing to this symmetrical electric capacity
Type alcohol sensor is tested, and can obtain its change to 1% alcohol quality fraction has higher sensitivity.
Embodiment 5
A. the polymer yarn for taking length to be 100cm is electrode base material；Weigh 78.06g 1,2- naphthoquinones -4- sulfonic acid
Sodium salt is dissolved in 100ml deionized water, is placed in after adding 5g pyrrole monomers in 25 DEG C of water-bath, using stir speed (S.S.) as 250r/
Min stirs 2min, pyrrole monomer is dispersed in the aqueous solution of surfactant, then adds polymer yarns line electrode base
Body material, continues stirring and above-mentioned mixed system is fully infiltrated on to polymer yarn；
B. the two hydration 5-sulphosalicylic acids for weighing 122.023g are dissolved in 120ml deionized waters, add 2.1925g weights
Potassium chromate, is placed in standby in 25 DEG C of environment after it is completely dissolved；Above-mentioned potassium bichromate acidic aqueous solution is added dropwise to
In the above-mentioned mixed system containing polymer yarn, pyrrole monomer and surfactant, continue the stir speed (S.S.) with 250r/min
12h is reacted in 0 DEG C of water-bath；The black product containing polymer yarn is taken out after the completion of reaction, successively with deionized water, anhydrous
Ethanol wash to cleaning solution it is colourless after, be placed under 60 DEG C of vacuum conditions dry after produce polypyrrole nanofibers conductive electrode material
Material；
C. two above-mentioned resulting polymers yarn base polypyrrole nanofibers conductive electrode materials are taken, with polyvinyl alcohol gel
Electrolyte is solid electrolyte, assembles cross fibrous crystal pipe；With 1mV/s sweep speed to this cross fibrous crystal pipe
Carry out on-off ratio test its on-off ratio be 1000.
Embodiment 6
A. it is electrode base material to take the native cellulose silk that length is 50cm；Weigh 4.6539g anthraquinone-2-sodium
Salt is dissolved in 100ml deionized water, is placed in after adding 3g pyrrole monomers in 30 DEG C of water-bath, using stir speed (S.S.) as 300r/min
2min is stirred, pyrrole monomer is dispersed in the aqueous solution of surfactant, native cellulose silk electrode base is then added
Body material, continues stirring to native cellulose silk and is fully infiltrated on above-mentioned mixed system；
B. the two hydration 5-sulphosalicylic acids for weighing 6.1011g are dissolved in 120ml deionized waters, add 18.0652g nine
Water ferric nitrate, is placed in standby in 30 DEG C of environment after it is completely dissolved；Above-mentioned nine water ferric nitrate acidic aqueous solution is added dropwise
Enter into the above-mentioned mixed system containing native cellulose silk, pyrrole monomer and surfactant, continue stirring with 300r/min
Mix speed and react 14h in 0 DEG C of water-bath；The black product of the plain silk of including natural fibers is taken out after the completion of reaction, spend successively from
Sub- water, absolute ethyl alcohol wash to cleaning solution it is colourless after, be placed in after being dried under 60 DEG C of vacuum conditions and produce polypyrrole nanofibers and lead
Electric electrode material；
C. two above-mentioned gained native cellulose silk base polypyrrole nanofibers conductive electrode materials are taken, it is solidifying with polyvinyl alcohol
Glue electrolyte is solid electrolyte, assembles cross fibrous crystal pipe；With 1mV/s sweep speed to this cross fibrous crystal
Pipe carry out on-off ratio test its on-off ratio be 1002.
Embodiment 7
A. it is electrode base material to take the rectangular polymer tunica fibrosa that area is 5cm × 10cm；The 1 of 26.02 g is weighed,
2- naphthoquinones -4- sulfonate sodiums are dissolved in 200ml deionized water, are placed in after adding 4.4g pyrrole monomers in 5 DEG C of water-bath, to stir
Mix speed and stir 2min for 350r/min, pyrrole monomer is dispersed in the aqueous solution of surfactant, then add poly-
Compound tunica fibrosa electrode base material, continues stirring and above-mentioned mixed system is fully infiltrated on to polymer fiber film；
B. the water p-methyl benzenesulfonic acid for weighing 27.3917g is dissolved in 180ml deionized waters, adds 4.0149g peroxidating
Hydrogen, is placed in standby in 5 DEG C of environment after it is completely dissolved；The acid aqueous solution of above-mentioned hydrogen peroxide is added dropwise to above-mentioned contain
In the mixed system for having polymer fiber film, pyrrole monomer and surfactant, continue the stir speed (S.S.) with 350r/min at 5 DEG C
Water-bath in react 18h；The black product containing polymer fiber film is taken out after the completion of reaction, successively with deionized water, anhydrous second
Alcohol wash to cleaning solution it is colourless after, be placed under 60 DEG C of vacuum conditions dry after produce polypyrrole nanofibers conductive electrode material；
C. the above-mentioned resulting polymers tunica fibrosa base polypyrrole nanofibers conductive electrode material of two panels is taken, with porous high water absorption
Sponge is intermediate medium, assembles symmetrical capacitor type formaldehyde sensor；With the formalin of different quality containing to this symmetrical electric capacity
Type formaldehyde sensor is tested, and can obtain its change to 0.1% formaldehyde mass fraction has higher sensitivity.
Embodiment 8
A. it is 6.28cm to take area2Conducting metal sill circular shaped foam nickel be electrode base material；Weigh
58.1738g anthraquinone-2-sulfonic acid sodium salt is dissolved in 250ml deionized water, and 0 DEG C of ice bath is placed in after addition 11g pyrrole monomers
In, 2min is stirred by 400r/min of stir speed (S.S.), pyrrole monomer is dispersed in the aqueous solution of surfactant, then
Foam nickel electrode matrix material is added, continues stirring and above-mentioned mixed system is fully infiltrated on to nickel foam；
B. the phosphoric acid for weighing 21.56g is dissolved in 200ml deionized waters, is added 85.1033g anhydrous ferric chlorides, is treated that its is complete
It is placed in after dissolving standby in 0 DEG C of ice bath；By above-mentioned anhydrous ferric chloride acidic aqueous solution be added dropwise to it is above-mentioned containing nickel foam,
In the mixed system of pyrrole monomer and surfactant, continue to react in 0 DEG C of ice bath with 400r/min stir speed (S.S.)
24h；The black product containing nickel foam is taken out after the completion of reaction, washs colourless to cleaning solution with deionized water, absolute ethyl alcohol successively
Afterwards, it is placed under 60 DEG C of vacuum conditions after drying lower dry and produces polypyrrole nanofibers conductive electrode material；
C. the Ni-based polypyrrole nanofibers conductive electrode material of above-mentioned gained foam is taken as positive electrode, with metal lithium sheet
As negative material, button-shaped lithium ion battery is assembled；Constant current is carried out to this button-shaped lithium ion battery with 0.2C current densities
Charge-discharge test obtains its specific capacity for 206mAh/g.
Embodiment 9
A. it is electrode base material to take the rectangular-shaped flexible fabric that area is 2cm × 10cm；Weigh 62.448g 1,2- naphthalenes
Quinone -4- sulfonate sodiums are dissolved in 150ml deionized water, are placed in after adding 6g pyrrole monomers in 0 DEG C of water-bath, with stir speed (S.S.)
2min is stirred for 250r/min, pyrrole monomer is dispersed in the aqueous solution of surfactant, then adds flexible fabric
Electrode base material, continues stirring and above-mentioned mixed system is fully infiltrated on to flexible fabric；
B. the hydrochloric acid for weighing 14.6g is dissolved in 100ml deionized waters, is added 28.941g potassium bichromates, is treated that it is completely dissolved
It is placed in afterwards standby in 0 DEG C of environment；Above-mentioned nine water ferric nitrate acidic aqueous solution is added dropwise to above-mentioned containing flexible fabric, pyrrole
In the mixed system for coughing up monomer and surfactant, continue to react 24h in 0 DEG C of water-bath with 250r/min stir speed (S.S.)；
The black product containing flexible fabric is taken out after the completion of reaction, successively with deionized water, absolute ethyl alcohol wash to cleaning solution it is colourless after,
It is placed in after being dried under 60 DEG C of vacuum conditions and produces polypyrrole nanofibers conductive electrode material；
C. two pieces of above-mentioned gained flexible fabric base polypyrrole nanofibers conductive electrode materials are taken, with polyvinyl alcohol gel electricity
Solution matter is solid electrolyte, assembles symmetric form flexible super capacitor；This ultracapacitor is carried out with 50mA/g current densities
Test gained specific capacity is 131F/g.
Embodiment 10
A. it is electrode base material to take the conductive carbon cloth of square carbon-based material that area is 5cm × 5cm；Weigh 23.2695g
Anthraquinone-2-sulfonic acid sodium salt be dissolved in 150ml deionized water, add 7.5g pyrrole monomers after be placed in 0 DEG C of water-bath, to stir
Mix speed and stir 2min for 300r/min, pyrrole monomer is dispersed in the aqueous solution of surfactant, then add and lead
Electrical carbon cloth electrode base material, continues stirring to conductive carbon cloth and is fully infiltrated on above-mentioned mixed system；
B. the water p-methyl benzenesulfonic acid for weighing 4.28g is dissolved in 150ml deionized waters, adds 25.5106g ammonium persulfates,
It is placed in after it is completely dissolved standby in 0 DEG C of environment；By above-mentioned ammonium persulfate acidic aqueous solution be added dropwise to it is above-mentioned containing
In the mixed system of conductive carbon cloth, pyrrole monomer and surfactant, continue the water-bath at 0 DEG C with 250r/min stir speed (S.S.)
Middle reaction 12h；The black product containing conductive carbon cloth is taken out after the completion of reaction, is washed successively with deionized water, absolute ethyl alcohol to washing
Wash liquid it is colourless after, be placed under 60 DEG C of vacuum conditions dry after produce polypyrrole nanofibers conductive electrode material；
C. the conductive carbon cloth base polypyrrole nanofibers conductive electrode material of above-mentioned gained is taken as anode material, with conductive carbon
Cloth assembles double-chamber microbiological fuel cell system as cathode material；Extrernal resistance, which is fixed, with 1000 Ω starts two-chamber microbial fuel
Battery system, test its maximum power density be 1612mW/m2。
Embodiment 11
A. the square polymer fiber film for taking area to be 15cm × 15cm is electrode base material；Weigh 42.1524 g
1,2- naphthoquinones -4- sulfonate sodiums be dissolved in 180ml deionized water, add 9g pyrrole monomers after be placed in 0 DEG C of water-bath, with
Stir speed (S.S.) is that 250r/min stirs 2min, pyrrole monomer is dispersed in the aqueous solution of surfactant, then adds
Polymer fiber film electrode base material, continues stirring and above-mentioned mixed system is fully infiltrated on to polymer fiber film；
B. the anhydrous ferric chloride for weighing 25.7838g is added in 200ml deionized waters, and 0 DEG C is placed in after it is completely dissolved
It is standby in environment；The above-mentioned anhydrous ferric chloride aqueous solution is added dropwise to above-mentioned containing polymer fiber film, pyrrole monomer and table
In the mixed system of face activating agent, continue to react 20h in 0 DEG C of water-bath with 250r/min stir speed (S.S.)；After the completion of reaction
Take out the black product containing polymer fiber film, successively with deionized water, absolute ethyl alcohol wash to cleaning solution it is colourless after, be placed in 60
Polypyrrole nanofibers conductive electrode material is produced after being dried under DEG C vacuum condition；
C. the above-mentioned resulting polymers tunica fibrosa base polypyrrole nanofibers conductive electrode material of two panels is taken, with porous high water absorption
Sponge is intermediate medium, assembles symmetrical capacitor type alcohol sensor；With the alcoholic solution of different quality containing to this symmetrical electric capacity
Type alcohol sensor is tested, and can obtain its change to 1% alcohol quality fraction has higher sensitivity.
Embodiment 12
A. it is electrode base material to take the conductive carbon cloth of square carbon-based material that area is 12cm × 12cm；Weigh 7.806
1,2- naphthoquinones -4- sulfonate sodiums be dissolved in 150ml deionized water, add 4.5g pyrrole monomers after be placed in 0 DEG C of water-bath,
2min is stirred by 100r/min of stir speed (S.S.), pyrrole monomer is dispersed in the aqueous solution of surfactant, Ran Houjia
Enter conductive carbon cloth electrode base material, continue stirring to conductive carbon cloth and be fully infiltrated on above-mentioned mixed system；
B. the potassium bichromate for weighing 8.4568g is added in 150ml deionized waters, and 0 DEG C of ring is placed in after it is completely dissolved
It is standby in border；Above-mentioned potassium dichromate aqueous solution is added dropwise to above-mentioned containing conductive carbon cloth, pyrrole monomer and surfactant
Mixed system in, continue 8h is reacted in 10 DEG C of water-bath with 100r/min stir speed (S.S.)；Take out to contain after the completion of reaction and lead
The black product of electrical carbon cloth, successively with deionized water, absolute ethyl alcohol wash to cleaning solution it is colourless after, be placed under 60 DEG C of vacuum conditions
Polypyrrole nanofibers conductive electrode material is produced after drying；
C. the conductive carbon cloth base polypyrrole nanofibers conductive electrode material of above-mentioned gained is taken as anode material, with conductive carbon
Cloth assembles double-chamber microbiological fuel cell system as cathode material；Extrernal resistance, which is fixed, with 1000 Ω starts two-chamber microbial fuel
Battery system, test its maximum power density be 1465mW/m2。
Embodiment 13
A. the polymer yarn for taking length to be 60cm is electrode base material；Weigh 4.6539g anthraquinone-2-sulfonic acid sodium salt
It is dissolved in 100ml deionized water, is placed in 10 DEG C of water-bath, is stirred by 250r/min of stir speed (S.S.) after adding 1g pyrrole monomers
2min is mixed, pyrrole monomer is dispersed in the aqueous solution of surfactant, polymer yarn electrode matrix material is then added
Material, continues stirring and above-mentioned mixed system is fully infiltrated on to polymer yarn；
B. the nine water ferric nitrates for weighing 1.0036g are added in 120ml deionized waters, and 10 DEG C are placed in after it is completely dissolved
It is standby in environment；Above-mentioned nine water iron nitrate aqueous solution is added dropwise to above-mentioned containing polymer yarn, pyrrole monomer and surface
In the mixed system of activating agent, continue to react 8h in 10 DEG C of water-bath with 250r/min stir speed (S.S.)；Taken after the completion of reaction
Go out the black product containing polymer yarn, successively with deionized water, absolute ethyl alcohol wash to cleaning solution it is colourless after, be placed in 60 DEG C it is true
Polypyrrole nanofibers conductive electrode material is produced after being dried under empty condition；
C. two above-mentioned resulting polymers yarn base polypyrrole nanofibers conductive electrode materials are taken, with polyvinyl alcohol gel
Electrolyte is solid electrolyte, assembles cross fibrous crystal pipe；With 1mV/s sweep speed to this cross fibrous crystal pipe
Carry out on-off ratio test its on-off ratio be 998.
Claims (5)
1. a kind of preparation method of polypyrrole nanofibers conductive electrode material, it is characterised in that：The preparation method according to
Lower step is carried out：
A. in the aqueous surfactant solution that concentration is 1mmol/L-3mol/L, 0.5g/L-50g/L pyrroles is sequentially added
Monomer and electrode base material, make electrode base material fully be infiltrated on scattered with 50r/min-400r/min stir speed (S.S.)
Have in the aqueous surfactant solution of pyrrole monomer；
B. above-mentioned mixed system temperature is adjusted to 0-30 DEG C, be added dropwise under 50r/min-400r/min stir speed (S.S.) with
Pyrrole monomer mol ratio is 10：1-1：10 oxidant neutral aqueous solution or concentration is 2mmol/L-4mol/L acid water
Solution, reacts 2-24 hours, the obtained product containing electrode base material is passed through successively under said temperature and stir speed (S.S.)
Deionized water, absolute ethyl alcohol wash and are polypyrrole nanofibers conductive electrode material after being dried under 60 DEG C of vacuum conditions.
2. a kind of preparation method of polypyrrole nanofibers conductive electrode material as claimed in claim 1, it is characterised in that：Institute
The surfactant stated is sulfonate type anion surfactant RSO3M, wherein, R is anthraquinone or naphthoquinones, and M is alkali metal.
3. a kind of preparation method of polypyrrole nanofibers conductive electrode material as claimed in claim 1, it is characterised in that：Institute
The electrode base material stated is conducting metal sill or carbon-based material or flexible fabric or polymer fiber film or polymer yarns
One kind in line or native cellulose silk.
4. a kind of preparation method of polypyrrole nanofibers conductive electrode material as claimed in claim 1, it is characterised in that：Institute
The acidic aqueous solution stated is matched somebody with somebody using one kind in a water p-methyl benzenesulfonic acid or two hydration 5-sulphosalicylic acids or phosphoric acid or hydrochloric acid
System.
5. a kind of preparation method of polypyrrole nanofibers conductive electrode material as claimed in claim 1, it is characterised in that：Institute
The oxidant stated is one kind in hydrogen peroxide or ammonium persulfate or nine water ferric nitrates or anhydrous ferric chloride or potassium bichromate.
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