CN108250744A - A kind of polyaniline/polypyrrole composite nano tube and preparation method thereof - Google Patents
A kind of polyaniline/polypyrrole composite nano tube and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of polyaniline/polypyrrole composite nano tube and preparation method thereof, the material is using nano-cellulose as nucleome and hard template, using methyl orange and neopelex as soft template, upper polypyrrole and polyaniline are coated using situ aggregation method, prepare nano-cellulose/polypyrrole/polyaniline composite nano fiber, finally nano-cellulose is dissolved with ionic liquid, obtains polypyrrole/polyaniline composite nanometer tube.The advantages of material is conductive good, specific capacitance is high, nanotube production rate is high, nanotube regularity is high, nanotube rule draw ratio is adjustable, preparation process is simple and environmentally-friendly, pollution-free, of low cost simultaneously, it is suitble to industrialized production, can be widely used in the fields such as ultracapacitor, battery, electromagnetic shielding, antistatic.
Description
Technical field
The present invention relates to the preparation fields of conductive material, and in particular to a kind of polyaniline/polypyrrole composite nano tube and its
Preparation method.
Background technology
Conducting polymer has the good characteristics such as electricity, electrochemistry, mechanics, optics, magnetics and is used for the energy, sensing
The numerous areas such as device, aerospace, military affairs.The pattern of conducting polymer and size pass the electrical property of conducting polymer, air-sensitive
Perceptual energy, catalytic performance have important influence, therefore the controlledly synthesis of conducting polymer pattern is conducting polymer synthesis neck
The research hotspot and difficult point in domain.In all kinds of conducting polymers, polyaniline and polypyrrole are simple, at low cost with synthesis technology
Honest and clean, the advantages that electric conductivity is excellent, fake capacitance energy storage characteristic and in the fields such as ultracapacitor, battery, electromagnetic shielding, antistatic
It is widely used.Currently, polyaniline and polypyrrole are applied more in terms of capacitor energy storage, and specific capacitance is evaluation capacitor
One of major parameter of performance, specific capacitance is bigger, and energy-storage property is better.However it is applied to the conducting polymer of capacitor at present
Most of is single polyaniline or polypyrrole, and the electric conductivity of polypyrrole is better than polyaniline, but polyaniline has than polypyrrole
Higher specific capacitance, in addition nanotube promotes capacitance maximum, therefore the exploitation of polyaniline/polypyrrole nanotube in all patterns
It is important R＆D direction.Chinese patent CN100497761C discloses one kind with MnO2Nanofiber or β-MnO2Nanotube is made
For template, by template from ablation controllable preparation polyaniline nanotube, but have the following disadvantages：1. under sulphuric acid environment
The polyaniline of preparation, electric conductivity are undesirable；2. use MnO2Nanofiber or β-MnO2For nanotube as template, cost is higher；③
From ablation MnO2Nanofiber or β-MnO2Nanotube generates effluent containing heavy metal ions, pollutes environment；4. the electric conductivity of polyaniline
Need to be further improved.Chinese patent CN103665376B methyl oranges and neopelex prepare double Micellar Gels,
And prepare polypyrrole in a template and obtain polypyrrole micro-nano mitron, which mainly exists with micro nanometer fiber, and micro-nano mitron contains
Measure it is less, and the specific capacitance of polypyrrole have it is to be hoisted.Chinese patent CN103224704B is prepared for the recessed soil of threadiness for nucleome
Then recessed soil/polyaniline/polypyrrole composite material dissolves recessed soil with nitration mixture and obtains polyaniline/polypyrrole composite nano tube, still
It has the following disadvantages：1. the regularity of polyaniline/polypyrrole composite nano tube is not good enough, length is shorter；2. recessed soil is in the molten of nitration mixture
It is slower to solve speed, influences efficiency；3. generating a large amount of spent acid, environment is polluted.Cellulose is synthesized by photosynthesis of plant, has nothing
Most resources reserve, it is of low cost, and the diameter of nano-cellulose is only 3~4nm, is highly suitable as fiber or tubular material
Preparation template use.Chinese patent CN103390510B electrochemically obtains poly- pyrrole in nano-cellulose synthesis polypyrrole
/ nano-cellulose composite material is coughed up, which has the following disadvantages：1. the reservation of nano-cellulose affects the conduction of polypyrrole
Performance and specific capacitance；2. the specific capacitance of polypyrrole has to be hoisted；3. electrochemistry formated polypyrrole complex process, energy consumption are big, yield
It is low.
Invention content
The object of the present invention is to provide a kind of polyaniline/polypyrrole composite nano tubes and preparation method thereof, which has
The advantages of electric conductivity is good, specific capacitance is high, nanotube production rate is high, nanotube regularity is high, nanotube rule draw ratio is adjustable, simultaneously
Preparation process is simple and environmentally-friendly, pollution-free, of low cost, is suitble to industrialized production.
The present invention provides a kind of polyaniline/polypyrrole composite nano tube and preparation method thereof, including following preparation process：
Step 1：Prepare nano-cellulose dispersion liquid
Nano-cellulose is added in deionized water, mechanical rapid dispersion obtains nano-cellulose dispersion liquid；
Step 2：Prepare the nano-cellulose dispersion liquid containing methyl orange and neopelex
Methyl orange and neopelex are added to nano-cellulose dispersion liquid to be stirred, contained after dissolving
The nano-cellulose dispersion liquid of methyl orange and neopelex；
Step 3：Prepare nano-cellulose/polypyrrole/polyaniline composite nano fiber
Aniline monomer, pyrrole monomer, Bronsted acid and dopant are added to containing methyl orange and neopelex
In nano-cellulose dispersion liquid, control system temperature be -20 DEG C~40 DEG C, be stirred continuously down, be added dropwise a concentration of 0.5mol/L~
The aqueous oxidizing agent solution of 5.5mol/L, reaction 0.5h~for 24 hours, it filters, is washed with deionized, obtains nano-cellulose/poly- pyrrole
Cough up/polyaniline composite nano fiber filter cake；
Step 4：Prepare polypyrrole/polyaniline composite nanometer tube
Nano-cellulose/polypyrrole/polyaniline composite nano fiber filter cake is added in ionic liquid, is stirred continuously molten
Nano-cellulose is solved, dissolution time is 0.2h~for 24 hours, is filtered, and washing is dried to obtain polypyrrole/polyphenyl at 60 DEG C~150 DEG C
Amine composite nano tube.
The beneficial effects of the invention are as follows：
1st, the present invention is using nano-cellulose as nucleome and hard template, using methyl orange and neopelex as soft mode
Plate, under the synergistic effect of soft or hard template, polyaniline/polypyrrole composite nano tube production rate height, the nanotube regularity of preparation
It is adjustable that high, nanotube advises draw ratio.
2nd, the pattern for preparing of the present invention and the controllable conductive good, ratio of polyaniline/polypyrrole composite nano tube of size
Capacitance is high, in ultracapacitor and field of batteries very advantageous.
3rd, the present invention is compound nano-cellulose/polypyrrole/polyaniline is made using nano-cellulose as nucleome and hard template
Nanofiber afterwards with ion liquid dissolving nano-cellulose, obtains polyaniline/polypyrrole composite nano tube, nano-cellulose exists
Solution rate is fast in ionic liquid, and the preparation process of polyaniline/polypyrrole composite nano tube is simple and environmentally-friendly, pollution-free, at low cost
It is honest and clean, low energy consumption, be suitble to industrialized production.
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention
It is further elaborated, it should be understood that the specific embodiments described herein are merely illustrative of the present invention, is not used to
Limit the present invention.
The embodiment of the present invention provides a kind of polyaniline/polypyrrole composite nano tube, including following preparation process：
Step 1：Prepare nano-cellulose dispersion liquid
Nano-cellulose is added in deionized water, mechanical rapid dispersion obtains nano-cellulose dispersion liquid；
Step 2：Prepare the nano-cellulose dispersion liquid containing methyl orange and neopelex
Methyl orange and neopelex are added to nano-cellulose dispersion liquid to be stirred, contained after dissolving
The nano-cellulose dispersion liquid of methyl orange and neopelex；
Step 3：Prepare nano-cellulose/polypyrrole/polyaniline composite nano fiber
Aniline monomer, pyrrole monomer, Bronsted acid and dopant are added to containing methyl orange and neopelex
In nano-cellulose dispersion liquid, control system temperature be -20 DEG C~40 DEG C, be stirred continuously down, be added dropwise a concentration of 0.5mol/L~
The aqueous oxidizing agent solution of 5.5mol/L, reaction 0.5h~for 24 hours, it filters, is washed with deionized, obtains nano-cellulose/poly- pyrrole
Cough up/polyaniline composite nano fiber filter cake；
Step 4：Prepare polypyrrole/polyaniline composite nanometer tube
Nano-cellulose/polypyrrole/polyaniline composite nano fiber filter cake is added in ionic liquid, is stirred continuously molten
Nano-cellulose is solved, dissolution time is 0.2h~for 24 hours, is filtered, and washing is dried to obtain polypyrrole/polyphenyl at 60 DEG C~150 DEG C
Amine composite nano tube.
Nano-cellulose described in step 1 and the mass ratio of deionized water are 0.05~0.4：1.Nano-cellulose is polyphenyl
The nucleome and hard template of amine/polypyrrole composite nano tube, are conducive to generate that nanotube regularity is high, nanotube rule draw ratio is adjustable
Polyaniline/polypyrrole composite nano tube.Nano-cellulose and deionized water ratio are too small, polyaniline/polypyrrole composite Nano
Pipe production rate is low；Nano-cellulose and deionized water ratio are excessive, nano-cellulose easily occur reunite sedimentation, cause polyaniline/
Polypyrrole composite nano tube can not generate.
The mass ratio of methyl orange, neopelex and nano-cellulose described in step 2 is 0.01~0.1：0.01
~0.1：1.Nano-cellulose is the soft template of polyaniline/polypyrrole composite nano tube, be conducive to generate nanotube regularity it is high,
Nanotube advises the adjustable polyaniline/polypyrrole composite nano tube of draw ratio.Methyl orange, neopelex and nanofiber
Plain ratio is too small, and polyaniline/polypyrrole composite nano tube production rate is low；Methyl orange, neopelex and nanofiber
Plain ratio is excessive, and soft template is excessive, limits the growth of nanotube, causes polyaniline/polypyrrole composite nano tube draw ratio too small.
Bronsted acid described in step 3 is p-methyl benzenesulfonic acid, camphorsulfonic acid, sulfosalicylic acid, dodecyl benzene sulfonic acid, naphthalene sulphur
Acid, dinonylnaphthalene sulfonic acid, polystyrolsulfon acid, sulfamic acid, aminobenzenesulfonic acid, oxalic acid, citric acid, tartaric acid, hydrochloric acid, sulphur
At least one of acid, nitric acid, perchloric acid and phosphoric acid.The electrons that Bronsted acid provides enter the conjugated backbone of polyaniline, cause
Polyaniline resonates, so as to assign layer/polyaniline conductive performance.Bronsted acid dosage is too small, and layer/polyaniline conductive performance is poor；Bronsted acid dosage
Excessive, cost is excessively high and wastewater treatment difficulty increases.
Dopant described in step 3 is at least one in dodecyl sodium sulfate, neopelex, odium stearate
Kind.Dopant assigns polypyrrole electric conductivity.The electrons that dopant provides enter the conjugated backbone of polypyrrole, cause polypyrrole
Resonance, so as to assign polypyrrole electric conductivity.Dopant dosage is too small, and polypyrrole electric conductivity is poor；Dopant dosage is excessive, into
This excessively high and wastewater treatment difficulty increases.
Oxidant described in step 3 is at least one of persulfate, iodate, permanganate, ferric trichloride.Oxidant
Free radical is provided for aniline and pyrroles, polyaniline and polypyrrole are polymerized to so as to cause.Oxidant is excessively too small, polymerization time mistake
Long and polymerization is incomplete；Oxidant is excessively excessive, and free radical is excessive, causes the degree of polymerization and molecular weight too low, leads to electric conductivity
Difference.
The mass ratio of aniline monomer, pyrrole monomer and nano-cellulose described in step 3 is 0.1~2.0：0.1~2.0：1,
The molar ratio of Bronsted acid and aniline monomer is 0.1~15.5：1, dopant is 0.1~1.0 with pyrrole monomer molar ratio：1, antioxygen
Agent is 0.5~1.5 with the molar ratio of aniline and pyrroles's total monomer content：1.
Ionic liquid described in step 4 for alkyl quaternary ammonium ion, alkyl quaternary see ion, the substitution of 1,3- dialkyl group imidazoles from
At least one of son, the alkyl-substituted pyridinium ions of N-, halide salt.After completion of polymerization, ion liquid dissolving nanofiber
Element obtains polypyrrole/polyaniline composite nanometer tube.Ionic liquid dosage is too small, and nano-cellulose dissolving is incomplete；Ionic liquid
Dosage is excessive, and cost is excessively high.
The mass ratio of ionic liquid described in step 4 and nano-cellulose/polypyrrole/polyaniline composite nano fiber for 1~
10：1.
In order to which technical problem solved by the invention, technical solution and advantageous effect is more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.
Embodiment 1：
Step S11：Prepare nano-cellulose dispersion liquid
Nano-cellulose is added in deionized water, mechanical rapid dispersion obtains nano-cellulose dispersion liquid, wherein nanometer
Cellulose and the mass ratio of deionized water are 0.05：1；
Step S12：Prepare the nano-cellulose dispersion liquid containing methyl orange and neopelex
Methyl orange and neopelex are added to nano-cellulose dispersion liquid to be stirred, contained after dissolving
The nano-cellulose dispersion liquid of methyl orange and neopelex, wherein methyl orange, neopelex and nanometer
The mass ratio of cellulose is 0.01：0.01：1；
Step S13：Prepare nano-cellulose/polypyrrole/polyaniline composite nano fiber
Aniline monomer, pyrrole monomer, hydrochloric acid and dodecyl sodium sulfate are added to containing methyl orange and detergent alkylate sulphur
In the nano-cellulose dispersion liquid of sour sodium, control system temperature is -20 DEG C, is stirred continuously down, is added dropwise a concentration of 0.5mol/L's
Acid iodide saline solution, reaction for 24 hours, filter, are washed with deionized, obtain nano-cellulose/polypyrrole/polyaniline composite Nano
The mass ratio of fiber filter cake, wherein aniline monomer, pyrrole monomer and nano-cellulose is 2.0：2.0：1, hydrochloric acid and aniline monomer
Molar ratio be 3.0：1, dodecyl sodium sulfate is 1.0 with pyrrole monomer molar ratio：1, iodate and aniline and pyrroles are always single
The molar ratio of body content is 1.5：1；
Step S14：Prepare polypyrrole/polyaniline composite nanometer tube
Nano-cellulose/polypyrrole/polyaniline composite nano fiber filter cake is added in alkyl quaternary ammonium ion liquid, no
Disconnected stirring and dissolving nano-cellulose, dissolution time 0.2h are filtered, and it is multiple to be dried to obtain polypyrrole/polyaniline at 60 DEG C for washing
Nanotube is closed, the mass ratio of wherein ionic liquid and nano-cellulose/polypyrrole/polyaniline composite nano fiber is 1：1.
Embodiment 2：
Step S21：Prepare nano-cellulose dispersion liquid
Nano-cellulose is added in deionized water, mechanical rapid dispersion obtains nano-cellulose dispersion liquid, wherein nanometer
Cellulose and the mass ratio of deionized water are 0.4：1；
Step S22：Prepare the nano-cellulose dispersion liquid containing methyl orange and neopelex
Methyl orange and neopelex are added to nano-cellulose dispersion liquid to be stirred, contained after dissolving
The nano-cellulose dispersion liquid of methyl orange and neopelex, wherein methyl orange, neopelex and nanometer
The mass ratio of cellulose is 0.1：0.1：1；
Step S23：Prepare nano-cellulose/polypyrrole/polyaniline composite nano fiber
Aniline monomer, pyrrole monomer, p-methyl benzenesulfonic acid and odium stearate are added to containing methyl orange and detergent alkylate
In the nano-cellulose dispersion liquid of sodium sulfonate, control system temperature is 40 DEG C, is stirred continuously down, is added dropwise a concentration of 5.5mol/L's
Permanganate water solution reacts 0.5h, filters, is washed with deionized, it is compound to obtain nano-cellulose/polypyrrole/polyaniline
The mass ratio of nanofiber filter cake, wherein aniline monomer, pyrrole monomer and nano-cellulose is 0.1：0.1：1, to methylbenzene sulphur
The molar ratio of acid and aniline monomer is 0.1：1, odium stearate is 0.1 with pyrrole monomer molar ratio：1, permanganate and aniline and
The molar ratio of pyrroles's total monomer content is 0.5：1；
Step S24：Prepare polypyrrole/polyaniline composite nanometer tube
Nano-cellulose/polypyrrole/polyaniline composite nano fiber filter cake is added to alkyl quaternary to see in ionic liquid, no
Disconnected stirring and dissolving nano-cellulose, for dissolution time for 24 hours, to filter, it is multiple to be dried to obtain polypyrrole/polyaniline at 150 DEG C for washing
Nanotube is closed, the mass ratio of wherein ionic liquid and nano-cellulose/polypyrrole/polyaniline composite nano fiber is 10：1.
Embodiment 3：
Step S31：Prepare nano-cellulose dispersion liquid
Nano-cellulose is added in deionized water, mechanical rapid dispersion obtains nano-cellulose dispersion liquid, wherein nanometer
Cellulose and the mass ratio of deionized water are 0.2：1；
Step S32：Prepare the nano-cellulose dispersion liquid containing methyl orange and neopelex
Methyl orange and neopelex are added to nano-cellulose dispersion liquid to be stirred, contained after dissolving
The nano-cellulose dispersion liquid of methyl orange and neopelex, wherein methyl orange, neopelex and nanometer
The mass ratio of cellulose is 0.03：0.03：1；
Step S33：Prepare nano-cellulose/polypyrrole/polyaniline composite nano fiber
Aniline monomer, pyrrole monomer, sulfosalicylic acid and neopelex are added to containing methyl orange and 12
In the nano-cellulose dispersion liquid of sodium alkyl benzene sulfonate, control system temperature is 20 DEG C, is stirred continuously down, is added dropwise a concentration of
The persulfate aqueous solution of 2.0mol/L reacts 6h, filters, is washed with deionized, and obtains nano-cellulose/polypyrrole/poly-
Aniline composite nano fiber filter cake, the wherein mass ratio of aniline monomer, pyrrole monomer and nano-cellulose are 0.5：0.5：1, sulphur
The molar ratio of base salicylic acid and aniline monomer is 0.5：1, neopelex is 0.5 with pyrrole monomer molar ratio：1, mistake
Sulfate is 1 with the molar ratio of aniline and pyrroles's total monomer content：1；
Step S34：Prepare polypyrrole/polyaniline composite nanometer tube
Nano-cellulose/polypyrrole/polyaniline composite nano fiber filter cake is added to the imidazoles that 1,3- dialkyl group replaces
In ionic liquid, dissolving nano-cellulose is stirred continuously, dissolution time 4h is filtered, and washing is dried to obtain poly- at 100 DEG C
Pyrroles/polyaniline composite nanometer tube, wherein ionic liquid and the matter of nano-cellulose/polypyrrole/polyaniline composite nano fiber
Amount is than being 5：1.
Embodiment 4：
Step S41：Prepare nano-cellulose dispersion liquid
Nano-cellulose is added in deionized water, mechanical rapid dispersion obtains nano-cellulose dispersion liquid, wherein nanometer
Cellulose and the mass ratio of deionized water are 0.25：1；
Step S42：Prepare the nano-cellulose dispersion liquid containing methyl orange and neopelex
Methyl orange and neopelex are added to nano-cellulose dispersion liquid to be stirred, contained after dissolving
The nano-cellulose dispersion liquid of methyl orange and neopelex, wherein methyl orange, neopelex and nanometer
The mass ratio of cellulose is 0.02：0.02：1；
Step S43：Prepare nano-cellulose/polypyrrole/polyaniline composite nano fiber
Aniline monomer, pyrrole monomer, polystyrolsulfon acid and dodecyl sodium sulfate are added to containing methyl orange and 12
In the nano-cellulose dispersion liquid of sodium alkyl benzene sulfonate, control system temperature is 25 DEG C, is stirred continuously down, is added dropwise a concentration of
The persulfate aqueous solution of 2.0mol/L reacts 4h, filters, is washed with deionized, and obtains nano-cellulose/polypyrrole/poly-
Aniline composite nano fiber filter cake, the wherein mass ratio of aniline monomer, pyrrole monomer and nano-cellulose are 0.8：0.8：1, gather
The molar ratio of styrene sulfonic acid and aniline monomer is 0.6：1, dodecyl sodium sulfate is 0.6 with pyrrole monomer molar ratio：1, mistake
Sulfate is 1 with the molar ratio of aniline and pyrroles's total monomer content：1；
Step S44：Prepare polypyrrole/polyaniline composite nanometer tube
Nano-cellulose/polypyrrole/polyaniline composite nano fiber filter cake is added to the alkyl-substituted pyridinium ions of N-
In liquid, be stirred continuously dissolving nano-cellulose, dissolution time 5h is filtered, washing, be dried to obtain at 80 DEG C polypyrrole/
Polyaniline composite nanometer tube, wherein ionic liquid and the mass ratio of nano-cellulose/polypyrrole/polyaniline composite nano fiber are
3：1.
Embodiment 5：
Step S51：Prepare nano-cellulose dispersion liquid
Nano-cellulose is added in deionized water, mechanical rapid dispersion obtains nano-cellulose dispersion liquid, wherein nanometer
Cellulose and the mass ratio of deionized water are 0.15：1；
Step S52：Prepare the nano-cellulose dispersion liquid containing methyl orange and neopelex
Methyl orange and neopelex are added to nano-cellulose dispersion liquid to be stirred, contained after dissolving
The nano-cellulose dispersion liquid of methyl orange and neopelex, wherein methyl orange, neopelex and nanometer
The mass ratio of cellulose is 0.04：0.02：1；
Step S53：Prepare nano-cellulose/polypyrrole/polyaniline composite nano fiber
Aniline monomer, pyrrole monomer, dinonylnaphthalene sulfonic acid and neopelex are added to containing methyl orange and ten
In the nano-cellulose dispersion liquid of dialkyl benzene sulfonic acids sodium, control system temperature is 30 DEG C, is stirred continuously down, is added dropwise a concentration of
The persulfate aqueous solution of 3.0mol/L reacts 5h, filters, is washed with deionized, and obtains nano-cellulose/polypyrrole/poly-
Aniline composite nano fiber filter cake, the wherein mass ratio of aniline monomer, pyrrole monomer and nano-cellulose are 1：1：1, dinonyl
The molar ratio of naphthalene sulfonic acids and aniline monomer is 0.8：1, neopelex is 0.6 with pyrrole monomer molar ratio：1, over cure
Hydrochlorate is 1 with the molar ratio of aniline and pyrroles's total monomer content：1；
Step S54：Prepare polypyrrole/polyaniline composite nanometer tube
Nano-cellulose/polypyrrole/polyaniline composite nano fiber filter cake is added to the alkyl-substituted pyridinium ions of N-
In liquid, be stirred continuously dissolving nano-cellulose, dissolution time 6h is filtered, washing, be dried to obtain at 100 DEG C polypyrrole/
Polyaniline composite nanometer tube, wherein ionic liquid and the mass ratio of nano-cellulose/polypyrrole/polyaniline composite nano fiber are
4：1.
Comparative example 1：
In embodiment 3, it is not added with people's soft template.
Comparative example 2：
In embodiment 3, it is added without hard template.
Comparative example 3：
In embodiment 3, hard template is changed to recessed soil, it is 1 that ionic liquid is changed to molar ratio：1 hydrofluoric acid and hydrochloric acid.
Comparative example 4：
In embodiment 3, it is added without aniline monomer.
Comparative example 5：
In embodiment 3, it is added without pyrrole monomer.
Correlated performance is tested：
The properties of product that above-described embodiment 1-5 and comparative example 1-5 are provided are as shown in table 1.
1 performance test table of table
| Sample | Resistivity Ω m | Specific capacitance F/g | Nanotube production rate % |
| Embodiment 1 | 0.3 | 402 | ≥90 |
| Embodiment 2 | 4 | 380 | ≥90 |
| Embodiment 3 | 0.1 | 412 | ≥90 |
| Embodiment 4 | 0.2 | 409 | ≥90 |
| Embodiment 5 | 0.3 | 410 | ≥90 |
| Comparative example 1 | 0.2 | 367 | 48 |
| Comparative example 2 | 0.2 | 338 | 36 |
| Comparative example 3 | 0.4 | 205 | 52 |
| Comparative example 4 | 0.1 | 289 | ≥90 |
| Comparative example 5 | 10 | 372 | ≥90 |
It can be seen that the polyaniline/polypyrrole composite nano tube tool of preparation of the embodiment of the present invention from the test result of upper table
It has conductivity, the features such as specific capacitance is high, nanotube production rate is high.It can be seen that compared with comparative example 1 by embodiment 3, soft mode
Plate affects nanotube production rate, nanotube regularity and nanotube the rule draw ratio of material, so as to higher specific capacitance；
It can be seen that compared with comparative example 2 by embodiment 3, hard template affects the nanotube production rate of material, nanotube regularity and receives
Mitron advises draw ratio, so as to higher specific capacitance；It can be seen that compared with comparative example 3 by embodiment 3, recessed soil is given birth to for hard template
Into polyaniline/polypyrrole composite nano tube electric conductivity, specific capacitance and 1 mitron production rate it is not good enough；By embodiment 3 and comparison
Example 4, which compares, can be seen that, polyaniline imparts the better specific capacitance of material；It can be seen that compared with comparative example 5 by embodiment 3, poly- pyrrole
It coughs up and imparts the better conductivity of material and specific capacitance.
It is that the polyaniline/polypyrrole composite nano tube provided the embodiment of the present invention is described in detail above.This
It applies specific embodiment in text to be expounded the principle of the present invention and embodiment, the explanation of embodiment is only intended to help
Assistant solves the method and its core concept of the present invention, and the foregoing is merely illustrative of the preferred embodiments of the present invention, not limiting
The system present invention, all any modification, equivalent and improvement made all within the spirits and principles of the present invention etc., should be included in
Within protection scope of the present invention.
Claims (9)
1. a kind of preparation method of polyaniline/polypyrrole composite nano tube, including following preparation process：
Step 1：Nano-cellulose is added in deionized water, mechanical rapid dispersion obtains nano-cellulose dispersion liquid；
Step 2：Methyl orange and neopelex are added to nano-cellulose dispersion liquid to be stirred, obtained after dissolving
Nano-cellulose dispersion liquid containing methyl orange and neopelex；
Step 3：Aniline monomer, pyrrole monomer, Bronsted acid and dopant are added to containing methyl orange and neopelex
Nano-cellulose dispersion liquid in, control system temperature be -20 DEG C~40 DEG C, be stirred continuously down, a concentration of 0.5mol/L be added dropwise
The aqueous oxidizing agent solution of~5.5mol/L, reaction 0.5h~for 24 hours, filters, is washed with deionized, and obtains nano-cellulose/poly-
Pyrroles/polyaniline composite nano fiber filter cake；
Step 4：Nano-cellulose/polypyrrole/polyaniline composite nano fiber filter cake is added in ionic liquid, is stirred continuously
Nano-cellulose is dissolved, dissolution time is 0.2h~for 24 hours, is filtered, washing, and polypyrrole/poly- is dried to obtain at 60 DEG C~150 DEG C
Aniline composite nano tube.
2. polyaniline/polypyrrole composite nano tube described in claim 1, which is characterized in that the nano-cellulose and deionization
The mass ratio of water is 0.05~0.4：1.
3. polyaniline/polypyrrole composite nano tube described in claim 1, which is characterized in that the methyl orange, detergent alkylate sulphur
The mass ratio of sour sodium and nano-cellulose is 0.01~0.1：0.01~0.1：1.
4. polyaniline/polypyrrole composite nano tube described in claim 1, which is characterized in that the Bronsted acid is to methylbenzene sulphur
Acid, camphorsulfonic acid, sulfosalicylic acid, dodecyl benzene sulfonic acid, naphthalene sulfonic acids, dinonylnaphthalene sulfonic acid, polystyrolsulfon acid, amino sulphur
At least one of acid, aminobenzenesulfonic acid, oxalic acid, citric acid, tartaric acid, hydrochloric acid, sulfuric acid, nitric acid, perchloric acid and phosphoric acid.
5. polyaniline/polypyrrole composite nano tube described in claim 1, which is characterized in that the dopant is dodecyl sulphur
At least one of sour sodium, neopelex, odium stearate.
6. polyaniline/polypyrrole composite nano tube described in claim 1, which is characterized in that the oxidant is persulfate, iodine
At least one of hydrochlorate, permanganate, ferric trichloride.
7. polyaniline/polypyrrole composite nano tube described in claim 1, which is characterized in that the aniline monomer, pyrrole monomer with
The mass ratio of nano-cellulose is 0.1~2.0：0.1~2.0：1, the molar ratio of Bronsted acid and aniline monomer is 0.1~15.5：
1, dopant is 0.1~1.0 with pyrrole monomer molar ratio：1, the molar ratio of antioxidant and aniline and pyrroles's total monomer content is
0.5~1.5：1.
8. polyaniline/polypyrrole composite nano tube described in claim 1, which is characterized in that the ionic liquid is quaternary ammonium alkyl
Ion, alkyl quaternary see ion, the imidazol ion of 1,3- dialkyl group substitution, the alkyl-substituted pyridinium ions of N-, in halide salt extremely
Few one kind.
9. polyaniline/polypyrrole composite nano tube described in claim 1, which is characterized in that the ionic liquid and nanofiber
The mass ratio of element/polypyrrole/polyaniline composite nano fiber is 1~10：1.
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| CN115642237A (en) * | 2022-10-28 | 2023-01-24 | 无锡零一未来新材料技术研究院有限公司 | Sodium ion composite cathode material and preparation method and application thereof |
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| EP2333003A1 (en) * | 2009-12-10 | 2011-06-15 | Stichting Dutch Polymer Institute | Process for the preparation of a conductive polymer composition |
| CN103224704A (en) * | 2013-04-22 | 2013-07-31 | 常州纳欧新材料科技有限公司 | Preparation method for polyaniline/polypyrrole binary composite nanotube |
| CN103665376A (en) * | 2013-12-18 | 2014-03-26 | 齐鲁工业大学 | Preparation method of polypyrrole micro/nano tube |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2333003A1 (en) * | 2009-12-10 | 2011-06-15 | Stichting Dutch Polymer Institute | Process for the preparation of a conductive polymer composition |
| CN103224704A (en) * | 2013-04-22 | 2013-07-31 | 常州纳欧新材料科技有限公司 | Preparation method for polyaniline/polypyrrole binary composite nanotube |
| CN103665376A (en) * | 2013-12-18 | 2014-03-26 | 齐鲁工业大学 | Preparation method of polypyrrole micro/nano tube |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115642237A (en) * | 2022-10-28 | 2023-01-24 | 无锡零一未来新材料技术研究院有限公司 | Sodium ion composite cathode material and preparation method and application thereof |
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