本研究內容主要分為四部分 (1)以熱閉環法聚合成新型多功能型聚醯亞胺-氯離子液體; (2)聚醯亞胺-氯離子液體應用於鋰硫電池黏著劑; (3)以聚醯亞胺-氯離子液體/聚丙烯腈複合式油性黏著劑提升鋰硫電池電化學穩定度; (4)以非臨場分析探討黏著劑與電極材料交互作用。
這個研究工作以發展具有離子液體功能聚醯亞胺-氯離子液體新型黏著劑PICl-IL，透過四步再結晶方式進行單體改質和熱閉環脫水聚合。黏著劑材料PICl-IL設計的概念主要為以離子液體官能基接枝於聚醯亞胺之側鏈，使聚合物本身玻璃轉化點溫度降低，有利於側鏈離子液體結構的擺動，並可提升材料離子導電性，由NMR和FTIR分析成功證實製備出聚醯亞胺-氯離子液體高分子。而電化學分析中，首先將硫承量控制約0.96 mg/cm^2，並進行50圈充放電循環測試，仍可維持719.8 mAh/g之電容量，明顯優於商業化黏著劑PVdF及NaCMC (~540 mAh/g)。而PICl-IL具有優異的捕捉多硫化物或多硫化鋰能力，有效使陰極表面硫的利用率提高，綜合上述結果顯示聚醯亞胺-氯離子液體除了能應用於黏著劑之外，亦可同時解決硫的利用率不足之問題。
本研究進一步提出複合式油性黏著劑之應用，以提升電化學穩定度，探討不同比例複合式黏著劑效應，結果顯示黏著劑比為 PICl-IL/PAN-10 (1:1) 經50圈於0.1C充放電循環後，碳硫電極可維持801.6 mAh/g之電容量，約等於52.8 %電容維持率 ; 相較之下，優於PICl-IL黏著劑之維持率，而由於聚丙烯腈的腈基結構，使PAN與多硫化物容易產生極性間的親和力。此外添加高極性PAN有助於使導電碳材和硫粉分散均勻，補足PICl-IL分散性及黏度不足之問題，PAN也提供良好導離性，因此充放電測試中，正極材料在高速率2 C下充放電測試，可逆電容仍然可達339.2 mAh/g。
研究結果顯示PICl-IL/PAN複合黏著劑具有良好互補的功能與提升碳硫材料的穩定性。此外，亦應用同步輻射光源之X光原子吸收光譜和X光電子能譜分析黏著劑與電極材料之交互作用機制。於首圈充放電中可觀察到新型黏著劑能有效減少與電解液的反應，生成SEI沉積於陰極材料表面上，減少硫含量的損失，其PICl-IL與PAN相較於商業化黏著劑PVdF及NaCMC耐化學性極佳，除了高黏度及好的分散性和導離度，也具有捕捉多硫化物的能力，因此能更有效使鋰硫電池的電化學循環獲得更穩定之提升。

This work mainly consists of four topics: (a) synthesis of novel polyimide-Cl ionic liquid by thermal cyclodehydration, (b) application of polyimide-Cl ionic liquid as a binder for Lithium–sulfur batteries, (c) polyimide-Cl ionic liquid/PAN composite binder for enhancing electrochemical stability of lithium-sulfur batteries, and (d) the interaction mechanism between binder and electrode materials by ex-situ analysis.
First, a novel multifunctional binder comprising of polymeric ionic liquid, polyimide-chlorine ionic liquid complex coupled with chlorine anions is developed, prepared by a four-step recrystallization method through thermal cyclodehydration. The concept of synthetic structure was mainly by grafting ionic liquid functional groups on the side chain of polyimide, in order to lower down the temperature of glass transition point of polymer and facilitate the swinging of the side chain, thereby, increasing the ionic conductivity, PICl-IL were synthesized and confirmed by NMR and FTIR. The loading amount of sulfur was fixed around 0.96 mg/cm2, and the discharge capacity delivers as 719.8 mAh/g, which is better than electrode with the commercial binder (~540 mAh/g). In addition, PICl can also trap the lithium polysulfides and minimize the shuttle effect and sulfur loss.
Next, composite binder with lipophilic compound was prepared. After optimization, the fabricated composite binder PICl-IL/PAN-10 (1:1) showed better capacity retention after 50 cycles with discharging-charging rate of 0.1 C. The composite binder showed a capacity of 801.6 mAh/g and retention of 82.8% at the 50th cycle, exceeding the retention of a commercial binder. The nitrile group on PAN backbone possess good affinity towards polysulfides Li2Sn (4≤n≤8) due to the strong dipole-dipole interactions. The addition of highly polar PAN helped disperse the conductive carbon and sulfur powder, which were poorly dispersed in PICl-IL and improved insufficient viscosity of PICL-IL, as well as increased the ionic conductivity. Therefore, PICl-IL/PAN-10 (1:1) can deliver a high reversible capacity of 339.2 mAh/g at 2 C-rate.
The results show that the compound binder has a good complementary function and enhance the stability of carbon/sulfur composite. Furthermore, the synchrotron-based X-ray absorption spectroscopy (XAS) and X-ray
photoelectron spectroscopy (XPS) were used to study the interaction mechanism between binder and electrode materials. It demonstrated that new PICl-IL/PAN binder can effectively reduce the reactions with the electrolyte at the first cycle, and SEI is formed on the surface of the cathode material, and decreases the loss of sulfur.
In conclusion, the PICl-IL/PAN binder exhibits better chemical resistance and excellent functions, such as strong adhesion, good dispersion and high ionic conductivity. As a result, the composite binder is capable of effectively trapping polysulfides to improve the electrochemical performance of sulfur composite cathode. PICl-IL is thought to be a promising multifunctional binder for Li-S batteries.

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