Li4Ti4.95Al0.05O12/C复合负极材料的制备及电性能研究

Li4Ti5O12是具有良好应用前景的锂离子电池负极材料之一.本研究以聚丙烯酰胺(PAM)为模板剂和碳源,采用改进的固相合成法制备锂离子电池负极材料Li4Ti4.95Al0.05O12和Li4Ti4.95Al0.05O12/C.利用X射线衍射仪、场发射扫描电镜等测试手段表征材料的物相结构和形貌.结果表明:Al掺杂未改变Li4Ti5O12的尖晶石结构,合成过程中PAM模板剂的引入能够有效调控材料微观形貌并降低颗粒团聚程度.采用恒流充放电和交流阻抗测试材料的电化学性能,Li4Ti4.95Al0.05O12/C复合材料的比容量和循环性能得到明显改善,0.2C倍率下首次充放电比容量分别达到159.2和160.8 mAh/g,5C倍率时仍有较好的循环性能.     

锂离子电池负极材料多孔Li4Ti5O12/C的制备与表征

将钛源、锂源和碳源三种化合物一起球磨湿混成均匀浆料,再依次经过喷雾干燥和高温煅烧制得晶粒表面包覆纳米碳层的多孔球形钛酸锂(Li4Ti5O12)材料.通过XRD、SEM、TEM、BET和电化学性能测试等分析手段表明,合成出的Li4Ti5O12/C材料为纳米一次粒子(晶粒)组成的球形二次粒子(颗粒),具有较大的比表面积,达到39.5 m2/g;在0.1C、1.0C和5.0C倍率下的首次放电比容量分别达到172.2、168.2和153.6 mAh/g,并表现出优良的循环性能.晶粒表面包覆碳的多孔Li4Ti5O12材料具有明显的高倍率性能和循环稳定性优势.     

球形纳米晶LiFePO4和Li4Ti5O12的制备及电池研究

分别通过"控制结晶"和"外凝胶"工艺合成了球形纳米晶LiFePO4/C和Li4Ti5O12/C材料.通过XRD、SEM、比表面及电化学性能测试等分析手段表明,合成的LiFePO4/C和Li4Ti5O12/C材料均为纳米一次粒子(晶粒)组成的球形二次粒子(颗粒),具有较大的比表面积,振实密度分别达到1.25和1.71g/cm3;1C倍率下的首次放电比容量分别达到144.0和144.2mAh/g,并表现出优良的循环性能.以LiFePO4/C和Li4Ti5O12/C为正负极材料组成的1.8V锂离子电池具有平稳的充放电电压平台和优异的循环性能.     

Li4Ti5O12负极材料的制备及其电化学性能研究

采用二步固相烧结法制备了Li4TiO12负极材料,优化了制备工艺条件.利用X射线衍射分析(XRD)、扫描电镜(SEM)等表征了材料的形貌和结构,并用充放电测试仪、循环伏安(CV)和交流阻抗(EIS)研究了材料的电化学性能.结果表明,合成的Li4Ti5O12具有单一的尖晶石结构和良好的电化学性能,0.1C首次放电比容量为158.9 mAh/g,循环20次后容量保持率为97.6％,1C倍率首次放电比容量为108.9mAh/g,循环20次后容量下降了3.05％.     

锂离子电池Li_4Ti_5O_(12)负极材料的尿素掺杂氮化修饰

Li4Ti5O12是最具前景的混合电动汽车用锂离子动力电池负极材料之一.为了提高其倍率性能,以尿素为氮源对Li4Ti5O12进行掺杂热处理,以在Li4Ti5O12颗粒表面自生长一层高电导TiN修饰膜,利用X射线衍射仪、扫描电镜、透射电镜、X射线能谱仪、Raman光谱仪和半电池充放电测试仪研究了材料的物相、结构、形貌、成分以及电化学性能.结果表明:氮化修饰Li4Ti5O12样品与未修饰样品具有相同的尖晶石Li4Ti5O12的衍射峰,氮化修饰后Li4Ti5O12颗粒表面自生长了一层均匀的薄膜,该薄膜不仅含有N元素,而且还具有TiN的Raman光谱特征振动峰;氮化修饰Li4Ti5O12样品的0.1C首次放电比容量比未修饰Li4Ti5O12样品有所降低,但是却展示了优异的电化学倍率性能和循环性能,3C倍率充放电比容量是未修饰Li4Ti5O12样品的2.6倍,0.1C充放电循环100次后其容量损失仅3%.     

高分散纳米晶Li_4Ti_5O_(12)电极材料的制备及电化学性能的研究

以月桂酸为分散剂,采用无水溶胶-凝胶法合成了高分散的Li4Ti5O12纳米晶.采用XRD、SEM、TG-DSC、激光粒度分析仪、交流阻抗以及恒流充放电测试,对材料的形貌、结构和电化学性能进行表征.结果表明,煅烧温度对Li4Ti5O12的结晶度、微观形貌及其电化学性能有显著的影响.800℃下热处理10h后的产物,颗粒尺寸细小均匀,约在120~275nm之间,显示出优异的电化学性能.在0.5和1C倍率下,首次放电比容量分别可达174.7和163.3mAh/g,经过50次放电循环后,放电容量循环性能优异.研究表明该高分散纳米颗粒的合成方法是适合制备高电化学性能的Li4Ti5O12材料的工艺方法.     

Li4Ti5O12-聚苯胺复合材料的制备与电化学性能

以醋酸锂和钛酸四丁酯为原料，以乙醇为溶剂，采用溶胶．凝胶法制备Li4Ti5O12；以苯胺、过硫酸铵为原料，以盐酸为溶剂，采用原位聚合法合成Li4Ti5O12-聚苯胺复合材料。采用x射线衍射、红外光谱和电化学测试等对复合材料进行了表征。结果表明，聚苯胺的加入明显提高了Li4Ti5O12的电子导电性能，Li4rri5O12-PAn复合材料具有比Li4Ti5O12更好的高倍率性能和循环稳定性。0.1C和2.0C放电时Li4Ti5O12-PAn的放电容量达到了191．3和148．9mAh．g^-1，经80次循环后二者平均每次循环容量衰减率分别为0．13％和0．61％。     

尖晶石钛酸锂的三乙醇胺辅助溶胶-凝胶法合成及其性能

以三乙醇胺为配位剂,Ti(OC4H9)4和LiAc·2H2O为原料,通过溶胶-凝胶法制备锂离子电池负极材料尖晶石Li4Ti5O12。通过X射线衍射、扫描电子显微镜、循环伏安、电化学阻抗和恒流充放电分析检测产物的结构、形貌及电化学性能。结果表明:配位剂的用量对Li4Ti5O12结构及电化学性能有显著影响,其中三乙醇胺与Ti摩尔比为0.8时,Li4Ti5O12具有良好的的电化学性能。1.0C下,其首次放电容量为153.0mAh·g-1,35次循环后放电容量仍为139.9mAh·g-1,容量保持率为91.5%。     

己二酸辅助溶胶-凝胶法合成Li_4Ti_5O_(12)及其电化学性能

以己二酸为络合剂,通过溶胶-凝胶法合成了具有优良电化学性能的电极材料Li4Ti5O12。采用XRD、SEM、恒流充放电测试对材料的结构、形貌和电化学性能进行了表征。结果表明:通过该法制备的样品为颗粒细小均匀的立方尖晶石Li4Ti5O12纯相,并显示出优良的电化学性能;0.1C倍率下首次放电比容量为169.59mAh/g,经过30充放电循环后仍然保持在158.17mAh/g。在2.0C倍率下,其可逆容量仍可达到124mAh/g,表现出良好的倍率性能。     

改进固相法制备Li4Ti4.95Nb0.05O12及其性能研究

为提高Li4Ti5O12的导电性和倍率性能,应用二步固相法制备了Nb掺杂的Li4Ti4.95Nb0.05O12负极材料,X射线衍射、扫描电镜、激光粒度分布仪、充放电测试、循环伏安和交流阻抗等测试结果表明,合成的样品具有单一的尖晶石结构和平稳的充放电平台,粒径分布均匀,Nb掺杂改性的Li4Ti5O12具有优良的电化学性能,0.1、0.5、1和10C首次放电比容量分别为174.1、159.7、147和123.3mAh/g。10C下,循环20次后容量保持为118.1mAh/g。     

Li4Ti5O12／C复合负极材料的一步固相合成及不同碳源的影响

采用固相合成的方法，以Li2CO3，TiO2为原料，分别以葡萄糖、柠檬酸、聚丙烯及三者的混合物作为碳源一步烧结合成了亚微米级的Li4Ti5O12／c复合负极材料,XRD结果显示其具有理想的尖晶石结构。研究结果表明，以葡萄糖作为碳源制备的Li4Ti5O12／c材料的性能最佳，其碳含量最高，为2．07％，0.5c和1c倍率下的放电容量分别达到了220和191mAh／g。     

Surface-Engineered Li4Ti5O12 Nanostructures for High-Power Li-Ion Batteries

Materials with high-power charge–discharge capabilities are of interest to overcome the power limitations of conventional Li-ion batteries.In this study,a unique solvothermal synthesis of Li4Ti5O12 nanoparticles is proposed by using an off-stoichiometric precursor ratio.A Li-deficient off-stoichiometry leads to the coexistence of phaseseparated crystalline nanoparticles of Li4Ti5O12 and TiO2 exhibiting reasonable high-rate performances.However,after the solvothermal process,an extended aging of the hydrolyzed solution leads to the formation of a Li4Ti5O12 nanoplate-like structure with a self-assembled disordered surface layer without crystalline TiO2.The Li4Ti5O12 nanoplates with the disordered surface layer deliver ultrahighrate performances for both charging and discharging in the range of 50–300C and reversible capacities of 156 and 113 mAh g−1 at these two rates,respectively.Furthermore,the electrode exhibits an ultrahigh-charging-rate capability up to 1200C(60 mAh g−1;discharge limited to 100C).Unlike previously reported high-rate half cells,we demonstrate a high-power Li-ion battery by coupling Li4Ti5O12 with a high-rate LiMn2O4 cathode.The full cell exhibits ultrafast charging/discharging for 140 and 12 s while retaining 97 and 66% of the anode theoretical capacity,respectively.Room-(25℃),low-(−10℃),and high-(55℃)temperature cycling data show the wide temperature operation range of the cell at a high rate of 100C.     

Carbon-coated Li_4Ti_5O_(12) Anode Materials Synthesized Using H_2TiO_3 as Ti Source

Two low-cost synthesis routes have been developed to fabricate carbon-coated Li4Ti5O12 by using H2TiO3 instead of anatase TiO2 as Ti source through solid-state reaction process. One route is a direct solid mixture of H2TiO3, Li2CO3 and pitch followed by high-temperature solid-state reaction. The other includes mixture of H2TiO3 and Li2CO3 with pitch dissolved in furanidine under vacuum and the same solid-state reaction procedure is followed after the mixture is totally dried. Microstructural investigations indicate that H2TiO3 exhibits secondary aggregates morphology with primary particle sizes of 10-20 nm. Carbon-coating layers with thickness of 2-3 nm have been observed on Li4Ti5O12 synthesized by the two routes. Cyclic performance, rate capability and electrochemical impedance spectrum of the two Li4Ti5O12/C composites have been performed, which indicate that Li4Ti5O12/C obtained by furanidine-assisted mixture exhibits better electrochemical performance than Li4Ti5O12/C synthesized by direct solid mixture. The possible reasons have been discussed. The low-cost synthesis routes of Li4Ti5O12/C using H2TiO3 as Ti source are expected to be more competitive than the traditional one for practical applications.     

锂离子电池负极材料球形钛酸锂的合成及性能

以3.98mol/L的四氯化钛为前驱体溶液,采用内凝胶法制备了具有尖晶石结构的球形钛酸锂(Li4Ti5O12)粉末。通过XRD、SEM及电化学性能测试等分析手段表明,合成的Li4Ti5O12材料均为纳米一次粒子(晶粒)组成的球形二次粒子(颗粒),且具有较大的比表面积。以这种流动性好、粒径分布均匀、结晶度好的球形钛酸锂为正极材料和Li片为负极材料组成的锂离子电池具有平稳的充放电电压平台和优异的循环性能。在1.0~2.5V充放电,其首次放电容量为173.8mAh/g,经30次充放电循环后,其放电比容量仍有170.2mAh/g。     

含碳纳米管导电剂改善Li_4Ti_5O_(12)电极电化学性能

采用一种较为实用的调浆方法,考察了碳纳米管与乙炔黑的复合物(CNTs/AB)导电剂、乙炔黑(AB)导电剂和碳纳米管(CNTs)导电剂对Li_4Ti_5O_(12)电化学性能的影响,并用恒流充放电、扫描电子显微镜(SEM)和交流阻抗(AC)对添加上述3种导电剂制备得到的电极片进行研究.结果表明,采用该调浆流程能够克服CNTs在使用时出现的团聚问题,CNTs/AB复合物在改善Li_4Ti_5O_(12)电化学性能尤其在容量发挥和倍率性能方面比单一AB和CNTs具有明显优势.CNTs/AB复合物中两者的质量百分比为1:2～1:1时,0.5C时,Li_4Ti_5O_(12)电极的首次放电容量可高达157.0mAh/g,10.0C时,其放电容量可达到128.3mAh/g.与单一导电剂AB和CNTs相比,CNTs与AB复合使用时,由于CNTs的高长径比和良好导电性能使之能够起到"桥梁"作用把部分没有与活性物质充分接触的颗粒状导电剂AB与活性物质连接起来,因此两者的有机结合提高了CNTs/AB与活性材料的接触面积,使电极片能够形成有效的导电网络,有利于Li_4Ti_5O_(12)导电性能的提高.     

负极活性材料Li4Ti5O12的研究进展

介绍了负极材料Li4Ti5O12的物理特性和电化学性能，详细介绍并评述了Li4Ti5O12在锂离子电池和不对称型超级电容器中的应用情况，总结了Li4Ti5O12的不同合成方法及材料的电化学改性研究进展．     

Optimized Li4Ti5O12 nanoparticles by solvothermal route for Li-ion batteries

Li4Ti5O12 (LTO) nanoparticles were successfully synthesized by solvothermal technique using cost-effective precursors in polyol medium and post-annealed at temperatures of 400, 500, and 600 degrees C. The XRD patterns of the samples were clearly indexed to the spinel shaped Li4Ti5O12 (space group, Fd-3 m). The particle size and morphology of samples were identified using field-emission SEM. The electrochemical performance of solvothermal samples revealed fairly high initial discharge/charge specific capacities in the range 230-235 and 170-190 mAh/g, at 1 C-rate, while that registered for the solid-state sample has been 160 and 150 mAh/g, respectively. Furthermore, among these samples, LTO annealed at 500 degrees C exhibited highly improved rate performances at C-rates as high as 30 and 60 C. This was attributed to the achievement of small particle sizes with high crystallinity in nano-scale dimensions and hence shorter diffusion paths combined with larger contact area at the electrode/electrolyte interface.     

碳源对液相法制备Li3V2（PO4）3/C的影响

以4种不同种类的有机物(柠檬酸、水杨酸、聚丙烯酸、蔗糖)为碳源,通过液相反应合成Li3V2(PO4)3/C复合材料。研究了不同碳源对复合材料的晶型结构、形貌及电化学性能的影响。结果表明,碳源对Li3V2(PO4)3/C材料的晶型结构没有影响,但对电化学性能影响较明显,其中采用柠檬酸为碳源制得的Li3V2(PO4)3/C复合材料电化学性能最好。进一步研究了柠檬酸的加入量对复合材料的电化学性能的影响,发现当柠檬酸加入量为钒与碳的物质的量比为1∶4时,样品的平均粒径较小,电化学性能最好,0.1C首次放电比容量为123.59mAhg-1,0.5C首次放电比容量也高达117.27mAhg-1,循环10次后,仍保持在117.19mAhg-1,容量几乎没有衰减,10C时比容量仍有105.43mAhg-1。