工學院: 材料科學與工程學研究所指導教授: 趙基揚楊孟哲Yang, Meng-ZheMeng-ZheYang2017-03-032018-06-282017-03-032018-06-282016http://ntur.lib.ntu.edu.tw//handle/246246/273117由於良好的化學穩定性及低成本，Poly(ethylene oxide) (PEO)系統固態高分子電解質受到廣泛研究，然而其室溫傳導度及離子遷移係數較差，必須升溫才可以應用。引入奈米陶瓷粒子於高分子主體PEO中，可以抑制PEO的結晶度，進而提升離子傳導性質。 本研究首將磷酸鋯衍生物lithium zirconium phosphate sulfophenylphosphonate (ZrSPPLi)導入PEO系統。ZrSPPLi為表面及內部皆飾有磺酸鋰之非晶質奈米粒子，其平均直徑大小為30nm。PEO-ZrSPPLi複合高分子電解質經由混合PEO(Mn~600K)、LiClO4、ZrSPPLi溶液於乙腈，並採用溶劑揮發法製備。我們系統化的研究ZrSPPLi添加量對PEO-ZrSPPLi複合電解質的熱性質，機械性質，傳導性質，電化學穩定性和鋰金屬電池充放電行為的影響。 在含有1wt%的ZrSPPLi之12系列電解質表現出最佳的傳導性質和電池充放電效率。由於ZrSPPLi抑制PEO的結晶度，其室溫的離子傳導度相較於無添加ZrSPPLi之電解質提升二倍。於60oC，鋰離子遷移係數自0.25提升到0.37，電化學穩定性可達4.8V，使用磷酸鋰鐵為陰極，鋰金屬為陽極，所組裝得鋰金屬電池，展性出優良的穩定性及庫倫效率。於0.8C的放電電容量可達138 mAh g-1。Poly(ethylene oxide)-based solid polymer electrolytes (SPE) have been the most studied solid state electrolyte system for lithium batteries because of good chemical stability and low cost. Nevertheless, low ion conductivity, low lithium transference number (tLi+) and the need of operating at elevated temperatures severely challenged the success of this system. Introducing ceramic nanofillers into PEO matrix to form nanocomposites has been the most adopted approach to enhance the transport properties of PEO-based SPEs by suppressing the crystallinity of PEO. In this research, lithium zirconium phosphate sulfophenylphosphonate (ZrSPPLi) is synthesized and incorporated into PEO for the first time . ZrSPPLi is an amorphous nanoparticle containing lithium sulfonate groups both within and at the surface of the globular particles with an average diameter of 30nm. The PEO-ZrSPPLi nanocomposites with different ZrSPPLi loading and EO/Li ratio are prepared by solvent-casting from the solution mixture of as-synthesized ZrSPPLi, PEO (Mn ~ 600k) and lithium perchlorate (LiClO4). Systematic studies regarding the loading amount of ZrSPPLi on ion conductivity, lithium transfer number( tLi+), mechanical property, thermal property as well as the performance of lithium metal battery and electrochemical stability are performed. The composite with 1 wt% ZrSPPLi loading in EO/Li = 12/1 matrix exhibits the best transport property and cell performance among all composites. Comparing to the reference SPE without ZrSPPLi, the ion conductivity at room temperature is 2 times higher due to significantly suppressed crystallinity of PEO. With the addition of 1 wt% ZrSPPLi, tLi+ at 60oC would increase to 0.37 from 0.25 of the pristine PEO SPE and the composite exhibits a stable electrochemical window of 4.8V. The LiFePO4 /(PEO)12LiClO4-1wt%ZrSPPLi /Li battery operating at 60oC demonstrates good capacity retention and columbic efficiency at various discharge rate. The discharge capacity could reach 138 mAh g-1 at 0.8C.5749196 bytesapplication/pdf論文公開時間: 2021/8/26論文使用權限: 同意有償授權(權利金給回饋學校)固態電解質鋰金屬電池聚氧乙烯磷酸鋯衍生物複合高分子電解質solid polymer electrolytelithium metal batteryPoly(ethylene oxide)PEOlithium zirconium phosphate sulfophenylphosphonate (ZrSPPLi)composite polymer electrolytethesis10.6342/NTU201603112http://ntur.lib.ntu.edu.tw/bitstream/246246/273117/1/ntu-105-R02527061-1.pdf