鋰離子電池在日常生活中極重要的科技，且被認為是最有發展潛力的儲能系統之一，為了在符合經濟效益的條件之下提升鋰離子電池的能量密度、庫倫效率、安全性以及環境友善度，新型電極材料的開發有其必要性。此研究中，含有苯醌結構的新穎有機配位基分子1,4-二氰基-2,3,5,6-四羥基苯(LH4)與銅離子反應形成兩種一維銅－苯醌配位高分子， [CuL(DMF)2]n (CLD) 和 [CuL(Py)2]n (CLP)，並用作為鋰離子電池的陰極材料。此中具苯醌結構的有機骨架，其共軛羰基在與鋰離子的反應過程中，可得失二個電子，因此金屬中心銅和有機骨架能夠進行協同氧化還原反應，提供多電子轉移過程。利用吡啶置換掉與銅軸向配位的二甲基甲醯胺分子，電池容量保有率以及倍率性能都有顯著的改善，在120 mA g-1 電流密度下的CLD可得電容量213 mAh g-1，而在45次循環充電之後尚有38.86 % 電池容量保有率；相較於在131 mA g-1電流密度下的CLP可得電容量240 mAh g-1，而在100次循環充電之後，電池容量保有率則高達66.25 %。CLP中的吡啶分子，強化π···π作用力，因此提供更多電子傳輸途徑，致使CLP呈現更加優越的倍率性能，尤其是在高電流密度1310 mA g-1下，電池容量保有率在100次循環後下降的非常少。非原位XPS和FT-IR揭示此兩種配位聚合物在放電/充電過程中的反應機制，Cu K-edge XANES和EXAFS的測量證實銅之價數和化學環境的變化，並藉由非原位與同步輻射原位Ｘ光繞射，以及高解析場發射穿透式電子顯微鏡證實在放電/充電過程中配位聚合物的結構資訊。對金屬有機陰極材料的充分了解可為新一代電池系統的設計策略奠定基礎。

Li-ion batteries (LIBs) have played a major role in our life and been considered as one of the most potential energy storage technologies. To enhance energy density, coulombic efficiency, safety, and environmental friendliness of LIBs with inexpensive price, new electrode materials must be developed to meet the requests of currently emerging applications especially in large-scale energy storage systems. Herein, a novel redox-active quinone-based organic bridging ligand, 1,4-dicyano-2,3,5,6-tetrahydroxybenzene (LH4), has been combined with copper building unit to form 1D copper-benzoquinoid coordination polymers (CPs), [CuL(DMF)2]n (CLD) and [CuL(Py)2]n (CLP), which have been used as cathode materials. The quinone-based organic building block is capable of two-electron reaction through the lithiation of its conjugated carbonyl groups. Both of the copper metal centers and organic moieties have demonstrated synergistic redox reaction allowing multiple-electron processes. By replacing the dimethylformamide (DMF) molecules which are axially coordinated to copper with pyridine (Py), both the capacity retention and rate capability are dramatically improved. For CLD at 120 mA g-1, a capacity as high as 213 mAh g-1 can be obtained with 38.86 % retention after 45 cycles whereas for CLP at 131 mA g-1, a capacity of 240 mAh g-1 can be delivered with 66.25 % retention after 100 cycles. The Py in CLP allows π···π interactions, thus providing electronic pathway along the 1D coordination polymer chain leading to superior rate capability as evidenced in CLP. A rate as high as 1310 mA g-1 can be achieved with very little capacity drop over 100 cycles. The reaction mechanism of the two coordination polymers during discharge/charge process is examined by ex-situ XPS and FT-IR. The valence changes and chemical environment of the copper species were clarified by Cu K-edge XANES and EXAFS measurements. In-house X-ray diffraction, synchrotron in-situ X-ray diffraction as well as HR-TEM were implemented to study the structural information of coordination polymers during discharge-charge processes. The comprehensively understanding of the metal-organic cathode materials for LIBs will provide the foundation of design strategies for next-generation battery systems.

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