鈦磷酸鹽與鈦矽酸鹽之合成、晶體結構與 性質研究;Syntheses, Crystal Structures and Properties of Titanium Phosphates and Titanium Silicates

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題名:	鈦磷酸鹽與鈦矽酸鹽之合成、晶體結構與性質研究;Syntheses, Crystal Structures and Properties of Titanium Phosphates and Titanium Silicates
作者:	趙子翎;Chao,Tzu-Ling
貢獻者:	化學學系
關鍵詞:	無機固態電解質;鈦磷酸鹽;高溫高壓水熱合成法;溶膠凝膠法;助熔劑法;固態反應;非線性光學;鈦矽酸鹽
日期:	2016-07-13
上傳時間:	2016-10-13 12:40:56 (UTC+8)
出版者:	國立中央大學
摘要:	本論文利用高溫高壓水熱法、溶膠-凝膠法、助熔劑法、頂晶熔鹽法以及固態反應合成兩系列的化合物，第一系列為鋰鉻鈦磷酸鹽化合物Li1+xCrxTi2-x(PO4)3 (A1)、Li1+xCrxTi2-x(PO4)3 (x≅0.5) (A2)；第二系列是鋰鈦矽酸鹽化合物Li2K4[(TiO)Si4O12] (LKTS, B1)、Li2Rb4[(TiO)Si4O12] (LRTS, B2)。兩系列化合物利用單晶X光繞射儀鑑定出化合物的晶體結構，輔以粉末X光繞射圖比對理論圖確定樣品純度後，分別進行離子導電及光學性質的測量。 A系列中的A1為NASICON type結構及A2為anti-NASICON type結構。兩化合物皆由PO4四面體與Ti(Cr)O6八面體以共角的方式連接形成三維骨架，Li+座落在結構內的孔道中。將A1做成固態鋰電池中測試其電池性能，結果顯示具有良好的穩定性，離子導電率和電容量分別為6.5×10-4 S·cm-1及6.4 mAh。 B系列中兩個為等結構化合物，矽氧四面體皆以Q2的方式連接形成一維單鏈，再由TiO5四角錐多面體上的四個氧原子與矽酸鏈共享形成三維骨架。非中心的結構展現強的二次倍頻訊號並且實現相位匹配及高雷射損傷閥值。量測熱重-示差掃描量熱分析以及紫外-可見-近紅外光漫反射光譜顯示結構穩定達800 oC，具有良好的熱穩定度和大的能隙(4.1 eV)，紫外吸收邊緣約在300 nm。 ;Two series of titanium phosphates and lithium titanium silicates were synthesized by the high-temperature, high-high-pressure hydrothermal method, sol-gel method, flux method, top-seeded solution growth and solid-state reaction. The series A denotes lithium chromium titanium phosphates, Li1+xCrxTi2-x(PO4)3 (A1) and Li1+xCrxTi2-x(PO4)3 (x≅0.5) (A2). The series B denotes titanosilicates, Li2K4[(TiO)Si4O12] (LKTS, B1) and Li2Rb4[(TiO)Si4O12] (LRTS, B2). All structures of those compounds are determined by single-crystal X-ray diffraction. The purity of each compound was confirmed by the good agreement between observed powder X-ray pattern and the calculated pattern derived from the single-crystal X-ray diffraction data. The properties of two series compounds were further characterized by different physical measurements respectively according to their structural features: ionic conductivity test for the series A and nonlinear optical measurements for the series B. A1 belongs to the NASICON structure, and A2 belongs to the anti-NASICON structure. Both A1 and A2 structures consist of Ti(Cr)O6 octahedra sharing all their corners with PO4 tetrahedra to form a 3-D framework. The lithium cations are located in the channels. A1 shows good stability as an electrolyte material for the lithium-ion battery. The ionic conductivity is 6.5×10-4 S·cm-1 and discharge capacity is 6.4 mAh. The SiO4 tetrahedra of B series are connected by sharing corners to form vierer single chain. The TiO5 square pyramid is connected by sharing its equatorial vertices with four silicate chains to form a 3-D framework. These two isostructural compounds are thermally stable, adopt a unique acentric crystal structure, transmitting at wavelengths of interest, and exhibit strong phase-matched Second Harmonic Generation (SHG) responses and high threshold to laser-induced damage.
顯示於類別:	[化學研究所] 博碩士論文

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