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| DC 欄位 | 值 | 語言 |
|---|---|---|
| dc.contributor.advisor | 趙基揚(Chi-Yang Chao) | |
| dc.contributor.author | Shih-Ping Tu | en |
| dc.contributor.author | 杜世平 | zh_TW |
| dc.date.accessioned | 2021-07-10T22:11:55Z | - |
| dc.date.available | 2021-07-10T22:11:55Z | - |
| dc.date.copyright | 2020-11-09 | |
| dc.date.issued | 2020 | |
| dc.date.submitted | 2020-11-03 | |
| dc.identifier.citation | Brissot, C.; Rosso, M.; Chazalviel, J. N.; Lascaud, S., 'Dendritic growth mechanisms in lithium/polymer cells'. Journal of Power Sources 1999, 81-82, 925-929. Liu, K. L., 'Block Polyelectrolyte for Ionic Conducting Membranes in Electrochemical Batteries'. 2017. Xu, W.; Wang, J.; Ding, F.; Chen, X.; Nasybulin, E.; Zhang, Y.; Zhang, J.-G., 'Lithium metal anodes for rechargeable batteries'. Energy Environmental Science 2014, 7 (2), 513-537. Peled, E.; Golodnitsky, D.; Ardel, G., 'Advanced Model for Solid Electrolyte Interphase Electrodes in Liquid and Polymer Electrolytes'. Journal of The Electrochemical Society 2019, 144 (8), L208-L210. Cohen, Y. S.; Cohen, Y.; Aurbach, D., 'Micromorphological Studies of Lithium Electrodes in Alkyl Carbonate Solutions Using in Situ Atomic Force Microscopy'. The Journal of Physical Chemistry B 2000, 104 (51), 12282-12291. Zhang, J.-G.; Xu, W.; Henderson, W. A., Lithium Metal Anodes and Rechargeable Lithium Metal Batteries. Springer International Publishing, 2017,194. Flamme, B.; Rodriguez Garcia, G.; Weil, M.; Haddad, M.; Phansavath, P.; Ratovelomanana-Vidal, V.; Chagnes, A., 'Guidelines to design organic electrolytes for lithium-ion batteries: environmental impact, physicochemical and electrochemical properties'. Green Chemistry 2017, 19 (8), 1828-1849. Zhang, H.; Li, C.; Piszcz, M.; Coya, E.; Rojo, T.; Rodriguez-Martinez, L. M.; Armand, M.; Zhou, Z., 'Single lithium-ion conducting solid polymer electrolytes: advances and perspectives'. Chemical Society Reviews 2017, 46 (3), 797-815. Hoffmann, J. F.; Pulst, M.; Kressler, J., 'Enhanced ion conductivity of poly(ethylene oxide)-based single ion conductors with lithium 1,2,3-triazolate end groups'. Journal of Applied Polymer Science 2019, 136 (3), 46949. Gao, H.; Guo, B.; Song, J.; Park, K.; Goodenough, J. B., 'A Composite Gel–Polymer/Glass–Fiber Electrolyte for Sodium-Ion Batteries'. Advanced Energy Materials 2015, 5 (9), 1402235. Kang, W.; Deng, N.; Ma, X.; Ju, J.; Li, L.; Liu, X.; Cheng, B., 'A thermostability gel polymer electrolyte with electrospun nanofiber separator of organic F-doped poly-m-phenyleneisophthalamide for lithium-ion battery'. Electrochimica Acta 2016, 216. Dai, K.; Ma, C.; Feng, Y.; Zhou, L.; Kuang, G.; Zhang, Y.; Lai, Y.; Cui, X.; Wei, W., 'A borate-rich, cross-linked gel polymer electrolyte with near-single ion conduction for lithium metal batteries'. Journal of Materials Chemistry A 2019, 7 (31), 18547-18557. Luo, G.; Yuan, B.; Guan, T.; Cheng, F.; Zhang, W.; Chen, J., 'Synthesis of Single Lithium-Ion Conducting Polymer Electrolyte Membrane for Solid-State Lithium Metal Batteries'. ACS Applied Energy Materials 2019, 2 (5), 3028-3034. Song, J.; Lee, H.; Choo, M.-J.; Park, J.-K.; Kim, H.-T., 'Ionomer-Liquid Electrolyte Hybrid Ionic Conductor for High Cycling Stability of Lithium Metal Electrodes'. Scientific Reports 2015, 5 (1), 14458. Weng, Y.-T.; Liu, H.-W.; Pei, A.; Shi, F.; Wang, H.; Lin, C.-Y.; Huang, S.-S.; Su, L.-Y.; Hsu, J.-P.; Fang, C.-C.; Cui, Y.; Wu, N.-L., 'An ultrathin ionomer interphase for high efficiency lithium anode in carbonate based electrolyte'. Nature Communications 2019, 10 (1), 5824. Matsen, M. W.; Bates, F. S., 'Unifying Weak- and Strong-Segregation Block Copolymer Theories'. Macromolecules 1996, 29 (4), 1091-1098. Liu, M.; Li, W.; Qiu, F.; Shi, A.-C., 'Theoretical Study of Phase Behavior of Frustrated ABC Linear Triblock Copolymers'. Macromolecules 2012, 45 (23), 9522-9530. Matsen, M. W.; Thompson, R. B., 'Equilibrium behavior of symmetric ABA triblock copolymer melts'. The Journal of Chemical Physics 1999, 111 (15), 7139-7146. Bouchet, R.; Maria, S.; Meziane, R.; Aboulaich, A.; Lienafa, L.; Bonnet, J.-P.; Phan, T. N. T.; Bertin, D.; Gigmes, D.; Devaux, D.; Denoyel, R.; Armand, M., 'Single-ion BAB triblock copolymers as highly efficient electrolytes for lithium-metal batteries'. Nature Materials 2013, 12 (5), 452-457. Liu, K.-L.; Chao, C.-H.; Lee, H.-C.; Tsao, C.-S.; Fang, J.; Wu, N.-L.; Chao, C.-Y., 'A novel non-porous separator based on single-ion conducting triblock copolymer for stable lithium electrodeposition'. Journal of Power Sources 2019, 419, 58-64. Szwarc, M., '‘Living’ Polymers'. Nature 1956, 178 (4543), 1168-1169. Bandermann, F.; Speikamp, H.-D.; Weigel, L., 'Bifunctional anionic initiators: A critical study and overview'. Die Makromolekulare Chemie 1985, 186 (10), 2017-2024. Foss, R. P.; Jacobson, H. W.; Sharkey, W. H., 'A New Difunctional Anionic Initiator'. Macromolecules 1977, 10 (2), 287-291. Beinert, G.; Lutz, P.; Franta, E.; Rempp, P., 'A bifunctional anionic initiator soluble in non-polar solvents'. Die Makromolekulare Chemie 1978, 179 (2), 551-555. Cameron, G. G.; Buchan, G. M., 'Addition of sec-butyllithium to m-diisopropenylbenzene'. Polymer 1979, 20 (9), 1129-1132. Lutz, P.; Franta, E.; Rempp, P., 'An efficient bifunctional lithium-organic initiator to be used in apolar solvents'. Polymer 1982, 23 (13), 1953-1959. Yu, Y. S.; Jerome, R.; Fayt, R.; Teyssie, P., 'Efficiency of the sec-Butyllithium/m-Diisopropenylbenzene Diadduct as an Anionic Polymerization Initiator in Apolar Solvents'. Macromolecules 1994, 27 (21), 5957-5963. Yu, Y. S.; Dubois, P.; Jérôme, R.; Teyssié, P., 'Difunctional Initiator Based on 1,3-Diisopropenylbenzene. 2. Kinetics and Mechanism of the sec-Butyllithium/1,3-Diisopropenylbenzene Reaction'. Macromolecules 1996, 29 (5), 1753-1761. Yu, Y. S.; Dubois, P.; Jérôme, R.; Teyssié, P., 'Difunctional Initiators Based on 1,3-Diisopropenylbenzene. 3. Synthesis of a Pure Dilithium Adduct and Its Use as Difunctional Anionic Polymerization Initiator'. Macromolecules 1996, 29 (8), 2738-2745. Chung, T. C.; Raate, M.; Berluche, E.; Schulz, D. N., 'Synthesis of functional hydrocarbon polymers with well-defined molecular structures'. Macromolecules 1988, 21 (7), 1903-1907. Mao, G.; Wang, J.; Clingman, S. R.; Ober, C. K.; Chen, J. T.; Thomas, E. L., 'Molecular Design, Synthesis, and Characterization of Liquid Crystal−Coil Diblock Copolymers with Azobenzene Side Groups'. Macromolecules 1997, 30 (9), 2556-2567. Sun, J.; Bayley, P.; MacFarlane, D. R.; Forsyth, M., 'Gel electrolytes based on lithium modified silica nano-particles'. Electrochimica Acta 2007, 52 (24), 7083-7090. Evans, J.; Vincent, C. A.; Bruce, P. G., 'Electrochemical measurement of transference numbers in polymer electrolytes'. Polymer 1987, 28 (13), 2324-2328. Avgeropoulos, A.; Paraskeva, S.; Hadjichristidis, N.; Thomas, E. L., 'Synthesis and Microphase Separation of Linear Triblock Terpolymers of Polystyrene, High 1,4-Polybutadiene, and High 3,4-Polyisoprene'. Macromolecules 2002, 35 (10), 4030-4035. Chen, D.; Shao, H.; Yao, W.; Huang, B., 'Fourier Transform Infrared Spectral Analysis of Polyisoprene of a Different Microstructure'. International Journal of Polymer Science 2013, 2013, 937284. | |
| dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/77618 | - |
| dc.description.abstract | 在此研究中，我們利用陰離子聚合以及後續的硼氫化-氧化及磺酸化反應成功合成出新型態ABA型三嵌段共聚高分子(聚(磺化異戊二烯-嵌段-異戊二烯-嵌段-磺化異戊二烯)，III-SO3Li)。接著我們利用溶劑揮發法將III-SO3Li製備成一張無孔洞的獨立膜並作為鋰金屬電池之鋰金屬負極。在分子的兩端之嵌段為聚磺酸化異戊二烯(簡寫為sPI)具有高接枝率的磺酸鋰(-SO3Li)基團，具有單離子導體特性可做為離子傳導鏈段並且延緩鋰枝晶生長；而中間的嵌段為聚異戊二烯是一個軟鏈段可提供膜材所需的柔軟度。接著我們利用TEM以及SAXS來確認此種ABA型高分子結構在成膜後理論上應具有鋰離子連續傳導通道的微相分離結構，同時我們可以由改變嵌段共聚高分子組成比例來調控其微相分離之結構大小。此外，分子兩個末端之sPI嵌段具有強大的離子交互作用力以及物理交聯，因此可提供膜材所需的機械強度。 我們所製備的單離子導體膜材在僅吸收不到10wt%的電解液情況下離子傳導度就可達到2 x 10-5 S cm-1同時鋰離子遷移係數也可達0.6。接著我們組裝鋰對稱電池進行galvanostatic cycling測試並且利用SEM確認了其在高電流密度下具有延緩鋰枝晶的能力。由以上結果顯示此ABA型三嵌段共聚高分子是具有作為鋰金屬電池之鋰金屬負極保護層的潛力。 | zh_TW |
| dc.description.abstract | In this work, novel ABA type triblock copolymers, poly(sulfonated isoprene-block-isoprene-block-sulfonated isoprene) (denoted as III-SO3Li), are synthesized via anionic polymerization and the following hydroboration/oxidation and sulfonation. Free standing non-porous membranes of III-SO3Li are fabricated from solvent casting to serve as the protection layer of lithium anode in lithium metal batteries. In III-SO3Li, the two terminal segments are single-ion conducting sulfonated polyisoprene (sPI) bearing pendant lithium sulfonate group (-SO3Li) in high grafting density for the purpose of lithium ion transportation and of mitigating lithium dendrite growth. The central soft polyisoprene segment is to provide the resulting membrane flexibility. The ABA type molecular architecture should allow the membrane to possess microphase separated structure with interconnected lithium ion conducting pathways, as suggested by TEM and SAXS studies. The domain sizes of the microstructure could be tailored by varying the composition of the block copolymer. In addition, the physical crosslinking and the strong ionic interaction between the two terminal sPI segments would promote the mechanical strength of the membrane. Upon uptaking less than 10 wt% liquid electrolytes, the III-SO3Li membranes exhibit ion conductivity around 2 x 10-5 S cm-1 and lithium transference number about 0.6. The galvanostatic cycling of Li/III-SO3Li/III cells and the associate SEM studies demonstrate the capability of III-SO3Li membrane to suppress the growth of dendritic lithium at high current density, susggesting the good potential of III-SO3Li to serving as the protective layer of lithium metal anode in lithum metal batteries. | en |
| dc.description.provenance | Made available in DSpace on 2021-07-10T22:11:55Z (GMT). No. of bitstreams: 1 U0001-0211202015470800.pdf: 3419814 bytes, checksum: 2b46378d6c8e75c370ddf5935c417a5f (MD5) Previous issue date: 2020 | en |
| dc.description.tableofcontents | 口試委員審定書 i 致謝 ii 中文摘要 iii Abstract iv 目錄 v 圖目錄 viii 表目錄 xii 第1章 緒論 1 1.1 研究背景 1 1.2 研究動機 1 第2章 文獻回顧 4 2.1 鋰金屬負極 4 2.1.1 鋰枝晶的成長模型 7 2.2 抑制鋰枝晶成長方式 9 2.2.1 單離子導體高分子 10 2.2.2 單離子導體高分子隔離膜 16 2.3 嵌段共聚高分子(SICBCP) 20 2.3.1 嵌段共聚高分子微結構 20 2.3.2 嵌段共聚高分子在鋰金屬電池的應用 22 2.4 雙官能基陰離子起始劑 26 2.4.1 前驅物及溶劑系統影響 27 2.4.2 DIB(1,3-diisopropenylbenzene) 29 第3章 實驗步驟與原理 34 3.1 實驗藥品 34 3.2 實驗儀器 36 3.3 材料製備 38 3.3.1 III的合成 38 3.3.2 III-OH的合成 41 3.3.3 III-SO3Li (sIII) 的合成 43 3.3.4 III-SO3Li (sIII) 薄膜製備 44 3.3.5 CR2032鈕扣型電池組裝 44 3.4 材料分析 45 3.4.1 合成鑑定 45 3.4.2 熱分析 45 3.4.3 薄膜微結構分析 46 3.4.4 薄膜機械強度分析 46 3.4.5 薄膜電解液吸收量量測 46 3.4.6 變溫電化學阻抗頻譜分析 47 3.4.7 變溫離子傳導度及鋰離子遷移係數量測 47 3.4.8 循環伏安法(CV) 48 3.4.9 Galvanostatic cycling量測 48 3.4.10 鋰金屬表面形貌分析 49 第4章 結果與討論 50 4.1 三嵌段共聚高分子的合成及其末端基改質 50 4.1.1 III的鑑定 50 4.1.2 III-OH的鑑定 56 4.1.3 III-SO3Li的鑑定 59 4.2 III-SO3Li薄膜製備 61 4.3 III-SO3Li的熱分析 62 4.4 III-SO3Li薄膜微結構 63 4.5 III-SO3Li薄膜的機械性質 65 4.6 III-SO3Li薄膜的電化學性質 66 4.6.1 變溫離子傳導度 66 4.6.2 鋰離子遷移係數 70 4.6.3 循環伏安法(CV)與電化學穩定性 74 4.6.4 Galvanostatic Cycling 測試 75 4.7 Galvanostatic cycling後的鋰金屬表面形貌分析 77 第5章 結論 79 第6章 未來展望 80 Appendix 81 References 83 | |
| dc.language.iso | zh-TW | |
| dc.subject | 鋰金屬電池 | zh_TW |
| dc.subject | 鋰枝晶 | zh_TW |
| dc.subject | 單離子導體 | zh_TW |
| dc.subject | 保護層 | zh_TW |
| dc.subject | 陰離子聚合 | zh_TW |
| dc.subject | 三嵌段共聚高分子 | zh_TW |
| dc.subject | single-ion conductor | en |
| dc.subject | triblock copolymer | en |
| dc.subject | lithium metal batteries | en |
| dc.subject | anionic polymerization | en |
| dc.subject | protective layer | en |
| dc.subject | lithium dendrite | en |
| dc.title | 帶有磺酸鋰側鏈之ABA型三嵌段共聚高分子:合成及其於鋰金屬的應用 | zh_TW |
| dc.title | ABA type Triblock Copolymers Bearing Pendant Lithium Sulfonates: Syntheses and Applications in Lithium Metal Batteries | en |
| dc.type | Thesis | |
| dc.date.schoolyear | 109-1 | |
| dc.description.degree | 碩士 | |
| dc.contributor.oralexamcommittee | 吳乃立(Nae-Lih Wu),戴子安(Chi-An Dai),胡芝瑋(Chih-Wei Hu) | |
| dc.subject.keyword | 三嵌段共聚高分子,陰離子聚合,保護層,單離子導體,鋰枝晶,鋰金屬電池, | zh_TW |
| dc.subject.keyword | triblock copolymer,anionic polymerization,protective layer,single-ion conductor,lithium dendrite,lithium metal batteries, | en |
| dc.relation.page | 86 | |
| dc.identifier.doi | 10.6342/NTU202004317 | |
| dc.rights.note | 未授權 | |
| dc.date.accepted | 2020-11-04 | |
| dc.contributor.author-college | 工學院 | zh_TW |
| dc.contributor.author-dept | 材料科學與工程學研究所 | zh_TW |
| 顯示於系所單位： | 材料科學與工程學系 | |
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