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PEDOT∶PSS及其纳米复合材料热电性质的研究进展

鲍程鹏 周亚杰 董岚 吴子华 李奕怀 谢华清 王元元

鲍程鹏, 周亚杰, 董岚, 等. PEDOT∶PSS及其纳米复合材料热电性质的研究进展[J]. 复合材料学报, 2023, 40(2): 649-664. doi: 10.13801/j.cnki.fhclxb.20220505.001
引用本文: 鲍程鹏, 周亚杰, 董岚, 等. PEDOT∶PSS及其纳米复合材料热电性质的研究进展[J]. 复合材料学报, 2023, 40(2): 649-664. doi: 10.13801/j.cnki.fhclxb.20220505.001
BAO Chengpeng, ZHOU Yajie, DONG Lan, et al. Research progress in thermoelectric properties of PEDOT∶PSS and its nanocomposites[J]. Acta Materiae Compositae Sinica, 2023, 40(2): 649-664. doi: 10.13801/j.cnki.fhclxb.20220505.001
Citation: BAO Chengpeng, ZHOU Yajie, DONG Lan, et al. Research progress in thermoelectric properties of PEDOT∶PSS and its nanocomposites[J]. Acta Materiae Compositae Sinica, 2023, 40(2): 649-664. doi: 10.13801/j.cnki.fhclxb.20220505.001

PEDOT∶PSS及其纳米复合材料热电性质的研究进展

doi: 10.13801/j.cnki.fhclxb.20220505.001
基金项目: 国家自然科学基金(51876111;52176081);上海市自然科学基金(21ZR1424500);上海市“曙光”项目(18SG54);上海市科委地方能力建设项目(22010500700)National Natural Science Foundation of China (51876111; 52176081); National Natural Science Foundation of Shanghai (21ZR1424500); “Shuguang Program”Supported by Shanghai Education Development Foundation and Shanghai Municipal Education Commission (18SG54); Local Capacity Building Project of Shanghai Science and Technology Commission (22010500700)
详细信息
    通讯作者:

    王元元,博士,教授,硕士生导师,研究方向为新能源材料与器件 E-mail: wangyuanyuan@sspu.edu.cn

  • 中图分类号: TK11+5

Research progress in thermoelectric properties of PEDOT∶PSS and its nanocomposites

  • 摘要: 近年来,随着能源危机的加剧,可以将热能与电能进行直接转换的热电材料得到了广泛的关注。在众多热电材料体系中,有机无机纳米复合热电材料具有独特优势。相比于无机材料,有机材料成本低、质量轻、机械柔韧性好、热导率较低。添加不同类型的添加材料构成纳米复合材料后,额外引入的声子-界面散射能进一步降低热导率,同时有机无机材料能带不匹配引起的载流子筛选效应进一步提升塞贝克(Seebeck)系数。因此,目前大量工作证明有机无机纳米复合热电材料有潜力获得高的热电优值(Figure of merit,ZT),在微型热电制冷器件、柔性可穿戴发电设备、温度传感器等领域均具有光明的应用前景。本文聚焦聚(3, 4-乙烯二氧噻吩)∶聚(苯乙烯磺酸盐)(PEDOT∶PSS)热电材料及以其为基底构成的纳米复合材料热电性能的研究工作,综述了提升PEDOT∶PSS热电性能的物理方法、化学试剂改性法等。进一步重点讨论了加入不同类型的无机填料的PEDOT∶PSS基纳米复合材料热电性质的研究进展,并揭示了其热电性能提升的内在机制。

     

  • 图  1  (a) 聚(3, 4-乙烯二氧噻吩)∶聚(苯乙烯磺酸盐)(PEDOT∶PSS)化学式;(b) PEDOT∶PSS电阻率随温度变化的性质[22];(c) 乙二醇(EG)处理的PEDOT∶PSS随时间变化的热电(TE)性能[28];(d) 用不同浓度的甲酸处理的PEDOT∶PSS薄膜的平均电导率[33]

    Figure  1.  (a) Chemical formula of poly(3, 4-ethylenedioxythiophene)∶poly(styrene sulfonate) (PEDOT∶PSS); (b) Dependence of electrical resistivity of PEDOT∶PSS on temperature[22]; (c) Thermoelectric (TE) performance of PEDOT∶PSS processed by ethylene glycol (EG) over time[28]; (d) Average conductivity of PEDOT∶PSS films treated with different concentrations of formic acid[33]

    DMSO—Dimethyl sulfoxide

    图  2  不同有机溶剂改性的PEDOT∶PSS薄膜的电导率(a)和塞贝克系数(b)随温度变化的性质[25]

    DMF—N, N-dimethyl formamide; THF—Tetrahydrofuran

    Figure  2.  Temperature dependences of the electrical conductivity (a) and Seebeck coefficient (b) of PEDOT∶PSS film prepared by modification with different organic solvents[25]

    图  3  EG处理前后PEDOT∶PSS的形态变化示意图[43]

    Figure  3.  Schematic diagram of morphological changes in the PEDOT∶PSS film before and after EG treatment[43]

    图  4  NaOH水溶液处理SWCNTs/PEDOT∶PSS的形态变化示意图及其功率因数随NaOH浓度变化图[44]

    SWCNTs—Single-walled carbon nanotubes

    Figure  4.  Schematic diagram of morphology change of SWCNTs/PEDOT∶PSS treated with NaOH aqueoussolution and its power factor change with NaOH concentration[44]

    图  5  纯PEDOT∶PSS薄膜和PEDOT∶PSS/MWCNTs复合薄膜的FTIR图谱[47]

    PXCY—Content of PSS is X mg and MWCNTs is Y mg

    Figure  5.  FTIR spectra of pure PEDOT∶PSS and nanocomposites composed of PEDOT∶PSS/MWCNTs[47]

    图  6  PEDOT∶PSS/Bi2Te3-NWs复合材料制备过程示意图[59]

    NWs—Nanowires; h-AB—As-prepared sample was designed as h-AB with varied Bi2Te3-NWs contents of 5wt%, 10wt%, 25wt%, 50wt%, and 60wt% in the dried composite; p-AB—Same amount PEDOT∶PSS were drop-cast upon the other surface of Bi2Te3-NWs pellet

    Figure  6.  Schematic illustration of preparation process of PEDOT∶PSS/Bi2Te3-NWs composites[59]

    图  7  不同BST NSs含量的Bi2Te3基于镍合金纳米片/PEDOT∶PSS复合膜的载体浓度和迁移率(插图显示了复合膜中的能量滤波效果)[60]

    BST NSs−Bi2Te3 based alloy nanosheet; EF—Fermi level; ΔE—Electrical conductivity with carrier concentration

    Figure  7.  Carrier concentration and mobility as a function of the content of BST NSs of the drop cast BST NSs/PEDOT∶PSS composite films (Inset shows the illustration of the energy filtering effect in the composite films)[60]

    图  8  Bi2Te3质子辐射的示意图和Bi2Te3/PEDOT∶PSS复合薄膜的合成(a)及其TEM图像(b)和HRTEM图像((c)~(e))(分别对应图(b)虚线的区域I、II和III)[62]

    Figure  8.  A schematic showing the proton irradiation of Bi2Te3 and the synthesis of Bi2Te3/PEDOT∶PSS composite thin films (a) and TEM image (b) and HRTEM images ((c)-(e)) (From the regions I, II and III marked in dashed squares, respectively)[62]

    图  9  复合薄膜内部结构[64]

    μ—Carrier mobility; σ—Conductivity

    Figure  9.  Internal structure of composite film[64]

    图  10  未镀铜离子(a)和镀铜离子(b)的Bi0.5Sb1.5Te3示意图[65]

    BST—Bi0.5Sb1.5Te3

    Figure  10.  Schematic diagram of Bi0.5Sb1.5Te3 uncoated (a) and copper-coated (b)[65]

    图  11  不同计量AgxTe的XRD图谱和晶体结构图[68]

    Figure  11.  XRD patterns and crystal structure of AgxTe at different measurements[68]

    图  12  利用Cu-Bi0.5Sb1.5Te3/PEDOT∶PSS复合薄膜自制的热电器件[65]

    Figure  12.  A thermoelectric device fabricated using Cu-Bi0.5Sb1.5Te3/PEDOT∶PSS composite film[65]

    表  1  试剂改性PEDOT∶PSS

    Table  1.   Reagent modification of PEDOT∶PSS

    Treatment methodConductivity/
    (S·cm–1)
    Seebeck coefficient/
    (μV·K–1)
    Power factor PF/
    (μW·(m·K2)–1)
    ZTRef.
    No processing0.2115.45×10−3[37]
    Apply alternating current137316.538.6[24]
    DMSO80[25]
    DMSO, EG1.75×10−3[26]
    DMSO, EG3001.07×10−2[27]
    DMSO, EG0.42(DMSO)
    0.28(EG)
    [28]
    DMSO, PEO167738.4±7.1157.35[29]
    DMF, ZnCl2140026.198.20.125[30]
    H2SO4 (pre-process)100[31]
    H2SO4 (post-process)4380[36]
    HCOOH2050[33]
    HCOOH190020.680.60.32[34]
    H2C2O4800[35]
    H2SO4, NaOH217039.23340.29-0.49[37]
    Thionyl chloride115.9[82]
    IL46.7[83]
    IL(X-ray)116338.8175[84]
    Notes: PEO—Polyethylene oxide; IL—Ionic liquid.
    下载: 导出CSV

    表  2  碳基材料复合PEDOT∶PSS

    Table  2.   Nanocomposites with PEDOT∶PSS matrix and carbon material additions

    Additive
    material
    Treatment
    method
    Conductivity/
    (S·cm–1)
    Seebeck coefficient/
    (μV·K–1)
    PF/
    (μW·(m·K2)–1)
    ZTRef.
    SWCNTs15.8[39]
    SWCNTs3085.426.95224[40]
    SWCNTsH2SO42667.6545.72[41]
    SWCNTsDMSO745.437.9108.7[42]
    CNTEG83147185[43]
    SWCNTsNaOH170155.65260.39[44]
    SWCNTsIon-exchange effect1602.633.4182.7[46]
    SWCNTsIL173221.965.7[85]
    GODs/SWCNTs103613.819.90.00322[86]
    C-dotsH2SO41753.92148.27[48]
    rGOBar-coating230[49]
    GOHydrazine hydrate30.251947.40.084[51]
    Notes: CNT—Carbon nano tube; GOD—Graphene quantum dot; C-dots—Carbon quantum dots; rGO—Reduced graphene oxide; GO—Graphite oxide.
    下载: 导出CSV

    表  3  PEDOT∶PSS与半导体TE材料复合提升热电性能

    Table  3.   PEDOT∶PSS composite with semiconductor TE material to improve thermoelectric properties

    Additive materialTreatment methodConductivity/(S·cm−1)
    Seebeck
    coefficient/
    (μV·K−1)
    PF/
    (μW·(m·K2)−1)
    ZTRef.
    Bi2Te3 nanowiresLayer-by-layer assembly40116.310.60.01[59]
    Bi2Te3Drop casting1295.2132.260.05[60]
    Bi2Te3 nanowiresSpin coating (PSVA)102647226[61]
    Bi2Te3Drop casting (proton irradiation)1350494320.18±0.03[62]
    Bi0.5Sb1.5Te3Drop casting8.3[64]
    Bi0.5Sb1.5Te3Drop casting (two-step reduction process)1285493080.484[21]
    Cu-Bi0.5Sb1.5Te3Drop casting (copper plating)227037.1312[65]
    Ag NWsDrop casting84.8418.328.552.42×10−3[75]
    Ag2TeVacuum filtration (wet-chemical method)397.275221.7[67]
    AgxTeTopotactic chemical transformation72[68]
    Ag2SeDrop casting58151.98178.59[72]
    ZnOSpin coating9.1220.4[69]
    SnSVacuum filtration19.527.8[70]
    Sb2Te3Polar organic solvents aided layer-by-layer10642.419.090.1[71]
    Bi2Te3 nanowires7.450.048[81]
    Note: PSVA—Polar solvent steam annealing.
    下载: 导出CSV
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  • 收稿日期:  2022-03-10
  • 修回日期:  2022-04-19
  • 录用日期:  2022-04-23
  • 网络出版日期:  2022-05-05
  • 刊出日期:  2023-02-15

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