锂离子电池负极材料Ge4+掺杂Li4Ti5O12的制备及其电化学性能研究

以Ti(OC₄H₉)₄、CH₃COOLi·2H₂O和GeO₂为原料, 采用溶胶-凝胶法合成了尖晶石型Li₄Ti_5-xGe_xO₁₂(x=0、0.05、0.1、0.15)电极材料。通过X射线衍射(XRD)、扫描电镜(SEM)、充放电测试、循环伏安(CV)以及交流阻抗对材料进行结构、形貌及电化学性能表征。研究结果表明, 适量Ge⁴⁺掺杂不会改变Li₄Ti₅O₁₂的尖晶石结构, 但对其颗粒尺寸和形貌均产生影响。由于掺Ge⁴⁺后样品的颗粒尺寸减小, 使得Ge⁴⁺掺杂Li₄Ti₅O₁₂倍率性得到不同程度的提高。其中Li₄Ti_4.9Ge_0.1O₁₂显示出较好的倍率性和循环稳定性, 0.2C下的首次放电容量为172.43 mAh/g, 5C下循环100次后比容量为140.62 mAh/g, 容量保持率为97.3%。     

Y3+掺杂Li4Ti5O12负极材料的电荷输运特性及电化学性能研究

以Li₂CO₃与锐钛矿型TiO₂为原料,六水合硝酸钇（Y（NO₃）₃·6H₂O）为钇源,采用球磨辅助固相法合成了Li₄Ti_5-xY_xO₁₂（x=0,0.05,0.10,0.15,0.20）负极材料。通过X射线衍射分析（XRD）、扫描电镜（SEM）、能谱仪（EDS）与X射线光电子能谱（XPS）分别对材料的物相与形貌进行表征分析,并利用电化学工作站对材料的电化学性能与电荷输运特性进行测试。结果表明,Y³⁺掺杂没有影响尖晶石型Li₄Ti₅O₁₂（LTO）材料的尖晶石结构,x=0.15时,Li₄Ti_4.85Y_0.15O₁₂样品的离子与电子电导率分别为2.68×10^-7 S·cm^-1和1.49×10^-9 S·cm^-1,比本征材料提升了1个数量级,表现出良好的电荷输运特性。电化学测试表明,Li₄Ti_4.85Y_0.15O₁₂样品在0.1 C倍率首次放电比容量可达171 mAh·g^-1,且在10 C与20 C高倍率下仍然拥有102 mAh·g^-1和79 mAh·g^-1的较高比容量,循环200周次后容量保持率分别为92.6%和89.1%,表现出良好的倍率特性。     

锂离子电池负极材料钛酸锂的研究进展

锂离子电池作为一种动力能源, 在电动汽车和各种储能系统中有着良好的应用前景。尖晶石结构的钛酸锂(Li₄Ti₅O₁₂)负极材料具有较高的脱嵌锂电位平台、优异的循环稳定性、以及突出的安全性能, 被认为是一种非常有潜力的锂离子电池负极材料, 在锂离子动力电池中具有巨大的发展潜力。然而, 尖晶石型Li₄Ti₅O₁₂存在着本征导电率低, 理论容量小等缺陷, 极大地限制了其规模化应用, 需要进一步改善和提高。本文总结了尖晶石型Li₄Ti₅O₁₂材料在结构形貌、制备方法和性能方面的研究进展, 深入分析和讨论了离子掺杂、碳表面改性和纳米化等改性方法对尖晶石型Li₄Ti₅O₁₂综合电化学性能的改善效果, 并展望了尖晶石型Li₄Ti₅O₁₂作为锂离子电池负极材料未来的发展方向。     

水热法制备锂离子二次电池用球形Li4Ti5O12负极材料及其电化学性能

以LiOH溶液和不同粒径的自制球形TiO₂为反应物, 通过水热法快速地合成了尖晶石型结构的球形Li₄Ti₅O₁₂, 并考察了材料合成的水热反应机理和电化学性能。TiO₂在100℃、5 mol/L LiOH溶液中经水热反应20 h得到前驱体, 再经800℃热处理2 h便可得到粒径大小不同(0.5~1.5 µm)且分布均匀的球形尖晶石Li₄Ti₅O₁₂材料。LiOH在水热反应条件下扩散到球形TiO₂内部, 得到在分子水平混合均匀的Li-Ti-O中间体, 利于高温下生成纯相的尖晶石Li₄Ti₅O₁₂。所得粒径大小不同的Li₄Ti₅O₁₂材料均表现出稳定的电化学循环充放电性能, 其中, 粒径为0.5 µm 的Li₄Ti₅O₁₂材料的电化学性能最好: 室温下, 以0.2 C的倍率进行充放电, 其可逆容量达到158 mAh/g, 70周后容量保持率高于99%; 同时还表现出优异的高温循环稳定性, 55℃下以0.2 C的倍率进行充放电, 50次循环后其可逆放电比容量仍能达到125 mAh/g。     

基于纳米多孔钛酸锂结构的染料敏化太阳电池复合光阳极研究

本研究探索了具有良好导电性能的多孔钛酸锂结构对传统氧化钛纳米晶光阳极的增强效果。以钛酸四丁酯、氢氧化锂为源, 采用溶胶-凝胶结合溶剂热反应和高温烧结方法, 制备了具有多孔结构的尖晶石型Li₄Ti₅O₁₂纳米粉体; 在表征其结晶性、微观形貌及孔结构的基础上, 将其与TiO₂纳米晶浆料复合, 制备复合光阳极, 并详细考察了钛酸锂掺量、结晶性和孔结构等对电池光电转换性能的影响规律。结果表明: 随热处理温度升高, Li₄Ti₅O₁₂结晶性增强, 晶粒尺寸明显增大, 比表面积下降。掺入Li₄Ti₅O₁₂粉体可以有效提高光阳极膜的染料负载量, 降低TiO₂/染料分子/电解液界面的电子传输阻抗, 从而明显提高复合光阳极的光电流密度(J_sc=13.91 mA/cm²)和开路电压(V_oc =0.8 V)。Li₄Ti₅O₁₂含量为1wt%的复合光阳极电池光电转化效率最好, 达到7.011%, 比纯TiO₂电池(效率: 5.384%)提高30%。     

湿化学法合成富锂和掺铝尖晶石型锰酸锂及其电性能的改善

采用湿化学法–后续热处理技术, 合成了尖晶石型锰酸锂正极材料Li_1.035Mn_1.965O₄ 和Li_1.035Al_0.035Mn_1.930O₄。X射线衍射(XRD)结果表明这两种材料呈现出良好的尖晶石型结构。透射电子显微镜(TEM)表明Li_1.035Al_0.035Mn_1.930O₄材料具有很好的结晶态。充放电测试表明Li_1.035Al_0.035Mn_1.930O₄材料具有优良的循环性能和倍率性能: 以0.5C充放电, 经过100次循环后放电容量保持率为96.4%, 经过4C放电后仍然能够保持0.5C放电态容量的79.6%。     

Sb掺杂O3型Na0.9Ni0.5Mn0.3Ti0.2O2钠离子电池正极材料

提高钠离子电池正极材料的循环稳定性和比容量是实现其广泛应用的关键,基于引入特定杂元素可优化正极材料结构稳定性和比容量的策略,本研究采用便捷的固相反应法制备O3-Na_0.9Ni_0.5Mn_0.3Ti_0.2O₂(NMTSb_x, x=0,0.02, 0.04, 0.06)系列层状氧化物正极材料,对比研究了Sb掺杂对Na_0.9Ni_0.5Mn_0.3Ti_0.2O₂正极材料储钠性能的影响。测试结果表明,引入Sb后过渡金属层中氧原子之间的静电斥力减小,晶格间距扩大,有利于Na⁺的脱嵌。且掺杂Sb所造成的强电子离域降低了整个系统的能量,获得了更有利于循环充放电的稳定性结构。在2.0～4.2 V测试范围下,未掺杂的NMTSb₀在1C(240mA·g^-1)倍率下初始放电比容量为122.8mAh·g^...     

四氧化三钴及掺杂材料电催化性能的研究进展

综述了Co₃O₄及掺杂材料的性质、结构和电催化性能。Co₃O₄中的钴离子是Co²⁺和Co³⁺的混合价。由于Co₃O₄具有独特的尖晶石晶体结构，有利于Co²⁺和Co³⁺离子之间的电子传导，具有空电子轨道且易实现晶格氧化可作为氧还原反应(ORR)催化剂。综述了Co₃O₄的电催化性能的影响因素主要由其表面积和电子态决定，表面积通过调整纳米结构的大小和形貌来调节，电子态可以通过掺入第三种元素或氧空位来调控。综述了Co₃O₄掺杂不同材料后均表现出优异的催化性能与良好甲醇耐受性。Co₃O₄与Pd掺杂可以提高金属Pd在载体表面的分散性，降低金属颗粒团聚；Co₃O₄与P的组合使催化剂的内在活性增强；Co_...     

钴钛共掺杂对LiNiO2正极材料电化学性能的影响

本文采用溶胶-凝胶法制备了钴和钛共掺杂的层状LiNi_0.82Co_0.15Ti_0.03O₂正极材料,研究了离子掺杂对LiNiO₂材料电化学性能的影响。XRD和XPS分析显示,钴和钛共掺杂可以抑制Li+和Ni2+离子在Li层的混排现象。电化学测试结果表明,钴单元素掺杂可以显著提高LiNiO₂材料的倍率性能,而钛单掺杂则提高了材料的循环稳定性。进一步地,通过钴钛共掺杂的协同作用,可以使LiNiO₂材料的倍率性能和循环稳定性同时得到极大的提高。在200 mA/g的电流密度下循环200次,LiNi_0.82Co_0.15Ti_0.03O₂材料的容量保持率高达94.4%,而未掺杂的LiNiO₂材料容量保持率仅为57.1%;且在1000 mA/g的电流密度下,放电比容量仍能维持在100 mAh/g左右。     

Er2O3掺杂Gd2(Zr0.8Ti0.2)2O7陶瓷的物理性能

用固相反应法制备(Gd_1-xEr_x)₂(Zr_0.8Ti_0.2)₂O₇(摩尔分数x=0,0.2,0.4)陶瓷并测试其晶体结构、显微形貌和物理性能,研究了Er₂O₃掺杂的影响。结果表明,(Gd_1-xEr_x)₂(Zr_0.8Ti_0.2)₂O₇陶瓷具有立方烧绿石结构,显微结构致密,在室温至1200℃高温相的稳定性良好;Er³⁺掺杂降低了陶瓷材料的热导率和平均热膨胀系数,当x=0.2时,其1000℃的热导率最低(为1.26 W·m^-1·k^-1)。同时,Er³⁺掺杂还提高了这种材料的硬度和断裂韧性。     

Effects of Ag doping and coating on the performance of lithium ion battery material Li4Ti5O12

Series of anode materials (Ag modified Li4TiO512) were acquired through two types of solid state calcination (doping and coating). The samples were characterized by XRD and their grain sizes were examined by laser particle-size analyzer and the morphology of them were obtained by SEM. At 0.5 C discharging rate, the first specific discharge capacities of Ag doped Li4Ti5O12 (the amounts of dopants were 0.1, 0.25, 0.5 and 1 wt% of the weight of Li4Ti5O12) were found to be 136.8, 135.5, 140.4 and 155.6 mAh/g respectively. However, the corresponding values of coated samples (the amounts of coating were of the weight of Li4Ti5O12) were respectively at the same condition. Obviously, the Ag coated samples possessed the higher capacities. The first specific discharge capacities of the Ag coated samples (the amounts of coating were 3.0, 5.0, 8.0 and 10 wt% of the weight of Li4Ti5O12) were 170.74, 175.31, 191.61 and 192.06 mAh/g.     

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.     

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。     

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.     

钛离子掺杂对LiFePO4结构和性能的影响

为提高LiFePO4的充放电性能，用Ti（Ⅳ）对LiFePO4进行掺杂．用电化学方法测量了Li1-xTixFePO4的充放电性能，用X射线衍射和里特沃尔特方法表征了掺杂LiFePO4的晶体结构．固相反应可以制备单相Li1-xTixFePO4（x=0．00、0．01、0．02、0．03、0．05和0．07，摩尔分数），其中Li0．98Ti0．02FePO4具有更好的电化学性能，在80mA／g的充放电电流下，第2次的放电比容量为136．606mAh／g，循环20次后为128．388mAh／g．研究表明，少量钛离子掺杂不仅改变了原子间距和位置、引起晶胞收缩，而且增加了LiFePO4中Fe^3＋／Fe^2＋共存态的浓度，提高了材料的导电能力，从而能有效地提高LiFePO4的比容量和循环性能．     

微波辅助固相法合成锂离子电池正极复合材料Li2FeSiO4/C

以Na2SiO3.9H2O和FeCl2.4H2O为原料,采用低热固相反应获得了分散均匀的β-FeOOH/SiO2前驱体;再以Li2CO3为锂源、聚乙烯醇和超导电炭黑为复合碳源,通过微波辅助固相法合成了Li2FeSiO4/C材料.通过X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)和恒电流充放电测试等方法对材料的结构、微观形貌及电化学性能进行表征.650℃下微波处理12 min可获得结晶好、晶粒细小均匀的Li2FeSiO4/C材料;在选用的微波合成体系下,超导碳和聚乙烯醇热分解的无定形碳不仅利于合成反应的顺利进行,而且提高了Li2FeSiO4的整体导电性能.制备的复合正极材料在60℃下0.05C倍率首次放电容量为129.6 mAh/g,0.5C倍率下为107.5 mAh/g,0.5C下15次循环后保持为104.8 mAh/g,具有较好的放电比容量和良好的循环稳定性能.结果表明,微波辅助固相合成工艺是制备Li2FeSiO4/C复合材料的一种很有前景的方法.     

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.     

水体系自组装法制备钛酸锂纳米负极材料研究

以偏钛酸粉末作为钛源,制备钛酸锂(Li4Ti5O12)纳米材料,Li4Ti5O12由含锂过氧化钛配合物分解自组装后经煅烧结晶而得。采用X射线衍射、扫描电子显微镜、氮气吸附-脱附和恒流充放电测试对材料结构、形貌和电化学性能进行表征。结果表明:水体系下,锂钛摩尔比为4∶5、于600℃煅烧5h得到的Li4Ti5O12纳米球颗粒粒径在500nm左右,且具有丰富的孔隙,比表面积达到22.947m2/g;在电流密度4000mA/g条件下,比容量为157mAh/g,电流密度500mA/g下循环400次放电容量保持率为95.2%。表明水体系自组装形成的Li4Ti5O12纳米负极材料可以缩短锂离子迁移距离,其多孔性可以增大电解液与电极活性材料的接触面积,使离子电子传输速率同时得到提高,从而获得优异的电化学性能。     

Preparation and electrochemical performance of hyper-networked Li4Ti5O12/carbon hybrid nanofiber sheets for a battery-supercapacitor hybrid system

Hyper-networked Li(4)Ti(5)O(12)/carbon hybrid nanofiber sheets that contain both a faradaically rechargeable battery-type component, namely Li(4)Ti(5)O(12), and a non-faradaically rechargeable supercapacitor-type component, namely N-enriched carbon, are prepared by electrospinning and their dual function as a negative electrode of lithium-ion batteries (LIBs) and a capacitor is tested for a new class of hybrid energy storage (denoted BatCap). An aqueous solution composed of polyvinylpyrrolidone, lithium hydroxide, titanium(IV) bis(ammonium-lactato)dihydroxide and ammonium persulfate is electrospun to obtain hyper-networked nanofiber sheets. Next, the sheets are exposed to pyrrole monomer vapor to prepare the polypyrrole-coated nanofiber sheets (PPy-HNS). The hyper-networked Li(4)Ti(5)O(12)/N-enriched carbon hybrid nanofiber sheets (LTO/C-HNS) are then obtained by a stepwise heat treatment of the PPy-HNS. The LTO/C-HNS deliver a specific capacity of 135 mAh g(-1) at 4000 mA g(-1) as a negative electrode for LIBs. In addition, potentiodynamic experiments are performed using a full cell with activated carbon (AC) as the positive electrode and LTO/C-HNS as the negative electrode to estimate the capacitance properties. This new asymmetric electrode system exhibits a high energy density of 91 W kg(-1) and 22 W kg(-1) at power densities of 50 W kg(-1) and 4000 W kg(-1), respectively, which are superior to the values observed for the AC [symbol: see text] AC symmetric electrode system.