CN106229403A - N type thermoelectric material that a kind of acid imide or naphthalimide are combined with CNT and preparation method thereof - Google Patents
N type thermoelectric material that a kind of acid imide or naphthalimide are combined with CNT and preparation method thereof Download PDFInfo
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- CN106229403A CN106229403A CN201610638905.0A CN201610638905A CN106229403A CN 106229403 A CN106229403 A CN 106229403A CN 201610638905 A CN201610638905 A CN 201610638905A CN 106229403 A CN106229403 A CN 106229403A
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- 239000000463 material Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002253 acid Substances 0.000 title abstract description 3
- XJHABGPPCLHLLV-UHFFFAOYSA-N benzo[de]isoquinoline-1,3-dione Chemical compound C1=CC(C(=O)NC2=O)=C3C2=CC=CC3=C1 XJHABGPPCLHLLV-UHFFFAOYSA-N 0.000 title abstract description 3
- 150000003949 imides Chemical class 0.000 title abstract description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000002114 nanocomposite Substances 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- 239000012528 membrane Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- 230000005619 thermoelectricity Effects 0.000 claims description 11
- 238000001291 vacuum drying Methods 0.000 claims description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- UDGSVBYJWHOHNN-UHFFFAOYSA-N n',n'-diethylethane-1,2-diamine Chemical compound CCN(CC)CCN UDGSVBYJWHOHNN-UHFFFAOYSA-N 0.000 claims description 7
- 239000000523 sample Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- -1 sucking filtration Chemical compound 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 230000006837 decompression Effects 0.000 claims description 3
- 150000002460 imidazoles Chemical class 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims 1
- 239000002109 single walled nanotube Substances 0.000 abstract description 16
- 239000002131 composite material Substances 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 238000012805 post-processing Methods 0.000 abstract description 2
- 150000008065 acid anhydrides Chemical class 0.000 abstract 1
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 239000013078 crystal Substances 0.000 abstract 1
- 231100000252 nontoxic Toxicity 0.000 abstract 1
- 230000003000 nontoxic effect Effects 0.000 abstract 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 abstract 1
- 239000002041 carbon nanotube Substances 0.000 description 23
- 239000010408 film Substances 0.000 description 8
- 229920001940 conductive polymer Polymers 0.000 description 4
- 239000002322 conducting polymer Substances 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000002305 electric material Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 229920000128 polypyrrole Polymers 0.000 description 2
- 229910002899 Bi2Te3 Inorganic materials 0.000 description 1
- 229910002665 PbTe Inorganic materials 0.000 description 1
- 229910017629 Sb2Te3 Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- OCGWQDWYSQAFTO-UHFFFAOYSA-N tellanylidenelead Chemical compound [Pb]=[Te] OCGWQDWYSQAFTO-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/856—Thermoelectric active materials comprising organic compositions
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/01—Manufacture or treatment
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Abstract
The present invention relates to a kind of 3,4,9,10 acid imides (PDIN) or Isosorbide-5-Nitrae, 5, N type nano composite thermoelectric materials that 8 naphthalimides (NDIN) are compound with CNT and preparation method thereof, particularly with 3,4,9,10 tetracarboxylic acid anhydrides (PD) or Isosorbide-5-Nitrae, 5,8 naphthalenetetracarbacidic acidic acid anhydrides (ND) are that Material synthesis PDIN or NDIN two kinds has the n little molecule of type conductive characteristic, then the method for preparing n type composite thermoelectric material compound with SWCN (SWCNT).N-type composite thermoelectric material of the present invention is with p type CNT cheap and easy to get as raw material, with DMSO solvent, with NDIN or PDIN for mixing body, the most ultrasonic mixing, and a kind of n type thermoelectric material prepared by high efficiency.The present invention forms a kind of stable n type thermoelectric material by CNT is coated on the surface of PDIN or NDIN crystal.A kind of high performance n type thermoelectric material is not only provided, provides a kind of preparation technology simple and convenient simultaneously, nontoxic, it is not necessary to post processing, there is the Organic thermoelectric material novel preparation method of flexibility.
Description
Technical field
The present invention relates to a kind of n-type nano composite thermoelectric materials and preparation method thereof, particularly a kind of with little molecule PD
Or the thermoelectric material being combined with SWCN after N, N-diethyl ethylenediamine in ND grafting and preparation method thereof.
Background technology
Thermoelectric material, as eco-friendly energy conversion material, has had shown that noticeable application prospect.
Performance for thermoelectric material can pass through nondimensional thermoelectric figure of merit ZT=S2σ T/ κ is evaluated.Wherein, S, σ,
T and κ is respectively Seebeck coefficient, electrical conductivity, absolute temperature and thermal conductivity.
Organic thermoelectricity is only at the starting stage, in addition it is also necessary to about form, chemistry and electronic structure are to three main warm
The impact of electrical quantity carries out the understanding of system.Owing to Organic thermoelectric material is generally of intrinsic lower thermal conductivity, therefore, generally use
Power factor (S2σ) replace the standard that thermoelectric figure of merit is passed judgment on as pyroelectric material performance.Today, from refuse and solar thermal energy
Carry out thermoelectric energy collection in large area and seem unremarkable, but put into some important effort, made to be possibly realized change
Obtain the remotest.
Organic thermoelectric material, as a kind of emerging green energy resource material, has been achieved for quickly developing [A. in recent years
M. Glaudell, et al., Adv. Energy Mater., 5, 1401072 (2015)】.Inorganic compared to traditional
Material, such as Bi2Te3, PbTe, Sb2Te3Deng green material is rare, shortcoming, organic thermoelectricity material such as thermal conductivity is high and toxicity is big
Material has obvious advantage, as abundant raw materials can be mass-produced, flexible, lower thermal conductivity, hypotoxicity and synthesis easily
Deng.In addition, it is necessary to it is emphasized that be with inorganic heat electric material significant difference, use organic focus material to prepare
Thermo-electric device and module have good mechanical flexibility, it is simple to be processed into various shape, prepared by beneficially large area, thus
They application in wearable electronic and various complex environment are made to have huge potentiality [D. S.
Montgomery, et al., Carbon, 96, 778 (2016); M. Piao, et al., Phys. Status
Solidi B, 12, 2529 (2013)】。
In recent years, conducting polymer and their composite are in terms of recycling low-quality used heat and producing electric energy
Application attracted scientists study greatly interest [C. Gao,et al., Compos. Sci. Technol.,
124, 52 (2016); Q. Zhang, et al., Adv. Mater., 26,6829 (2014)], wherein, typical case the most
Conducting polymer include PEDOT (poly (3,4-ethylenedioxythiophene), PANI (polyaniline) with
And PPy(polypyrrole).But conducting polymer major part is p-type thermoelectric material, and scientist to high-performance and stablizes
N-type Organic thermoelectric material seldom study.On the one hand it is owing to the exposure of n-type Organic thermoelectric material in atmosphere can be the most unstable
Fixed, thermoelectricity capability can drastically decline [M. Shim, et al., J. Am. Chem. Soc.,123 , 11512(2001)],
On the other hand the thermoelectricity capability of n-type Organic thermoelectric material is the highest, and its Seebeck coefficient and electrical conductivity can not take into account raising,
Cause power factor prominent [S. M. Kim,et al.,J. Am. Chem. Soc. , 131 , 327(2009)].
The n-type Organic thermoelectric material of most study utilizes PEI to be combined with CNT as electron donor exactly, and pure half
Conductor CNT (CNTs) building-up process is deposited the doping of aerial oxygen and the hydroxyl on CNTs surface or carboxyl etc.
Group causes the defect of conjugated structure, thus, pure semiconductor CNTs have typical p-type feature [P. G. Collins,et al., Science 287, 1801 (2000); K. Bradley, et al., Phys. Rev. Lett.,85, 4361
(2000)】.Electronics is injected CNT by PEI, by its by p-type be transformed into N-shaped [H. Bark,et al., Macromol.
Res., 23, 795 (2015); Y. Nonoguchi, et al., Sci. Rep., 3, 3344 (2013)】.By electricity
Sub-donor doping (such as PEI) carries out the most original electron concentration increasing CNTs, and then realizes the p-type feature of pure CNTs to n-type
The transformation of feature.But owing to PEI has the characteristic of hygroscopicity and absorbing carbon dioxide so that PEI carbon nano tube compound material
Unstable in atmosphere, it is easy to lose N-shaped characteristic, be changed into p-type.And the intrinsic electrical insulation property of macromole PEI can not be kept away
The electrical conductivity lower so as not to result in CNTs.Therefore, being there is great challenge of the organic n-type thermoelectric material of Development of Novel
The work of property.
Recently, people do thermoelectric material research with n-type conducting polymer and have been achieved for development, some n-type conduction height
The Seebeck coefficient of molecule is had outstanding performance and can be reached-600 μ V K-1, but shortcoming to be exactly electrical conductivity the lowest, less than 1 S cm-1。
【B.Russ, et al., Advanced Materials .,3473,3477(2014)】。
Having high match shell coefficient and the n-type Organic thermoelectric material of high conductivity to prepare, we utilize N-shaped simultaneously
Little molecule PDIN or NDIN that conduct electricity is combined with CNT and is prepared for excellent performance and stable n-type Organic thermoelectric material.First
First, we by first carrying out grafting and modifying to organic molecule PD, ND, organic thermoelectricity material that synthesis PDIN and NDIN two kinds is novel
Material, then be combined with PDIN or NDIN and CNT and be prepared for a kind of stable high-performance n-type nano composite thermoelectric materials.With
Time, such n-type nano composite thermoelectric materials can also improve its heat further by adulterating or being combined with organic conductive polymer
Electrical property.Therefore, the synthetic method of this thermoelectric material has significant importance, it should improving conducting material thermoelectricity performance as far as possible
Meanwhile, keep easy and simple to handle, low cost, the efficiency of synthetic method high and the feature such as environmental friendliness, it is simple to prepared by scale amount.
Summary of the invention
It is an object of the invention to provide and a kind of novel there is high performance n-type nano composite thermoelectric materials.The present invention
Also provide for the synthetic method of a kind of described thermoelectric material.Utilize carbon nano-tube material electrical conductivity height, stable in properties and one can be entered
The step feature such as derivatization, it is provided that a kind of using PDIN or NDIN as mixing body, using DMSO as solvent, and then prepares and has n-
The gentleness of type thermoelectric material characteristic, efficient, easy preparation method.The present invention relates to a kind of n-type nano composite thermoelectric materials and
Its preparation method, particularly a kind of with little molecule PD, ND grafting is answered with SWCN after N, N-diethyl ethylenediamine
Thermoelectric material closed and preparation method thereof.
The present invention is to utilize ND, and PD little molecule grafting upper N, N-diethyl ethylenediamine synthesis NDIN and PDIN two kinds has n-type to be led
The little molecule of electrical characteristics, is then combined with SWCN and is prepared as a kind of novel n-type thermoelectric material.N-shaped of the present invention
Thermoelectric material has and highlights very much thermoelectric property and be with p-type CNT cheap and easy to get as raw material, with DMSO solvent, with
NDIN and PDIN for mixing body, the most ultrasonic mixing, a kind of N-type thermoelectric material prepared by high efficiency, the nano combined heat of N-type
The preparation method of electric material comprises the following steps:
(1) by 0.74 g ND or PD, 14.1g imidazoles, 1 g N, N-diethyl ethylenediamine is placed on the round-bottomed flask of 50 mL, adds
Heat is to 130 DEG C, and reflux under nitrogen atmosphere 2 h；
(2) dropping to room temperature after reaction completely, be suspended in methanol, sucking filtration, methanol washs；
(3) product vacuum that sucking filtration obtains is dried to obtain NDIN and PDIN；
(4) a certain amount of NDIN or PDIN organic molecule and CNT are joined in DMSO solvent, utilize Probe Ultrasonic Searching
Instrument ultrasonic disperse 30 min;
(5) ultrasonic disperse 3 h in water bath sonicator instrument put into by the mixed liquor of step (4)；
(6) reactant mixture that step (5) obtains is carried out decompression sucking filtration and obtains black filter membrane；
(7) the black filter membrane that step (6) obtains is put into 50 DEG C of dry 4 h in vacuum drying oven, obtains the nano combined thermoelectricity of n-type
Material.
Reaction described in step (1) refluxes in 2 h in a nitrogen atmosphere, and the time can be 3 h or 4 h, it is therefore preferable to 2
h。
Step (2) is suspended in methanol, sucking filtration, and in methanol washing, methanol can be changed to ethanol, it is preferred that be methanol
Washing.
Described in step (4), a certain amount of NDIN or PDIN organic molecule and CNT are joined DMSO solvent
In, NDIN or PDIN organic molecule can be 2:10,5:10,10:10,20:10,30:10 with the mass ratio of CNT, excellent
Selection of land is 10:10.
Described in step (4), a certain amount of NDIN or PDIN organic molecule and CNT are joined DMSO solvent
In, solvent can be selected else as toluene, ethanol, THF, NMP etc., it is therefore preferable to DMSO.
Described in step (4), a certain amount of NDIN or PDIN organic molecule and CNT are joined DMSO solvent
In, CNT can be SWCN, it is also possible to for multi-walled carbon nano-tubes, it is therefore preferable to SWCN.
Step (4) utilizes in Probe Ultrasonic Searching instrument ultrasonic disperse 30 min, and the ultrasonic disperse time can be 30 min, 1 h, 2 h,
It is preferably 30 min.
Ultrasonic disperse 3 h in water bath sonicator instrument put into by the mixed liquor by step (4) described in step (5), and the time can be
1.5 h, 3 h, 8 h, it is therefore preferable to 8 h.
The black filter membrane that step (6) obtains being put in vacuum drying oven 50 DEG C be dried 4 h described in step (7), obtains n-
In type nano composite thermoelectric materials, the temperature of vacuum drying oven can be 50 DEG C, 60 DEG C, 70 DEG C, and drying time can be 2 h, 3 h, 4
H, 5 h, it is therefore preferable at 50 DEG C, be dried 4 h.
The present invention not only has easy to operate, the feature such as post processing is simple, with low cost and good film-forming property, easily realizes
Prepared by the scale amount of superior performance n-type thermoelectric material, and by the doping of little molecule PDIN or NDIN and SWCN
In conjunction with, the greatly stabilisation n-type character of composite, it is provided that a kind of high performance n-type thermoelectric material preparation method.
N-type thermoelectric material of the present invention has and highlights very much thermoelectric property and be with p-type CNT cheap and easy to get as raw material,
With DMSO solvent, with NDIN and PDIN for mixing body, the most ultrasonic mixing, a kind of N-type thermoelectric material prepared by high efficiency.
The present invention make use of the n-type little molecule PDIN/NDIN height Seebeck coefficient of conduction and single high conductivity dexterously
Prepare novel thermoelectric material so that it is have both high Seebeck coefficient and high conductivity simultaneously.And for preparing high-performance thermoelectricity material
Material provides the high-performance n-type nano composite thermoelectric materials novel preparation method of a kind of mild condition, environmental protection, stable in properties.
Detailed description of the invention
Embodiment 1
(1) by 0.74 g ND or PD, 14.1g imidazoles, 1 g N, N-diethyl ethylenediamine is placed on the round-bottomed flask of 50 mL, adds
Heat is to 130 DEG C, and reflux under nitrogen atmosphere 2 h；
(2) dropping to room temperature after reaction completely, be suspended in methanol, sucking filtration, methanol washs；
(3) product vacuum that sucking filtration obtains is dried to obtain NDIN and PDIN；
(4) 10 mg NDIN or PDIN organic molecule and 10 mg CNTs are joined in 15 mL DMSO solvents,
Utilize Probe Ultrasonic Searching instrument ultrasonic disperse 30 min;
(5) ultrasonic disperse 3 h in water bath sonicator instrument put into by the mixed liquor of step (4)；
(6) reactant mixture that step (5) obtains is carried out decompression sucking filtration and obtains black filter membrane；
(7) the black filter membrane that step (6) obtains is put into 50 DEG C of dry 4 h in vacuum drying oven, obtains the nano combined thermoelectricity of n-type
Material NDIN-SWCNT, its film conductivity is 410 ± 20 S cm-1, Seebeck coefficient is-56 ± 0.5 μ V K-1, PF value
It is 134 ± 9 μ W m-1 K-2.The electrical conductivity of PDIN-SWCNT composite thermoelectric material thin film is 300 ± 10 S cm-1, Seebeck
Coefficient is-51 ± 0.5 μ V K-1, PF value is 78 ± 4 μ W m-1 K-2。
Embodiment 2
Method and steps as described in embodiment 1, simply changes the DMSO solvent in step (4) and makees ethanol.The NDIN-obtained
SWCNT membrane sample Seebeck coefficient respectively electrical conductivity is 400 ± 10 S cm-1, Seebeck coefficient is-46 ± 0.8 μ V K-1, PF value is 85 ± 2 μ W m-1 K-2.The electrical conductivity of PDIN-SWCNT composite thermoelectric material thin film is 310 ± 7 Scm-1,
Seebeck coefficient is-45 ± 0.5 μ V K-1, PF value is 63 ± 3 μ W m-1 K-2。
Embodiment 3
Method and steps as described in embodiment 1, simply changes the DMSO solvent in step (4) and does toluene.The NDIN-obtained
SWCNT membrane sample Seebeck coefficient respectively electrical conductivity is 410 ± 9 S cm-1, Seebeck coefficient is-54 ± 0.8 μ V K-1, PF value is 120 ± 8 μ W m-1 K-2.The electrical conductivity of PDIN-SWCNT composite thermoelectric material thin film is 320 ± 6 S cm-1,
Seebeck coefficient is-45 ± 0.7 μ V K-1, PF value is 63 ± 5 μ W m-1 K-2。
Embodiment 4
Method and steps as described in embodiment 1, simply by 10 mg NDIN in step (4) or PDIN organic molecule and 10
Mg CNT joins in 15 ml DMSO solvents, changes NDIN or PDIN mass and is respectively 20 mg.Obtain NDIN-
SWCNT pyroelectric film electrical conductivity is 190 ± 6 S cm-1, Seebeck coefficient is-59 ± 0.7 μ V K-1, PF value is 68 ± 2 μ W m-1 K-2.The electrical conductivity of the PDIN-SWCNT pyroelectric film material obtained is 180 ± 7 Scm-1, Seebeck coefficient is-52 ± 0.8
μV K-1, PF value is 49 ± 3 μ W m-1 K-2。
Embodiment 5
Method and steps as described in embodiment 1, is simply 20:10 by the little molecule of the step (4) in step (5) with carbon pipe ratio
Ultrasonic disperse 8 h in water bath sonicator instrument put into by mixed liquor.The electrical conductivity of the NDIN-SWCNT composite obtained is 187 ± 6 S
cm-1, Seebeck coefficient is-59 ± 0.9 μ V K-1, PF value is 67 ± 3 μ W m-1 K.The PDIN-SWCNT pyroelectric film material obtained
The electrical conductivity of material is 183 ± 7 S cm-1, Seebeck coefficient is-51 ± 0.8 μ V K-1, PF value is 48 ± 1 μ W m-1 K-2。
Embodiment 6
Method and steps as described in embodiment 1, simply puts into 50 DEG C dry 4 in vacuum drying oven by the black filter membrane in step (7)
H changes into and is placed on 70 DEG C of baking 4 h in vacuum drying oven.The electrical conductivity of the NDIN-SWCNT thermoelectric material film obtained is 410 ± 7 S
cm-1, Seebeck coefficient is-53 ± 0.8 μ V K-1, PF value is 115 ± 6 μ W m-1 K-2.The PDIN-SWCNT pyroelectric film obtained
The electrical conductivity of material is 310 ± 4 S cm-1, Seebeck coefficient is-48 ± 0.8 μ V K-1, PF value is 71 ± 5 μ W m-1 K-2。
Embodiment 7
Method and steps as described in embodiment 1, simply puts into 50 DEG C dry 4 in vacuum drying oven by the black filter membrane in step (7)
H changes into and is placed on 50 DEG C of baking 2 h in vacuum drying oven.The electrical conductivity of the NDIN-SWCNT thermoelectric material film obtained is 380 ± 4 S
cm-1, Seebeck coefficient is-52 ± 0.5 μ V K-1, PF value is 103 ± 2 μ W m-1 K-2.The PDIN-SWCNT pyroelectric film obtained
The electrical conductivity of material is 290 ± 8 S cm-1, Seebeck coefficient is-46 ± 0.8 μ V K-1, PF value is 61 ± 3 μ W m-1 K-2。
Claims (10)
1. a n-type nano composite thermoelectric materials compound with CNT for PDIN or NDIN.
2. thermoelectricity material compound with SWCN after with a N, N-diethyl ethylenediamine in little molecule PD or ND grafting
Material and preparation method thereof, is characterized in that: the method comprises the following steps:
(1) by 0.74 g ND or PD, 14.1g imidazoles, 1 g N, N-diethyl ethylenediamine is placed on the round-bottomed flask of 50 mL, adds
Heat is to 130 DEG C, and reflux under nitrogen atmosphere 2 h；
(2) dropping to room temperature after reaction completely, be suspended in methanol, sucking filtration, methanol washs；
(3) product vacuum that sucking filtration obtains is dried to obtain NDIN or PDIN；
(4) a certain amount of NDIN or PDIN organic molecule and CNT are joined in DMSO solvent, utilize Probe Ultrasonic Searching
Instrument ultrasonic disperse 30 min;
(5) ultrasonic disperse 3 h in water bath sonicator instrument put into by the mixed liquor of step (4)；
(6) reactant mixture that step (5) obtains is carried out decompression sucking filtration and obtains black filter membrane；
(7) the black filter membrane that step (6) obtains is put into 50 DEG C of dry 4 h in vacuum drying oven and obtains n-type nano combined thermoelectricity material
Material.
Method the most according to claim 2, is characterized in that: the reaction described in step (1) refluxes 2 h in a nitrogen atmosphere
In, the time can be 3 h or 4 h, it is therefore preferable to 2 h.
Method the most according to claim 2, is characterized in that: step (2) is suspended in methanol, sucking filtration, in methanol washing, and first
Alcohol can be changed to ethanol, it is therefore preferable to methanol.
Method the most according to claim 2, is characterized in that: described in step (4) by organic for a certain amount of NDIN or PDIN
Little molecule and CNT join in DMSO solvent, NDIN or PDIN organic molecule with the mass ratio of CNT can be
2:10,5:10,10:10,20:10,30:10, it is therefore preferable to 10:10.
Method the most according to claim 2, is characterized in that: described in step (4) by organic for a certain amount of NDIN or PDIN
Little molecule and CNT join in DMSO solvent, and solvent can be selected else as toluene, ethanol, THF, NMP etc., it is therefore preferable to
DMSO。
Method the most according to claim 2, is characterized in that: described in step (4) by organic for a certain amount of NDIN or PDIN
Little molecule and CNT join in DMSO solvent, and CNT can be SWCN, it is also possible to receive for many walls carbon
Mitron, it is therefore preferable to SWCN.
Method the most according to claim 2, is characterized in that: step (4) utilizes in Probe Ultrasonic Searching instrument ultrasonic disperse 30 min,
The ultrasonic disperse time can be 30 min, 1 h, 2 h, preferably status 30 min.
Method the most according to claim 2, is characterized in that: water-bath put into by the mixed liquor by step (4) described in step (5)
Ultrasonic disperse 3 h in Ultrasound Instrument, the time can be 3 h, 5 h, 8 h, it is therefore preferable to 8 h.
Method the most according to claim 2, is characterized in that: black filter membrane step (6) obtained described in step (7)
Putting into 50 DEG C of dry 4 h in vacuum drying oven and obtain in n-type nano composite thermoelectric materials, the temperature of vacuum drying oven can be 50 DEG C, 6
0 DEG C, 70 DEG C, drying time can be 2 h, 3 h, 4 h, 5 h, it is therefore preferable to is dried 4 h at 50 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610638905.0A CN106229403A (en) | 2016-08-08 | 2016-08-08 | N type thermoelectric material that a kind of acid imide or naphthalimide are combined with CNT and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610638905.0A CN106229403A (en) | 2016-08-08 | 2016-08-08 | N type thermoelectric material that a kind of acid imide or naphthalimide are combined with CNT and preparation method thereof |
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| CN109103326A (en) * | 2018-07-06 | 2018-12-28 | 深圳大学 | A kind of N-shaped acridine/carbon nano-tube composite heat electric material and preparation method thereof |
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| CN110190178A (en) * | 2019-04-29 | 2019-08-30 | 哈尔滨工业大学（深圳） | A kind of composite thermoelectric material, preparation method and thermo-electric device |
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| CN109244228A (en) * | 2018-08-14 | 2019-01-18 | 深圳大学 | A kind of organic composite thermal electric film and preparation method thereof |
| CN109786756A (en) * | 2019-01-09 | 2019-05-21 | 上海交通大学 | A kind of method and its application preparing flexible lithium ion battery electrode |
| CN109880066A (en) * | 2019-02-28 | 2019-06-14 | 深圳大学 | A kind of Han Xi Pin unit conjugated polymer and the preparation method and application thereof |
| CN110190178A (en) * | 2019-04-29 | 2019-08-30 | 哈尔滨工业大学（深圳） | A kind of composite thermoelectric material, preparation method and thermo-electric device |
| CN110581210A (en) * | 2019-09-17 | 2019-12-17 | 嘉兴学院 | preparation method of PPy-SWCNTs nano composite thermoelectric film and nano composite thermoelectric film |
| CN110581210B (en) * | 2019-09-17 | 2023-06-23 | 嘉兴学院 | Preparation method of PPy-SWCNTs nano composite thermoelectric film and nano composite thermoelectric film |
| CN111223982A (en) * | 2020-03-03 | 2020-06-02 | 西安交通大学 | Preparation method of n-type multi-walled carbon nanotube thermoelectric material with stable air and high performance |
| CN111223982B (en) * | 2020-03-03 | 2022-10-25 | 西安交通大学 | Preparation method of n-type multi-walled carbon nanotube thermoelectric material with stable air and high performance |
| CN111354848A (en) * | 2020-03-26 | 2020-06-30 | 西安交通大学 | Preparation method of high-performance n-type layered multi-walled carbon nanotube/graphene oxide thermoelectric material in mass production |
| CN111354848B (en) * | 2020-03-26 | 2022-02-01 | 西安交通大学 | Preparation method of high-performance n-type layered multi-walled carbon nanotube/graphene oxide thermoelectric material in mass production |
| CN113161472A (en) * | 2021-03-22 | 2021-07-23 | 东莞理工学院 | Flexible organic thermoelectric composite film, preparation method and application thereof |
| CN115172578A (en) * | 2022-07-01 | 2022-10-11 | 武汉工程大学 | Carbon nitride/carbon nanotube composite film and preparation method and application thereof |
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