基于Soret效应的n型离子热电储能器件研究

21世纪以来，随着可穿戴设备的流行和快速发展，为可穿戴设备提供可持续性热转化能源已成为世界科技研究的热点方向。传统的半导体电子热电器件，被广泛的应用于中高温度段的热能收集中。然而，对于低品位的热能收集（温度＜100 °C），尤其是在“自功能可穿戴热电设备”领域，半导体热电器件的较低单位温度热响应电压和其坚硬的物理属性，通常导致了其很难被灵活的应用起来。兴起于2010年，基于Soret效应的新型高品质离子热电器件，能够在有限的温差范围内产生mV·K^-1级别的电压响应，并且还具备较低的热导率和优异的机械柔韧性，因此成为了为可穿戴设备提供热转化能源的最有竞争力的候选者之一。具有正热电势的 p 型离子热电器件和具有负热电势的 n 型离子热电器件堆叠而成的离子热电堆的设计对于低品位的集热和温度传感非常重要。然而，迄今为止，具有负热电势的高质量离子热电材料却很少被报道。并且，有效调节聚合物网络与电解质阴离子/阳离子之间的相互作用是实现显著热电势的重要方法。本文旨在设计更多种类的离子-聚合物相互作用在实现具有负离子热电势的新型离子热电材料中的应用，并且以具备成本效益和不受外界湿度环境影响的无机盐离子作为主要的电解质材料，进而将离子热电器件应用于可穿戴式热能收集过程。主要研究内容和结果如下：

首先，本文将NaOH电解质分散到通过冷冻-解冻工艺制备的聚乙烯醇（PVA）水凝胶中，接着通过100 °C的热退火工艺和去离子水完全溶胀过程，PVA聚合物网络和Na⁺之间牢固的配位结构可以稳定地存在于PVA-NaOH水凝胶中。PVA水凝胶的热退火过程一方面促进了聚合物网络中大量的结晶畴的形成，并赋予了离子热电材料良好的机械拉伸性能。另一方面，热退火过程也伴随着水分的蒸发和Na⁺逐步从水合相互作用中挣脱出来，并建立Na⁺和PVA聚合物网络的配位相互作用。此外，PVA聚合物网络中的坚固的结晶畴也起到稳定Na⁺-PVA配位结构的作用。研究结果表明，对热退火的PVA-NaOH水凝胶施加温度梯度，获得了高达-37.61 mV·K^-1的负离子热电势。基于Soret效应的离子热电势，取决于电解质材料中离子的差异化热输运速率。Na⁺的热输运速率受到稳定的Na⁺-PVA配位结构所束缚，而OH^-由于离子水合相互作用表现出远高于Na⁺的热输运速率，进而导致了PVA-NaOH水凝胶表现出优异的负离子热电势。

为了进一步开发具有成本效益的无机电解质基负离子热电势型材料，结合过渡金属氯化物阴离子的复杂化学构型，本论文利用了CuCl₂水性电解质中[CuCl₄]²⁻离子的特异性，且结合Cu²⁺和具有高Gutmann供体数的聚乙二醇（PEO20K）的配位相互作用，以及Cu²⁺和聚阴离子电解质羧化纤维素间的相互作用，获得了2mm厚、具有负离子热电势的CuCl₂-PEO20K-[PVA-羧化纤维素]水性薄膜。Cu²⁺-PEO20K的配位相互作用是基于Gutmann供体规则的理论分析来验证的，羧化纤维素具有-22 mV的Zeta电位、Cu²⁺-羧化纤维素的配位相互作用则是基于X射线光电子能谱技术来验证。对于CuCl₂水性电介质中[CuCl₄]^2-离子的存在，拉曼光谱表明其主要以[Cu(H₂O)_xCl₄]^2- 和 [CuCl₄]^2-两种离子类型体现。并且，结合[CuCl₄]^2-离子的特殊颜色（黄色），显色反应的表观现象观察也证明了本论文的结论。对于[CuCl₄]²⁻离子的特异性，通过对比其他过渡金属氯化物（CaCl₂，FeCl₃，CoCl₂和ZnCl₂），只有含有CuCl₂电解质的复合材料表现出独特的负离子热电势，而其他电解质的热电势为正值。具体的，CuCl₂-PEO20K-[PVA-羧化纤维素]水性薄膜的最优热电性能为：-26.25 mV·K^-1的热电势、8.47 mS·cm^-1的离子电导率和0.466 W·m^-1·K^-1的热导率。

结合以上基于单一种类的离子-聚合物相互作用实现的负离子热电势材料研究，和考虑到[CuCl₄]^2-离子的特异性热输运行为，本文进一步发展了将不同类型的离子-聚合物相互作用集成到同一个热电装置中的研究实验。制备富含大量氨基（-NH₂）和羟基（-OH）的PVA-壳聚糖气凝胶，然后将含有CuCl₂离子的聚阳离子电解质（聚二烯丙基二甲基氯化铵，PDDA）水性聚合物溶液渗透到PVA-壳聚糖气凝胶中。根据Gutmann供体规则和傅里叶变换近红外光谱，壳聚糖中的-NH₂和Cu²⁺间具有强烈的配位相互作用，而PDDA中大量被固定的正电荷和Cu²⁺间能产生强烈的库伦斥力相互作用，再结合[CuCl₄]^2-离子的热响应行为，实现了-28.4 mV·K^-1的热电势。并且，受益于聚阳离子电解质聚合物主链上的高电荷密度，CuCl₂-PDDA-[PVA-壳聚糖气凝胶]材料实现了高达40.5 mS·cm^-1的离子电导率。我们设想这一系列的具有负离子热电势的材料具有很多的潜在应用，包括超灵敏离子热电堆的设计、温度传感和低品位热能收集。

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