CN109119528A - A kind of carbon nanotube and the preparation method and application thereof of charge-transfer complex modification - Google Patents
A kind of carbon nanotube and the preparation method and application thereof of charge-transfer complex modification Download PDFInfo
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Abstract
本发明公开一种电荷转移复合物修饰的碳纳米管及其制备方法与应用，所述电荷转移复合物的结构式为其中，X1、X2、X3、X4独立地选自H、F中的一种。以所述电荷转移复合物修饰的碳纳米管作为热电材料，用热电材料的分散液在柔性衬底上制备出热电薄膜阵列；用铜箔将热电薄膜进行串联，用铜箔从所述柔性衬底首端的热电薄膜处引出热端，用铜箔从所述柔性衬底末端的热电薄膜处引出冷端，然后将柔性衬底卷成筒状，即制得有机热电器件。电荷转移复合物能在分子间起到高效的电荷转移作用，利于半导体材料间的电荷传输，提高碳纳米管的热电性能。本发明有机热电器件的制备方法简单、易操作，有利于实现工业化生产。
The invention discloses a carbon nanotube modified by a charge transfer compound and a preparation method and application thereof. The structural formula of the charge transfer compound is as follows: Wherein, X 1 , X 2 , X 3 and X 4 are independently selected from one of H and F. Using the carbon nanotubes modified by the charge transfer compound as a thermoelectric material, a thermoelectric thin film array is prepared on a flexible substrate with a dispersion of the thermoelectric material; the thermoelectric thin films are connected in series with copper foil, and copper foil is used from the flexible substrate. The hot end is drawn from the thermoelectric film at the bottom end, the cold end is drawn from the thermoelectric film at the end of the flexible substrate with copper foil, and then the flexible substrate is rolled into a cylindrical shape to obtain an organic thermoelectric device. The charge transfer complex can play an efficient charge transfer function between molecules, which is beneficial to the charge transfer between semiconductor materials and improves the thermoelectric properties of carbon nanotubes. The preparation method of the organic thermoelectric device of the invention is simple and easy to operate, and is favorable for realizing industrialized production.
Description
Technical field
The present invention relates to the carbon nanometers that organic thermo-electric device technical field more particularly to a kind of charge-transfer complex are modified
Pipe and the preparation method and application thereof.
Background technique
With the quickening of whole world process of industrialization, the energy consumption in global range is also being constantly increasing.50% with
On industrial production used in thermal energy all dissipate in air without meaning, meanwhile, it is raw in order to cool down building and industry
The a large amount of energy can also be expended by producing equipment.Therefore, how effectively to recycle industrial waste heat and efficiently realize heat
Can with the conversion of the other forms energy, at science and industry urgent problem to be solved.
Thermoelectric material can directly mutually convert thermal energy with electric energy, have in Waste Heat Recovery and green refrigeration field huge
Big application potential.Compared to inorganic block thermoelectric material, flexible thermoelectric material has many advantages, such as bent, small in size, light weight,
Apply also for preparation wearable electronic.Carbon-based thermoelectric material is nontoxic and abundant raw materials, solution processable, and can realize
High-energy conversion efficiency.The performance for further increasing carbon nanotube base thermoelectricity material, it is mutual to the efficient thermal energy of realization and electric energy
Conversion has important application value and scientific meaning.Power factor P=S2δ (S: Seebeck coefficient, δ: conductivity), S and δ are these
The relationship for that length that disappear；The currently used method for improving conducting material thermoelectricity performance has chemical doping, physics compound and synthesizing new knot
The methods of structure, however, above method largely can all influence the S and δ of material simultaneously, the thermoelectricity capability for causing the material final is several
Do not have greatly improved.
Therefore, the existing technology needs to be improved and developed.
Summary of the invention
In view of above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a kind of carbon of charge-transfer complex modification
Nanotube and the preparation method and application thereof, it is intended to which solving existing thermoelectricity capability improved method causes the thermoelectricity parameter of thermoelectric material same
Shi Bianhua, and final thermoelectricity capability is almost without promotion, and the problem of can not achieve high-energy conversion efficiency.
Technical scheme is as follows:
The carbon nanotube of a kind of charge-transfer complex modification, wherein the structural formula of the charge-transfer complex isWherein, X1、X2、X3、X4Independently selected from one of H, F.
The carbon nanotube of the charge-transfer complex modification, wherein X1=X2=X3=X4=H or X1=X2=X3=
X4=F.
The carbon nanotube of the charge-transfer complex modification, wherein the carbon nanotube is single-walled carbon nanotube.
The carbon nanotube of the charge-transfer complex modification, wherein the carbon based on charge-transfer complex modification is received
The total weight of mitron, the content of the charge-transfer complex are less than or equal to 5wt%, and the content of the charge-transfer complex
It is not 0.
A kind of preparation method of the carbon nanotube of charge-transfer complex modification as described above, wherein comprising steps of
A, in a solvent by carbon nanotube dispersion, first ultrasound 5-15h, then magnetic agitation 24-72h, obtains uniform carbon
Nanotube dispersion liquid；
B, TTF, four cyano benzoquinone's diformazan alkyl compound are carried out respectively using solvent identical with step A molten
Solution, the molar ratio then according to TTF and four cyano benzoquinone's diformazan alkyl compound are that 0.7-1.5:1 mixes two kinds of solution
It closes, obtains charge-transfer complex solution；
Wherein, the structural formula of TTF isThe structural formula of the four cyano benzoquinone diformazan alkyl compound
ForX1、X2、X3、X4Independently selected from one of H, F；
C, it is multiple to obtain electric charge transfer by ultrasound 0.5-2h after mixing carbon nano tube dispersion liquid with charge-transfer complex solution
The carbon nano tube dispersion liquid for closing object modification, is removed under reduced pressure solvent, dry, obtains the carbon nanotube of charge-transfer complex modification.
The preparation method of the carbon nanotube of the charge-transfer complex modification, wherein in step A, the solvent is
Chlorobenzene or methylene chloride.
A kind of preparation method of organic thermo-electric device, wherein comprising steps of
D, thermal electric film array is prepared on flexible substrates with the dispersion liquid of thermoelectric material, the thermoelectric material is as above
The carbon nanotube of the charge-transfer complex modification；
F, thermal electric film is connected with copper foil, draws heat from the thermal electric film of the flexible substrate head end with copper foil
End, draws cold end with copper foil from the thermal electric film of the flexible substrate end, flexible substrate is then rolled into tubular, is obtained
Organic thermo-electric device.
The preparation method of organic thermo-electric device, wherein in step F, with copper foil by thermal electric film with end to end
Mode connect.
The preparation method of organic thermo-electric device, wherein the flexible substrate is Kapton or polyester
Film.
A kind of organic thermo-electric device, wherein be made using the preparation method of organic thermo-electric device as described above.
The utility model has the advantages that the present invention is by modifying carbon nanotube with charge-transfer complex, it can be in hardly shadow
In the case where ringing the original S of carbon nanotube, its δ is improved, to improve its conversion efficiency of thermoelectric；The charge-transfer complex can be
It is intermolecular to form efficient electric charge transfer effect, be conducive to the charge transmission between semiconductor material, greatly improve carbon nanometer
The thermoelectricity capability of pipe is, it can be achieved that efficient conversion efficiency of thermoelectric.The carbon nanotube of the charge-transfer complex modification is a kind of
New thermoelectric materials can generate more electric energy using flexibility thermo-electric device made of the material in the case where low calorie, have
Conducive to the utilization efficiency improved to environment waste heat.The preparation method of organic thermo-electric device of the invention is simple, easy to operate, is conducive to
Realize industrialized production.
Detailed description of the invention
Fig. 1 is the schematic diagram of internal structure of the organic thermo-electric device of the present invention.
Fig. 2 is the SEM figure of the carbon nano-tube film of TTF-TCNQ modification in the embodiment of the present invention 1.
Fig. 3 is the carbon nano-tube film thermo-electric device of TTF-TCNQ modification in the embodiment of the present invention 1 when the temperature difference is 9.2 DEG C
U-I curve and P-I curve.
Fig. 4 is TTF-F in the embodiment of the present invention 24The SEM figure of the carbon nano-tube film of TCNQ modification.
Fig. 5 is TTF-F in the embodiment of the present invention 24The carbon nano-tube film thermo-electric device of TCNQ modification is 22.9 in the temperature difference
DEG C when U-I curve and P-I curve.
Fig. 6 is the SEM figure of the carbon nano-tube film of TTF modification in the embodiment of the present invention 3.
Fig. 7 is the △ V- △ T curve of the carbon nano-tube film thermo-electric device of TTF modification in the embodiment of the present invention 3.
Specific embodiment
The present invention provides a kind of carbon nanotube and the preparation method and application thereof of charge-transfer complex modification, to make this hair
Bright purpose, technical solution and effect are clearer, clear, and the present invention is described in more detail below.It should be appreciated that herein
Described specific embodiment is only used to explain the present invention, is not intended to limit the present invention.
A kind of carbon nanotube of charge-transfer complex modification of the present invention, wherein the electric charge transfer is multiple
Close object structural formula beWherein, X1、X2、X3、X4Independently selected from H,
One of F.
The carbon nanotube of charge-transfer complex modification of the invention is a kind of new thermoelectric materials, is made using the material
Flexible thermo-electric device more electric energy can be generated in the case where low calorie, be conducive to improve effect utilized to environment waste heat
Rate.
Specifically, the charge-transfer complex is named as TTF-FnTCNQ, wherein n refers to that the single electric charge transfer is multiple
Containing the number of F atom in adduct molecule, n=0,1,2,3,4.Work as X1=X2=X3=X4When=H, the electric charge transfer is compound
Object isThe title TTF-F of the charge-transfer complex0TCNQ or TTF-TCNQ；
Work as X1=X2=X3=X4=F, the charge-transfer complex areThe charge
The title TTF-F of transfer complex4TCNQ.Preferably, X1=X2=X3=X4=H or X1=X2=X3=X4=F.
Further, the carbon nanotube is single-walled carbon nanotube.
Further, the total weight of the carbon nanotube based on charge-transfer complex modification, the charge-transfer complex
Content is less than or equal to 5wt%, and the content of the charge-transfer complex is not 0；Preferably, the charge-transfer complex
Content is 0.05-1wt%；For example, 0.07wt%.
The present invention also provides a kind of preparation methods of the carbon nanotube of charge-transfer complex modification, wherein comprising steps of
A, carbon nanotube is dispersed in solvent (preferably chlorobenzene or methylene chloride), first ultrasound 5-15h (preferably 10h), connects
Magnetic agitation 24-72h (preferably 48h), obtain uniform carbon nano tube dispersion liquid；
B, TTF, four cyano benzoquinone's diformazan alkyl compound are carried out respectively using solvent identical with step A molten
Solution, the molar ratio then according to TTF and four cyano benzoquinone diformazan alkyl compound are 0.7-1.5:1 (preferably 1:1) by two
Kind solution mixing, obtains charge-transfer complex solution；
Wherein, the structural formula of TTF isThe structural formula of the four cyano benzoquinone diformazan alkyl compound
ForX1、X2、X3、X4Independently selected from one of H, F；
C, ultrasound 0.5-2h (preferably 1h), obtains electricity after mixing carbon nano tube dispersion liquid with charge-transfer complex solution
The carbon nano tube dispersion liquid of lotus transfer complex modification, is removed under reduced pressure solvent, dry, obtains the carbon of charge-transfer complex modification
Nanotube.
The present invention also provides a kind of preparation methods of organic thermo-electric device, wherein comprising steps of
D, thermal electric film array is prepared on flexible substrates with the dispersion liquid of thermoelectric material, the thermoelectric material is as above
The carbon nanotube of the charge-transfer complex modification；
F, thermal electric film is connected with copper foil, draws heat from the thermal electric film of the flexible substrate head end with copper foil
End, draws cold end with copper foil from the thermal electric film of the flexible substrate end, flexible substrate is then rolled into tubular, is obtained
Organic thermo-electric device.
Further, in step F, thermal electric film is connected in end to end mode with copper foil.
Further, the flexible substrate is Kapton or polyester film.
The present invention also provides a kind of organic thermo-electric devices, wherein using the preparation side of organic thermo-electric device as described above
Method is made.Specifically, the internal structure of organic thermo-electric device produced by the present invention is as shown in Figure 1, comprising: flexible substrate 1；Thermoelectricity
Film 2 is the carbon nano-tube film of charge-transfer complex modification；The connecting material 3 of thermal electric film is copper foil；Cold lead 4 is
Copper foil；Hot end lead 5 is copper foil.
Below by embodiment, the present invention is described in detail.
The preparation and its application of the carbon nanotube of 1 TTF-TCNQ of embodiment modification
(1) 8mg single-walled nanotube (SWCNT) is weighed respectively and measures 8mL chlorobenzene is placed in ultrasound 10h in 25mL round-bottomed flask
Afterwards, the SWCNT dispersion liquid that concentration is 1mg/mL is transferred to magnetic agitation 48h in 10mL reagent bottle with disposable plastic dropper,
Obtain uniform SWCNT dispersion liquid；
(2) tetrathiafulvalene (Tetrathiafulvalene, TTF), 7,7,8,8- four cyano benzoquinone's diformazans are weighed
Alkane (7,7,8,8-Tetracyanoquinodimethane, TCNQ) each 1mg, is respectively placed in 5mL reagent bottle, and respectively measure
5mL chlorobenzene is added in reagent bottle, and compound concentration is 1mg/5mL TTF solution and TCNQ solution respectively, by TTF solution and TCNQ
Solution is 1:1 mixing with molar ratio, obtains TTF-TCNQ solution, concentration 1mg/5mL；
(3) after the TTF-TCNQ solution that step (2) obtains being diluted to 1mg/60mL, pipetting 336 μ L concentration is 1mg/
It is mixed in reagent bottle where the SWCNT dispersion liquid of 60mL TTF-TCNQ solution addition step (1) with SWCNT dispersion liquid, ultrasound
1h obtains the carbon nano tube dispersion liquid of TTF-TCNQ modification；The carbon nanotube point of TTF-TCNQ modification is removed at reduced pressure conditions
Chlorobenzene in dispersion liquid, and be dried, the carbon nanotube of TTF-TCNQ modification can be obtained.
With polyimides (Polyimide, PI) film as flexible substrate, by TTF- made from the present embodiment step (3)
The carbon nano tube dispersion liquid of TCNQ modification prepares the carbon nanotube of TTF-TCNQ modification on flexible substrates by the way of drop coating
Membrane array is connected the carbon nano-tube film that TTF-TCNQ is modified in end to end mode with copper foil after film is dry, and
Hot end and cold end are drawn from the carbon nano-tube film that the TTF-TCNQ of the head end of flexible substrate and end is modified respectively with copper foil,
Then flexible substrate is rolled into tubular, obtains the carbon nano-tube film thermo-electric device of TTF-TCNQ modification.To TTF- obtained
The carbon nano-tube film of TCNQ modification carries out field emission scanning electron microscope (Field emission scanning
Electron microscope, abbreviation SEM) test, SEM figure is as shown in Figure 2.The carbon of TTF-TCNQ obtained modification is received
Mitron thin film thermoelectric device is tested, when the temperature difference is 9.2 DEG C, the voltage-current curve (i.e. U-I curve) and function that measure
Rate-current curve (i.e. P-I curve) is as shown in Figure 3；It is found that the producible maximum power of the device is when the temperature difference is 9.2 DEG C
4.29nW。
2 TTF-F of embodiment4The preparation and its application of the carbon nanotube of TCNQ modification
(1) 8mg single-walled nanotube (SWCNT) is weighed respectively and measures 8mL chlorobenzene is placed in ultrasound 10h in 25mL round-bottomed flask
Afterwards, concentration is transferred to magnetic agitation 48h in 10mL reagent bottle with disposable plastic dropper for 1mg/mL SWCNT dispersion liquid, obtained
To uniform SWCNT dispersion liquid；
(2) tetrathiafulvalene (Tetrathiafulvalene, TTF), 2,3,5,6- tetra- fluoro- 7,7' are weighed respectively, 8,8'-
Four cyanogen dimethyl-parabenzoquinones (2,3,5,6-Tetrafluoro-7,7,8,8-tetracyanoquinodimethane, F4TCNQ)
Each 1mg is placed in 5mL reagent bottle, and respectively measure 5mL chlorobenzene as solvent, compound concentration be 1mg/5mL TTF solution with
F4TCNQ solution, by TTF solution and F4TCNQ solution is 1:1 mixing with molar ratio, obtains TTF-F4TCNQ solution, concentration are
1mg/5mL；
(3) by the TTF-F of step (2)4After TCNQ solution is diluted to 1mg/60mL, pipetting 336 μ L concentration is 1mg/60mL
TTF-F4It is mixed in reagent bottle where the SWCNT dispersion liquid of TCNQ solution addition step (1) with SWCNT dispersion liquid, ultrasonic 1h,
Obtain TTF-F4The carbon nano tube dispersion liquid of TCNQ modification；TTF-F is removed at reduced pressure conditions4The carbon nanotube point of TCNQ modification
Chlorobenzene in dispersion liquid, and be dried, TTF-F can be obtained4The carbon nanotube of TCNQ modification.
Using PI film as flexible substrate, by TTF-F obtained in the present embodiment step (3)4The carbon nanometer of TCNQ modification
Pipe dispersion liquid prepares TTF-F on flexible substrates by the way of drop coating4The carbon nano-tube film array of TCNQ modification, film are dry
Afterwards, with copper foil by TTF-F4The carbon nano-tube film of TCNQ modification is connected in end to end mode, and is distinguished with copper foil
From the TTF-F of flexible substrate head end and end4Hot end and cold end are drawn at the carbon nano-tube film of TCNQ modification, it then will be flexible
Substrate is rolled into tubular, obtains TTF-F4The carbon nano-tube film thermo-electric device of TCNQ modification.To TTF-F obtained4TCNQ modification
Carbon nano-tube film carry out field emission scanning electron microscope (Field emission scanning electron
Microscope, abbreviation SEM) test, SEM figure is as shown in Figure 4.To TTF-F obtained4The carbon nano-tube film of TCNQ modification
Thermo-electric device is tested, and when the temperature difference is 22.9 DEG C, the U-I curve and P-I curve measured as shown in figure 5, it is found that be in the temperature difference
At 22.9 DEG C, the producible maximum power of the device is 0.58nW.
The preparation and its application of the carbon nanotube of embodiment 3TTF modification
(1) 8mg single-walled nanotube (SWCNT) is weighed respectively and measures 8mL chlorobenzene is placed in ultrasound 10h in 25mL round-bottomed flask
Afterwards, concentration is transferred to magnetic agitation 48h in 10mL reagent bottle with disposable plastic dropper for 1mg/mL SWCNT dispersion liquid, obtained
To uniform SWCNT dispersion liquid；
(2) it weighs tetrathiafulvalene (Tetrathiafulvalene, TTF) 1mg to be placed in 5mL reagent bottle, and measures 5mL
For chlorobenzene as solvent, compound concentration is the TTF solution of 1mg/5mL；
(3) after the TTF solution of step (2) being diluted to 1mg/60mL, it is molten to pipette the TTF that 480 μ L concentration are 1mg/60mL
It is mixed in reagent bottle where the SWCNT dispersion liquid of liquid addition step (1) with SWCNT dispersion liquid, ultrasonic 1h, obtains TTF modification
Carbon nano tube dispersion liquid；The chlorobenzene in the carbon nano tube dispersion liquid of TTF modification is removed at reduced pressure conditions, and is dried,
The carbon nanotube of TTF modification can be obtained.
Using PI film as flexible substrate, by the carbon nano tube dispersion liquid of the TTF prepared modification by the way of drop coating
The carbon nano-tube film array of TTF modification is prepared on flexible substrates, after film is dry, with copper foil by carbon nano-tube film with head and the tail phase
The mode connect is connected, and draws hot end and cold end from the carbon nano-tube film of substrate head end and end respectively with copper foil,
Then flexible substrate is rolled into tubular, obtains the carbon nano-tube film thermo-electric device of TTF modification.To TTF obtained modification
Carbon nano-tube film carries out field emission scanning electron microscope (Field emission scanning electron
Microscope, abbreviation SEM) test, SEM figure is as shown in Figure 6.To the carbon nano-tube film thermoelectricity device of TTF obtained modification
Part is tested, and the linear relationship (i.e. △ V- △ T curve) measured between potential difference-temperature difference is as shown in Figure 7；It is found that working as the temperature difference
When reaching 40 DEG C, the maximum potential difference which generates is up to 4.4mV.
In conclusion carbon nanotube of a kind of charge-transfer complex modification provided by the invention and preparation method thereof with answer
With the present invention can have little influence on carbon nanometer by carrying out rationalization modification to carbon nanotube with charge-transfer complex
In the case where managing original S, its δ is improved, to improve its conversion efficiency of thermoelectric；The charge-transfer complex can be in intermolecular shape
It is acted at efficient electric charge transfer, is conducive to the charge transmission between semiconductor material, greatly improves the thermoelectricity of carbon nanotube
Performance is, it can be achieved that efficient conversion efficiency of thermoelectric.The carbon nanotube of the charge-transfer complex modification is a kind of novel thermoelectricity
Material can generate more electric energy using flexibility thermo-electric device made of the material in the case where low calorie, be conducive to improve
To the utilization efficiency of environment waste heat.The preparation method of organic thermo-electric device of the invention is simple, easy to operate, is advantageously implemented industry
Metaplasia produces.
It should be understood that the application of the present invention is not limited to the above for those of ordinary skills can
With improvement or transformation based on the above description, all these modifications and variations all should belong to the guarantor of appended claims of the present invention
Protect range.
Claims (10)
1. a kind of carbon nanotube of charge-transfer complex modification, which is characterized in that the structural formula of the charge-transfer complex
ForWherein, X1、X2、X3、X4Independently selected from one of H, F.
2. the carbon nanotube of charge-transfer complex modification according to claim 1, which is characterized in that X1=X2=X3=X4
=H or X1=X2=X3=X4=F.
3. the carbon nanotube of charge-transfer complex modification according to claim 1, which is characterized in that the carbon nanotube
For single-walled carbon nanotube.
4. the carbon nanotube of charge-transfer complex modification according to claim 1, which is characterized in that be based on electric charge transfer
The total weight of the carbon nanotube of compound modification, the content of the charge-transfer complex are less than or equal to 5wt%, and the charge
The content of transfer complex is not 0.
5. a kind of preparation method of the carbon nanotube of the charge-transfer complex modification as described in claim 1-4 is any, special
Sign is, comprising steps of
A, in a solvent by carbon nanotube dispersion, first ultrasound 5-15h, then magnetic agitation 24-72h, obtains uniform carbon nanometer
Pipe dispersion liquid；
B, TTF, four cyano benzoquinone's diformazan alkyl compound are dissolved using solvent identical with step A respectively, is connect
According to TTF and the molar ratio of four cyano benzoquinone's diformazan alkyl compound be that 0.7-1.5:1 mixes two kinds of solution, obtain
Charge-transfer complex solution；
Wherein, the structural formula of TTF isThe structural formula of the four cyano benzoquinone diformazan alkyl compound isX1、X2、X3、X4Independently selected from one of H, F；
C, ultrasound 0.5-2h, obtains charge-transfer complex after mixing carbon nano tube dispersion liquid with charge-transfer complex solution
Solvent is removed under reduced pressure in the carbon nano tube dispersion liquid of modification, dry, obtains the carbon nanotube of charge-transfer complex modification.
6. the preparation method of the carbon nanotube of charge-transfer complex modification according to claim 5, which is characterized in that step
In rapid A, the solvent is chlorobenzene or methylene chloride.
7. a kind of preparation method of organic thermo-electric device, which is characterized in that comprising steps of
D, thermal electric film array is prepared on flexible substrates with the dispersion liquid of thermoelectric material, the thermoelectric material is claim
The carbon nanotube of any charge-transfer complex modification of 1-4；
F, thermal electric film is connected with copper foil, draws hot end from the thermal electric film of the flexible substrate head end with copper foil,
Cold end is drawn from the thermal electric film of the flexible substrate end with copper foil, and flexible substrate is then rolled into tubular, has been obtained
Machine thermo-electric device.
8. the preparation method of organic thermo-electric device according to claim 7, which is characterized in that, will be hot with copper foil in step F
Conductive film is connected in end to end mode.
9. the preparation method of organic thermo-electric device according to claim 7, which is characterized in that the flexible substrate is polyamides
Imines film or polyester film.
10. a kind of organic thermo-electric device, which is characterized in that using such as organic thermo-electric device as described in claim 7-9 is any
Preparation method is made.
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| CN117886794A (en) * | 2024-01-10 | 2024-04-16 | 苏州大学 | Organic electronic transfer compound with near infrared two-region photo-thermal characteristic, preparation of nanofiber photo-thermal film and thermal response display application of nanofiber photo-thermal film |
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