全球的初級能源消耗中，約有72%的能量會以廢熱的形式損失，其中低溫廢熱佔整體廢熱的63%。在廢熱回收技術中，熱電材料被視為具有潛力的技術之一。相較於傳統的電子熱電材料，近期的研究指出離子熱電材料具有良好的柔韌性、材料簡單與成本低的特性，並在低溫下有較高的賽貝克係數，在穿戴式裝置與低溫廢熱回收更具應用潛力。在先前的研究中，奈米通道電解液與一般電解液相比有較佳的賽貝克係數。然而，在過往針對奈米通道電解液的熱電響應研究中，並未探討如表面滑移效應、溶液pH值與空間電荷的影響。因此，本論文以數值模擬方法研究了上述三個效應對奈米通道電解液的離子熱電響應的影響。

首先，本論文針對流體滑移對奈米通道離子熱電響應的影響進行研究。研究結果發現流體滑移可以提高熱滲透流，進而提升短路電流。然而，滑移效應也會增強電滲透流，這使奈米通道的電導率也受到增強，導致滑移效應並未顯著影響開路電壓。當滑移長度在10~50 nm，高2 nm與長2000 nm奈米通道的正規化最大功率密度可達到10 mW K-2 m-2，此相較於傳統的熱離子電容或熱電池高了一個數量級。

接著，本論文針對pH值對具弱酸性表面官能團奈米通道的離子熱電響應的影響進行研究。結果表示，在半徑為0.4 nm與長為50 nm，pH 9的奈米通道的表面電荷為-32 mC/m2，此時的正規化最大功率密度可達到211 mW K-2 m-2，這比pH 5環境下表面電荷為-0.4 mC/m2的奈米通道大三個數量級。

最後，本論文針對空間電荷對奈米通道離子熱電響應的影響進行研究。在奈米通道中加入空間電荷後，空間電荷會與表面電荷產生顯著的協同效應，這增強了賽貝克係數和離子熱電電流。此外，我們發現在狹窄的通道中，離子傳輸主要受到表面電荷密度的影響。隨著通道尺寸的增大，表面的效應降低，使得空間電荷與其協同效應的影響變得顯著。在半徑為10 nm長度為5000 nm，加入空間電荷的奈米通道的正規化最大功率密度為10.8 mW K-2 m-2，比只有表面電荷的奈米通道大10倍。

整體而言，研究結果顯示了表面效應(滑移效應與pH值)與空間效應(空間電荷)對奈米受限電解液的離子熱電響應的影響，這些發現為開發用於低階廢熱回收的高性能離子熱電發電機提供了許多重要的資訊。

Approximately 72% of the world's primary energy consumption is lost as waste heat, with low-grade waste heat accounting for 63% of the total waste heat. Thermoelectric materials are considered one of the potential technologies for waste heat energy conversion. Compared to conventional electronic thermoelectric materials, recent studies have indicated that ionic thermoelectric materials exhibit good flexibility, abundant materials, low cost, and exhibit higher Seebeck coefficients at low temperature, making them suitable for applications in wearable devices and low-grade waste heat energy conversion. Previous research has shown that nanoconfined electrolytes have better Seebeck coefficients compared to bulk electrolytes. However, studies on the thermoelectric response of nanoconfined electrolytes have not thoroughly discussed the effects of hydrodynamic slippage on surface, the pH value of solution, and space charge density. Consequently, this dissertation explores the effects of these three factors on the ionic thermoelectric response in nanoconfinement via numerical simulations.

First, this dissertation investigated the effects of hydrodynamic slippage on ionic thermoelectric response in nanochannel. The result shown that hydrodynamic slippage enhances thermoosmotic flow, thereby increasing the short-circuit current. However, hydrodynamic slippage also enhances electroosmotic flow, which in turn increases the conductivity of the nanochannel, resulting in insignificant influence on the open-circuit voltage. By introducing a slip length of 10 nm to 50 nm, a normalized maximum power density of 10 mW K⁻² m⁻² can be achieved in a nanochannel with a length is 2000 nm and a height is 2nm, which is an order of magnitude higher than typical thermionic capacitors and thermocells.

Next, this dissertation studied the effect of pH value on ionic thermoelectric response in nanochannel with weak acids functional group by considering the effect of charge-regulation with varying pH value of KCl solutions. The results showed that in nanochannel with a radius of 0.4 nm and a length of 50 nm, the surface charge density is -32 mC/m2 at pH 9, the normalized maximum power density can reach 211 mW K-2 m-2, which is three orders of magnitude higher than that of a channel at pH 5 with a surface charge density of -0.4 mC/m2.

Finally, this dissertation investigated the effect of space charge on the ionic thermoelectric response in nanochannel. Introducing space charge into nanochannel results in a significant synergistic effect with surface charges, enhancing the Seebeck coefficient and ionic thermoelectric current. Furthermore, the result indicated that in narrow channels, ion transport is primarily influenced by surface charge density. As the channel size increases, surface effects diminish, making the influence of space charge density and synergistic effects more significant. In a nanochannel with a radius of 10 nm and a length of 5000 nm, the normalized maximum power density with introduced space charge density is 10.8 mW K-2 m-2, which is 10 times higher than that of the nanochannel absence space charge density.

Overall, the results demonstrate the impact of surface effects (hydrodynamic slippage and pH value) and space effects (space charge density) on the ionic thermoelectric response of nanoconfined electrolytes. These findings provide valuable insights for developing high-performance ionic thermoelectric generators for low-grade waste heat recovery.

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