Li_4Ti_5O_(12)/Li_(1.3)Al_(0.3)Ti_(1.7)(PO_4)_3复合负极材料的制备及性能

采用溶胶-凝胶法合成了Li_4Ti_5O_(12)/Li_(1.3)Al_(0.3)Ti_(1.7)(PO_4)_3复合负极材料,通过X射线衍射、扫描电子显微镜、恒电流充放电、循环伏安和电化学阻抗研究复合材料的结构、形貌及电化学性能。结果表明:溶胶-凝胶法能合成纯相Li_4Ti_5O_(12)/Li_(1.3)Al_(0.3)Ti_(1.7)(PO_4)_3复合负极材料颗粒均匀。与纯相Li_4Ti_5O_(12)相比,引入Li_(1.3)Al_(0.3)Ti_(1.7)(PO_4)_3的Li_4Ti_5O_(12)复合负极材料具有更低的锂离子嵌入/脱出阻抗,Li_(1.3)Al_(0.3)Ti_(1.7)(PO_4)_3质量分数为1%、2%、3%、4%、5%的Li4Ti5O12复合负极材料首次放电容量比纯相Li_4Ti_5O_(12)分别提高了6.2%、11.8%、15.5%、8.0%和2.0%。充放电循环20次后,Li_(1.3)Al_(0.3)Ti_(1.7)(PO_4)_3质量分数为3%的Li_4Ti_5O_(12)复合负极材料循环性能最好,平均每次循环容量衰减率为0.022%。     

制备方法对尖晶石Li4Ti5O12负极材料的性质影响

采用高温固相法、热聚合法和改良溶胶-凝胶法制备锂离子电池负极材料Li4Ti5O12。通过X-射线衍射、扫描电镜、恒电流充放电及电化学阻抗等技术和手段表征合成产物的结构、形貌及电化学性能。结果表明：溶胶-凝胶法合成的粉末为纯相Li4Ti5O12,而高温固相法和聚合法合成的Li4Ti5O12则存在TiO2杂相。高温固相法合成的Li4Ti5O12粉末晶粒最大,溶胶-凝胶法合成的粉末晶粒最小,分布最为均匀,晶粒尺寸约为80nm。高温固相法、热聚合法和溶胶-凝胶法制备的Li4Ti5O12粉末首次放电容量分别为161.6mAh/g、165.9mAh/g和171.5mAh/g,循环25次后的容量保持率分别为84.7%、87.7%和94.3%,溶胶-凝胶法合成的Li4Ti5O12粉末电化学性能最好。     

Li3PO4助熔剂添加对Li1.3Al0.3Ti1.7(PO4)3性质的影响研究

采用溶胶-凝胶法合成Li1.3Al0.3Ti1.7(PO4)3粉末,向Li1.3Al0.3Ti1.7(PO4)3粉末中添加不同摩尔分数的Li3PO4助熔剂烧结制备锂离子固体电解质Li1.3Al0.3Ti1.7(PO4)3烧结片。通过X射线衍射仪、扫描电子显微镜研究合成产物的结构与形貌,采用循环伏安及交流阻抗技术研究合成产物的氧化-还原电位、离子电导率和活化能。结果表明,添加与未添加Li3PO4助熔剂的Li1.3Al0.3Ti1.7(PO4)3烧结片具有相似的X射线衍射结果。添加Li3PO4的Li1.3Al0.3Ti1.7(PO4)3烧结片空隙率较小,更为致密。添加Li3PO4对Li1.3Al0.3Ti1.7(PO4)3的氧化-还原电位影响不大。在所有添加Li3PO4助熔剂的Li1.3Al0.3Ti1.7(PO4)3烧结片中,添加摩尔分数1%Li3PO4的烧结片具有最高的离子电导率6.15×10-4S.cm-1和最低的活化能0.314 2 eV。     

助熔剂LiBO2对Li1.3Al0.3Ti1.7(PO4)3性质的影响

采用溶胶-凝胶法合成了Li1.3Al0.3.Ti1.7(PO4)3粉末,然后添加不同摩尔分数的LiBO2助熔剂在900℃烧结2h制备了Li1.3Al0.3.Ti1.7(PO4)3烧结片样品.通过X射线衍射和扫描电子显微镜分析了合成产物的相组成与形貌,采用循环伏安及交流阻抗技术研究了产物的氧化-还原电位、离子电导率与活化...     

固体电解质包覆LiMn2O4正极材料的合成及表征

采用湿化学法制备Li1.3Al0.3Ti1.7(PO4)3包覆LiMn2O4。采用X射线衍射、扫描电镜、恒电流充放电等技术对合成产物进行物相、形貌和电化学分析。结果表明:Li1.3Al0.3Ti1.7(PO4)3包覆LiMn2O4与LiMn2O4有相似的X射线衍射结果,且包覆后的LiMn2O4循环伏安峰电流和电荷转移阻抗变化不大。室温及55℃,以0.2 C充放电倍率循环40次时,Li1.3Al0.3Ti1.7(PO4)3包覆LiMn2O4的容量保持率分别为98.2%和93.7%,未包覆的LiMn2O4的容量保持率分别为85.4%和79.1%。当以2 C倍率室温充放电循环时,Li1.3Al0.3Ti1.7(PO4)3包覆LiMn2O4的容量保持率比未包覆的LiMn2O4高8%;55℃充放电循环时,Li1.3Al0.3Ti1.7(PO4)3包覆LiMn2O4的容量保持率比未包覆的LiMn2O4高11.1%。     

制备方法对尖晶石Li_4Ti_5O_(12)负极材料性质的影响

采用高温固相法、热聚合法和改良溶胶-凝胶法制备锂离子电池负极材料Li4Ti5O12。通过X射线衍射、扫描电镜、恒电流充放电及电化学阻抗表征了合成产物的结构、形貌及电化学性能。结果表明,溶胶-凝胶法合成的粉末为纯相Li4Ti5O12,而高温固相法和聚合法合成的Li4Ti5O12则存在TiO2杂相。高温固相法合成的Li4Ti5O12粉末晶粒最大,溶胶-凝胶法合成的粉末晶粒最小,分布最为均匀,晶粒尺寸约为80 nm。高温固相法、热聚合法和溶胶-凝胶法制备的Li4Ti5O12粉末首次放电容量分别为161.6、165.9 mA·h/g和171.5 mA·h/g,循环25次后的容量保持率分别为84.7%、87.7%和94.3%,溶胶-凝胶法合成的Li4Ti5O12粉末电化学性能最好。     

不同热处理方式对Li1.3Al0.3Ti1.7(PO4)3薄膜性质的影响研究

采用快速退火和常规退火两种不同热处理方式制备Li1.3Al0.3Ti1.7(PO4)3薄膜,用X射线衍射、扫描电子显微镜、循环伏安及交流阻抗等技术分析检测薄膜物相、形貌、电化学窗口、离子电导率及电导活化能。结果表明,两种退火方式制备的薄膜均为纯相Li1.3Al0.3Ti1.7(PO4)3,制备的薄膜均匀、无龟裂,但采用快速退火制备的薄膜晶粒比采用常规退火制备的薄膜要小,薄膜更光滑更致密。两种退火方式制备的薄膜电化学窗口都超过了2.4 V,薄膜离子电导率分别为2.7×10-6 S/cm和1.4×10-6 S/cm。采用快速退火制备的Li1.3 Al0.3 Ti1.7(PO4)3薄膜离子电导活化能比采用常规退火制备的薄膜要小。     

Li4Ti5O12@C复合材料的制备及其性质研究

本文以葡萄糖为碳源,采用原位复合法制备锂离子电池复合负极材料Li4Ti5O12@C,同时探讨了不同碳包覆量对Li4Ti5O12的影响。通过X-射线衍射和扫描电子显微镜对合成出的材料结构及表面形貌进行表征,采用恒电流充放电和电化学阻抗等技术对其进行电化学性能测试。结果表明：碳包覆量为3 %的Li4Ti5O12颗粒均匀且电化学性能最好。在0.5 C下,首次放电比容量为185.9 mAh/g,循环50次后,其放电比容量仍为161.5 mAh/g。在2.0 C下,首次放电比容量为99.9 mAh/g,材料表现出优良的电化学性能。     

以竹叶为碳源制备Li4Ti5O12/C复合材料

以钛酸四丁酯、醋酸锂、柠檬酸和竹炭为原料,采用两步煅烧和溶胶-凝胶法制备锂离子电池Li4Ti5O12/C负极材料。采用XRD、SEM表征材料的微观结构和形貌。采用恒流充放电、交流阻抗和循环伏安法研究材料的电化学性能。结果显示,Li4Ti5O12/C具有良好的结晶度,颗粒表面光滑,分散均匀,粒径为200~300 nm。10 C倍率下,Li4Ti5O12/C的首次放电比容量为180.4 mA•h/g,循环300圈后为167.5 mA•h/g,容量保持率为92.8%,远高于Li4Ti5O12的46.9%。在20 C大倍率下,Li4Ti5O12/C和Li4Ti5O12的容量保持率分别为68.9%和41.3%     

二次锂离子电池负极材料Li4Ti5O12的研究进展

Li4Ti5O12由于其长的循环寿命及高的安全性能,成为二次锂离子电池,特别是动力电池的优秀候选材料.本文综述了负极材料Li4Ti5O12的结构、合成方法、物理特性和电化学性能,着重介绍了各种元素的掺杂对Li4Ti5O12循环容量、充放电电压平台及高倍率性能的影响.     

Hydrothermal synthesis of spherical Li4Ti5O12 material for a novel durable Li4Ti5O12/LiMn2O4 full lithium ion battery

Pure spherical Li₄Ti₅O₁₂ spinel material is quickly synthesized via an efficient hydrothermal procedure. The obtained Li₄Ti₅O₁₂ particle size is about 0.5 µm. The Li₄Ti₅O₁₂ has an initial discharge capacity of 162.2 mA h g⁻¹ and capacity retention of 97.5% after 100 cycles at a rate of 0.2 C. Then, a 2.5 V and long-lasting Li-ion cell with a LiMn₂O₄ cathode and a Li₄Ti₅O₁₂ anode is developed. Electrochemical measurements of the cell indicate that the Li₄Ti₅O₁₂/LiMn₂O₄ full cell, with a weight ratio of 1.5 between cathode and anode, exhibits excellent electrochemical performance, delivering a reversible capacity of 130 mA h g⁻¹ at room temperature. The full cell also exhibits outstanding electrochemical performances at high temperature, as it has an initial discharge capacity of 109.6 mA h g⁻¹, along with a capacity retention rate of 88.9% after 100 cycles at 55 °C.     

Chemically driven synthesis of Ti3+ self-doped Li4Ti5O12 spinel in molten salt

Surface doping of Li₄Ti₅O₁₂ (LTO) with Ti³⁺ ions is an effective way to enhance its electrochemical properties for lithium ion batteries (LIBs). Herein, a molten salt approach was reported to synthesize Ti³⁺ self-doped LTO powder. The reaction mechanism and the role of molten salt for the synthesis have been systemically discussed. Finally, electrochemical performance of the LTO powder was preliminarily evaluated as anode material of LIBs. The molten salt accelerated the mass transportation for the formation of LTO by transferring a solid diffusion to the diffusion of ions in a liquid media. Self-doping of Ti³⁺ ions on the surface of LTO particles was achieved by controlling equilibriums of chemical reactions in the reactor. Electrochemical performance of the LTO powders was effectively promoted by doping Ti³⁺ ions on the surface. The discharge capacity of the Ti³⁺ self-doped LTO powder prepared at 850°C was 171 mAhg⁻¹, and the capacity dacayed 9.9% after 200 cycles at a rate of 0.5 C.     

无定形TiO2合成尖晶石Li4Ti5O12的性能

用无定形TiO2与Li2CO3高温固相反应合成了性能良好的"零应变"电极材料Li4Ti5O12. XRD, SEM和激光粒度分析表明,产物结晶度好,无杂质相,为纯立方尖晶石相,Li4Ti5O12颗粒呈砾石状形貌,有团聚现象,平均粒度约2.66 μm. Li4Ti5O12电极具有较宽的充放电平台,循环性能稳定. 以0.1 C电流比率恒电流充放电,首次放电容量和循环容量分别达180和150 mA·h/g. 交流阻抗谱研究发现,Li4Ti5O12不同嵌锂程度下的电导率对其电极的电化学阻抗具有较大影响,电极的Warburg阻抗曲线斜率与其荷电状态相关.     

Conductive PProDOT-Me2–capped Li4Ti5O12 microspheres with an optimized Ti3+/Ti4+ ratio for enhanced and rapid lithium-ion storage

Li₄Ti₅O₁₂ (LTO) has attracted much attention for its use as an anode material within lithium-ion batteries (LIBs), owing to its excellent safety and outstanding cyclability. Unfortunately, the poor electronic conductivity of LTO greatly limits the rate capability of the LIBs and, therefore, its practical applications. The conductivity of LTO can be enhanced significantly through thermal treatment under hypoxic conditions to form oxygen vacancies. The defective LTO with oxygen vacancies has a much higher electric conductivity, owing to partial reduction of the Ti ions (from Ti⁴⁺ to Ti³⁺). Too many oxygen vacancies generated in the LTO will, however, also cause severe lattice distortion, inhibiting ionic transfer. In this study, we optimized the Ti³⁺/Ti⁴⁺ ratio of LTO by annealing it under various conditions. We also modified the surface of LTO with a thin layer of poly (dimethyl 3,4-propylenedioxythiophene) (PProDOT-Me₂) through in situ chemical polymerization. Studies of the surface morphology and chemical composition confirmed that PProDOT-Me₂ had been successfully capped on the LTO surface. Combining the effects of the optimal Ti³⁺/Ti⁴⁺ ratio and the surface modification with PProDOT-Me₂ resulted in the charge and ionic transport properties of LTO both improving significantly. Accordingly, the nanocomposites displayed greatly enhanced rate capabilities, relative to those of the unmodified material.     

Li4Ti5O12/Fe3O4复合材料的制备及其电化学性能

以醋酸锂和钛酸四正丁酯为原料,制备了纯相Li_4Ti_5O_(12),再用简单的水热法合成Li_4Ti_5O_(12)/Fe_3O_4复合材料作为锂离子电池的负极材料,通过XRD、SEM以及电池测试系统对纯相Li_4Ti_5O_(12)和Li_4Ti_5O_(12)/Fe_3O_4复合材料进行了结构、形貌及电化学性能测试。结果表明,制得的复合物具有较好的球形结构且粒径较小(200～300 nm),综合电化学性能较好。由于复合的Fe_3O_4有较高的理论容量,该Li_4Ti_5O_(12)/Fe_3O_4复合材料表现出比纯相Li_4Ti_5O_(12)大的容量,在1.0 C下循环100圈后,Li_4Ti_5O_(12)/Fe_3O_4的放电比容量仍能达到470.2 m A·h/g,同时也表现出比纯相Li_4Ti_5O_(12)更优的倍率性能。     

Nickel percolation and coarsening in sintered Li4Ti5O12 anode composite

Inherently safe all-solid-state lithium-ion battery anodes with high electronic and ionic conductivity are sought to enable next-generation electric propulsion systems. In novel architectural concepts, multifunctionality of battery materials will provide simultaneous mechanical load bearing and electrochemical energy storage functionality for systems level mass savings. Co-processing of strain-free lithium titanate anode and nickel current collector was explored to provide structural integrity and electrical conductivity for a load-bearing anode with bulk current collection capability. In this study, the effects of processing conditions on densification, electrical conductivity, and microstructural evolution were characterized for Li₄Ti₅O₁₂-Ni (LTO-Ni) composites. Densification of LTO-Ni was achieved at 900°C and above, and nickel content had minimal effect on final density compared to sintering temperature and time. Electronic conductivity was modeled by percolation theory, exhibiting a large dependence on nickel content and bulk density. Bulk electrical conductivity greater than 1 S/cm was achieved at volume fractions above the percolation threshold. Modeling of microstructural evolution applied Ostwald ripening theories to describe diffusion governing the growth of average nickel particle size and the change in size distributions. Volume fraction effects resulted in larger average Nickel particle sizes and an activation energy of 1.04 eV was measured for nickel particle coarsening.     

Li_4Ti_(4.95)Nb_(0.05)O_(12)负极材料的制备及其电化学性能研究

采用二步固相法制备了Li_4Ti_(4.95)Nb_(0.05)O_(12)负极材料,扫描电镜、激光粒度分布仪、充放电测试和循环伏安等测试结果表明:合成的样品粒径分布均匀,Nb掺杂改性的Li_4Ti_5O_(12)具有优良的电化学性能,0.1 C、0.5 C、1 C和10 C首次放电比容量分别为174.1 m Ah/g、159.7 m Ah/g、147 m Ah/g和123.3 m Ah/g。10 C下,循环20次后容量保持为118.1 m Ah/g。