https://scholars.lib.ntu.edu.tw/handle/123456789/630129
標題: | Spiro-Twisted Benzoxazine Derivatives Bearing Nitrile Group for All-Solid-State Polymer Electrolytes in Lithium Batteries | 作者: | Lee, Jen Yu Yu, Tsung Yu Yeh, Shih Chieh NAE-LIH WU RU-JONG JENG |
關鍵字: | benzoxazine | lithium-ion batteries (LIBs) | semi-interpenetrating polymer network | spiro-twisted | 公開日期: | 1-七月-2022 | 出版社: | MDPI | 卷: | 14 | 期: | 14 | 來源出版物: | Polymers | 摘要: | In this study, two nitrile-functionalized spiro-twisted benzoxazine monomers, namely 2,2′-((6,6,6′,6′-tetramethyl-6,6′,7,7′-tetrahydro-2H,2′H-8,8′-spirobi[indeno[5,6-e][1,3]oxazin]-3,3′(4H,4′H)-diyl)bis(4,1-phenylene))diacetonitrile (TSBZBC) and 4,4′-(6,6,6′,6′-tetramethyl-6,6′,7,7′-tetrahydro-2H,2′H-8,8′-spirobi[indeno[5,6-e][1,3]oxazin]-3,3′(4H,4′H)-diyl)dibenzonitrile (TSBZBN) were successfully developed as cross-linkable precursors. In addition, the incorporation of the nitrile group by covalent bonding onto the crosslinked spiro-twisted molecular chains improve the miscibility of SPE membranes with lithium salts while maintaining good mechanical properties. Owing to the presence of a high fractional free volume of spiro-twisted matrix, the –CN groups would have more space for rotation and vibration to assist lithium migration, especially for the benzyl cyanide-containing SPE. When combined with poly (ethylene oxide) (PEO) electrolytes, a new type of CN-containing semi-interpenetrating polymer networks for solid polymer electrolytes (SPEs) were prepared. The PEO-TSBZBC and PEO-TSBZBN composite SPEs (with 20 wt% crosslinked structure in the polymer) are denoted as the BC20 and BN20, respectively. The BC20 sample exhibited an ionic conductivity (σ) of 3.23 × 10−4 S cm−1 at 80 °C and a Li+ ion transference number of 0.187. The LiFePO4 (LFP)|BC20|Li sample exhibited a satisfactory charge–discharge capacity of 163.6 mAh g−1 at 0.1 C (with approximately 100% coulombic efficiency). Furthermore, the Li|BC20|Li cell was more stable during the Li plating/stripping process than the Li|BN20|Li and Li|PEO|Li samples. The Li|BC20|Li symmetric cell could be cycled continuously for more than 2700 h without short-circuiting. In addition, the specific capacity of the LFP|BC20|Li cell retained 87% of the original value after 50 cycles. |
URI: | https://scholars.lib.ntu.edu.tw/handle/123456789/630129 | ISSN: | 2073-4360 | DOI: | 10.3390/polym14142869 |
顯示於: | 化學工程學系 |
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