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標題: | 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 ABA type Triblock Copolymers Bearing Pendant Lithium Sulfonates: Syntheses and Applications in Lithium Metal Batteries |
作者: | Shih-Ping Tu 杜世平 |
指導教授: | 趙基揚(Chi-Yang Chao) |
關鍵字: | 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, triblock copolymer,anionic polymerization,protective layer,single-ion conductor,lithium dendrite,lithium metal batteries, |
出版年 : | 2020 |
學位: | 碩士 |
摘要: | 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。 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. |
URI: | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/77618 |
DOI: | 10.6342/NTU202004317 |
全文授權: | 未授權 |
顯示於系所單位: | 材料科學與工程學系 |
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