有机溶剂浸泡法回收再利用锂离子电池钛酸锂负极材料

利用有机溶剂法回收了废旧锂离子电池中的钛酸锂负极材料,并对回收的钛酸锂材料的结构、形貌和电化学性能进行了测试。XRD结果表明,材料除炭后添加适量锂源进一步合成得到的产物具有尖晶石结构,且不含其他的杂质。SEM图像显示,其颗粒分布均匀、无团聚现象。EIS结果表明,最终回收的钛酸锂电极材料比未添加锂源进行煅烧处理的材料具有较小的电荷转移阻抗和较高的锂离子扩散系数。在0.1 C倍率下,经过100次循环后其容量保持率为92.4%,具有优异的循环稳定性和可逆性,可以实现循环利用。     

薄膜锂离子电池负极材料的研究进展

全固态薄膜锂离子电池是锂离子电池的最新研究领域,其能量密度高、厚度薄、循环寿命长、可靠度高。薄膜化的负极材料是锂离子电池的重要组成部分,负极薄膜材料制备方法的研究取得了较大的进展,未来研究重点是低成本、低能耗、高综合电化学性能的负极薄膜材料以及可批量生产的薄膜制备技术。对薄膜化的硅负极材料、金属或合金薄膜材料、氧化物薄膜材料和复合薄膜材料近几年来的研究状况进行了综述,并对其发展前景进行了展望。     

锂离子电池Si-Ni负极材料的制备研究

采用胶体钯活化液赋予硅粉催化活性,以硫酸镍为主盐、次磷酸钠为还原剂、柠檬酸盐为络合剂实施化学复合镀,并分别考查复合镀时间、加热温度和硅粉装载量对薄膜硅负极性能的影响,找出相对最优的Si-Ni复合镀工艺条件,并对制备的Si-Ni负极材料的性能进行表征。     

Al掺杂锰酸锂材料在水系锂离子电池中的循环稳定性

水系锂离子电池具有优良的安全性能和高离子导电性等优点,得到了广泛研究.LiMn2O4材料在水系锂离子电池中较差的循环稳定性使其应用受到限制.为了改善这一缺陷,以乙炔黑为模板,采用简单的高温固相法合成了Al掺杂的LiMn2O4材料(LiMn1.9Al0.1O4),并应用于水系锂离子全电池中.实验结果表明,在0.1 A/g...     

锂离子电池Al2O3-SiO/C负极材料的制备和电化学性能CSCD

本文首先以SiO、沥青为原料,制备了SiO/C复合材料.然后以SiO/C复合材料,硝酸铝,氨水,尿素为原料,利用水浴加热和高温热处理的方法,制备出了Al2O3-SiO/C复合材料.采用激光粒度分析、比表面积测试仪、XRD、SEM对样品进行了物相结构分析和微现形貌的表征测试.电化学测试表明:加入尿素的A12O3-SiO/C复合材料具有最佳电化学性能,首次效率高达74.81％,充电比容量为1436.4mA·h/g,表现了优异的电化学性能.     

钛酸锂基锂离子电池及其健康状态研究进展

锂离子电池的高功率密度和高能量密度等特性使其成为电动汽车能源和新能源电网储能的重要载体。功率性能和安全特性是锂离子电池发展的两个主要挑战。钛酸锂Li₄Ti₅O₁₂材料因具有良好的结构稳定性、安全性能、长循环寿命、高功率特性和高低温放电性能,被认为是锂电池负极材料的良好备选。综述了以钛酸锂材料为负极的锂离子电池的相关工作,介绍了钛酸锂材料的结构、电化学特性、制备方法和作为电池负极材料面临的主要问题,重点介绍了钛酸锂负极电池的全电池性能和健康状态研究等方面。     

Ca/Cu共掺杂的O3-NaFe0.5Mn0.5O2钠离子电池正极材料的电化学性能研究

层状过渡金属氧化物由于其较高的理论比容量和较低的经济成本,被视为一种具有良好应用前景的钠离子电池正极材料。采用溶胶-凝胶法和热处理的方式,制备Ca/Cu共掺杂的铁锰基层状氧化物(O3-Na_0.9Ca_0.05Fe_0.45Mn_0.45Cu_0.1O₂)。采用X射线衍射仪(XRD)、场发射扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)等对该O3型铁锰基层状氧化物正极材料进行表征分析。结果表明,在32 mA/g电流密度下该材料具有205.2 m A·h/g的高比容量,循环50圈之后仍具有67.64%的容量保持率,在160 m A/g下循环100圈后依然具有81.4 m A·h/g的放电比容量。由于Ca的掺入,引起Na⁺空位的增加,并且Cu的掺入提高了Mn的价态,从而提高了Na⁺的扩散速率,抑制了Mn³⁺的Jahn-Teller效应,缓解了晶格应力,有效提高了材料的结构稳...     

动力锂离子电池正极材料磷酸铁锂的研究进展

磷酸铁锂具有价廉、环保、热稳定性好等优点,是理想的锂离子动力电池正极材料之一,因此受到行业的广泛关注。本文阐述了磷酸铁锂的结构和性能特点,介绍了磷酸铁锂的制备方法和研究新进展,基于目前研究现状讨论了存在的问题。     

钛铌氧化物用于锂离子电池负极的研究进展

钛铌氧化物(TNO)负极材料因其具有较高的比容量、安全的嵌锂电位、快速嵌锂通道和稳定的嵌锂结构已成为当前高功率、长寿命锂离子动力电池负极首选材料之一.然而,其较低的电子电导率限制了TNO负极材料高倍率性能的发挥.本文通过对近期相关研究的探讨,综述了TNO的结构特点、制备方法及改性策略,着重讨论了几种不同Ti/Nb比例材料的晶体结构及其氧化还原与插层赝电容的协同嵌锂机制,阐明其快速导锂机理;同时介绍了固相反应法、溶胶凝胶法、静电纺丝法、模板法和溶剂热法等几种TNO材料先进制备工艺及各自优势;重点分析了元素掺杂、缺陷设计以及与导电材料复合等改性方案对TNO电子传导特性的影响和对电化学性能的改善效果.最后,本文还对TNO作为负极材料在锂离子全电池和混合锂离子电容器两种储能体系中的研究现状、存在问题及应用前景进行了分析和阐述.综合分析表明,在TNO的改性方案中,元素掺杂和缺陷设计可以改变TNO的电子结构,导电材料复合结构设计可为其构建多维电子通路,而多种改性方案的迭代可明显提高TNO材料的倍率性能和循环稳定性,有望使其在高功率储能器件中获得良好应用.     

Electrochemical behaviors of wax-coated Li powder/Li4Ti5O12 cells

The wax-coated Li powder specimen was effectively synthesized using the drop emulsion technique (DET). The wax layer on the powder was verified by SEM, Focused Ion Beam (FIB), EDX and XPS. The porosity of a sintered wax-coated Li electrode was measured by linear sweep voltammetry (LSV) and compared with that of a bare, i.e., un-coated Li electrode. The electrochemical behavior of the wax-coated Li powder anode cell was examined by the impedance analysis and cyclic testing methods. The cyclic behavior of the wax-coated Li powder anode with the Li₄Ti₅O₁₂ (LTO) cathode cell was examined at a constant current density of 0.35 mA cm⁻² with the cut-off voltages of 1.2–2.0 V at 25 °C. Over 90% of the initial capacity of the cell remained even after the 300th cycle. The wax-coated Li powder was confirmed to be a stable anode material.     

Preparation and electrochemical properties of Li4Ti5O12 thin film electrodes by pulsed laser deposition

Spinel Li₄Ti₅O₁₂ thin film anode material for lithium-ion batteries is prepared by pulsed laser deposition. Thin film anodes are deposited at ambient temperature, then annealed at three different temperatures under an argon gas flow and the influence of annealing temperatures on their electrochemical performances is studied. The microstructure and morphology of the films are characterized by XRD, SEM and AFM. Electrochemical properties of the films are evaluated by using galvanostatic discharge/charge tests, cyclic voltammetry and a.c. impedance spectroscopy. The results reveal that all annealed films crystallize and exhibit good cycle performance. The optimum annealing temperature is about 700 °C. The steady-state discharge capacity of the films is about 157 mAh g⁻¹ at a medium discharge/charge current density of 10 μA cm⁻². At a considerably higher discharge/charge current density of 60 μA cm⁻² (about 3.45 C) the discharge capacity of the films remains steady at a relative high value (146 mAh g⁻¹). The cycleability of the films is excellent. This implies that such films are suitable for electrodes to be used at high discharge/charge current density.     

Li4Ti5O12/Sn composite anodes for lithium-ion batteries: Synthesis and electrochemical performance

Li₄Ti₅O₁₂/tin phase composites are successfully prepared by cellulose-assisted combustion synthesis of Li₄Ti₅O₁₂ matrix and precipitation of the tin phase. The effect of firing temperature on the particulate morphologies, particle size, specific surface area and electrochemical performance of Li₄Ti₅O₁₂/tin oxide composites is systematically investigated by SEM, XRD, TG, BET and charge-discharge characterizations. The grain growth of tin phase is suppressed by forming composite with Li₄Ti₅O₁₂ at a calcination of 500 °C, due to the steric effect of Li₄Ti₅O₁₂ and chemical interaction between Li₄Ti₅O₁₂ and tin oxide. The experimental results indicate that Li₄Ti₅O₁₂/tin phase composite fired at 500 °C has the best electrochemical performance. A capacity of 224 mAh g⁻¹ is maintained after 50 cycles at 100 mA g⁻¹ current density, which is still higher than 195 mAh g⁻¹ for the pure Li₄Ti₅O₁₂ after the same charge/discharge cycles. It suggests Li₄Ti₅O₁₂/tin phase composite may be a potential anode of lithium-ion batteries through optimizing the synthesis process.     

Nanosized Li4Ti5O12/graphene hybrid materials with low polarization for high rate lithium ion batteries

We report a simple strategy to prepare a hybrid of lithium titanate (Li₄Ti₅O₁₂, LTO) nanoparticles well-dispersed on electrical conductive graphene nanosheets as an anode material for high rate lithium ion batteries. Lithium ion transport is facilitated by making pure phase Li₄Ti₅O₁₂ particles in a nanosize to shorten the ion transport path. Electron transport is improved by forming a conductive graphene network throughout the insulating Li₄Ti₅O₁₂ nanoparticles. The charge transfer resistance at the particle/electrolyte interface is reduced from 53.9 Ω to 36.2 Ω and the peak currents measured by a cyclic voltammogram are increased at each scan rate. The difference between charge and discharge plateau potentials becomes much smaller at all discharge rates because of lowered polarization. With 5 wt.% graphene, the hybrid materials deliver a specific capacity of 122 mAh g⁻¹ even at a very high charge/discharge rate of 30 C and exhibit an excellent cycling performance, with the first discharge capacity of 132.2 mAh g⁻¹ and less than 6% discharge capacity loss over 300 cycles at 20 C. The outstanding electrochemical performance and acceptable initial columbic efficiency of the nano-Li₄Ti₅O₁₂/graphene hybrid with 5 wt.% graphene make it a promising anode material for high rate lithium ion batteries.     

Synthesis of pristine and carbon-coated Li4Ti5O12 and their low-temperature electrochemical performance

Pristine and carbon-coated Li₄Ti₅O₁₂ oxide electrodes are synthesized by a cellulose-assisted combustion technique with sucrose as organic carbon source and their low-temperature electrochemical performance as anodes for lithium-ion batteries are investigated. X-ray diffraction (XRD), infrared spectroscopy (IR), Raman spectroscopy, thermogravimetric analysis (TGA) and scanning electron microscopy (SEM) are applied to characterize the phase structure, composition, and morphology of the composites. It is found that the sequence of sucrose addition has significant effect on the phase formation of Li₄Ti₅O₁₂. Carbon-coated Li₄Ti₅O₁₂ is successfully prepared by coating the pre-crystallized Li₄Ti₅O₁₂ phase with sucrose followed by thermal treatment. Electrochemical lithium insertion/extraction performance is evaluated by the galvanostatic charge/discharge tests, electrochemical impedance spectroscopy (EIS), and cyclic voltammetry (CV), from room temperature (25 °C) to −20 °C. The carbon-coated composite anode materials show improved lithium insertion/extraction capacity and electrode kinetics, especially at high rates and low temperature. Both of the two samples show fairly stable cycling performance at various temperatures, which is highly promising for practical applications in power sources of electric or electric-hybrid vehicles.     

Lithium diffusion in Li4Ti5O12 at high temperatures

Synthesis of the spinel lithium titanate Li₄Ti₅O₁₂ by an alkoxide-free sol-gel method is described. This method yields highly pure and crystalline Li₄Ti₅O₁₂ samples at relatively low temperature (850 °C) and via short thermal treatment (2 h). ⁶Li magic angle spinning nuclear magnetic resonance (MAS NMR) measurements on these samples were carried out at high magnetic field (21.1 T) and over a wide temperature range (295-680 K). The temperature dependence of the chemical shifts and integral intensities of the three ⁶Li resonances demonstrates the migration of lithium ions from the tetrahedral 8a to the octahedral 16c sites and the progressive phase transition from a spinel to a defective NaCl-type structure. This defective structure has an increased number of vacancies at the 8a site, which facilitate lithium diffusion through 16c → 8a → 16c pathways, hence providing an explanation for the reported increase in conductivity at high temperatures. Molecular dynamics simulations of the spinel oxides Li_4+xTi₅O₁₂, with 0 ≤ x ≤ 3, were also performed with a potential shell model in the temperature range 300-700 K. The simulations support the conclusions drawn from the NMR measurements and show a significant timescale separation between lithium diffusion through 8a and 16c sites and that out of the 16d sites.     

Effects of preparation conditions on the electrochemical and morphological characteristics of Li4Ti5O12 powders prepared by spray pyrolysis

Li₄Ti₅O₁₂ anode powders were prepared by post-treatment of the precursor powders obtained by spray pyrolysis at various preparation conditions. The precursor powders had fine size, narrow size distribution, dense inner structure and homogeneous composition when the flow rate of the carrier gas and the preparation temperature were 10 l min⁻¹ and 800 °C. The spherical shapes of the precursor powders obtained at the optimum preparation conditions maintained after post-treatment at a temperature of 800 °C. The mean sizes of the Li₄Ti₅O₁₂ powders were controlled by changing the concentrations of the spray solution. The initial discharge capacities and cycle properties of the Li₄Ti₅O₁₂ powders were strongly affected by the preparation temperatures of the precursor powders. The optimum preparation temperature of the precursor powders was 800 °C when the flow rate of the carrier gas was 10 l min⁻¹. The discharge capacities and cycle properties of the Li₄Ti₅O₁₂ powders were not affected by flow rates of the carrier gas. The Li₄Ti₅O₁₂ powders had good cycle properties irrespective of the concentrations of the spray solution. However, the Li₄Ti₅O₁₂ powders obtained from the spray solutions with high concentration above 0.5 M had high discharge capacities than those obtained from the spray solutions with low concentration below 0.1 M.     

High-rate nano-crystalline Li4Ti5O12 attached on carbon nano-fibers for hybrid supercapacitors

A lithium titanate (Li₄Ti₅O₁₂)-based electrode which can operate at unusually high current density (300 C) was developed as negative electrode for hybrid capacitors. The high-rate Li₄Ti₅O₁₂ electrode has a unique nano-structure consisting of unusually small nano-crystalline Li₄Ti₅O₁₂ (ca. 5-20 nm) grafted onto carbon nano-fiber anchors (nc-Li₄Ti₅O₁₂/CNF). This nano-structured nc-Li₄Ti₅O₁₂/CNF composite are prepared by simple sol-gel method under ultra-centrifugal force (65,000 N) followed by instantaneous annealing at 900 °C for 3 min. A model hybrid capacitor cell consisting of a negative nc-Li₄Ti₅O₁₂/CNF composite electrode and a positive activated carbon electrode showed high energy density of 40 Wh L⁻¹ and high power density of 7.5 kW L⁻¹ comparable to conventional EDLCs.