CN107146842B - Self-supporting flexibility PEDOT nanofiber/SWCNTs composite thermoelectric material film and preparation method thereof - Google Patents
Self-supporting flexibility PEDOT nanofiber/SWCNTs composite thermoelectric material film and preparation method thereof Download PDFInfo
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- H10N10/856—Thermoelectric active materials comprising organic compositions
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- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
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Abstract
The present invention relates to a kind of self-supporting flexibility PEDOT nanofiber/SWCNTs composite thermoelectric material films and preparation method thereof, it is made up of following steps: (1) taking anionic surfactant to be dissolved in deionized water, oxidant is added, is stirred under oil bath, obtains mixed solution A；(2) EDOT monomer is taken to be added in mixed solution A, oil bath reaction is cooling, separates, and cleaning obtains PEDOT nanofiber, is scattered in spare in methanol；(3) it takes SWCNTs ultrasonic disperse in methanol, then ultrasound after mixing with PEDOT methanol solution, obtains mixed solution B；(4) mixed solution B is filtered using vacuum filtration method onto miillpore filter again, is dried to get the self-supporting flexibility PEDOT nanofiber/SWCNTs composite thermoelectric material film is arrived.Compared with prior art, the present invention is effectively compounded with the high conductivity of PEDOT and the high Seebeck coefficient of SWCNTs, and power factor at room temperature is up to 14.4 μ V/mK2, in addition, preparation method is simple, yield is high, and repeatability is high.
Description
Technical field
The present invention relates to flexible electronics field, more particularly, to a kind of self-supporting flexibility PEDOT nanofiber/
SWCNTs composite thermoelectric material film and preparation method thereof.
Background technique
Recently, flexible electronics due to have it is soft, deformable, light, portable, can large-area applications, and can be with rotation
The characteristics such as the molten liquefaction process such as painting, spray printing, coining and R2R manufacture are compatible have caused more and more extensive concern.Wherein construct
The flexible material and its device of wearable energy acquisition are an important development directions of flexible electronic.
Thermoelectric material is a kind of environmentally friendly " green " energy conversion material, can be directly realized by thermal energy and electric energy
Mutually conversion, and it is free from environmental pollution.The thermo-electric device generation technology constructed with thermoelectric material can not have using waste-heat power generation and exploitation
There is the solar energy being fully utilized.Thermoelectric energy switch technology has been obtained as the new technique of environmental harmony type energy conversion
The great attention of many advanced countries, the world.The thermoelectric material of current research is based on inorganic semiconductor, however thermal conductivity is high, money
Source is rare, and processing cost height etc., which constrains it, further to be developed, and thermoelectricity capability is difficult to obtain breakthrough progress always.It is conductive high
The appearance of molecule provides a brand-new direction for the research of thermoelectric material.Abundant raw materials, light weight, thermal conductivity are low, easy
Processing, solution-processible, and be conducting polymer the features such as band structure is abundant as thermoelectric material of new generation and wearable
Electronic equipment provides Potential feasibility.
The poly- 3,4- ethylenedioxy thiophene (PEDOT) of conducting polymer and pass through polyphenyl vinyl (Poly-
Styrenesulfonate, PSS) the PEDOT:PSS aqueous solution formed is adulterated due to low-down thermal conductivity and doping
Processing can match in excellence or beauty ITO electro-conductive glass high conductivity and cause the extensive concern in thermoelectricity field.But current commercialization PEDOT:PSS
Aqueous solution (content of PEDOT:PSS is only 1~1.3wt%) it is expensive (about 1000 $/KG), with it for cost of material compared with
It is high.EDOT monomer price is lower, but the obtained PEDOT of traditional in-situ oxidizing-polymerizing is powdered, the Wu Fayong of micron-scale
Make flexible electronics, and conductivity is lower, be generally lower than 100S/cm, higher thermoelectricity capability can not be provided.According to
Foulger et al. report, one-dimensional PEDOT nanofiber conductivity with higher and film forming characteristics (Small, 2006,
2,1164-1169), but its Seebeck coefficient is still lower, limits its further thermoelectric applications.
With with high Seebeck coefficient inorganic thermoelectric material or nano-carbon material it is compound be improve Organic thermoelectric material
One common method of performance.Carbon nanotube (CNTs) is due to very suitable with good electric conductivity, mechanical performance and thermal stability
The thermoelectricity capability that cooperation is the filler of polymer to improve composite material.Fan etc. is prepared for polyaniline by chemical oxidization method
PANI/CNT composite material, due to two components of Seebeck coefficient ratio of the reason composite material of carrier energy filtering effect
Will be big (Advanced Materials, 2010,22,535-539).However, the performance of the material is still lower, and make
Composite material be it is powdered, be not used to flexible electronics.
Summary of the invention
It is flexible that it is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of self-supportings
PEDOT nanofiber/SWCNTs composite thermoelectric material film and preparation method thereof.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of self-supporting flexibility PEDOT nanofiber/SWCNTs composite thermoelectric material film, is received by one-dimensional PEDOT
Rice fiber and one-dimensional SWCNTs, which interweave, forms conductive network structure, wherein the mass content of SWCNTs is 5-55wt%.
As preferred embodiment, the diameter of the PEDOT nanofiber is 30-200nm, the SWCNTs
Diameter be less than 10nm.
Self-supporting flexibility PEDOT nanofiber/SWCNTs composite thermoelectric material film preparation method, including following step
It is rapid:
(1) it takes anionic surfactant to be dissolved in deionized water, oxidant is added, stirs, is mixed under oil bath
Solution A；
(2) EDOT monomer is taken to be added in the mixed solution A of step (1), oil bath reaction is after the reaction was completed, cooling, point
From cleaning obtains PEDOT nanofiber, is scattered in spare in methanol；
(3) it takes SWCNTs to be scattered in methanol, then ultrasound after mixing with the PEDOT methanol solution that step (2) obtains, obtains
Mixed solution B；
(4) the mixed solution B of step (3) is filtered using vacuum filtration method onto miillpore filter again, is dried to get institute is arrived
State self-supporting flexibility PEDOT nanofiber/SWCNTs composite thermoelectric material film.
As preferred embodiment, anionic surfactant described in step (1) is lauryl sodium sulfate
(SDS), the oxidant is FeCl3。
As preferred embodiment, the concentration of anionic surfactant is 0.2-0.4M, step in step (1)
(2) in, the molar ratio of EDOT monomer, oxidant and anionic surfactant is 1:(1-10): (1-10).
As preferred embodiment, the process conditions of oil bath stirring in step (1) are as follows: 40-60 DEG C of temperature, the time is
0.5-1.5h；
The process conditions that oil bath is reacted in step (2) are as follows: 40-60 DEG C of temperature, time 3-7h.
As preferred embodiment, concentration of the PEDOT nanofiber dispersion in methanol is 3-15mg/ in step (2)
ml。
As preferred embodiment, the additional amount of SWCNTs and PEDOT methanol solution meets in step (3): SWCNTs
For the 5-55wt% of SWCNTs and PEDOT (being equivalent to last obtained composite thermoelectric material film) gross weight.
As preferred embodiment, ultrasonic time is 15-30min, ultrasonic power 100-200W, frequency in step (3)
Rate is 40-60KHz.
As preferred embodiment, in step (4): the miillpore filter is the nylon leaching film of 0.22 micron pore size；
The vacuum filtration time is 5-15min；
Drying condition are as follows: be dried in vacuo at 60 DEG C.
The flexible self-supporting that PEDOT nanofiber/SWCNTs could be made by vacuum filtration method of the invention is thin
Film, in addition, other methods such as tabletting, spin coating, drop coating can only obtain the composite material of block or depend on certain substrates
On film, ultrasound be for make two kinds of components be uniformly mixed, raw material dosage change the thermoelectricity capability of composite material can be caused
It influences.During the preparation process, the anionic surfactant SDS that the present invention uses will form micella after being added to the water, when its is dense
When degree is greater than 0.2M, rodlike micella will form, EDOT monomer is added after micellar solution due to its hydrophobicity, and EDOT monomer can move
It is moved into inside rod-shaped micelle, in FeCl3Polymerization reaction occurs under the action of oxidant inside micella, the template of rod-shaped micelle is made
With making EDOT aggregate into one-dimensional PEDOT nanofiber, excessive surfactant is removed with oxygen finally by eccentric cleaning
Agent has just obtained PEDOT nanofiber, it has good dispersibility in methyl alcohol, by after ultrasonic disperse and equally
The compound thermal electric film that two kinds of one-dimensional materials are constituted is made in one-dimensional SWCNTs under vacuum filtration.
The present invention is prepared for having high conductivity first in anionic surfactant with self-assembled micelle soft template method
With the methanol dispersion liquid of the PEDOT nanofiber (nanofiber) of the one-dimentional structure of good filming characteristic, then with SWCNTs
Using the miillpore filter of 0.22 micron pore size, self assembly forms a film under vacuum filtration, and propping up certainly for Automatic-falling is made after vacuum drying
Support PEDOT nanofiber/SWCNs flexibility thermoelectric material.One-dimensional PEDOT nanofiber and one-dimensional SWCNTs is woven into
Good conductive network channel, composite material in combination with highly conductive characteristic possessed by PEDOT nanofiber and
The higher Seebeck coefficient of SWCNTs improves the whole thermoelectricity capability of composite material using the synergistic effect of the two.
Compared with prior art, the invention has the following advantages that
(1) with EDOT monomer, the self-assembled micelle soft template method polymerization in anionic surfactant is made one-dimensional to the present invention
PEDOT nanofiber, preparation method is simple, and yield is higher, and more compared with the commercialization PEDOT:PSS solution of price
Add economical and practical.
(2) PEDOT nanofiber structure one-dimensional in the present invention, specific surface area with higher and excellent conductance
Rate, good filming performance, compound by carrying out with SWCNTs, self assembly forms a film under vacuum filtration method, and performance can be made
Excellent self-supporting flexibility thermoelectric material.
(3) PEDOT nanofiber/SWCNTs composite material prepared by the present invention, can be used as it is a kind of have excellent performance have
Machine thermoelectric material；
(4) PEDOT nanofiber/SWCNTs composite material prepared by the present invention has good flexibility, Ke Yisui
Meaning is bent and is cut into arbitrary shape, perfectly solves traditional solution oxide and polymerize PEDOT powder obtained because difficult
Molten, infusibility and the problem of can not form a film, provide the foundation for it as flexible wearable electronic device applications；
(5) PEDOT nanofiber/SWCNTs composite thermoelectric material of the present invention combines PEDOT
Nanofiber and the advantage of SWCNTs respectively improve the whole pyroelectricity of composite material using the synergistic effect of the two
Energy.
Detailed description of the invention
Fig. 1 is self-supporting flexibility PEDOT nanofiber/SWCNTs (19.2wt%) compound thermoelectric film material of preparation
Photo
Fig. 2 is transmission electron microscope (TEM) shape appearance figure for preparing resulting one-dimensional PEDOT nanofiber；
Fig. 3 is field emission scanning electron microscope (FESEM) pattern for preparing resulting one-dimensional PEDOT nanofiber
Figure；
Fig. 4 is the field hair of flexible self-supporting PEDOT nanofiber/SWCNTs (19.2wt%) film in embodiment 1
Penetrate Scanning Electron microscope (FESEM)；
Fig. 5 is the PEDOT nanofiber/SWCNTs THIN COMPOSITE membrane material for the different SWCNTs contents that the present invention is prepared
The thermoelectricity capability of material.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
In following each embodiments, SWCNTs used is commercial product, is purchased from Chengdu organic chemistry Co., Ltd, the Chinese Academy of Sciences, is produced
Product model TNST.
Embodiment 1
The compound thermoelectric film material of a kind of self-supporting flexibility PEDOT nanofiber/SWCNTs, first with FeCl3For oxygen
Agent prepares the methanol dispersion liquid of PEDOT nanofiber using self-assembled micelle soft template method, then by it with SWCNTs's
Methanol dispersion liquid ultrasonic mixing is formed a film using the miillpore filter of 0.22 micron pore size in vacuum filtration self assembly, after vacuum drying
Composite membrane is split away off from principal and subordinate's miillpore filter, obtains the PEDOT nanofiber/SWCNTs thermal electric film of self-supporting.Its
It is middle to prepare surfactant SDS used in PEDOT nanofiber, oxidant FeCl3, EDOT monomer three's molar ratio is 30:
The mass fraction of 15:7, SWCNTs in the composite is in 6.7wt%.
The above-mentioned flexible thin-film material with excellent thermoelectricity capability the preparation method is as follows:
(1) preparation of PEDOT nanofiber:
The SDS of 30mmol is added in 100ml deionized water, 15min is stirred to being completely dissolved, is added 15mmol's
FeCl3, stirred 1 hour under 50 ° of oil baths, the EDOT monomer of 7mmol be then slowly dropped under continuous stirring, under 50 ° of oil baths
Reaction 6 hours.Reaction terminates, and after solution is cooled to room temperature, is centrifuged and is washed repeatedly with deionized water, methanol to supernatant change
To be colourless, methanol 45mL ultrasound 30min is then added.The methanol dispersion liquid of PEDOT nanofiber can be obtained.
(2) preparation of the compound thermoelectric film material of self-supporting flexibility PEDOT nanofiber/SWCNTs:
The SWCNTs of 1.1mg is added in 5mL methanol, ultrasonic 30min keeps SWCNTs evenly dispersed, is denoted as solution A；It takes
PEDOT nanofiber methanol dispersion liquid in 5mL step (1), ultrasonic 30min are denoted as solution B；Solution B is added in solution A
In, then mixed liquor, is then poured on the miillpore filter of 0.22 micron pore size by ultrasound 30min, and 10min is filtered by vacuum, and takes out
12 hours dry in 60 DEG C of vacuum drying ovens after filter, PEDOT nanofiber/SWCNTs film is by pyrocondensation in drying process
Influence to split away off to obtain from filter membrane automatically can be obtained self-supporting flexible PEDOT nanofiber/SWCNTs thermoelectricity it is thin
Film.
Fig. 1 is self-supporting flexibility PEDOT nanofiber/SWCNTs (19.2wt%) compound thermoelectric film material of preparation
Photo, it can be seen that the film of preparation is separated from miillpore filter, and have good flexibility, can arbitrarily be bent.
Fig. 2 is the transmission electron microscope picture of PEDOT nanofiber, as shown in Figure 2, surfactant SDS, oxidant FeCl3,
When EDOT monomer three's molar ratio is 30:15:7, PEDOT nanofiber fibre diameter obtained is in 30-50nm or so, and portion
Divide and is gathered into pencil.Fig. 3 is the scanning electron microscope diagram piece of PEDOT nanofiber, it can be observed that a clearly wiener
Rice fiber morphology.The scanning electron microscope diagram piece for the PEDOT nanofiber/SWCNTs laminated film that Fig. 4 is,
PEDOT nanofiber and SWCNTs is one-dimentional structure, and after compound, PEDOT nanofiber and SWCNTs are woven into conduction
Network structure, wherein diameter lesser (< 10nm) is SWCNTs, and diameter is slightly PEDOT nanofiber.
Fig. 5 is the thermoelectricity capability picture of composite material obtained by the present invention, and wherein conductivity is tested using Hall effect
Instrument (Ecopia HMS3000, four probe method) measures；Seebeck coefficient is thin by acquiring using homemade thermoelectricity capability tester
Thermoelectromotive force when the difference temperature difference of film both ends measures.In Fig. 5 A, in composite material, SWCNTs content raising conductivity is in
Downward trend, Seebeck coefficient are in raising trend, and this is mainly due to the Conductivity Ratio PEDOT nanofiber of SWCNTs
Low, and caused by Seebeck coefficient wants height, when SWCNTs content is 53.6wt%, conductivity has dropped 36%, and Seebeck
Coefficient increases 73%, due to square proportional, the power factor of final composite material of power factor PF and Seebeck coefficient
In rising trend with the raising of SWCNTs content, power factor when SWCNTs content is 53.6wt% is than pure PEDOT
Nanofiber's improves nearly 2 times (Fig. 5 B).
Embodiment 2
The compound thermoelectric film material of a kind of self-supporting flexibility PEDOT nanofiber/SWCNTs, first with FeCl3For oxygen
Agent prepares the methanol dispersion liquid of PEDOT nanofiber using self-assembled micelle soft template method, then by it with SWCNTs's
Methanol dispersion liquid ultrasonic mixing is formed a film using the miillpore filter of 0.22 micron pore size in vacuum filtration self assembly, after vacuum drying
Composite membrane is split away off from principal and subordinate's miillpore filter, obtains the PEDOT nanofiber/SWCNTs thermal electric film of self-supporting.Its
It is middle to prepare surfactant SDS used in PEDOT nanofiber, oxidant FeCl3, EDOT monomer three's molar ratio is 30:
The mass fraction of 15:7, SWCNTs in the composite is in 12.1wt%.
The above-mentioned flexible thin-film material with excellent thermoelectricity capability the preparation method is as follows:
(1) preparation of PEDOT nanofiber is according to embodiment 1.
(2) preparation of the compound thermoelectric film material of self-supporting flexibility PEDOT nanofiber/SWCNTs: by 2.5 mg's
SWCNTs is added in 5mL methanol, and ultrasonic 30min keeps SWCNTs evenly dispersed, is denoted as solution A；It takes in 5mL step (1)
PEDOT nanofiber methanol dispersion liquid, ultrasonic 30min are denoted as solution B；Solution A is added in solution B, it is then ultrasonic
Then mixed liquor is poured on the miillpore filter of 0.22 micron pore size by 30min, vacuum filtration 10min, 60 after suction filtration
12 hours dry in DEG C vacuum drying oven, PEDOT nanofiber/SWCNTs film epitome of being heated is rung automatically from filter membrane in drying process
On split away off to obtain flexible PEDOT nanofiber/SWCNTs (12.1wt%) thermal electric film that self-supporting can be obtained.
The conductivity of combination electrode material obtained at room temperature is 281.9S/cm, and Seebeck coefficient is 18.4 μ V/K, function
The rate factor is 9.5 μ V/mK2。
Embodiment 3
The compound thermoelectric film material of a kind of self-supporting flexibility PEDOT nanofiber/SWCNTs, first with FeCl3For oxygen
Agent prepares the methanol dispersion liquid of PEDOT nanofiber using self-assembled micelle soft template method, then by it with SWCNTs's
Methanol dispersion liquid ultrasonic mixing is formed a film using the miillpore filter of 0.22 micron pore size in vacuum filtration self assembly, after vacuum drying
Composite membrane is split away off from principal and subordinate's miillpore filter, obtains the PEDOT nanofiber/SWCNTs thermal electric film of self-supporting.Its
It is middle to prepare surfactant SDS used in PEDOT nanofiber, oxidant FeCl3, EDOT monomer three's molar ratio is 30:
The mass fraction of 15:7, SWCNTs in the composite is in 19.2wt%.
The above-mentioned flexible thin-film material with excellent thermoelectricity capability the preparation method is as follows:
(1) preparation of PEDOT nanofiber is according to embodiment 1.
(2) preparation of the compound thermoelectric film material of self-supporting flexibility PEDOT nanofiber/SWCNTs: by 4.3 mg's
SWCNTs is added in 5mL methanol, and ultrasonic 30min keeps SWCNTs evenly dispersed, is denoted as solution A；It takes in 5mL step (1)
PEDOT nanofiber methanol dispersion liquid, ultrasonic 30min are denoted as solution B；Solution A is added in solution B, it is then ultrasonic
Then mixed liquor is poured on the miillpore filter of 0.22 micron pore size by 30min, vacuum filtration 10min, 60 after suction filtration
12 hours dry in DEG C vacuum drying oven, PEDOT nanofiber/SWCNTs film epitome of being heated is rung automatically from filter membrane in drying process
On split away off to obtain flexible PEDOT nanofiber/SWCNTs (19.2wt%) thermal electric film that self-supporting can be obtained.
The conductivity of combination electrode material obtained at room temperature is 263.3S/cm, and Seebeck coefficient is 20.5 μ V/K, function
The rate factor is 11.1 μ V/mK2
Embodiment 4
A kind of compound thermoelectric film material of self-supporting flexibility PEDOT nanofiber/SWCNTs, preparation method are as follows:
(1) preparation of PEDOT nanofiber is according to embodiment 1.
(2) preparation of the compound thermoelectric film material of self-supporting flexibility PEDOT nanofiber/SWCNTs: by 10 mg's
SWCNTs is added in 5mL methanol, and ultrasonic 30min keeps SWCNTs evenly dispersed, is denoted as solution A；It takes in 5mL step (1)
PEDOT nanofiber methanol dispersion liquid, ultrasonic 30min are denoted as solution B；Solution A is added in solution B, it is then ultrasonic
Then mixed liquor is poured on the miillpore filter of 0.22 micron pore size by 30min, vacuum filtration 10min, 60 after suction filtration
12 hours dry in DEG C vacuum drying oven, PEDOT nanofiber/SWCNTs film epitome of being heated is rung automatically from filter membrane in drying process
On split away off to obtain flexible PEDOT nanofiber/SWCNTs (35.4wt%) thermal electric film that self-supporting can be obtained.
The conductivity of combination electrode material obtained at room temperature is 228.8S/cm, and Seebeck coefficient is 24.3 μ V/K, function
The rate factor is 13.5 μ V/mK2。
Embodiment 5
A kind of compound thermoelectric film material of self-supporting flexibility PEDOT nanofiber/SWCNTs, preparation method are as follows:
(1) preparation of PEDOT nanofiber is according to embodiment 1.
(2) preparation of the compound thermoelectric film material of self-supporting flexibility PEDOT nanofiber/SWCNTs: by 23.3 mg's
SWCNTs is added in 5mL methanol, and ultrasonic 30min keeps SWCNTs evenly dispersed, is denoted as solution A；It takes in 5mL step (1)
PEDOT nanofiber methanol dispersion liquid, ultrasonic 30min are denoted as solution B；Solution A is added in solution B, it is then ultrasonic
Then mixed liquor is poured on the miillpore filter of 0.22 micron pore size by 30min, vacuum filtration 10min, 60 after suction filtration
12 hours dry in DEG C vacuum drying oven, PEDOT nanofiber/SWCNTs film epitome of being heated is rung automatically from filter membrane in drying process
On split away off to obtain flexible PEDOT nanofiber/SWCNTs (53.6wt%) thermal electric film that self-supporting can be obtained.
The conductivity of combination electrode material obtained at room temperature is 217.4S/cm, and Seebeck coefficient is 26.2 μ V/K, function
The rate factor is 14.4 μ V/mK2。
Embodiment 6
Compared with Example 1, the overwhelming majority all, in addition in the present embodiment 1 SWCNTs additive amount satisfaction: it is last
In composite material, the content of SWCNTs is 5wt%.
Embodiment 7
Compared with Example 1, the overwhelming majority all, in addition in the present embodiment 1 SWCNTs additive amount satisfaction: it is last
In composite material, the content of SWCNTs is 55wt%.
Embodiment 8
A kind of compound thermoelectric film material of self-supporting flexibility PEDOT nanofiber/SWCNTs, preparation method are as follows:
(1) preparation of PEDOT nanofiber:
The SDS of 20mmol is added in 100ml deionized water, 15min is stirred to being completely dissolved, is added 7mmol's
FeCl3, stirred 1.5 hours under 40 ° of oil baths, be then slowly dropped into the EDOT monomer of 7mmol, 40 ° of oil baths under continuous stirring
Lower reaction 7 hours.Reaction terminates, and after solution is cooled to room temperature, is centrifuged and is washed repeatedly with deionized water, methanol to supernatant
It becomes colorless, then adds methanol 40mL, ultrasonic 30min.The methanol dispersion liquid of PEDOT nanofiber can be obtained.
(2) preparation of the compound thermoelectric film material of self-supporting flexibility PEDOT nanofiber/SWCNTs:
The SWCNTs of 23.3mg is added in 5mL methanol, in ultrasonic power 100W, ultrasound under the conditions of frequency is 40KHz
30min keeps SWCNTs evenly dispersed, is denoted as solution A；The PEDOT nanofiber methanol dispersion liquid in 5mL step (1) is taken,
Ultrasonic 15min, is denoted as solution B；Solution A is added in solution B, then ultrasound 15min, it is micro- to be then poured into 0.22 for mixed liquor
On the miillpore filter of metre hole diameter, 5min, 12 hours dry in 60 DEG C of vacuum drying ovens, drying process after suction filtration is filtered by vacuum
The heated epitome of middle PEDOT nanofiber/SWCNTs film, which rings to split away off to obtain from filter membrane automatically, can be obtained self-supporting
Flexible PEDOT nanofiber/SWCNTs thermal electric film.
Embodiment 9
A kind of compound thermoelectric film material of self-supporting flexibility PEDOT nanofiber/SWCNTs, preparation method are as follows:
(1) preparation of PEDOT nanofiber:
The SDS of 7mmol is added in 100ml deionized water, 15min is stirred to being completely dissolved, is added 70mmol's
FeCl3, stirred 0.5 hour under 60 ° of oil baths, be then slowly dropped into the EDOT monomer of 7mmol, 60 ° of oil baths under continuous stirring
Lower reaction 3 hours.Reaction terminates, and after solution is cooled to room temperature, is centrifuged and is washed repeatedly with deionized water, methanol to supernatant
It becomes colorless, then adds methanol 50mL, ultrasonic 30min.The methanol dispersion liquid of PEDOT nanofiber can be obtained.
(2) preparation of the compound thermoelectric film material of self-supporting flexibility PEDOT nanofiber/SWCNTs:
The SWCNTs of 23.3mg is added in 5mL methanol, in ultrasonic power 200W, ultrasound under the conditions of frequency is 60KHz
20min keeps SWCNTs evenly dispersed, is denoted as solution A；The PEDOT nanofiber methanol dispersion liquid in 5mL step (1) is taken,
Ultrasonic 20min, is denoted as solution B；Solution A is added in solution B, then ultrasound 25min, it is micro- to be then poured into 0.22 for mixed liquor
On the miillpore filter of metre hole diameter, 5min, 12 hours dry in 60 DEG C of vacuum drying ovens, drying process after suction filtration is filtered by vacuum
The heated epitome of middle PEDOT nanofiber/SWCNTs film, which rings to split away off to obtain from filter membrane automatically, can be obtained self-supporting
Flexible PEDOT nanofiber/SWCNTs thermal electric film.
Embodiment 10
A kind of compound thermoelectric film material of self-supporting flexibility PEDOT nanofiber/SWCNTs, preparation method are as follows:
(1) preparation of PEDOT nanofiber:
The SDS of 70mmol is added in 100ml deionized water, 15min is stirred to being completely dissolved, is added 70mmol's
FeCl3, stirred 0.5 hour under 60 ° of oil baths, be then slowly dropped into the EDOT monomer of 7mmol, 60 ° of oil baths under continuous stirring
Lower reaction 3 hours.Reaction terminates, and after solution is cooled to room temperature, is centrifuged and is washed repeatedly with deionized water, methanol to supernatant
It becomes colorless, then adds methanol 45mL, ultrasonic 30min.The methanol dispersion liquid of PEDOT nanofiber can be obtained.
(2) preparation of the compound thermoelectric film material of self-supporting flexibility PEDOT nanofiber/SWCNTs:
The SWCNTs of 23.3mg is added in 5mL methanol, in ultrasonic power 150W, ultrasound under the conditions of frequency is 50KHz
25min keeps SWCNTs evenly dispersed, is denoted as solution A；The PEDOT nanofiber methanol dispersion liquid in 5mL step (1) is taken,
Ultrasonic 20min, is denoted as solution B；Solution A is added in solution B, then ultrasound 25min, it is micro- to be then poured into 0.22 for mixed liquor
On the miillpore filter of metre hole diameter, 5min, 12 hours dry in 60 DEG C of vacuum drying ovens, drying process after suction filtration is filtered by vacuum
The heated epitome of middle PEDOT nanofiber/SWCNTs film, which rings to split away off to obtain from filter membrane automatically, can be obtained self-supporting
Flexible PEDOT nanofiber/SWCNTs thermal electric film.
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, ability
Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be of the invention
Within protection scope.
Claims (8)
1. a kind of preparation method of self-supporting flexibility PEDOT nanofiber/SWCNTs composite thermoelectric material film, feature exist
In, composite thermoelectric material film forms conductive network structure by one-dimensional PEDOT nanofiber and one-dimensional SWCNTs intertexture,
In, the mass content of SWCNTs is 5-55wt%；
The preparation method comprises the following steps:
(1) it takes anionic surfactant to be dissolved in deionized water, oxidant is added, is stirred under oil bath, obtains mixed solution
A；
(2) EDOT monomer is taken to be added in the mixed solution A of step (1), oil bath reaction is after the reaction was completed, cooling, separation, clearly
It washes, obtains PEDOT nanofiber, be scattered in spare in methanol；
(3) it takes SWCNTs to be scattered in methanol, then ultrasound after mixing with the PEDOT methanol solution that step (2) obtains, is mixed
Solution B；
(4) the mixed solution B of step (3) is filtered using vacuum filtration method on miillpore filter again, it is dry to get to it is described from
Support flexibility PEDOT nanofiber/SWCNTs composite thermoelectric material film；
The additional amount of SWCNTs and PEDOT methanol solution meets in step (3): SWCNTs is the 5- of SWCNTs and PEDOT gross weight
55wt%.
2. a kind of self-supporting flexibility PEDOT nanofiber/SWCNTs composite thermoelectric material film according to claim 1
Preparation method, which is characterized in that the diameter of the PEDOT nanofiber is 30-200nm, and the diameter of the SWCNTs is small
In 10nm.
3. a kind of self-supporting flexibility PEDOT nanofiber/SWCNTs composite thermoelectric material film according to claim 1
Preparation method, which is characterized in that anionic surfactant described in step (1) is lauryl sodium sulfate, described
Oxidant is FeCl3。
4. a kind of self-supporting flexibility PEDOT nanofiber/SWCNTs composite thermoelectric material film according to claim 1
Preparation method, which is characterized in that the concentration of anionic surfactant is 0.2-0.4M in step (1), in step (2),
The molar ratio of EDOT monomer, oxidant and anionic surfactant is 1:(1-10): (1-10).
5. a kind of self-supporting flexibility PEDOT nanofiber/SWCNTs composite thermoelectric material film according to claim 1
Preparation method, which is characterized in that the process conditions that oil bath is stirred in step (1) are as follows: 40-60 DEG C of temperature, time 0.5-1.5h；
The process conditions that oil bath is reacted in step (2) are as follows: 40-60 DEG C of temperature, time 3-7h.
6. a kind of self-supporting flexibility PEDOT nanofiber/SWCNTs composite thermoelectric material film according to claim 3
Preparation method, which is characterized in that concentration of the PEDOT nanofiber dispersion in methanol is 3-15mg/ml in step (2).
7. a kind of self-supporting flexibility PEDOT nanofiber/SWCNTs composite thermoelectric material film according to claim 1
Preparation method, which is characterized in that ultrasonic time is 15-30min, ultrasonic power 100-200W, frequency 40- in step (3)
60KHz。
8. a kind of self-supporting flexibility PEDOT nanofiber/SWCNTs composite thermoelectric material film according to claim 1
Preparation method, which is characterized in that in step (4): the miillpore filter is the nylon leaching film of 0.22 micron pore size；
The vacuum filtration time is 5-15min；
Drying condition are as follows: be dried in vacuo at 60 DEG C.
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| CN108504049A (en) * | 2018-03-13 | 2018-09-07 | 东华大学 | A kind of preparation method of the compound thermal electric film of macromolecule |
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| CN113707799A (en) * | 2021-08-17 | 2021-11-26 | 上海应用技术大学 | Preparation method of flexible self-supporting PEDOT nanowire thermoelectric material |
| CN113809225B (en) * | 2021-09-17 | 2022-11-22 | 陕西科技大学 | SnS/C-PEDOT PSS flexible thermoelectric film and preparation method thereof |
| CN114316223B (en) | 2021-12-31 | 2022-09-27 | 华中科技大学 | Alcohol dispersion liquid of conductive polyethylene dioxythiophene and preparation method and application thereof |
| CN114752090B (en) * | 2022-03-21 | 2024-03-22 | 复旦大学 | Co/PEDOT composite flexible self-supporting film and preparation and application thereof |
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