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MWCNT/PEDOT复合材料的微观结构和热电性能

李重阳 宋小勇 陈莉莉 陶颖 陈志权 赵宾

李重阳, 宋小勇, 陈莉莉, 等. MWCNT/PEDOT复合材料的微观结构和热电性能[J]. 复合材料学报, 2023, 40(2): 860-871. doi: 10.13801/j.cnki.fhclxb.20220307.002
引用本文: 李重阳, 宋小勇, 陈莉莉, 等. MWCNT/PEDOT复合材料的微观结构和热电性能[J]. 复合材料学报, 2023, 40(2): 860-871. doi: 10.13801/j.cnki.fhclxb.20220307.002
LI Chongyang, SONG Xiaoyong, CHEN Lili, et al. Microstructure and thermoelectric properties of MWCNT/PEDOT composites[J]. Acta Materiae Compositae Sinica, 2023, 40(2): 860-871. doi: 10.13801/j.cnki.fhclxb.20220307.002
Citation: LI Chongyang, SONG Xiaoyong, CHEN Lili, et al. Microstructure and thermoelectric properties of MWCNT/PEDOT composites[J]. Acta Materiae Compositae Sinica, 2023, 40(2): 860-871. doi: 10.13801/j.cnki.fhclxb.20220307.002

MWCNT/PEDOT复合材料的微观结构和热电性能

doi: 10.13801/j.cnki.fhclxb.20220307.002
基金项目: 国家自然科学基金(11805295;11665017)National Natural Science Foundation of China (11805295; 11665017)
详细信息
    通讯作者:

    李重阳,博士,讲师,研究方向为正电子湮没谱学及多孔材料微观结构表征 E-mail: lichongyang@ncwu.edu.cn

  • 中图分类号: O59;O631.2

Microstructure and thermoelectric properties of MWCNT/PEDOT composites

  • 摘要: 热电转换技术能将大量的废弃热能转换为电能以重新利用,是一种绿色能源转换技术,可以有效提高能源利用效率,缓解煤炭、石油等主要化石类能源过度开采、使用带来的能源危机及环境污染问题,因此受到科研工作者的广泛关注,是近年来的研究热点。基于此,本文以电子型导电高聚物中机能较优的聚(3, 4-乙烯二氧噻吩)(PEDOT)作为研究主体,通过化学原位氧化聚合将多壁碳纳米管(MWCNT)复合到载体中得到MWCNT/PEDOT复合材料。利用XRD、拉曼、TEM及正电子湮没寿命(PAL)等方法对MWCNT/PEDOT复合材料的形貌和微观结构进行了系统研究,研究表明:当MWCNT含量高于24.9wt%时,复合材料中出现MWCNT团聚现象,其分散性变差。同时,MWCNT/PEDOT复合材料的热电性能测试结果显示,未掺杂PEDOT的电导率仅为7.5 S·m−1,而MWCNT含量为30.1wt%时,该复合材料的电导率高达566.59 S·m−1,提高近76倍。同时,30.1wt%MWCNT/PEDOT的功率因子(814.3×10−4 μW·(m·K2)−1)相对于未掺杂PEDOT(14.5×10−4 μW·(m·K2)−1)提高约56倍,这主要是由于PEDOT分子链与MWCNT掺杂物间π-π相互作用及MWCNT的高导电性。随着MWCNT含量的增加,PAL测试结果中第一寿命成分τ1(即正电子在材料中湮没的第一寿命成分)的下降证实了该复合材料中MWCNT与PEDOT间界面变小或者界面间相互作用减弱,导致其热导率相对于未掺杂PEDOT有一定的上升,但远远低于功率因子的升高。最终,该MWCNT/PEDOT复合材料的热电优值(即热电材料ZT值)由0.015×10−4升至0.45×10−4,增加了约30倍。结果表明:掺杂的高电导率MWCNT能够极大地提高PEDOT类电子型导电聚合物的热电性能。

     

  • 图  1  不同多壁碳纳米管(MWCNT)含量的MWCNT/聚(3, 4-乙烯二氧噻吩)(PEDOT)复合材料的XRD图谱

    Figure  1.  XRD patterns of different multiwall carbon nanotubes (MWCNT) contents of MWCNT/poly(3, 4-ethylenedioxythiophene) (PEDOT) composites

    图  2  不同MWCNT含量的MWCNT/PEDOT复合材料的拉曼光谱图(图2(b)图2(a)的局部放大图)

    Figure  2.  Raman spectrogram of different MWCNT contents of MWCNT/PEDOT composites (Fig.2(b) is the local magnified view of Fig.2(a))

    图  3  不同MWCNT含量的MWCNT/PEDOT复合材料 ((a)~(e)) 及纯净MWCNT (f) 的高分辨TEM图像

    ((a)-(e)) MWCNT content is 0wt%, 11.4wt%, 19.7wt%, 24.9wt% and 30.1wt%, respectively

    Figure  3.  High resolution TEM images of different MWCNT contents of MWCNT/PEDOT composites ((a)-(e)) and pure MWCNT (f)

    图  4  不同MWCNT含量的MWCNT/PEDOT复合材料的正电子寿命$ {\tau }_{1} $$ {\tau }_{2} $及对应强度I1I2的变化曲线

    Figure  4.  Variation of positron lifetime $ {\tau }_{1} $, $ {\tau }_{2} $ and intensity I1, I2 measured for MWCNT/PEDOT as a function of MWCNT content

    图  5  不同MWCNT含量的MWCNT/PEDOT复合材料冷压后电导率 (a)、塞贝克系数 (b) 和功率因子 (c) 随测试温度的变化曲线

    Figure  5.  Variation of electrical conductivity (a), Seebeck coefficient (b) and power factor (c) for MWCNT/PEDOT composites with various MWCNT contents as a function of temperature

    图  6  室温下不同MWCNT含量的MWCNT/PEDOT复合材料的电导率 (a)、塞贝克系数 (b) 和功率因子 (c) 的变化曲线

    Figure  6.  Electrical conductivity (a), Seebeck coefficient (b) and power factor (c) for MWCNT/PEDOT composites with various MWCNT contents measured at room temperature

    图  7  (a) 30~111oC间不同MWCNT含量的MWCNT/PEDOT复合材料的热扩散系数;室温下不同MWCNT含量的MWCNT/PEDOT复合材料的晶格热导率 (b)、热导率 (c) 和热电优值ZT值 (d) 变化曲线

    Figure  7.  (a) Thermal diffusivity of the MWCNT/PEDOT composites with various MWCNT contents between 30-110oC; Lattice thermal conductivity (b), thermal conductivity (c) and thermoelectric figure of merit ZT value (d) for the MWCNT/PEDOT composites with various MWCNT contents at room temperature

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  • 收稿日期:  2022-01-20
  • 修回日期:  2022-02-16
  • 录用日期:  2022-02-26
  • 网络出版日期:  2022-03-09
  • 刊出日期:  2023-02-15

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