CN108963066A - A kind of preparation method of flexibility thermoelectric material - Google Patents
A kind of preparation method of flexibility thermoelectric material Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of flexible thermoelectric material, which comprises the following steps: 1) preparation of thermoelectric material；1.1) sulfonic acid solutions are mixed with PEDOT:PSS dispersion liquid, is stirred, obtain the sample conducting solution of doping PEDOT:PSS dispersion liquid；1.2) conducting solution obtained in step 1.1) is coated on pretreated substrate, after carrying out heated at constant temperature processing, cooled to room temperature；2) post-processing of thermoelectric material；2.1) hydrazine hydrate solution is mixed with dimethyl sulfoxide, is stirred, obtain mixture A；2.2) mixture A obtained in step 2.1) is uniformly coated on substrate heat treated obtained in step 1.2), after being handled by heated at constant temperature, cooled to room temperature obtains target product.
Description
Technical field
The present invention relates to Organic thermoelectric material field, the preparation method of specifically a kind of flexibility thermoelectric material.
Background technique
Thermal energy and the directly mutual inversion of phases of electric energy can be had huge application potential by thermoelectric material in Waste Heat Recovery.
Conducting polymer has low thermal conductivity, abundant raw material, cheap, easy processing molding etc. excellent compared to traditional inorganic thermoelectric material
Point, flexible bendable characteristic apply also for preparation wearable electronic.So flexibility thermoelectric material and device research at present
Field receives extensive concern in the industry.
Wherein, poly- (3,4- Ethylenedioxy Thiophene)-poly- (styrene sulfonic acid) (PEDOT:PSS) is because of its lower thermal conductivity
Rate and excellent flexible characteristic after molding, have broad application prospects in thermoelectric material field.
But thermoelectric material conductivity prepared by PEDOT:PSS is lower than 1S/cm, Seebeck coefficient is lower than 15 μ V/K, institute
Greatly to limit its application range.
By the research of a large number of researchers, the distinct methods for improving its thermoelectricity capability have been found, for example, material at
(multiple) solution processing-water cleaning method after type.However post processing mode repeatedly will affect the quality and preparation of product
Repeatability, also will increase its production technology difficulty and the production time, increase industrial cost.
Therefore, being obtained by regulation to PEDOT:PSS solution and simple process after molding has higher pyroelectricity
The flexible thermoelectric material of energy has extremely strong realistic meaning and commercial value.
Summary of the invention
Present invention aim to address problems of the prior art, provide a kind of preparation side of flexible thermoelectric material
Method.
To realize the present invention purpose and the technical solution adopted is that such, a kind of preparation method of flexibility thermoelectric material,
Characterized by comprising the following steps:
1) preparation of thermoelectric material
1.1) sulfonic acid solutions are mixed with PEDOT:PSS dispersion liquid, is stirred, obtain doping PEDOT:PSS dispersion liquid
Sample conducting solution；
1.2) conducting solution obtained in step 1.1) is coated on pretreated substrate, after heated at constant temperature processing,
Cooled to room temperature；
2) post-processing of thermoelectric material
2.1) hydrazine hydrate solution is mixed with dimethyl sulfoxide, after stirring, obtains mixture A；
The concentration of hydrazine hydrate solution is 0.01~0.5vol% in the mixture A；
The concentration of hydrazine hydrate is 80vol% in the hydrazine hydrate solution；
2.2) mixture A obtained in step 2.1) is uniformly coated on base heat treated obtained in step 1.2)
On piece, after being handled by heated at constant temperature, cooled to room temperature obtains target product；
Coated weight is 50~70 μ L/cm on the substrate2。
Further, the sulfonic acid in the step 1.1) include methanesulfonic acid, benzene sulfonic acid, 4- chlorobenzenesulfonic acid, 4- hydroxy benzene sulfonic acid,
One of p-methyl benzenesulfonic acid, 4- ethyl phenenyl azochlorosulfonate acid, naphthalene sulfonic acids or camphorsulfonic acid.
Further, the concentration of the sulfonic acid solutions in the step 1.1) is 0.001~0.5mol/L.
Further, the substrate in the step 1.2) includes substrate of glass or plastic, transparent substrate flexible；The plastics
Transparent substrates include polyethylene terephthalate substrate, polyethylene naphthalate substrate or polyimide substrate.
Further, in the heated at constant temperature treatment process in the step 1.2): temperature be 100~150 DEG C, the time be 5~
60min；
In heated at constant temperature treatment process in the step 2.2): temperature is 100~150 DEG C, and the time is 5~60min.
Further, the coating procedure in the step 1.3) and step 2.2) includes spin coating spin-coating method, vacuum filtration, crack
The coating of formula extrusion pressing type, inkjet printing or roll-to-roll printing technology and scraper preparation process；The slit type extrusion pressing type coating, ink-jet
Printing or roll-to-roll printing technology, are directly produced under the cryogenic conditions of room temperature~200 DEG C, without carrying out heat treatment step.
A certain proportion of acid solution is added in the aqueous dispersion liquid of PEDOT:PSS in the explanation of value, the present invention；This
Thermoelectric material prepared by solution can greatly improve its electric conductivity while keep lower thermal conductivity.
Easy solution post-processing and without cleaning process in the present invention, reduces part conductivity within an acceptable range,
But its Seebeck coefficient is substantially increased, its pyroelectricity is made to have obtained biggish promotion；Therefore, the method in the present invention improves
The yields of product, and reduce production cost.
The solution have the advantages that unquestionable, the present invention has the effect that
1) present invention devises a kind of completely new solution formula based on PEDOT:PSS, can prepare work by ink print
Skill, as spin coating spin-coating method (spin coating), slit type extrusion pressing type are coated with (slot die coating), inkjet printing
(inkjet printing) or roll-to-roll printing technology (roll-to-roll printing) etc., take the photograph in room temperature or lower than 200
The low temperature of family name's degree directly prepares the thermoelectric material with excellent conductive capability and mechanical flexibility in substrates of different, and passes through
Easy solution post-processes and without cleaning process, so that the thermoelectricity capability of flexible thermoelectric material has further higher promotion；
2) method in the present invention reduces preparation process and production cycle, reduces production cost, is large scale preparation
Flexible thermoelectric material provides feasible program, for the later period thermo-electric device flexible direction application provide new method.
Detailed description of the invention
Fig. 1 is thermoelectric material production flow diagram；
Fig. 2 is using the processing method in the present invention based on flexible thermo-electric device prepared by PEDOT:PSS；
In figure: Fig. 2 a is flexible thermo-electric device pictorial diagram；Fig. 2 b is flexible thermo-electric device application test chart.
Specific embodiment
Below with reference to embodiment, the invention will be further described, but should not be construed the above-mentioned subject area of the present invention only
It is limited to following embodiments.Without departing from the idea case in the present invention described above, according to ordinary skill knowledge and used
With means, various replacements and change are made, should all include within the scope of the present invention.
Embodiment 1:
PEDOT:PSS is purchased from Heraeus company of Germany, product type PH1000 in embodiment.Sulfonic acid used is purchased from
Adamas Reagent company.Other solvents are purchased from Sinopharm Chemical Reagent Co., Ltd..
A kind of preparation method of flexibility thermoelectric material, which comprises the following steps:
1) preparation of thermoelectric material
1.1) benzene sulfonic acid is mixed with PEDOT:PSS dispersion liquid, is stirred, obtain doping PEDOT:PSS dispersion liquid
Sample conducting solution；
The concentration of the benzene sulfonic acid is 0.06mol/L；
The whipping process are as follows: be put into magnetic stir bar in the reagent bottle prepared, and reagent bottle is placed on magnetic agitation
On device, setting speed is 450~500rpm, is periodically stirred for 10~30min；
1.2) substrate is pre-processed；
The preprocessing process includes cleaning and removing residual processing；
The cleaning process of the substrate includes:
I) square glass substrate that size after segmentation is 15mm × 15mm is numbered, by the glass substrate after number
Be placed on polyfluortetraethylecleaning cleaning bracket, place a stent into capacity be 300ml beaker in, into beaker be added 120ml go from
Sub- water and 5%~10% dish washing liquid, the deionized water there was not glass substrate；
II) container A is sealed with masking foil after, container A is placed in the ultrasonic cleaner equipped with water and is cleaned；
The ultrasonic time is 10min, and the supersonic frequency is 40kHz, and the ultrasonic power is 80W；
III) container A is taken out after, topple over liquid in clean container, replace it with the clean deionized water of equal volume,
After container A is covered masking foil again, it is placed in ultrasonic cleaner and is cleaned；
The step III) it is repeated 3 times；
The ultrasonic time is 10min, and the supersonic frequency is 40kHz, and the ultrasonic power is 80W；
IV) container A is taken out after, topple over liquid in clean container, replace it with the acetone of equal volume, by container A weight
After new covering masking foil, it is placed in ultrasonic cleaner and is cleaned；
The ultrasonic time is 10min, and the supersonic frequency is 40kHz, and the ultrasonic power is 80W；
V) container A is taken out after, topple over liquid in clean container, replace it with the isopropanol that volume there was not substrate at least,
Container A is covered into masking foil, stores cleaned substrate.
The substrate includes: except residual treatment process
VI) by the step V) in be stored in after the substrate in isopropyl acetone takes out, dried up with high pure nitrogen；
VII) substrate after drying is placed in the culture dish of pre- dedusting, culture dish is placed in UV ozone processing instrument,
It is taken out after processing 15min, it is spare.
1.3) conducting solution obtained in step 1.1) is coated on substrate pretreated obtained in step 1.2),
Obtain the substrate of uniform fold conducting solution；
The coating procedure are as follows: by step VII) obtained in the glass substrate crossed of ozone treatment, be placed in the rotation of sol evenning machine
At center, 70~100 μ L sample dispersion liquid of uniform fold in glass substrate opens sol evenning machine and carries out rejection film；The level-one of sol evenning machine
Revolving speed is set as 1500rpm, time 30s, and Second-Stage Rotating Speed is set as 3000rpm, time 3s；
1.4) after substrate obtained in step 1.3) being carried out heated at constant temperature processing, cooled to room temperature；
In the heated at constant temperature treatment process: temperature is 120 DEG C, time 15min；
2) post-processing of thermoelectric material
2.1) hydrazine hydrate solution is mixed with dimethyl sulfoxide, is stirred, obtain mixture A；
The concentration of hydrazine hydrate solution is 0.01~0.5vol% in the mixture A；
In hydrazine hydrate solution, the concentration of the hydrazine hydrate is 80vol%；
2.2) mixture A obtained in step 2.1) is uniformly coated on base heat treated obtained in step 1.3)
On piece places 10min at room temperature；
Coated weight is 50~70 μ L/cm on the substrate2；
2.3) by substrate obtained in step 2.2), after being handled by heated at constant temperature, cooled to room temperature obtains target
Product；
In the heated at constant temperature treatment process: temperature is 120 DEG C, time 15min.
Embodiment 2:
PEDOT:PSS is purchased from Heraeus company of Germany, product type PH1000 in embodiment.Sulfonic acid used is purchased from
Adamas Reagent company.Other solvents are purchased from Sinopharm Chemical Reagent Co., Ltd..
A kind of preparation method of flexibility thermoelectric material, which comprises the following steps:
1) preparation of thermoelectric material
1.1) 4- hydroxy benzene sulfonic acid is mixed with PEDOT:PSS dispersion liquid, is stirred, obtain PEDOT:PSS points of doping
The sample conducting solution of dispersion liquid；
The concentration of the 4- hydroxy benzene sulfonic acid is 0.06mol/L；
The whipping process are as follows: be put into magnetic stir bar in the reagent bottle prepared, and reagent bottle is placed on magnetic agitation
On device, setting speed is 450~500rpm, is periodically stirred for 10~30min；
1.2) substrate is pre-processed；
The preprocessing process includes cleaning and removing residual processing；
The cleaning process of the substrate includes:
I) square glass substrate that size after segmentation is 15mm × 15mm is numbered, by the glass substrate after number
Be placed on polyfluortetraethylecleaning cleaning bracket, place a stent into capacity be 300ml beaker in, into beaker be added 120ml go from
Sub- water and 5%~10% dish washing liquid, the deionized water there was not glass substrate；
II) container A is sealed with masking foil after, container A is placed in the ultrasonic cleaner equipped with water and is cleaned；
The ultrasonic time is 10min, and the supersonic frequency is 40kHz, and the ultrasonic power is 80W；
III) container A is taken out after, topple over liquid in clean container, replace it with the clean deionized water of equal volume,
After container A is covered masking foil again, it is placed in ultrasonic cleaner and is cleaned；
The step III) it is repeated 3 times；
The ultrasonic time is 10min, and the supersonic frequency is 40kHz, and the ultrasonic power is 80W；
IV) container A is taken out after, topple over liquid in clean container, replace it with the acetone of equal volume, by container A weight
After new covering masking foil, it is placed in ultrasonic cleaner and is cleaned；
The ultrasonic time is 10min, and the supersonic frequency is 40kHz, and the ultrasonic power is 80W；
V) container A is taken out after, topple over liquid in clean container, replace it with the isopropanol that volume there was not substrate at least,
Container A is covered into masking foil, stores cleaned substrate.
The substrate includes: except residual treatment process
VI) by the step V) in be stored in after the substrate in isopropyl acetone takes out, dried up with high pure nitrogen；
VII) substrate after drying is placed in the culture dish of pre- dedusting, culture dish is placed in UV ozone processing instrument,
It is taken out after processing 15min, it is spare.
1.3) conducting solution obtained in step 1.1) is coated on substrate pretreated obtained in step 1.2),
Obtain the substrate of uniform fold conducting solution；
The coating procedure are as follows: by step VII) obtained in the glass substrate crossed of ozone treatment, be placed in the rotation of sol evenning machine
At center, 70~100 μ L sample dispersion liquid of uniform fold in glass substrate opens sol evenning machine and carries out rejection film；The level-one of sol evenning machine
Revolving speed is set as 1500rpm, time 30s, and Second-Stage Rotating Speed is set as 3000rpm, time 3s；
1.4) after substrate obtained in step 1.3) being carried out heated at constant temperature processing, cooled to room temperature；
In the heated at constant temperature treatment process: temperature is 120 DEG C, time 15min；
2) post-processing of thermoelectric material
2.1) hydrazine hydrate solution is mixed with dimethyl sulfoxide, is stirred, obtain mixture A；
The concentration of hydrazine hydrate solution is 0.01~0.5vol% in the mixture A；
In hydrazine hydrate solution, the concentration of the hydrazine hydrate is 80vol%；
2.2) mixture A obtained in step 2.1) is uniformly coated on base heat treated obtained in step 1.3)
On piece places 10min at room temperature；
Coated weight is 50~70 μ L/cm on the substrate2；
2.3) by substrate obtained in step 2.2), after being handled by heated at constant temperature, cooled to room temperature obtains target
Product；
In the heated at constant temperature treatment process: temperature is 120 DEG C, time 15min.
Embodiment 3:
PEDOT:PSS is purchased from Heraeus company of Germany, product type PH1000 in embodiment.Sulfonic acid used is purchased from
Adamas Reagent company.Other solvents are purchased from Sinopharm Chemical Reagent Co., Ltd..
A kind of preparation method of flexibility thermoelectric material, which comprises the following steps:
1) preparation of thermoelectric material
1.1) methanesulfonic acid is mixed with PEDOT:PSS dispersion liquid, is stirred, obtain doping PEDOT:PSS dispersion liquid
Sample conducting solution；
The concentration of the methanesulfonic acid is 0.06mol/L；
The whipping process are as follows: be put into magnetic stir bar in the reagent bottle prepared, and reagent bottle is placed on magnetic agitation
On device, setting speed is 450~500rpm, is periodically stirred for 10~30min；
1.2) substrate is pre-processed；
The preprocessing process includes cleaning and removing residual processing；
The cleaning process of the substrate includes:
I) square glass substrate that size after segmentation is 15mm × 15mm is numbered, by the glass substrate after number
Be placed on polyfluortetraethylecleaning cleaning bracket, place a stent into capacity be 300ml beaker in, into beaker be added 120ml go from
Sub- water and 5%~10% dish washing liquid, the deionized water there was not glass substrate；
II) container A is sealed with masking foil after, container A is placed in the ultrasonic cleaner equipped with water and is cleaned；
The ultrasonic time is 10min, and the supersonic frequency is 40kHz, and the ultrasonic power is 80W；
III) container A is taken out after, topple over liquid in clean container, replace it with the clean deionized water of equal volume,
After container A is covered masking foil again, it is placed in ultrasonic cleaner and is cleaned；
The step III) it is repeated 3 times；
The ultrasonic time is 10min, and the supersonic frequency is 40kHz, and the ultrasonic power is 80W；
IV) container A is taken out after, topple over liquid in clean container, replace it with the acetone of equal volume, by container A weight
After new covering masking foil, it is placed in ultrasonic cleaner and is cleaned；
The ultrasonic time is 10min, and the supersonic frequency is 40kHz, and the ultrasonic power is 80W；
V) container A is taken out after, topple over liquid in clean container, replace it with the isopropanol that volume there was not substrate at least,
Container A is covered into masking foil, stores cleaned substrate.
The substrate includes: except residual treatment process
VI) by the step V) in be stored in after the substrate in isopropyl acetone takes out, dried up with high pure nitrogen；
VII) substrate after drying is placed in the culture dish of pre- dedusting, culture dish is placed in UV ozone processing instrument,
It is taken out after processing 15min, it is spare.
1.3) conducting solution obtained in step 1.1) is coated on substrate pretreated obtained in step 1.2),
Obtain the substrate of uniform fold conducting solution；
The coating procedure are as follows: by step VII) obtained in the glass substrate crossed of ozone treatment, be placed in the rotation of sol evenning machine
At center, 70~100 μ L sample dispersion liquid of uniform fold in glass substrate opens sol evenning machine and carries out rejection film；The level-one of sol evenning machine
Revolving speed is set as 1500rpm, time 30s, and Second-Stage Rotating Speed is set as 3000rpm, time 3s；
1.4) after substrate obtained in step 1.3) being carried out heated at constant temperature processing, cooled to room temperature；
In the heated at constant temperature treatment process: temperature is 120 DEG C, time 15min；
2) post-processing of thermoelectric material
2.1) hydrazine hydrate solution is mixed with dimethyl sulfoxide, is stirred, obtain mixture A；
The concentration of hydrazine hydrate solution is 0.01~0.5vol% in the mixture A；
In hydrazine hydrate solution, the concentration of the hydrazine hydrate is 80vol%；
2.2) mixture A obtained in step 2.1) is uniformly coated on base heat treated obtained in step 1.3)
On piece places 10min at room temperature；
Coated weight is 50~70 μ L/cm on the substrate2.
2.3) by substrate obtained in step 2.2), after being handled by heated at constant temperature, cooled to room temperature obtains target
Product；
In the heated at constant temperature treatment process: temperature is 120 DEG C, time 15min.
Embodiment 4:
PEDOT:PSS is purchased from Heraeus company of Germany, product type PH1000 in embodiment.Sulfonic acid used is purchased from
Adamas Reagent company.Other solvents are purchased from Sinopharm Chemical Reagent Co., Ltd..
A kind of preparation method of flexibility thermoelectric material, which comprises the following steps:
1) preparation of thermoelectric material
1.1) naphthalene sulfonic acids is mixed with PEDOT:PSS dispersion liquid, is stirred, obtain doping PEDOT:PSS dispersion liquid
Sample conducting solution；
The concentration of the naphthalene sulfonic acids is 0.06mol/L；
The whipping process are as follows: be put into magnetic stir bar in the reagent bottle prepared, and reagent bottle is placed on magnetic agitation
On device, setting speed is 450~500rpm, is periodically stirred for 10~30min；
1.2) substrate is pre-processed；
The preprocessing process includes cleaning and removing residual processing；
The cleaning process of the substrate includes:
I) square glass substrate that size after segmentation is 15mm × 15mm is numbered, by the glass substrate after number
Be placed on polyfluortetraethylecleaning cleaning bracket, place a stent into capacity be 300ml beaker in, into beaker be added 120ml go from
Sub- water and 5%~10% dish washing liquid, the deionized water there was not glass substrate；
II) container A is sealed with masking foil after, container A is placed in the ultrasonic cleaner equipped with water and is cleaned；
The ultrasonic time is 10min, and the supersonic frequency is 40kHz, and the ultrasonic power is 80W；
III) container A is taken out after, topple over liquid in clean container, replace it with the clean deionized water of equal volume,
After container A is covered masking foil again, it is placed in ultrasonic cleaner and is cleaned；
The step III) it is repeated 3 times；
The ultrasonic time is 10min, and the supersonic frequency is 40kHz, and the ultrasonic power is 80W；
IV) container A is taken out after, topple over liquid in clean container, replace it with the acetone of equal volume, by container A weight
After new covering masking foil, it is placed in ultrasonic cleaner and is cleaned；
The ultrasonic time is 10min, and the supersonic frequency is 40kHz, and the ultrasonic power is 80W；
V) container A is taken out after, topple over liquid in clean container, replace it with the isopropanol that volume there was not substrate at least,
Container A is covered into masking foil, stores cleaned substrate.
The substrate includes: except residual treatment process
VI) by the step V) in be stored in after the substrate in isopropyl acetone takes out, dried up with high pure nitrogen；
VII) substrate after drying is placed in the culture dish of pre- dedusting, culture dish is placed in UV ozone processing instrument,
It is taken out after processing 15min, it is spare.
1.3) conducting solution obtained in step 1.1) is coated on substrate pretreated obtained in step 1.2),
Obtain the substrate of uniform fold conducting solution；
The coating procedure are as follows: by step VII) obtained in the glass substrate crossed of ozone treatment, be placed in the rotation of sol evenning machine
At center, 70~100 μ L sample dispersion liquid of uniform fold in glass substrate opens sol evenning machine and carries out rejection film；The level-one of sol evenning machine
Revolving speed is set as 1500rpm, time 30s, and Second-Stage Rotating Speed is set as 3000rpm, time 3s；
1.4) after substrate obtained in step 1.3) being carried out heated at constant temperature processing, cooled to room temperature；
In the heated at constant temperature treatment process: temperature is 120 DEG C, time 15min；
2) post-processing of thermoelectric material
2.1) hydrazine hydrate solution is mixed with dimethyl sulfoxide, is stirred, obtain mixture A；
The concentration of hydrazine hydrate solution is 0.01~0.5vol% in the mixture A；
In hydrazine hydrate solution, the concentration of the hydrazine hydrate is 80vol%；
2.2) mixture A obtained in step 2.1) is uniformly coated on base heat treated obtained in step 1.3)
On piece places 10min at room temperature；
Coated weight is 50~70 μ L/cm on the substrate2.
2.3) by substrate obtained in step 2.2), after being handled by heated at constant temperature, cooled to room temperature obtains target
Product；
In the heated at constant temperature treatment process: temperature is 120 DEG C, time 15min.
Experimental result:
Product obtained in Examples 1 to 4 is tested, specifically includes the following steps:
1) sample sheet resistance is measured using multimeter (keithley2400), utilizes step instrument (Bruker Dimension
EDGE thickness of sample) is measured, conductivity is calculated according to sheet resistance and thickness of sample；
2) sample Seebeck coefficient is measured using thin film thermoelectric tester (MRS-3RT, JouleYacht)；
3) sample power factor is calculated according to the conductivity and Seebeck coefficient that measure.
Obtained test result is as shown in table 1: wherein after benzene sulfonic acid, 4- hydroxy benzene sulfonic acid, methanesulfonic acid, naphthalene sulfonic acids doping simultaneously
The sample power factor of processing is respectively 203.1,162.1,115.8,75.4 μ W/mK2。
Table 1
Claims (6)
1. a kind of preparation method of flexibility thermoelectric material, which comprises the following steps:
1) preparation of thermoelectric material
1.1) sulfonic acid solutions are mixed with PEDOT:PSS dispersion liquid, is stirred, obtain doping PEDOT:PSS dispersion liquid
Sample conducting solution；
1.2) conducting solution obtained in step 1.1) is coated on pretreated substrate, it is natural after heated at constant temperature processing
It is cooled to room temperature；
2) post-processing of thermoelectric material
2.1) hydrazine hydrate solution is mixed with dimethyl sulfoxide, after stirring, obtains mixture A；
The concentration of hydrazine hydrate solution is 0.01~0.5vol% in the mixture A；
The concentration of hydrazine hydrate is 80vol% in the hydrazine hydrate solution.
2.2) mixture A obtained in step 2.1) is uniformly coated on substrate heat treated obtained in step 1.2)
On, after being handled by heated at constant temperature, cooled to room temperature obtains target product；
Coated weight is 50~70 μ L/cm on the substrate2。
2. a kind of preparation method of flexible thermoelectric material according to claim 1 or 2, it is characterised in that: the step
1.1) sulfonic acid in includes methanesulfonic acid, benzene sulfonic acid, 4- chlorobenzenesulfonic acid, 4- hydroxy benzene sulfonic acid, p-methyl benzenesulfonic acid, 4- ethylo benzene sulphur
One of acid, naphthalene sulfonic acids or camphorsulfonic acid.
3. a kind of preparation method of flexible thermoelectric material according to claim 1, it is characterised in that: in the step 1.1)
Sulfonic acid solutions concentration be 0.001~0.5mol/L.
4. a kind of preparation method of flexible thermoelectric material according to claim 1, it is characterised in that: in the step 1.2)
Substrate include substrate of glass or plastic, transparent substrate flexible；The plastic, transparent substrate includes polyethylene terephthalate
Ester group piece, polyethylene naphthalate substrate or polyimide substrate.
5. a kind of preparation method of flexible thermoelectric material according to claim 1, it is characterised in that: in the step 1.2)
Heated at constant temperature treatment process in: temperature be 100~150 DEG C, the time be 5~60min；
In heated at constant temperature treatment process in the step 2.2): temperature is 100~150 DEG C, and the time is 5~60min.
6. a kind of preparation method of flexible thermoelectric material according to claim 1, it is characterised in that: the step 1.3) and
Coating procedure in step 2.2) includes spin coating spin-coating method, vacuum filtration, the coating of slit type extrusion pressing type, inkjet printing or roll-to-roll
Printing technology and scraper preparation process；Slit type extrusion pressing type coating, inkjet printing or roll-to-roll printing technology, room temperature~
It is directly produced under 200 DEG C of cryogenic conditions, without carrying out heat treatment step.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114105838A (en) * | 2021-11-19 | 2022-03-01 | 北京大学深圳研究生院 | Flexible thermoelectric material and preparation method thereof |
| CN116751473A (en) * | 2023-06-20 | 2023-09-15 | 重庆大学 | High-temperature-resistant far infrared coating and preparation method thereof |
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| CN114105838A (en) * | 2021-11-19 | 2022-03-01 | 北京大学深圳研究生院 | Flexible thermoelectric material and preparation method thereof |
| CN116751473A (en) * | 2023-06-20 | 2023-09-15 | 重庆大学 | High-temperature-resistant far infrared coating and preparation method thereof |
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Application publication date: 20181207 |