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高能球磨輔助固相法制備Zr摻雜的鈦酸鋰
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國家自然科學(xué)基金 (21171116);國家國際科技合作專項 (2012 DFG11660)


Synthesis of Zr Doped Li4Ti5O12 by a High-Energy Ball-Milling Modified Solid-State Method
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    摘要:

    采用改進的高溫固相法合成Zr4+摻雜的Li4Ti5O12,研究了原位包覆技術(shù)、高能球磨和金屬元素摻雜對其晶型、相結(jié)構(gòu)、顆粒形貌以及電化學(xué)性能的影響。結(jié)果表明:改進后的高溫固相法能有效阻止顆粒團聚、提升顆粒的均勻分散度;Zr4+摻雜能降低電極極化、提升鋰離子擴散系數(shù),從而改善電化學(xué)性能。所得Li4Ti4.95Zr0.05O12在0.5 C倍率下首次放電比容量達176 mAh·g-1,在40 C高倍率下仍達52 mAh·g-1。另探討了不同離子半徑的Zr4+和Ce4+對摻雜效果的影響,結(jié)果表明較小離子半徑的元素摻雜效果較好

    Abstract:

    Zr4+ doped Li4Ti5O12 was synthesized from Li2CO3, ZrO2 and tetrabutyl titanate by a modified solid-state method. The effects of the in-situ coating, high energy ball-milling and Zr-doping on crystalline structure, particle size, morphology and electrochemical performance of Li4Ti5O12 were investigated. The samples were tested by XRD, SEM and electrochemical workstation. The results show that the in-situ coating and ball-milling can decrease the particle size and prevent the aggregation of nanoparticles. Zr-doping obviously improves the rate capability of Li4Ti5O12 via the generation of less electrode polarization and higher Li+ diffusion coefficient. Li4Ti4.95Zr0.05O12 exhibits an excellent rate capability and cycling stability. At the charge-discharge rate of 0.5 and 40C, its discharge capacities are 176 and 52 mAh·g-1, respectively. After 10 cycles, there is less than 0.5% reduction in reversible capacity at 1, 2, 5, 10, 20 and 40 C. Compared to Ce-doping, it also shows better crystallization and electrochemical performance due to its smaller ionic radius.

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張遙遙,王 丹,汪元元,張春明,何丹農(nóng),夏永姚.高能球磨輔助固相法制備Zr摻雜的鈦酸鋰[J].稀有金屬材料與工程,2014,43(9):2237~2241.[Zhang Yaoyao, Wang Dan, Wang Yuanyuan, Zhang Chunming, He Dannong, Xia Yongyao. Synthesis of Zr Doped Li4Ti5O12 by a High-Energy Ball-Milling Modified Solid-State Method[J]. Rare Metal Materials and Engineering,2014,43(9):2237~2241.]
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  • 收稿日期:2013-09-29
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  • 在線發(fā)布日期: 2015-02-25
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