臺灣博碩士論文加值系統

奈米流體鹽差能源近年來廣泛受到國際研究團隊關注，主因即是其可利用離子選擇性奈米通道將海水和淡水間之鹽度差異轉化為電能。最近研究已經證明奈米流體鹽差能源性能高度依賴於微米尺度通道中所不能觀察到的兩種獨特的離子傳輸現象，即離子電流整流和離子濃度極化，前者能夠放大奈米流體系統的離子電流，後者則是能降低奈米通道中鹽差發電的實際驅動力，亦即通道中之有效離子濃度比，這意味著開發下世代高性能鹽差能源發電裝置之重要關鍵即是發展一種具有離子電流整流但離子濃度極化效應不顯著的奈米流體裝置。因此，我們利用多次陽極氧化技術製造了可用於高效鹽差能源轉換之分枝型氧化鋁奈米通道薄膜，實驗結果證明此分枝型奈米通道薄膜即使在高鹽濃度500 mM環境下，亦能展現離子電流整流效應，因此本研究開發之分枝型氧化鋁奈米通道膜可以產生比傳統圓柱氧化鋁奈米通道薄膜更高的鹽差能源發電密度。此外，我們亦充分研究了分枝型氧化鋁奈米通道薄膜的支撐層和選擇層長度對鹽差能源轉換效能之影響，我們發現當分枝型氧化鋁奈米通道膜的選擇層通道長度越短時，鹽差能源轉換效能越高，在鹽濃度差異為500 mM/1 mM時，分枝型氧化鋁奈米通道薄膜的最大功率密度(支撐層長10微米，選擇層長0.31微米)可高達4.73 W/m2，此為目前多孔奈米通道薄膜中的最高新紀錄。為了說明分枝型氧化鋁奈米通道薄膜相關可顯著提升鹽差能源轉換效能的潛在物理機制，我們還進行了嚴謹電腦模擬分析，根據模擬結果顯示，分枝型氧化鋁奈米通道中鹽差發電的明顯增強是由於通道中有效濃度比相對傳統圓柱奈米通道能明顯有效提升。結果上述成果顯示，本論文使用的分枝型奈米通道薄膜是具有下一代鹽差發電應用的高潛力應用。

Nanofluidic salinity gradient power (NSGP), which can convert salinity difference between seawater and fresh eater into electricity with ion-selective nanochannels, have attracted considerable attention in recent years. Recent studies have demonstrated that the performance of NSGP highly depends on two unique ion transport phenomena that cannot be observed in microscale channels, i.e., ion current rectification (ICR) and ion concentration polarization (ICP). The former is capable of amplifying the ionic current of the nanofluidic systems and the later will decrease the effective concentration ratio (ECR), the actual driving force of NSGP, in the nanochannel. This implies that the key towards to the next-generation high-performance salinity gradient power is to develop a nanofluidic device with rectification but insignificant ICP effect. As a consequence, we fabricated the branched alumina nanochannels (BANs) membranes for salinity gradient power applications. Experimental results show that the BAN membranes rectify even at high KCl concentration up to 500 mM. In addition, the BAN membrane can generate significantly higher salinity gradient power density than the conventional cylindrical alumina nanochannels (CANs) membranes. The influences of the lengths of the stem-side and branch-side of BAN membranes are investigated thoroughly. In general, the shorter the branch-side channel length of the BAN membrane, the higher the NSGP performance. The maximum power density of the BAN membrane (with stem length of 10 m and branch length of 0.31 m) is as high as 4.73 W/m2 under a KCl difference of 500 mM/1 mM, which reaches a record-high value compared with other nanoporous membranes. To elucidate the underlying physical mechanism of the BAN membrane that can significantly enhance the salinity gradient power, we also perform the numerical modeling based on the Poisson-Nernst-Planck and Navier-Stokes equations. Modeling results reveal that the apparent enhancement of salinity gradient power in the branched nanochannels results from the appreciable increase in the ECR in the channel. The results show that the present BAN membranes have a high potential for next-generation salinity gradient power application.

摘要 i
Abstract ii
誌謝 iv
目錄 v
表目錄 vii
圖目錄 viii
符號說明 xv
第一章 緒論 1
1-1 前言 1
1-2 文獻回顧 3
1-3 研究動機 10
第二章 原理機制 12
2-1 鹽差能源轉換 12
2-2 電雙層 14
2-3 離子選擇性 17
2-4離子濃度極化 18
2-5 離子電流整流 19
第三章 實驗方法 22
3-1 實驗藥品與設備 22
3-1-1 實驗藥品 22
3-1-2 製程設備 23
3-1-3 鹽差能源轉換實驗架設 25
3-1-4 分析儀器 25
3-2實驗方法 26
3-2-1 分枝型氧化鋁奈米通道陣列製程 26
3-2-2 圓柱型氧化鋁奈米通道製程 28
3-2-3 離子電流整流實驗 31
3-2-4 鹽差能源轉換實驗 31
第四章 理論模擬 33
4-1 系統描述 33
4-2 主控方程式 34
4-3 單一奈米通道邊界條件 35
4-4 離子電流計算 38
第五章 結果與討論 40
5-1 不同類型之氧化鋁奈米通道分析 40
5-2 氧化鋁奈米通道內之離子傳輸行為 43
5-3 鹽差能源轉換實驗 43
5-3-1 電流(Isc)電壓(Voc)量測 43
5-3-2 外接電阻之能源轉換量測 44
5-4 單根奈米通道鹽差能源轉換理論模擬 46
第六章 結論 80
參考文獻 82

(1)Staff, J. C. E., Solar energy. J. Chem. Educ. 1979, 56, 264.
(2)Mitridis, E.; Schutzius, T. M.; Sicher, A.; Hail, C. U.; Eghlidi, H.; Poulikakos, D., Metasurfaces Leveraging Solar Energy for Icephobicity. ACS Nano. 2018, 12, 7009-7017.
(3)Kannan, N.; Vakeesan, D., Solar Energy for Future World:-A Review. Renew. Sust. Energ. Rev. 2016, 62, 1092-1105.
(4)Freitag, M.; Teuscher, J.; Saygili, Y.; Zhang, X.; Giordano, F.; Liska, P.; Hua, J.; Zakeeruddin, S. M.; Moser, J.-E.; Grätzel, M., Dye-Sensitized Solar Cells for Efficient Power Generation Under Ambient Lighting. Nature Photon. 2017, 11, 372.
(5)Yang, B.; Yu, T.; Shu, H.; Dong, J.; Jiang, L., Robust Sliding-Mode Control of Wind Energy Conversion Systems for Optimal Power Extraction Via Nonlinear Perturbation Observers. Appl. Energy 2018, 210, 711-723.
(6)Foley, A. M.; Leahy, P. G.; Marvuglia, A.; McKeogh, E. J., Current Methods and Advances in Forecasting of Wind Power Generation. Renew. Energ. 2012, 37, 1-8.
(7)Zhou, W.; Lou, C.; Li, Z.; Lu, L.; Yang, H., Current Status of Research on Optimum Sizing of Stand-Alone Hybrid Solar–Wind Power Generation Systems. Appl. Energy 2010, 87, 380-389.
(8)Rudd, J. W.; Hecky, R.; Harris, R.; Kelly, C., Are Hydroelectric Reservoirs Significant Sources of Greenhouse Gases. Ambio. 1993, 22, 246-248.
(9)Özcan, E. C.; Ünlüsoy, S.; Eren, T., A Combined Goal Programming–AHP Approach Supported with TOPSIS for Maintenance Strategy Selection in Hydroelectric Power Plants. Renew. Sust. Energ. Rev. 2017, 78, 1410-1423.
(10)Ma, T.; Yang, H.; Lu, L.; Peng, J., Pumped Storage-Based Standalone Photovoltaic Power Generation System: Modeling and Techno-Economic Optimization. Appl. Energy 2015, 137, 649-659.
(11)Fang, W.; Huang, Q.; Huang, S.; Yang, J.; Meng, E.; Li, Y., Optimal Sizing of Utility-Scale Photovoltaic Power Generation Complementarily Operating with Hydropower: A Case Study of The World’s Largest Hydro-Photovoltaic Plant. Energy Convers. Manage. 2017, 136, 161-172.
(12)Farfan, J.; Breyer, C., Structural Changes of Global Power Generation Capacity Towards Sustainability and The Risk of Stranded Investments Supported by A Sustainability Indicator. J. Clean Prod. 2017, 141, 370-384.
(13)Merz, C. R.; Moreno, W. A.; Barger, M.; Lipka, S. M., Salinity Gradient Power (SGP): A Developmental Roadmap Covering Existing Generation Technologies and Recent Investigative Results into The Feasibility of Bipolar Membrane-Based Salinity Gradient Power Generation. Tech. Innov. 2012, 14, 249-275.
(14)Post, J. W.; Veerman, J.; Hamelers, H. V.; Euverink, G. J.; Metz, S. J.; Nymeijer, K.; Buisman, C. J., Salinity-Gradient Power: Evaluation of Pressure-Retarded Osmosis and Reverse Electrodialysis. J. Membr. Sci. 2007, 288, 218-230.
(15)Brauns, E., Salinity Gradient Power by Reverse Electrodialysis: Effect of Model Parameters on Electrical Power Output. Desalination 2009, 237, 378-391.
(16)Alvarez-Silva, O.; Osorio, A. F., Salinity Gradient Energy Potential in Colombia Considering Site Specific Constraints. Renew. Energy 2015, 74, 737-748.
(17)Długołȩcki, P.; Gambier, A.; Nijmeijer, K.; Wessling, M., Practical Potential of Reverse Electrodialysis as Process for Sustainable Energy Generation. Environ. Sci. Technol. 2009, 43, 6888-6894.
(18)Tedesco, M.; Scalici, C.; Vaccari, D.; Cipollina, A.; Tamburini, A.; Micale, G., Performance of The First Reverse Electrodialysis Pilot Plant for Power Production from Saline Waters and Concentrated Brines. J. Membr. Sci. 2016, 500, 33-45.
(19)Tedesco, M.; Cipollina, A.; Tamburini, A.; Micale, G., Towards 1 kW Power Production in A Reverse Electrodialysis Pilot Plant with Saline Waters and Concentrated Brines. J. Membr. Sci. 2017, 522, 226-236.
(20)Li, X.; Jin, X.; Zhao, N.; Angelidaki, I.; Zhang, Y., Novel Bio-Electro-Fenton Technology for Azo Dye Wastewater Treatment Using Microbial Reverse-Electrodialysis Electrolysis Cell. Bioresour. Technol. 2017, 228, 322-329.
(21)Mei, Y.; Tang, C. Y., Co-Locating Reverse Electrodialysis with Reverse Osmosis Desalination: Synergies and Implications. J. Membr. Sci. 2017, 539, 305-312.
(22)Tedesco, M.; Hamelers, H.; Biesheuvel, P., Nernst-Planck Transport Theory for (Reverse) Electrodialysis: II. Effect of Water Transport Through Ion-Exchange Membranes. J. Membr. Sci. 2017, 531, 172-182.
(23)Yeh, L. H.; Chen, F.; Chiou, Y. T.; Su, Y. S., Anomalous pH‐Dependent Nanofluidic Salinity Gradient Power. Small 2017, 13, 1702691.
(24)Guler, E.; Zhang, Y.; Saakes, M.; Nijmeijer, K., Tailor‐Made Anion‐Exchange Membranes for Salinity Gradient Power Generation Using Reverse Electrodialysis. ChemSusChem. 2012, 5, 2262-2270.
(25)Zhang, Z.; Sui, X.; Li, P.; Xie, G.; Kong, X. Y.; Xiao, K.; Gao, L.; Wen, L.; Jiang, L., Ultrathin and Ion-Selective Janus Membranes for High-Performance Osmotic Energy Conversion. J. Am. Chem. Soc. 2017, 139, 8905-8914.
(26)Yu, Y.; Nakano, M.; Ikeda, T., Photomechanics: Directed Bending of A Polymer Film by Light. Nature 2003, 425, 145.
(27)Lu, L.; Chen, W.; Xu, T.; Yu, L., High-Performance Ternary Blend Polymer Solar Cells Involving Both Energy Transfer and Hole Relay Processes. Nat. Commun. 2015, 6, 7327.
(28)Chen, Q.; Shen, Y.; Zhang, S.; Zhang, Q., Polymer-Based Dielectrics with High Energy Storage Density. Ann. Rev. Mater. Res. 2015, 45, 433-458.
(29)Cao, L.; Xiao, F.; Feng, Y.; Zhu, W.; Geng, W.; Yang, J.; Zhang, X.; Li, N.; Guo, W.; Jiang, L., Anomalous Channel‐Length Dependence in Nanofluidic Osmotic Energy Conversion. Adv. Funct. Mater. 2017, 27, 1604302.
(30)Gao, J.; Guo, W.; Feng, D.; Wang, H.; Zhao, D.; Jiang, L., High-Performance Ionic Diode Membrane for Salinity Gradient Power Generation. J. Am. Chem. Soc. 2014, 136, 12265-12272.
(31)Cao, L.; Guo, W.; Ma, W.; Wang, L.; Xia, F.; Wang, S.; Wang, Y.; Jiang, L.; Zhu, D., Towards Understanding the Nanofluidic Reverse Electrodialysis System: Well Matched Charge Selectivity and Ionic Composition. Energy Environ. Sci. 2011, 4, 2259-2266.
(32)Guo, W.; Cao, L.; Xia, J.; Nie, F. Q.; Ma, W.; Xue, J.; Song, Y.; Zhu, D.; Wang, Y.; Jiang, L., Energy Harvesting with Single‐Ion‐Selective Nanopores: A Concentration‐Gradient‐Driven Nanofluidic Power Source. Adv. Funct. Mater. 2010, 20, 1339-1344.
(33)Pattle, R. E., Production of Electric Power by Mixing Fresh and Salt Water in The Hydroelectric Pile. Nature 1954, 174, 660-660.
(34)Weinstein, J. N.; Leitz, F. B., Electric Power from Differences in Salinity: the Dialytic Battery. Science 1976, 191, 557-559.
(35)Kim, D.-K.; Duan, C.; Chen, Y.-F.; Majumdar, A., Power Generation from Concentration Gradient by Reverse Electrodialysis In Ion-Selective Nanochannels. Microfluid. Nanofluid. 2010, 9, 1215-1224.
(36)Guo, W.; Cao, L.; Xia, J.; Nie, F. Q.; Ma, W.; Xue, J.; Song, Y.; Zhu, D.; Wang, Y.; Jiang, L., Energy Harvesting with Single‐Ion‐Selective Nanopores: A Concentration‐Gradient‐Driven Nanofluidic Power Source. Adv. Funct. Mater. 2010, 20, 1339-1344.
(37)Siria, A.; Poncharal, P.; Biance, A.-L.; Fulcrand, R.; Blase, X.; Purcell, S. T.; Bocquet, L., Giant osmotic energy conversion measured in a single transmembrane boron nitride nanotube. Nature 2013, 494, 455-458.
(38)Feng, J.; Graf, M.; Liu, K.; Ovchinnikov, D.; Dumcenco, D.; Heiranian, M.; Nandigana, V.; Aluru, N. R.; Kis, A.; Radenovic, A., Single-Layer MoS2 Nanopores as Nanopower Generators. Nature 2016, 536, 197-200.
(39)Yeh, L.-H.; Zhang, M.; Qian, S.; Hsu, J.-P.; Tseng, S., Ion Concentration Polarization in Polyelectrolyte-Modified Nanopores. J. Phys. Chem. C 2012, 116, 8672-8677.
(40)Gao, J.; Guo, W.; Feng, D.; Wang, H.; Zhao, D.; Jiang, L., High-Performance Ionic Diode Membrane for Salinity Gradient Power Generation. J. Am. Chem. Soc. 2014, 136, 12265-12272.
(41)Lee, S.; Kim, H.; Kim, D.-K., Power Generation from Concentration Gradient by Reverse Electrodialysis in Dense Silica Membranes for Microfluidic and Nanofluidic Systems. Energies 2016, 9, 49.
(42)Zhu, X.; Zhou, Y.; Hao, J.; Bao, B.; Bian, X.; Jiang, X.; Pang, J.; Zhang, H.; Jiang, Z.; Jiang, L., A Charge-Density-Tunable Three/Two-Dimensional Polymer/Graphene Oxide Heterogeneous Nanoporous Membrane for Ion Transport. ACS Nano. 2017, 11, 10816-10824.
(43)Kwon, K.; Lee, S. J.; Li, L.; Han, C.; Kim, D., Energy Harvesting System Using Reverse Electrodialysis with Nanoporous Polycarbonate Track-Etch Membranes. Int. J. Environ. Eenr. Chem. 2014, 38, 530-537.
(44)Feng, J.; Graf, M.; Liu, K.; Ovchinnikov, D.; Dumcenco, D.; Heiranian, M.; Nandigana, V.; Aluru, N. R.; Kis, A.; Radenovic, A., Single-Layer MoS 2 Nanopores as Nanopower Generators. Nature 2016, 536, 197.
(45)Siria, A.; Poncharal, P.; Biance, A.-L.; Fulcrand, R.; Blase, X.; Purcell, S. T.; Bocquet, L., Giant Osmotic Energy Conversion Measured in a Single Transmembrane Boron Nitride Nanotube. Nature 2013, 494, 455.
(46)Tsai, T.-C.; Liu, C.-W.; Yang, R.-J., Power Generation by Reverse Electrodialysis in a Microfluidic Device with a Nafion Ion-Selective Membrane. Micromachines 2016, 7, 205.
(47)Ji, J.; Kang, Q.; Zhou, Y.; Feng, Y.; Chen, X.; Yuan, J.; Guo, W.; Wei, Y.; Jiang, L., Osmotic Power Generation with Positively and Negatively Charged 2D Nanofluidic Membrane Pairs. Adv. Funct. Mater. 2017, 27, 1603623.
(48)Kwak, S. H.; Kwon, S.-R.; Baek, S.; Lim, S.-M.; Joo, Y.-C.; Chung, T. D., Densely Charged Polyelectrolyte-Stuffed Nanochannel Arrays for Power Generation from Salinity Gradient. Sci. Rep. 2016, 6, 26416.
(49)Zhang, Z.; Kong, X.-Y.; Xiao, K.; Liu, Q.; Xie, G.; Li, P.; Ma, J.; Tian, Y.; Wen, L.; Jiang, L., Engineered Asymmetric Heterogeneous Membrane: A Concentration-Gradient-Driven Energy Harvesting Device. J. Am. Chem. Soc. 2015, 137, 14765-14772.
(50)Gao, J.; Feng, Y.; Guo, W.; Jiang, L., Nanofluidics in Two-Dimensional Layered Materials: Inspirations from Nature. Chem. Soc. Rev. 2017, 46, 5400-5424.
(51)Li, R.; Jiang, J.; Liu, Q.; Xie, Z.; Zhai, J., Hybrid Nanochannel Membrane Based on Polymer/MOF for High-Performance Salinity Gradient Power Generation. Nano. Energy 2018, 53, 643-649.
(52)Zhang, Z.; Wen, L.; Jiang, L., Bioinspired Smart Asymmetric Nanochannel Membranes. Chem. Soc. Rev. 2018, 47, 322-356.
(53)Xu, J.; Lavan, D. A., Designing Artificial Cells to Harness The Biological Ion Concentration Gradient. Nature Nanotech. 2008, 3, 666.
(54)Gotter, A. L.; Kaetzel, M. A.; Dedman, J. R., Electrophorus Electricus as a Model System for The Study of Membrane Excitability. Comp. Biochem. Physiol. A. Mol Integr. Physiol. 1998, 119, 225-241.
(55)Kohonen, M. M.; Karaman, M. E.; Pashley, R. M., Debye Length in Multivalent Electrolyte Solutions. Langmuir 2000, 16, 5749-5753.
(56)Tadmor, R.; Hernandez-Zapata, E.; Chen, N.; Pincus, P.; Israelachvili, J. N., Debye Length and Double-Layer Forces in Polyelectrolyte Solutions. Macromolecules 2002, 35, 2380-2388.
(57)Butt, H.-J., Measuring Electrostatic, Van Der Waals, and Hydration Forces in Electrolyte Solutions with An Atomic Force Microscope. Biophys. J. 1991, 60, 1438-1444.
(58)Daiguji, H., Ion Transport in Nanofluidic Channels. Chem. Soc. Rev. 2010, 39, 901-911.
(59)Schoch, R. B.; Han, J.; Renaud, P., Transport Phenomena in Nanofluidics. Rev. Mod. Phys. 2008, 80, 839.
(60)Kim, S. J.; Ko, S. H.; Kang, K. H.; Han, J., Direct Seawater Desalination by Ion Concentration Polarization. Nature Nanotech. 2010, 5, 297.
(61)Yeh, L.-H.; Zhang, M.; Qian, S., Ion Transport in a pH-Regulated Nanopore. Anal. Chem. 2013, 85, 7527-7534.
(62)Ma, Y.; Yeh, L.-H.; Qian, S., pH-Regulated Ionic Conductance in a Nanopore. Electrochem. Commun. 2014, 43, 91-94.
(63)Ma, Y.; Yeh, L.-H.; Lin, C.-Y.; Mei, L.; Qian, S., pH-Regulated Ionic Conductance in a Nanochannel with Overlapped Electric Double Layers. Anal. Chem. 2015, 87, 4508-4514.
(64)Zhang, M.; Ai, Y.; Kim, D.-S.; Jeong, J.-H.; Joo, S. W.; Qian, S., Electrophoretic Motion of a Soft Spherical Particle in a Nanopore. Colloids Surf., B 2011, 88, 165-174.
(65)Cheng‐Yong, L.; Feng‐Xiang, M.; Zeng‐Qiang, W.; Hong‐Li, G.; Wen‐Ting, S.; Kang, W.; Xing‐Hua, X., Solution‐pH‐Modulated Rectification of Ionic Current in Highly Ordered Nanochannel Arrays Patterned with Chemical Functional Groups at Designed Positions. Adv. Funct. Mater. 2013, 23, 3836-3844.
(66)Kittaka, S., Isoelectric Point of Al2O3, Cr2O3 and Fe2O3. I. Effect of Heat Treatment. J. Colloid Interface Sci. 1974, 48, 327-333.
(67)Ramos-Tejada, M. M.; Durán, J. D. G.; Ontiveros-Ortega, A.; Espinosa-Jimenez, M.; Perea-Carpio, R.; Chibowski, E., Investigation of Alumina/(+)-Catechin System Properties. Part II: ζ-Potential and Surface Free Energy Changes of Alumina. Colloids Surf., B 2002, 24, 309-320.