Research Progress of Cellulose-based Thermoelectric Composites
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摘要: 随着全球经济的蓬勃发展,人类对于能源的需求越来越大,因此对于绿色环保型热电材料的研究和应用已经刻不容缓。纤维素作为自然界中含量最丰富的天然高分子,具有丰富的三维网络结构以及优异的热稳定性,是作为柔性热电复合材料的理想基底之一,对其大规模开发利用符合绿色可持续发展的理念。纤维素基热电复合材料可以将人体、化石能源等产生的废热充分转化为电能,具有性能稳定、绿色环保、使用寿命长、低成本、易加工等优点。本文综述了近年来纤维素基复合材料的发展现状及应用领域,着重从聚合物复合材料、碳基复合材料和Bi-Te合金复合材料3个方面进行阐述。并对纤维素基复合材料面对的挑战以及未来的研究趋势进行了总结和展望。Abstract: With the booming development of the global economy, the human demand for energy is increasing, so the research and application of green thermoelectric materials is urgent.As the most abundant natural polymer in nature, cellulose has rich three-dimensional network structure and excellent thermal stability. It is one of the ideal substrates for flexible thermoelectric composite materials. The large-scale development and utilization of cellulose is in line with the concept of green and sustainable development. Cellulose-based thermoelectric composite material can fully convert the waste heat generated by human body and fossil energy into electric energy, which has the advantages of stable performance, green and environmental protection, long service life, low cost and easy processing. This paper summarizes the development status and application field of cellulose matrix composite in recent years, focusing on polymer composite, carbon matrix composite and Bi-Te alloy composite. The challenges of cellulose matrix composites and the future research trends are summarized and discussed.
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图 2 (a) 纤维素纱线工艺流程图[21];(b) 纤维素纱线图[21];(c) 不同温度梯度下热电性能图[21];(d) 折叠后和原始相对应的电导率(σ/σ0)和Seebeck系数(S/S0)[22];(e) 电导率随折叠次数的变化[22];(f) 纤维素海绵浸入式组件示意图[23]
Figure 2. (a) Process flow chart of cellulose yarn[21]; (b) Photograph of cellulose yarn[21]; (c) Hemoelectric performance diagram at different temperature gradients[21]; (d) Corresponding conductivity (σ/σ0) and Seebeck coefficient (S/S0) after folding and the original[22]; (e) Electrical conductivity changes with the number of folds[22]; (f) Schematic diagram of the cellulose sponge immersion assembly[23]
PEDOT∶PSS—Poly(3,4-ethylenedioxythiophene)∶poly(styrene sulfonate); EG—Ethylene glycol; DMSO—Dimethyl sulfoxide; Vtp—Open-circuit voltage; I—Load current; P—Power; ΔT—Temperature gradients; PEI—Polyethyleneimine
图 3 (a) 甲基纤维素(MC)/PP复合膜制备示意图[24];(b) 二甲基亚砜(DMSO)处理前后复合膜的功率因子[24];(c) 纳米纤维素(NFC)-聚3,4-乙烯二氧噻吩∶聚苯乙烯磺酸盐(PEDOT∶PSS)气凝胶工艺图[25];(d) NFC-PEDOT∶PSS和硅化物微粒之间接触示意图[25];(e) 离子热电纸照片及NFC和PSSNa的化学结构[27];(f) NFC-PSSNa样品拉伸强度与应变的关系[27];(g) 复合薄与纯PSSNa膜的热电性能与湿度的关系[27]
Figure 3. (a) Schematic diagram of the preparation of the MC/ PP composite membrane[24]; (b) Power factor of the composite membrane before and after DMSO treatment[24]; (c) NFC-PEDOT∶PSS aerogel process diagram[25]; (d) Schematic diagram of contacts between NFC-PEDOT∶PSS and silicate particles[25]; (e) Ion thermoelectric paper photographs and the chemical structures of the NFC and PSSNa[27]; (f) Relations between tensile strength and strain of the NFC-PSSNa samples[27]; (g) Relationship between the thermoelectric properties and humidity of composite thin and pure PSSNa membrane[27]
MC—Methyl cellulose; PVDF—Polyvinylidene fluoride resin; PF—Power factor; NFC—Nanofibrillated cellulose; PSSNa—Sodium polystyrene sulfonate; ZT—Dimensionless figure of merit
图 4 (a) 纸基独立式纸基热电发生器 (TEG)制备工艺图[30];(b) TEG在10 K温差下拟合的功率曲线[30];(c) 多壁碳纳米管(MWCNT)/羧化纳米纤维素纤维(C-CNF) 纸基TEG制造工艺图[29];(d) 气溶胶喷射打印示意图[31];(e) 不同层数碳纳米管(CNT)/羟丙基纤维素(HPC)复合膜的功率因子[31]
Figure 4. (a) Process diagram of paper-based thermoelectric generator (TEG) preparation[30]; (b) Power curves fitted by TEG at 10 K temperature difference[30]; (c) Multi-walled carbon nanotubes (MWCNT)/carboxylated cellulose nanofibers (C-CNF) paper-based TEG manufacturing process diagram[29]; (d) Schematic diagram of the aerosol jet printing[31]; (e) Power factor of the carbon nanotubes (CNT)/hydroxypropyl cellulose (HPC) composite membranes of different layers[31]
TE—Thermoelectricity; TEMPO—2,2,6,6-tetramethylpiperidine oxide
图 5 (a) CNT/纤维素纳米纤维(CNF)气凝胶的制备示意图[33];(b) 热电(TE)气凝胶在30 K温差下的功率曲线[33];(c) 柔性多孔PEDOT/单壁碳纳米管 (SWCNT)/细菌纤维素 (BC)薄膜制备示意图[34];输出电压 (d) 和输出功率 (e) 作为输出电流在不同温度下沿温度梯度的函数[34]
Figure 5. (a) Schematic diagram of the preparation of the CNT/Cellulose nanofibers (CNF) aerogels[33]; (b) Power curves of thermoelectricity (TE) aerogels at 30 K temperature difference[33]; (c) Schematic diagram of the preparation of flexible porous poly (3,4-ethylenedioxythiophene)/single-walled carbon nanotubes/bacterial cellulose (PEDOT/SWCNT/BC) thin films[34]; Output voltage (d) and the output power (e) act as a function of the output current along a temperature gradient at different temperatures[34]
PTFE—Polytetrafluoroethylene; EDOT—3,4-ethylenedioxythiophene
图 7 (a) 传感器的变化电流对于按压、手指弯曲和手臂弯曲[41];(b) 传感器在反复弯曲和释放2000次循环下的电流变化[41];(c) 聚合物MIEC气凝胶在不同压力、温度和湿度下电流I-电压V曲线的变化[44]
Figure 7. (a) Changing current of the sensor applied for pressing, finger bending, and arm bending[41]; (b) Current changes of the sensor during repeated bending and release of 2000 cycles[41]; (c) Changes of current I-voltage V curves for polymer MIEC aerogels at different pressure, temperature and humidity[44]
p—Pressure; RH—Relative humidity;Vpeak—Voltage peak; Ve—Constant value of t>20 min
图 8 (a) 皮肤温度和纺织品温度随周围环境的变化[46];(b) 用于LED灯泡的TEG设备及电路图[46];(c) TEG设备潜在应用[46];(d) 热电纸的制备流程图及应用[47];(e) 热电发电机利用烧杯的热能和侧视图及在水温为40℃和60℃时的输出电压图[48]
Figure 8. (a) Skin temperature and textile temperature change with the surrounding environment[46]; (b) TEG equipment and circuit diagrams for LED light bulbs[46]; (c) Potential applications of the TEG equipment[46]; (d) Flow chart and application of thermoelectric paper preparation[47]; (e) Thermoelectric generator uses the heat and side view of the beaker and the output voltage diagram at a water temperature of 40℃ and 60℃[48]
表 1 不同纤维素基复合材料制备方法分析
Table 1. Analysis of the preparation methods of different cellulose matrix composites
Method Material T/K S/(µV·K−1) σ/(S·cm−1) PF/(μW·m−1 ·K−2) Ref. Dip coating PEDOT 300 20.5 22.13 0.97 [22] Screen printing PEDOT 340 22.1 331.5 16.2 [24] Freeze drying PEDOT 300 88 5.4 4 [25] Template printing MWCNT 300 12.7 128 2.06 [29] Jet printing SWCNT 300 43 1100 208 [31] In situ polymerization PEDOT, SWCNT 300 19 290.6 12 [34] Drop casting Bi0.46Sb1.34Te3.2 300 226 141 611 [37] -
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