CN113248534A - 一种有机小分子热电材料及其制备方法 - Google Patents
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- 239000000463 material Substances 0.000 title claims abstract description 39
- 150000003384 small molecules Chemical class 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- LDUGPANERTUNPV-UHFFFAOYSA-N 2,9-dibromo-6,13-bis[3-(dimethylamino)propyl]-6,13-diazatetracyclo[6.6.2.04,16.011,15]hexadeca-1,3,8,10,15-pentaene-5,7,12,14-tetrone Chemical compound C1=C(Br)C(C(N(CCCN(C)C)C2=O)=O)=C3C2=CC(Br)=C2C(=O)N(CCCN(C)C)C(=O)C1=C32 LDUGPANERTUNPV-UHFFFAOYSA-N 0.000 claims abstract description 5
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- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000012065 filter cake Substances 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 abstract description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 abstract description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 238000006069 Suzuki reaction reaction Methods 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 4
- 238000004528 spin coating Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000007605 air drying Methods 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000007602 hot air drying Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 229910002899 Bi2Te3 Inorganic materials 0.000 description 1
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- 229910002665 PbTe Inorganic materials 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
- OCGWQDWYSQAFTO-UHFFFAOYSA-N tellanylidenelead Chemical compound [Pb]=[Te] OCGWQDWYSQAFTO-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
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- C—CHEMISTRY; METALLURGY
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
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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
Abstract
本发明公开了一种有机小分子热电材料及其制备方法,所述制备方法包括:通过4,9‑二溴‑2,7‑双(3‑(二甲基氨基)丙基)苯并[lmn][3,8]菲咯啉‑1,3,6,8(2H,7H)‑四酮和(1‑(叔丁氧羰基)‑5‑((叔丁基二甲基甲硅烷基)氧基)‑1H‑吲哚‑2‑基)硼酸进行suzuki偶联反应,获得本发明有机小分子热电材料。本发明制备的有机小分子热电材料具有良好的溶液加工性,能溶于二甲基亚砜、四氢呋喃、二氯甲烷等常用有机溶剂;制备的小分子热电材料具有高电导率和高功率因数,并且具有较高的空气稳定性。所述有机小分子热电材料的化学结构式为:
Description
技术领域
本发明属于热电材料技术领域,具体涉及一种有机小分子有机热电材料及其制备方法,属新材料技术领域。
背景技术
热电材料是一种利用固体内部载流子运动实现热能和电能直接相互转换的功能材料,在温差发电和电制冷方面具有广阔的应用前景。
目前使用的热电材料主要是无机热电材料,如Bi2Te3,GeTe和PbTe等。无机热电材料具有高的功率因数,但表现出较差的机械性能,特别是塑性和可加工性差,在弯曲、拉伸和压缩应力下易于断裂导致器件损坏,限制了无机热电材料的大范围应用。
与无机热电材料相比,有机热电材料具有良好的溶液加工性能、优良的柔韧性和广泛的原料来源,是无机热电材料的必要补充。
有机分子较低的电导率决定了有机热电材料的功率因数低于无机热电材料,这导致有机热电材料的广泛应用受到限制。虽然通过外掺杂的方式,可以提高有机热电材料的电导率,但是掺杂体系的不稳定性导致热电器件的寿命较短。因此,开发本征高电导率有机热电材料,对于提高有机热电器件的寿命,具有重要实际意义。
发明内容
为了克服现有有机热电材料电导率低以及功率因数低的缺点,本发明提供一种高电导率、合成简单、可以溶液加工的有机小分子热电材料,并提供其制备方法。
本发明是通过以下技术方案实现的:
一种有机小分子热电材料的制备方法,其特征在于,包括以下制备步骤:
在氮气保护下,向干燥的反应釜内,加入1.0摩尔份的4,9-二溴-2,7-双(3-(二甲基氨基)丙基)苯并[lmn][3,8]菲咯啉-1,3,6,8(2H,7H)-四酮和1.0摩尔份的(1-(叔丁氧羰基)-5-((叔丁基二甲基甲硅烷基)氧基)-1H-吲哚-2-基)硼酸和2.0升二甲基亚砜和2.50摩尔份的碳酸钾和0.10摩尔份的四(三苯基膦)钯,室温机械搅拌1.0小时,将反应釜温度升高到100-110℃,恒温在100-110℃机械搅拌反应12.0-14.0小时,停止搅拌,降至室温,将反应釜内所有溶液倒入2.0升丙酮中,机械搅拌0.5小时,抽滤,取滤饼,将滤饼倒入2.0升甲醇中,机械搅拌0.5小时,抽滤,取滤饼,将滤饼放入真空烘箱,70℃真空干燥24.0小时,得有机小分子热电材料产物。产物结构式如下:
将所述有机小分子热电材料溶解在二甲基亚砜、四氢呋喃、二氯甲烷等常用有机溶剂中,通过旋涂或刮涂成膜方式,可以得到均匀致密的热电薄膜,这非常适合热电器件的制作。
通过旋涂或者刮涂方式加工的不同厚度的本发明提供的有机小分子热电材料薄膜产品,电导率高于25.0S cm-1,功率因数高于65.5μW m-1k-2。
通过旋涂或者刮涂方式加工的不同厚度的本发明提供的有机小分子热电材料薄膜产品,在空气环境下表现出优良的热稳定性。
本发明的有益效果是:本发明方法制备的有机小分子热电材料具有良好的溶液加工性,能溶于二甲基亚砜、四氢呋喃、二氯甲烷等常用有机溶剂,具有高电导率和高功率因数,并且具有较高的空气稳定性。
具体实施方式
以下对本发明的原理和特征进行描述,所举实施例只用于解释本发明,并非用于限定本发明的范围。
实施例1:
在氮气保护下,向干燥的反应釜内,加入1.0摩尔份的4,9-二溴-2,7-双(3-(二甲基氨基)丙基)苯并[lmn][3,8]菲咯啉-1,3,6,8(2H,7H)-四酮和1.0摩尔份的(1-(叔丁氧羰基)-5-((叔丁基二甲基甲硅烷基)氧基)-1H-吲哚-2-基)硼酸和2.0升二甲基亚砜和2.50摩尔份的碳酸钾和0.10摩尔份的四(三苯基膦)钯,室温机械搅拌1.0小时,将反应釜温度升高到100℃,恒温在100℃机械搅拌反应12.0小时,停止搅拌,降至室温,将反应釜内所有溶液倒入2.0升丙酮中,机械搅拌0.5小时,抽滤,取滤饼,将滤饼倒入2.0升甲醇中,机械搅拌0.5小时,抽滤,取滤饼,将滤饼放入真空烘箱,70℃真空干燥24.0小时,得有机小分子热电材料产物。
实施例2:
在氮气保护下,向干燥的反应釜内,加入1.0摩尔份的4,9-二溴-2,7-双(3-(二甲基氨基)丙基)苯并[lmn][3,8]菲咯啉-1,3,6,8(2H,7H)-四酮和1.0摩尔份的(1-(叔丁氧羰基)-5-((叔丁基二甲基甲硅烷基)氧基)-1H-吲哚-2-基)硼酸和2.0升二甲基亚砜和2.50摩尔份的碳酸钾和0.10摩尔份的四(三苯基膦)钯,室温机械搅拌1.0小时,将反应釜温度升高到110℃,恒温在110℃机械搅拌反应14.0小时,停止搅拌,降至室温,将反应釜内所有溶液倒入2.0升丙酮中,机械搅拌0.5小时,抽滤,取滤饼,将滤饼倒入2.0升甲醇中,机械搅拌0.5小时,抽滤,取滤饼,将滤饼放入真空烘箱,70℃真空干燥24.0小时,得有机小分子热电材料产物。
通过下面的试验测试本发明的有机小分子热电材料的性能。
将实施例1制备的有机小分子热电材料溶解在二甲基亚砜溶液中,浓度为1.0克每毫升,通过线棒涂布其刮涂在玻璃板上,刮涂厚度为10微米,使用电热鼓风干燥箱鼓风干燥除去溶剂,鼓风温度为150℃,鼓风干燥时间为2.0小时,室温下测试薄膜的性能,性能测试结果如表1。
将实施例2制备的有机小分子热电材料溶解在四氢呋喃溶液中,浓度为1.0克每毫升,通过线棒涂布其刮涂在玻璃板上,刮涂厚度为10微米,使用电热鼓风干燥箱鼓风干燥除去溶剂,鼓风温度为150℃,鼓风干燥时间为2.0小时,室温下测试薄膜的性能,性能测试结果如表1。
薄膜电导率的测试方法:使用四探针法测试薄膜电导率。
薄膜功率因数的测试方法:使用热电性能分析系统(ZEM-3)测试薄膜的功率因数。
表1:有机小分子热电薄膜的性能测表
以上所述是本发明的优选实施例,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也视为本发明的保护范围。
Claims (1)
1.一种有机小分子热电材料的制备方法,其特征在于,所述的制备方法包括:
在氮气保护下,向干燥的反应釜内,加入1.0摩尔份的4,9-二溴-2,7-双(3-(二甲基氨基)丙基)苯并[lmn][3,8]菲咯啉-1,3,6,8(2H,7H)-四酮和1.0摩尔份的(1-(叔丁氧羰基)-5-((叔丁基二甲基甲硅烷基)氧基)-1H-吲哚-2-基)硼酸和2.0升二甲基亚砜和2.50摩尔份的碳酸钾和0.10摩尔份的四(三苯基膦)钯,室温机械搅拌1.0小时,将反应釜温度升高到100-110℃,恒温在100-110℃机械搅拌反应12.0-14.0小时,停止搅拌,降至室温,将反应釜内所有溶液倒入2.0升丙酮中,机械搅拌0.5小时,抽滤,取滤饼,将滤饼倒入2.0升甲醇中,机械搅拌0.5小时,抽滤,取滤饼,将滤饼放入真空烘箱,70℃真空干燥24.0小时,得有机小分子热电材料产物,产物结构式如下:
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