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为了获得高热电性能薄膜材料, 采用抗坏血酸(VC)作为还原剂对PEDOT-Tos-PPP薄膜进行后处理, 研究了不同浓度的VC水溶液对薄膜热电性能的影响, 并研究了后处理薄膜在空气中的稳定性. 结果表明, 经浓度为20%的VC水溶液处理后, 薄膜功率因子呈现最大值55.6 μW·m–1·K–2, 是处理之前(32.6 μW·m–1·K–2)的1.7倍, 室温下最大的ZT值为0.032. 经过VC处理后PEDOT薄膜的电导率和Seebeck系数在空气中表现出不稳定的特性, 主要是由于空气中的氧气导致薄膜表面中性态PEDOT进一步发生氧化引起的.
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关键词:
- 聚3, 4-乙撑二氧噻吩 /
- 薄膜 /
- 后处理 /
- 热电性能
Thermoelectric (TE) material is a kind of energy conversion material, which can be used for power generation and refrigeration. Until now, traditional inorganic TE materials have shown high dimensionless thermoelectric figure of merit (ZT) values. But their expensive raw material and high processing cost, heavy metal pollution and poor processability limit their broad applications. Poly(3,4-ethylenedioxythiophene) (PEDOT) conducting polymers possess some excellent features, such as high electrical conductivity, low thermal conductivity, flexibility, low cost, abundance, and light weight. More and more attention has recently been paid to the TE properties of PEDOT polymers and PEDOT polymer based nanocomposites. Ascorbic acid (VC) is used as a reducing agent to tune the PEDOT-Tos-PPP film. The PEDOT-Tos-PPP films via VPP technique are treated with VC solutions with different concentrations. The TE properties of the films before and after being treated with VC at different concentrations are measured. The effect of concentration of VC aqueous solution on the thermoelectric properties and stabilities of the film are studied. The results indicate that the power factor of the film after being treated with 20% VC is 55.6 μW·m–1·K–2, which is 1.7 times as high as that of the pristine PEDOT-Tos-PPP film (34.4 μW·m–1·K–2). The maximum ZT value at room temperature is 0.032. After the VC treatment, the conductivity and Seebeck coefficient of the PEDOT film show unstable characteristics in the air, which is mainly due to the further oxidation of the neutral state on the PEDOT film surface in the air.-
Keywords:
- poly (3, 4-ethylenedioxythiophene) /
- film /
- post-treatment /
- thermoelectric property
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图 1 PEDOT-Tos-PPP薄膜经过不同浓度的VC水溶液后处理室温下(295 K)的热电性能
Fig. 1. Thermoelectric performance of PEDOT-Tos-PPP films after post-treatment with different concentrations of VC aqueous solution at room temperature (295 K).
图 2 PEDOT-Tos-PPP薄膜经过20% VC水溶液处理后在空气中的稳定性
Fig. 2. Thermoelectric stability of PEDOT-Tos-PPP film in air after treatment with 20% VC aqueous solution.
图 4 未处理、经过VC后处理的新鲜样品及后处理样品在空气中放置一段时间后的UV-Vis-NIR光谱图
Fig. 4. UV-Vis-NIR spectra of untreated, VC post-treated fresh samples and post-treated samples in air for a period of time.
图 5 VPP法制备的PEDOT-Tos-PPP薄膜、经过VC后处理的新鲜样品及后处理样品在空气中放置一段时间后的XPS分析 (a) Survey谱; (b) S2p分谱; (c) C1s分谱; (d) O1s分谱
Fig. 5. XPS of PEDOT-Tos-PPP film prepared by the VPP method, fresh samples after VC post-treatment, and post-treated samples in the air for a period of time: (a) Survey spectrum; (b) S2p spectrum; (c) C1s spectrum; (d) O1s spectrum.
图 3 未处理和经过20% VC水溶液处理后放置空气中2 d后(a)电导率、(b) Seebeck系数和(c)功率因子随温度的变化, 图(a)中的插图为ln(σ)-T–1/3
Fig. 3. The relationship between (a) conductivity, (b) Seebeck coefficient, and (c) power factor with temperature in untreated and 20% VC aqueous solution in air for 2 d. The inset in Fig. (a) is the relations between ln(σ) and T–1/3.
图 6 未处理、经过不同浓度的VC水溶液处理后PEDOT-Tos-PPP薄膜的Raman光谱图
Fig. 6. Raman of untreated PEDOT-Tos-PPP films and films after treatment with different concentrations of VC aqueous solution.
图 7 (a) VPP法制备的PEDOT-Tos-PPP薄膜、(b) 经过VC后处理的新鲜样品及(c)后处理的样品在空气中放置一段时间后的FESEM照片
Fig. 7. FESEM of (a) PEDOT-Tos-PPP film prepared by VPP method, (b) fresh sample after VC post-treatment, and (c) post-treated sample in the air for a period of time.
表 1 不同方法改善PEDOT热电性能的对比
Table 1. Comparison of different methods to improve PEDOT thermoelectric performance.
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[1] Bubnova O, Khan Z U, Malti A, Braun S, Fahlman M, Berggren M, Crispin X 2011 Nat. Mater. 10 429
Google Scholar
[2] Kim G, Shao L, Zhang K, Pipe K P 2013 Nat. Mater. 12 719
Google Scholar
[3] 陶颖, 祁宁, 王波, 陈志权, 唐新峰 2018 67 197201
Google Scholar
Tao Y, Qi N, Wang B, Chen Z Q, Tang X F 2018 Acta Phys. Sin. 67 197201
Google Scholar
[4] 许易, 许小言, 张薇, 欧阳滔, 唐超 2019 68 247202
Google Scholar
Xu Y, Xu X Y, Zhang W, Ouyang T, Tang C 2019 Acta Phys. Sin. 68 247202
Google Scholar
[5] 李小亚, 陈炎, 郝峰, 包晔峰, 陈立东 2017 中国材料进展 36 270
Li X Y, Chen Y, Hao F, Bao Y F, Chen L D 2017 Materials China 36 270
[6] Wang Y, Yang L, Shi X L, Shi X, Chen L, Dargusch M S, Zou J, Chen Z G 2019 Adv. Mater. 31 1807916
Google Scholar
[7] Culebras M, Gómez C M, Cantarero A 2014 J. Mater. Chem. A 2 10109
Google Scholar
[8] Lee S H, Park H, Kim S, Son W, Cheong I W, Kim J H 2014 J. Mater. Chem. A 2 7288
Google Scholar
[9] Park H, Lee S H, Kim F S, Choi H H, Cheong I W, Kim J H 2014 J. Mater. Chem. A 2 6532
Google Scholar
[10] Bubnova O, Berggren M, Crispin X 2012 J. Am. Chem. Soc. 134 16456
Google Scholar
[11] Park T, Park C, Kim B, Shin H, Kim E 2013 Energy Environ. Sci. 6 788
Google Scholar
[12] Gao J, Liu F, Liu Y, Ma N, Wang Z, Zhang X 2010 Chem. Mater. 22 2213
Google Scholar
[13] Bubnova O, Khan Z U, Wang H, Braun S, Evans D R, Fabretto M, Hojati-Talemi P, Dagnelund D, Arlin J B, Geerts Y H, Desbief S, Breiby D W, Andreasen J W, Lazzaroni R, Chen W M M, Zozoulenko I, Fahlman M, Murphy P J, Berggren M, Crispin X 2014 Nat. Mater. 13 190
Google Scholar
[14] Mott N F, Davis E A 1979
[15] Jiang F X, Xu J K, Lu B Y, Xie Y, Huang R J, Li L F 2008 Chin. Phys. Lett. 25 2202
Google Scholar
[16] Scholdt M, Do H, Lang J, Gall A, Colsmann A, Lemmer U, Koenig J D, Winkler M, Boettner H 2010 J. Electron. Mater. 39 1589
Google Scholar
[17] Kim D, Kim Y, Choi K, Grunlan J C, Yu C 2010 ACS Nano 4 513
Google Scholar
[18] Yu C, Choi K, Yin L, Grunlan J C 2011 ACS Nano 5 7885
Google Scholar
[19] Xia Y, Sun K, Ouyang J 2012 Adv. Mater. 24 2436
Google Scholar
[20] Im S G, Gleason K K 2007 Macromolecules 40 6552
Google Scholar
[21] Bubnova O, Crispin X 2012 Energy Environ. Sci. 5 9345
Google Scholar
[22] Łapkowski M, Proń A 2000 Synth. Met. 110 79
Google Scholar
[23] Crispin X, Marciniak S, Osikowicz W, Zotti G, Gon A W D v d, Louwet F, Fahlman M, Groenendaal L, Schryver F D, Salaneck W R 2003 J. Polym. Sci., Part B: Polym. Phys. 41 2561
Google Scholar
[24] Lindell L, Burquel A, Jakobsson F L, Lemaur V, Berggren M, Lazzaroni R, Cornil J, Salaneck W R, Crispin X 2006 Chem. Mater. 18 4246
Google Scholar
[25] Spanninga S A, Martin D C, Chen Z 2009 J. Phys. Chem. C 113 5585
[26] Wang T, Qi Y, Xu J, Hu X, Chen P 2005 Appl. Surf. Sci. 250 188
Google Scholar
[27] Xing K, Fahlman M, Chen X, Inganäs O, Salaneck W 1997 Synth. Met. 89 161
Google Scholar
[28] Garreau S, Louarn G, Buisson J P, Froyer G, Lefrant S 1999 Macromolecules 32 6807
Google Scholar
[29] Silva R A, Goulart Silva G, Pimenta M A 2001 J. Raman Spectrosc. 32 369
Google Scholar
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