CN109944063A - A kind of preparation method of heat to electricity conversion space fabric - Google Patents
A kind of preparation method of heat to electricity conversion space fabric Download PDFInfo
- Publication number
- CN109944063A CN109944063A CN201910160372.3A CN201910160372A CN109944063A CN 109944063 A CN109944063 A CN 109944063A CN 201910160372 A CN201910160372 A CN 201910160372A CN 109944063 A CN109944063 A CN 109944063A
- Authority
- CN
- China
- Prior art keywords
- solution
- heat
- composite material
- space fabric
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention discloses a kind of preparation methods of heat to electricity conversion space fabric, which is characterized in that surfactant mixed dispersion liquid is made in ionic surface active agent, inorganic thermoelectric material, solvent；Oxidizing agent solution is made in oxidant and solvent；The two is mixed, and polymer monomer is added, forms thermoelectric composite material mixed solution；Thermoelectric composite material mixed solution is added in solvent, clean thermoelectric composite material solution is obtained；Dispersing agent is added, p-type thermoelectric composite material solution is obtained；Yarn is infiltrated in p-type thermoelectric composite material solution, dries, then penetrates yarn in space fabric；The yarn that the injection of macromolecule polymer solution compartment of terrain is penetrated to fabric, is then dried, and heat to electricity conversion space fabric is made.Preparation method of the present invention is simple, easy to operate, can mass production, preparation process no pollution to the environment.And textile structural thermo-electric device prepared by the present invention has both flexibility and pyroelectricity, application prospect are extensive.
Description
Technical field
The present invention relates to a kind of preparation methods of heat to electricity conversion space fabric, belong to functional fabric technical field.
Background technique
The shortage of traditional energy substance promotes the development of new cleaning fuel material, thermoelectric material (also referred to as heat to electricity conversion
Material) attract the concern of whole world scientist.It can be a kind of new by the thermoelectric material that thermal energy and electric energy are mutually converted
The clean energy resource material of type, development prospect are wide.Currently, the energy conversion efficiency and Qi Ke of raising thermoelectric generator (TEG) are worn
The property worn is one of currently the most important research hotspot.
Textile garment system based on fiber has manufactured and used thousands of years via the mankind, because of its draw ratio one
As be not less than 50, and be it is soft and deformable, breathe freely, it is durable and washable, therefore be the ideal load of thermoelectric generator
Body.Although advantageous, the development of fiber base thermoelectric generator also encounters many challenges.Such as pass through needle in current existing research
Thermoelectricity generating device that organization method is constituted with wire is pressed into glass fabric by small thermoelectric semiconductor patch and forms thermoelectricity
Device, thermoelectric material anchor on silk fabric, prepare soft thermoelectric generator etc..Such as CN108649116A is disclosed
A kind of stretchable wearable spring like thermo-electric device, be passed through with inorganic thermoelectric material be coated in template be stripped again it is obtained；
A kind of flexible thermo-electric device that CN108305935A is announced, be by the method for welding by flexible base board, p-type, N-type semiconductor,
Electrode etc. is connected, and realizes flexible using partition is increased between flexible base board；One kind that CN104934526A is announced is flexible
The heterogeneous flexible thermoelectric conversion element folded, is to generate temperature ladder using the overlapping region of black alkene layer and two-dimensional semiconductor crystal layer
Degree causes Seebeck effect, generates open-circuit voltage, and carry out heat to electricity conversion.
However there is the wearing comforts poor, flexibility of the above thermoelectricity generating device and changeability is poor, thermoelectric material with knit
The problems such as object combination effect is poor, easy to fall off.
Summary of the invention
Problem to be solved by this invention is: flexibility and the thermoelectricity capability of existing flexibility thermoelectric material cannot both with ask
Topic.
In order to solve the above-mentioned technical problems, the present invention provides a kind of preparation methods of heat to electricity conversion space fabric, special
Sign is, comprising the following steps:
Ionic surface active agent, inorganic thermoelectric material are added in the first volatile solvent, after agitation by the first step
Ultrasound keeps surfactant evenly dispersed in the first volatile solvent, obtains surfactant mixed dispersion liquid；
Step 2: oxidant is dissolved in the second volatile solvent, oxidizing agent solution is obtained；
Step 3: oxidizing agent solution is mixed with surfactant mixed dispersion liquid, simultaneously mechanical stirring is heated, is mixed
Solution；
Step 4: polymer monomer is added in the mixed solution that third step obtains, continue heating and mechanical stirring, gathers
In-situ polymerization occurs in a solvent for monomer adduct, forms thermoelectric composite material mixed solution；
Step 5: thermoelectric composite material mixed solution is added in third volatile solvent, it is super by multiple water-bath
Sound, suction filtration are washed, and clean thermoelectric composite material solution is obtained；
Step 6: dispersing agent is added in clean thermoelectric composite material solution, by ultrasound, filter, obtains p-type heat
Composite solution；
Step 7: yarn is infiltrated in p-type thermoelectric composite material solution, dries, yarn is then penetrated into space fabric
In；
Step 8: macromolecule polymer solution ambient separation to be injected to the yarn for penetrating fabric, then dry, heat is made
Electric conversion interval fabric.Ambient separation is that a unit forms dot matrix (vertical view) with the line segment being arranged in fabric, the unit
Macromolecule polymer solution is injected, then eight units around the unit are not injected into macromolecule polymer solution.
Preferably, the first volatile solvent in the first step, the second volatile solvent in second step, the 5th
Third volatile solvent in step is any one or a few the mixture in ethyl alcohol, methanol, acetone and water；Described first
Ionic surface active agent in step is in dodecyl sodium sulfate, neopelex and cetyl trimethylammonium bromide
Any one or a few mixture；Inorganic thermoelectric material in the first step is multi-walled carbon nanotube, single
The mixture of pipe or both；Oxidant in the second step is the mixture of ferric trichloride, p-methyl benzenesulfonic acid iron or both.
Preferably, the ionic surface active agent in the first step, inorganic thermoelectric material and the first volatile solvent
Ratio is 1g:(0.5~3) g:(10~20) mL；The ratio of oxidant and the second volatile solvent is 1g in the second step:
(1~3) mL；The ratio of thermoelectric composite material solution and third volatile solvent is 1mg:(1~2 in 5th step) mL.
Preferably, power ultrasonic in the first step is 220~300W, and ultrasonic time is 30~40min, ultrasonic temperature
It is 5~10 DEG C.
Preferably, the third step, the heating temperature in the 4th step are 50~70 DEG C, and heating time is 7~18h, mechanical
Mixing speed is 1000~1500 revolutions per seconds.
Preferably, the polymer monomer in the 4th step is the mixture of aniline, pyrroles and thiophene or both.
Preferably, in the 5th step water bath sonicator ultrasonic power be 180~220W, ultrasonic time be 20~
40min, ultrasonic temperature are room temperature.
Preferably, the dispersing agent in the 6th step is the mixture of dimethyl sulfoxide, methyl sulfoxide or both；Dispersing agent
Percent by volume in clean thermoelectric composite material solution is 2%~5%.
Preferably, the macromolecule polymer solution in the 8th step is polyetherimide, polyvinyl alcohol and polyethylene pyrrole
The mixture of one or more of pyrrolidone；The temperature than drying in the 8th step is 40-60 DEG C, drying time 1-2
Hour.
Compared with prior art, the beneficial effects of the present invention are:
Preparation method is simple, easy to operate, can mass production, preparation process no pollution to the environment.And this method synthesizes
Thermoelectric composite material thermoelectricity capability it is good, flexibility is good, can arbitrarily be bent, have certain elongation strain, can satisfy
The requirement of flexible wearable can be applied to thermo-electric device such as thermoelectric generator, refrigerator etc..
The present invention uses on the p-type thermoelectricity yarn for having penetrated fabric, injects to ambient separation the N-type thermoelectricity slurry prepared
Material, then heat to electricity conversion space fabric is made with the method that vacuum drying oven is dried.The present invention takes into account the flexibility and thermoelectricity of thermoelectric material
Property, realize the higher energy conversion efficiency of textile structural thermo-electric device and wearable property.It is related to using chemistry polymerizing in situ method
Nanocomposite is prepared, is related to p-type thermoelectricity slurry being effectively coated on cellulose yarn, be related in an orderly manner in space fabric
Yarn is penetrated, is related to the yarn by the way that N-type thermoelectricity slurry ambient separation to be injected to incoming fabric, and then between preparation heat to electricity conversion
It is a kind of novel, easy flexible heat to electricity conversion yarn preparation method and fast and convenient textile structural thermoelectricity device every fabric
The preparation method of part.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of heat to electricity conversion space fabric produced by the present invention；
Fig. 2 is output voltage when heat to electricity conversion space fabric made from embodiment 3 is mounted on three different human bodies
Tables of data.
Fig. 3 is the data for the function that heat to electricity conversion space fabric output voltage V made from embodiment 3 changes with number of bends
Table (wherein V0 is initial output voltage).
Fig. 4 is the tables of data that heat to electricity conversion space fabric output voltage made from embodiment 3 changes over time.
Specific embodiment
In order to make the present invention more obvious and understandable, hereby with preferred embodiment, and attached drawing is cooperated to be described in detail below.
Embodiment 1
Prepare poly- 3,4 ethene dioxythiophenes of p-type/single-walled carbon nanotube thermoelectric composite material:
(1) dodecyl sodium sulfate (SDS), single-walled carbon nanotube are dissolved in deionized water, wherein dodecyl sulphur
The ratio of sour sodium, single-walled carbon nanotube and deionized water is 1g:1g-4g:10ml, and glass bar Probe Ultrasonic Searching after mixing evenly obtains
To finely dispersed dodecyl sodium sulfate mixed solution.Then ferric trichloride is dissolved in the water, wherein ferric trichloride and water
Ratio be 1g:2ml, glass bar stirs evenly, the liquor ferri trichloridi sufficiently dissolved.
(2) liquor ferri trichloridi is added in dodecyl sodium sulfate mixed solution, heats 65 DEG C, mixing speed 1500
Revolutions per second, mechanical stirring 1 hour.
(3) 3,4 ethene dioxythiophene monomers are added in above-mentioned solution, 50 DEG C of heating, 1000 revolutions per seconds of mixing speed,
Mechanical stirring 6 hours.
(4) methanol and water 1:1 are mixed to join in above-mentioned solution, water bath sonicator 40 minutes, ultrasonic power 200W, are carried out
Filtering and washing.This process is repeated as many times, until obtaining clean thermoelectric composite material solution.
(5) clean thermoelectric composite material solution is impregnated in methyl alcohol, the dimethyl sulfoxide of 5vol% is added, probe is super
Sound 30 minutes, ultrasonic power 300W, so that p-type poly- 3,4 ethene dioxythiophenes/single-walled carbon nanotube thermoelectric composite material be made.
Embodiment 2
Prepare poly- 3,4 ethene dioxythiophenes of p-type/multi-walled carbon nanotube thermoelectric composite material:
(1) neopelex (SDS), multi-walled carbon nanotube are dissolved in ethyl alcohol, wherein detergent alkylate sulphur
The ratio of sour sodium, multi-walled carbon nanotube and ethyl alcohol is 1g:1g-2g:15ml, and glass bar Probe Ultrasonic Searching after mixing evenly is divided
Dissipate uniform neopelex mixed solution.Then ferric trichloride is dissolved in the water, wherein ferric trichloride and water
Ratio is 1g:1.5ml, and glass bar stirs evenly, the liquor ferri trichloridi sufficiently dissolved.
(2) liquor ferri trichloridi is added in neopelex mixed solution, heats 70 DEG C, mixing speed 2000
Revolutions per second, mechanical stirring 1 hour.
(3) 3,4 ethene dioxythiophene monomers are added in above-mentioned solution, 55 DEG C of heating, 1200 revolutions per seconds of mixing speed,
Mechanical stirring 8 hours.
(4) methanol and water 1:1 are mixed to join in above-mentioned solution, water bath sonicator 30 minutes, ultrasonic power 200W, are carried out
Filtering and washing.This process is repeated as many times, until obtaining clean thermoelectric composite material solution.
(5) clean thermoelectric composite material solution is impregnated in methyl alcohol, the dimethyl sulfoxide of 5vol% is added, probe is super
Sound 30 minutes, ultrasonic power 300W, so that p-type poly- 3,4 ethene dioxythiophenes/multi-walled carbon nanotube thermoelectric composite material be made.
Embodiment 3
Prepare heat to electricity conversion space fabric:
(1) that yarn is infiltrated on poly- 3,4 ethene dioxythiophenes of p-type made from embodiment 1/single-walled carbon nanotube thermoelectricity is compound
In material, then drying penetrates space fabric.
(2) polyetherimide ambient separation is injected to the yarn for penetrating fabric, is dried, so that heat to electricity conversion interval be made
Fabric (as shown in Figure 1, the yarn 2 that surface is coated with p-type thermoelectric composite material is equipped in space fabric 1, high molecular polymer
The part injection that solution, i.e. N-type thermoelectricity slurry 3 expose from yarn 2 from 1 surface of space fabric).
(3) performance for testing made heat to electricity conversion space fabric, when contact human body, the generator of manufacture by human body with it is all
The temperature difference enclosed is converted to electric energy, and voltage output is 1.5~2mV, when within heat to electricity conversion space fabric is bent 80 times, output
Voltage change is negligible, and output voltage keeps stable in air, slight change is only detected, even if after one month
Also the 95% of initial value is kept, as in Figure 2-4.
Claims (9)
1. a kind of preparation method of heat to electricity conversion space fabric, which comprises the following steps:
Ionic surface active agent, inorganic thermoelectric material are added in the first volatile solvent, surpass after agitation by the first step
Sound keeps surfactant evenly dispersed in the first volatile solvent, obtains surfactant mixed dispersion liquid；
Step 2: oxidant is dissolved in the second volatile solvent, oxidizing agent solution is obtained；
Step 3: oxidizing agent solution is mixed with surfactant mixed dispersion liquid, simultaneously mechanical stirring is heated, obtains mixing molten
Liquid；
Step 4: polymer monomer is added in the mixed solution that third step obtains, continue heating and mechanical stirring, polymer
In-situ polymerization occurs in a solvent for monomer, forms thermoelectric composite material mixed solution；
Step 5: thermoelectric composite material mixed solution is added in third volatile solvent, pass through multiple water bath sonicator, pumping
Filter is washed, and clean thermoelectric composite material solution is obtained；
Step 6: dispersing agent is added in clean thermoelectric composite material solution, by ultrasound, filters, it is multiple to obtain p-type thermoelectricity
Condensation material solution；
Step 7: yarn is infiltrated in p-type thermoelectric composite material solution, dries, then penetrate yarn in space fabric；
Step 8: macromolecule polymer solution ambient separation to be injected to the yarn for penetrating fabric, then dry, thermoelectricity is made and turns
Change space fabric.
2. the preparation method of heat to electricity conversion space fabric as described in claim 1, which is characterized in that in the first step
The third volatile solvent in the second volatile solvent, the 5th step in one volatile solvent, second step is ethyl alcohol, first
Any one or a few mixture in alcohol, acetone and water；Ionic surface active agent in the first step is dodecyl
Any one or a few mixture in sodium sulfonate, neopelex and cetyl trimethylammonium bromide；It is described
Inorganic thermoelectric material in the first step is the mixture of multi-walled carbon nanotube, single-walled carbon nanotube or both；In the second step
Oxidant be ferric trichloride, p-methyl benzenesulfonic acid iron or both mixture.
3. the preparation method of heat to electricity conversion space fabric as described in claim 1, which is characterized in that in the first step from
The ratio of sub- surfactant, inorganic thermoelectric material and the first volatile solvent is 1g:
(0.5~3) g:(10~20) mL；In the second step ratio of oxidant and the second volatile solvent be 1g:(1~
3)mL；The ratio of thermoelectric composite material solution and third volatile solvent is 1mg:(1~2 in 5th step) mL.
4. the preparation method of heat to electricity conversion space fabric as described in claim 1, which is characterized in that ultrasonic in the first step
Power be 220~300W, ultrasonic time be 30~40min, ultrasonic temperature be 5~10 DEG C.
5. the preparation method of heat to electricity conversion space fabric as described in claim 1, which is characterized in that the third step, the 4th
Heating temperature in step is 50~70 DEG C, and heating time is 7~18h, and mechanical stirring speed is 1000~1500 revolutions per seconds.
6. the preparation method of heat to electricity conversion space fabric as described in claim 1, which is characterized in that poly- in the 4th step
Monomer adduct is the mixture of aniline, pyrroles and thiophene or both.
7. the preparation method of heat to electricity conversion space fabric as described in claim 1, which is characterized in that water-bath in the 5th step
The ultrasonic power of ultrasound is 180~220W, and ultrasonic time is 20~40min, and ultrasonic temperature is room temperature.
8. the preparation method of heat to electricity conversion space fabric as described in claim 1, which is characterized in that point in the 6th step
Powder is the mixture of dimethyl sulfoxide, methyl sulfoxide or both；Body of the dispersing agent in clean thermoelectric composite material solution
Product percentage is 2%~5%.
9. the preparation method of heat to electricity conversion space fabric as described in claim 1, which is characterized in that the height in the 8th step
Molecularly Imprinted Polymer solution is the mixture of one or more of polyetherimide, polyvinyl alcohol and polyvinylpyrrolidone；Institute
Stating than the temperature dried in the 8th step is 40-60 DEG C, and drying time is 1-2 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910160372.3A CN109944063A (en) | 2019-03-04 | 2019-03-04 | A kind of preparation method of heat to electricity conversion space fabric |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910160372.3A CN109944063A (en) | 2019-03-04 | 2019-03-04 | A kind of preparation method of heat to electricity conversion space fabric |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109944063A true CN109944063A (en) | 2019-06-28 |
Family
ID=67007842
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910160372.3A Pending CN109944063A (en) | 2019-03-04 | 2019-03-04 | A kind of preparation method of heat to electricity conversion space fabric |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109944063A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016151634A1 (en) * | 2015-03-25 | 2016-09-29 | 国立大学法人奈良先端科学技術大学院大学 | Functional element having cell series structure of π-type thermoelectric conversion elements, and method for manufacturing same |
| CN108103634A (en) * | 2017-10-30 | 2018-06-01 | 东华镜月（苏州）纺织技术研究有限公司 | The preparation method of textile structural thermoelectric conversion element |
| CN108470818A (en) * | 2018-03-13 | 2018-08-31 | 东华大学 | A kind of preparation method of flexible film-like thermo-electric device |
| CN109295707A (en) * | 2018-10-10 | 2019-02-01 | 东华大学 | A kind of flexible thermal conducting nanofiber film and its preparation and application |
-
2019
- 2019-03-04 CN CN201910160372.3A patent/CN109944063A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016151634A1 (en) * | 2015-03-25 | 2016-09-29 | 国立大学法人奈良先端科学技術大学院大学 | Functional element having cell series structure of π-type thermoelectric conversion elements, and method for manufacturing same |
| CN108103634A (en) * | 2017-10-30 | 2018-06-01 | 东华镜月（苏州）纺织技术研究有限公司 | The preparation method of textile structural thermoelectric conversion element |
| CN108470818A (en) * | 2018-03-13 | 2018-08-31 | 东华大学 | A kind of preparation method of flexible film-like thermo-electric device |
| CN109295707A (en) * | 2018-10-10 | 2019-02-01 | 东华大学 | A kind of flexible thermal conducting nanofiber film and its preparation and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107146842B (en) | Self-supporting flexibility PEDOT nanofiber/SWCNTs composite thermoelectric material film and preparation method thereof | |
| Zhao et al. | Advances in organic thermoelectric materials and devices for smart applications | |
| CN108470818A (en) | A kind of preparation method of flexible film-like thermo-electric device | |
| Zhang et al. | Synergistic work of photo-thermoelectric and hydroelectric effects of hierarchical structure photo-thermoelectric textile for solar energy harvesting and solar steam generation simultaneously | |
| Song et al. | Silk-inspired stretchable fiber-shaped supercapacitors with ultrahigh volumetric capacitance and energy density for wearable electronics | |
| Luo et al. | In-situ polymerization of PPy/cellulose composite sponge with high elasticity and conductivity for the application of pressure sensor | |
| Shao et al. | Fabrication of polyaniline/graphene/polyester textile electrode materials for flexible supercapacitors with high capacitance and cycling stability | |
| CN110736559A (en) | Flexible temperature-pressure sensor and preparation method and application thereof | |
| Huang et al. | Functional flexible and wearable supercapacitors | |
| CN103050192B (en) | A kind of elastic conductor based on nano silver wire and its preparation method and application | |
| CN110136968A (en) | Electric polypyrrole hydrogel electrode material, preparation method and stretchable supercapacitor | |
| CN101781459A (en) | Graphene/polyaniline conductive composite material and preparation method thereof | |
| CN105140042B (en) | A kind of preparation method and applications of bacteria cellulose/activated carbon fiber/CNT membrane material | |
| CN106012544A (en) | Graphene/polyaniline conductive cotton fabric production method | |
| CN109295698A (en) | A kind of preparation method of the uvioresistant cotton fabric of conductive energy | |
| WO2016151634A1 (en) | Functional element having cell series structure of π-type thermoelectric conversion elements, and method for manufacturing same | |
| CN106971865B (en) | A kind of Polymerization of Polyaniline/carbon Nanotube with high specific capacitance/cotton fabric composite and flexible electrode and its preparation and application | |
| Villanueva et al. | Mechanical, in-situ electrical and thermal properties of wearable conductive textile yarn coated with polypyrrole/carbon black composite | |
| CN104538201A (en) | Method for preparing textile fiber and PPy nanowire composite super capacitor | |
| CN103066314A (en) | Fabric morphological polymer battery and preparation method thereof | |
| CN107195470B (en) | The nanotube-shaped composite material and preparation method of nickel cobalt iron ternary metal oxide | |
| CN102532894B (en) | Preparation method of graphite oxide/polypyrrole composite material | |
| CN102561042A (en) | Preparation method for dendritic-nanometer-structure polyaniline air-sensitive sensor | |
| Liu et al. | A flexible and knittable fiber supercapacitor for wearable energy storage with high energy density and mechanical robustness | |
| CN108611792A (en) | A kind of stretchable conductive material and application thereof based on Modal knitted fabric |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190628 |