本研究探討交聯固態高分子電解質(SPE)於鋰金屬二次電池之應用，設計合成含聚醚鏈段之可交聯高分子，並將其以兩種不同交聯方式製作成SPE，期望其具高離子電導度與高機械強度，以利於鋰金屬二次電池之應用。
　　本實驗以Jeffamine ED-2003、雙酚A(Bisphenol A)、及聚甲醛(Paraformaldehyde)合成含聚醚鏈段之聚氧代氮代苯并環己烷(PBz-PEG)，將其與鋰鹽混合後，利用熱交聯或雙硫醇交聯劑製成交聯SPE。本實驗設計利用PBz-PEG結構中非晶之聚醚鏈段幫助鋰離子傳遞，而氧代氮代苯并環己烷官能基則可提供穩固的交聯結構，並同時抑制聚醚的結晶與增加SPE機械性質，此外氧代氮代苯并環己烷官能基具高極性，推測可幫助鋰離子傳遞，使SPE於室溫下擁有高離子電導度4.3 × 10-5 (S cm-1)，而穩固的交聯結構則可抑制枝晶鋰生長，提供電池循環高穩定性。
　　本篇研究中，探討了熱交聯與雙硫醇交聯SPE對於鋰金屬電極穩定性之影響，以及鋰鹽種類、鋰離子濃度、塑化劑比例、與黏著劑種類的最佳化挑選，並解釋其機制及影響原因。
　　該SPE具有良好的枝晶鋰抑制能力，在Li/Li電池量測中，短路前可承受704小時(507 C cm-2)之0.2(mA cm-2)等電流充放電。在0.2 C、60 ℃下，Li/LiFePO4電池之電容量高達142 (mAh g-1)，且在100圈循環後可維持93%的初始電容量。在30 ℃、40 ℃、50 ℃溫度環境下，電池仍能維持一定的電容量，代表SPE可被應用在寬廣的溫度範圍下。本實驗為SPE領域展示了新穎材料之應用，為固態鋰金屬二次電池開啟了新的契機。

All-solid-state lithium metal secondary batteries (LMB) have great promise to be next generation rechargeable batteries. Among various categories of electrolyte, solid polymer electrolytes (SPE) possess the ability of lithium dendrite growth resistance which could increase cycle life and coulombic efficiency of LMB. Also, the absence of flammable organic solvent in SPE could ensure the safety of batteries. However, most SPE suffer from low ionic conductivity due to the crystallization of polyether chain, limiting the practical application.
Herein, we developed a novel benzoxazine-crosslinked polyether based SPE. Benzoxazine groups were introduced into polyether chain as crosslinking sites which could suppress crystallization and provide mechanical strength to SPE. Additionally, under the effects of high polarity of benzoxazine and good Li+ conductibility of polyether chain, the SPE exhibited high ionic conductivity (~ 4.3 × 10-5 S cm-1) at ambient temperature without addition of plasticizer. Moreover, the mechanical strength of SPE provided by crosslinked structure had excellent resistance to lithium dendrite growth.
Different effects of both thermal and dithiol crosslinked SPEs on LMB were examined, respectively. The optimization of types of Li salts, Li salts concentration, plasticizer amount and types of binders had been done to improve the battery performance. Furthermore, attempts have been made to clarify the effects and causes.
To investigate performance on practical application, Li/Li cell and Li/LiFePO4 cell tests were conducted. Li/Li cell test results showed excellent lithium dendrite suppression ability of SPE. SPE could resist the dendrite growth for 704 hours (507 C cm-2) without internal short circuit. Capacity as high as 142 (mAh g-1) was obtained in Li/LiFePO4 cell at the rate of 0.2 C under 60 ℃, and 93% initial capacity was maintained after 100 cycles. The cell was also performed under 30, 40, 50 ℃ to assure the capability of SPE in various temperature. This study has opened up a novel crosslinking system for SPE and offer a new opportunity for solid-state LMB development.

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