无机固体电解质Li_7La_3Zr_2O_(12)的研究进展
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摘要
目前,采用固体电解质代替传统电解液发展新型全固态锂离子电池,已成为解决电池安全问题、提高电池储能密度的一项重要的技术方法。固体电解质材料作为全固态锂电池的核心,它的性能很大程度上决定了电池的各项性能指标。迄今被研究过的无机固体电解质材料有很多,包括NASICON型、LISICON型、钙钛矿型和石榴石型等晶态固体电解质,和氧化物及硫化物等玻璃态固体电解质,其中石榴石型结构的Li_7La_3Zr_2O_(12)材料具有优异的综合电化学性能,使其更具实际应用潜力和研究价值。实验与理论计算结果表明该材料具有较高的锂离子电导率(10~(-4)～10~(-3)S·cm~(-1)),能与负极金属锂及大部分正极材料稳定接触,电化学窗口高达6 V。根据近年来国内外在该类材料上的研究现状,主要从Li7La3Zr2O12的晶体结构特征、制备方法及掺杂改性等方面进行了详细介绍,最后阐述了Li_7La_3Zr_2O_(12)固态电解质材料在全固态锂电池中的发展前景及面临的挑战。
At present,replacing traditional electrolytes with solid electrolytes to develop new all-solid-state lithium ion batteries has become an important technical method to solve the battery safety problems and improve the battery energy density.As the core material of all-solid-state lithium ion batteries,the performance of the solid electrolyte largely determines the performance of the battery. So far,many inorganic solid electrolyte materials have been studied,including crystalline solid electrolyte such as NASICON-type,LISICON-type,perovskite-type,and garnet-type and other glassy solid electrolyte such as oxide and sulfide. Among them,the garnet-type Li_7La_3Zr_2O_(12) has excellent comprehensively electrochemical performance,which promises it a more practical application potential and more research value. Experiments and theoretical calculations show that this material has a high lithium ion conductivity( 10~(-4)～10~(-3) S·cm~(-1)),and can contact with the negative metal lithium and most of the cathode material in a more stable state,and its electrochemical window is as wide as 6 V. In this paper,we will introduce the crystal structure,preparation method and doping modification of Li_7La_3Zr_2O_(12) in detail basing on the research status at home and abroad in recent years,and then expound the development prospects and challenges of Li_7La_3Zr_2O_(12) as a solid electrolyte applying in all-solid-state lithium ion batteries.
At present,replacing traditional electrolytes with solid electrolytes to develop new all-solid-state lithium ion batteries has become an important technical method to solve the battery safety problems and improve the battery energy density.As the core material of all-solid-state lithium ion batteries,the performance of the solid electrolyte largely determines the performance of the battery. So far,many inorganic solid electrolyte materials have been studied,including crystalline solid electrolyte such as NASICON-type,LISICON-type,perovskite-type,and garnet-type and other glassy solid electrolyte such as oxide and sulfide. Among them,the garnet-type Li_7La_3Zr_2O_(12) has excellent comprehensively electrochemical performance,which promises it a more practical application potential and more research value. Experiments and theoretical calculations show that this material has a high lithium ion conductivity( 10~(-4)～10~(-3) S·cm~(-1)),and can contact with the negative metal lithium and most of the cathode material in a more stable state,and its electrochemical window is as wide as 6 V. In this paper,we will introduce the crystal structure,preparation method and doping modification of Li_7La_3Zr_2O_(12) in detail basing on the research status at home and abroad in recent years,and then expound the development prospects and challenges of Li_7La_3Zr_2O_(12) as a solid electrolyte applying in all-solid-state lithium ion batteries.
引文
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[72]Ramakumar S,Satyanarayana L,Manorama S V,et al.Physical Chemistry Chemical Physics Pccp[J],2013,15(27):11327.
[73]Cao Z Z,Ren W,Liu J R,et al.J Inorg Mater[J],2014,29:220.
[74]Ohta S,Kobayashi T,Asaoka T.Journal of Power Sources[J],2011,196(6):3342-3345.
[75]Liu C,Rui K,Shen C,et al.Journal of Power Sources[J],2015,282:286-293.
[76]Murugan R,Ramakumar S,Janani N.Electrochemistry Communications[J],2011,13(12):1373-1375.
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[78]Rangasamy E,Wolfenstine J,Sakamoto J.Solid State Ionics[J],2011,206(1):6.
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[82]Geiger C A,Alekseev E,Lazic B,et al.Inorganic Chemistry[J],2011,50(3):1089-1097.
[83]Narayanan S,Ramezanipour F,Thangadurai V.Journal of Physical Chemistry C[J],2012,116(38):20154-20162.
[84]Murugan R,Thangadurai V,Weppner W.Angewandte Chemie[J],2007,34(27):437-440.
[85]Logéat A,K9hler T,Eisele U,et al.Solid State Ionics[J],2012,206(3):33-38.