氮摻雜階層式多孔碳奈米結構和有機金屬框架材料在高性能柔性膠態超級電容器之應用

N-doped Hierarchical Porous Carbon Nanostructure and Metal Organic Frameworks Material for High Performance Flexible Gel-Type Supercapacitors

鄭博元(Po-Yuan. Cheng)

指導教授 ： 呂世源

國立清華大學/工學院/化學工程學系/碩士(2019年)

摘要

隨著便攜式和柔性電子設備的日益普及和重要性，近年來對靈活且高效的能量存儲設備的需求不斷增長。超級電容器因其高功率密度和長循環壽命而引起了很多研究的關注。開發高性能柔性固態超級電容器已經付出了相當大的努力。
本研究以二氧化矽奈米球為硬模板，具有良好導電性和柔韌性之碳布為集電板。並利用多巴胺易於附著在無機物表面或有機物的特性，在碳布和二氧化矽奈米球的表面上聚合，再經過高溫碳化和氫氧化鈉水溶液蝕刻，形成具有階層式孔洞和氮摻雜之碳奈米結構。此碳結構未經過任何化學性活化就具有1049.4 m2 g-1的高比表面積及2.37 cm2 g-1的高孔隙率。
以氮摻雜階層式孔洞之碳奈米結構 /碳布複合材料作為柔性膠態對稱超級電容器的電極材料，展現優異的電化學性質。此對稱式超級電容器在功率密度為0.5kW kg-1時表現出24.3Wh kg-1的高能量密度，並且在10kW kg-1的高功率密度下保持10.3Wh kg-1的能量密度。此對稱式超級電容器的循環穩定性非常好，在10 A / g的8000次循環操作後保有78％的高比電容保持率。

關鍵字

介孔二氧化矽球 ； 階層式碳奈米結構 ； 超級電容器 ； 柔性基板 ； 膠態電解質 ； 碳布

並列摘要

N-doped hierarchical porous carbon nanostructure (NHPCN) was created on carbon cloth (CC), through a self-assembled mesoporous silica spheres templating process, to fabricate high performance flexible gel-type symmetric supercapacitors (NHPCN@CC//NHPCN@CC). The NHPCN@CC//NHPCN@CC cell exhibited outstanding capacitive performances, delivering a high energy density of 24.3 Wh kg-1 at the power density of 0.5 kW kg-1 and maintaining a decent energy density of 10.3 Wh kg-1 at a high power density of 10 kW kg-1, among the highest for carbon based gel-type, symmetric supercapacitors. The success may be attributed to the continuous hollow, thin features of the NHPCN, with the hollow structure enabling local, fast adsorption/desorption of electrolyte ions for generation of electric double layer capacitances, and the thin carbon shells offering large amounts of exposed surface areas to accommodate electric double layer capacitances and pseudo-capacitances. The cycling stability of the NHPCN@CC//NHPCN@CC cell was excellent, exhibiting a high specific capacitance retention rate of 78% after 8000 cycle operations at 10 A g-1. The mechanical robustness of the NHPCN@CC//NHPCN@CC cell was also excellent, maintaining high energy and power densities even at a large bending angle of 135o.

並列關鍵字

mesoporous silica sphere ； hierarchical carbon nanostructure ； supercapacitor ； flexible substrate ； gel-type electrolyte ； carbon cloth

參考文獻

[1] C. Largeot, C. Portet, J. Chmiola, P.L. Taberna, Y. Gogotsi, P. Simon, Relation between the ion size and pore size for an electric double-layer capacitor, Journal of the American Chemical Society 130 (2008) 2730.

[2] S. Pandey, U.N. Maiti, K. Palanisamy, P. Nikolaev, S. Arepalli, Ultrasonicated double wall carbon nanotubes for enhanced electric double layer capacitance, Applied Physics Letters 104 (2014) 356-378.

[3] A.S. Arico, P. Bruce, B. Scrosati, J.M. Tarascon, W. Van Schalkwijk, Nanostructured materials for advanced energy conversion and storage devices, Nature Materials 4 (2005) 366-377.

[4] R. Kotz, M. Carlen, Principles and applications of electrochemical capacitors, Electrochimica Acta 45 (2000) 2483-2498.

[5] C. Liu, F. Li, L.P. Ma, H.M. Cheng, Advanced materials for energy storage, Advanced Materials 22 (2010) E28.