锂离子电池正极材料磷酸亚铁锂的改性进展

橄榄石型结构的磷酸亚铁锂(L iFePO4)作为一种新型的锂离子电池正极材料,具有材料来源广泛、价格便宜、理论比容量高(约170 mA.h/g)、热稳定性好、无吸湿性、对环境友好等优点,可望成为新一代首选的可替代钴酸锂(L iCoO2)的锂离子二次电池正极材料。分析了锂离子电池正极材料橄榄石型磷酸亚铁锂的结构特点和锂离子在充放电时的脱嵌模型,评述了近年来国内外对于改善磷酸亚铁锂的电化学性能所进行的改性研究,重点介绍了优化合成工艺、提高离子扩散效率、添加导电材料等方法对锂离子电池正极材料磷酸亚铁锂的影响,并对其发展方向作了展望。     

锂离子电池负极材料钛酸锌锂的研究进展

报道了钛酸锌锂材料研究现状。对钛酸锌锂的结构与性能、合成方法和改性方法进行阐述。最后对钛酸锌锂负极材料进行总结和展望。     

无机溶胶法制备钛酸锂的研究

采用无机溶胶工艺方法制备纳米级钛酸锂,考察了原料硫酸氧钛的浓度、pH值的控制、分散剂的种类及添加量对溶胶前驱体稳定性的影响,实验得到制备稳定溶胶的最佳工艺条件为:反应物TiOSO4浓度18%,有机分散剂为高聚物醇类,加入比例为0.3%,pH值≤2,按该条件可制的稳定的溶胶前驱体。通过电化学性能应用试验比较,结果表明无机溶胶工艺法很明显的改善了高倍率电流电池容量的保持率及电池的循环性能。     

柠檬酸包覆钛酸锂负极材料的改性研究

采用柠檬酸(C6H8O7·H2O)作碳源制备Li4Ti5O12/C复合材料,利用X射线粉末衍射仪(XRD)和扫描电子显微镜(SEM)研究了柠檬酸添加量对材料结构和形貌的影响。研究结果表明:添加不同量的柠檬酸,所制备的样品均为尖晶石型结构。随着柠檬酸添加量的增加,材料颗粒粒径逐渐增大,分布更加均匀,团聚也逐渐加剧。在1.0~2.5V的电压范围内,对样品进行恒流充放电测试,柠檬酸(C6H8O7·H2O)的添加量为6%时,制备的Li4Ti5O12/C复合材料具有最佳的电化学性能,0.2C和1C的放电比容量分别为171.3m Ah/g和165.4m Ah/g。     

共沉淀法合成磷酸亚铁锂正极材料及性能研究

采用共沉淀法合成了橄榄石型磷酸亚铁锂正极材料。利用X射线衍射，扫描电子显微镜，振实密度测定以及电化学测试等方法对该材料进行了结构表征和性能测试。结果表明：在较宽的温度范围内，都能形成单一的橄榄石型晶体结构，并具有较高的振实密度。其中，在650℃下合成的产物结构完整，表面形貌较好，粒径分布均匀，振实密度高达1．67g／cm^3。在室温及0．05C倍率下，该材料的首次放电容量为133．6mA·h／g，循环20次后，未见明显衰减。     

锂离子电池负极材料钛酸锂的研究进展

尖晶石型钛酸锂(Li_4Ti_5O_(12))作为锂离子电池负极材料具有平稳快速的充放性能和优良的循环性能,与商品化碳材料相比其安全性和电化学性能更胜一筹,被广泛应用于现代电子移动设备、新能源汽车与各类储能系统等方面。因而,被认为是最具有发展潜力的电池负极材料之一。重点概述了尖晶石Li_4Ti_5O_(12)负极材料的制备方法和优缺点以及尖晶石Li_4Ti_5O_(12)的掺杂改性研究,并对其发展前景进行了展望。     

锂离子电池负极材料钛酸锂的研究进展

尖晶石型钛酸锂(Li_4Ti_5O_(12))作为锂离子电池负极材料具有平稳快速的充放性能和优良的循环性能,与商品化碳材料相比其安全性和电化学性能更胜一筹,被广泛应用于现代电子移动设备、新能源汽车与各类储能系统等方面。因而,被认为是最具有发展潜力的电池负极材料之一。重点概述了尖晶石Li_4Ti_5O_(12)负极材料的制备方法和优缺点以及尖晶石Li_4Ti_5O_(12)的掺杂改性研究,并对其发展前景进行了展望。     

锂离子电池材料钛酸锂钠的研究进展

Na₂Li₂Ti₆O₁₄电池具有较低的电位平台（1.3 V）以及经济成本低的特点,对便携式电子设备、能源汽车、生态环境等领域具有重大意义。由于钛酸锂钠电池固有离子电导率低的特点,因此提高钛酸锂钠电池锂离子扩散系数是目前研究中的主流方向,为此综述了钛酸锂钠的结构特点以及合成方法对钛酸锂钠材料粒径、形貌及电池电化学性能的影响;对比了不同掺杂离子和表面包覆改性对钛酸锂钠电池的放电比容量、循环性能及离子扩散系数的影响。掺入适量元素铌具有更高的锂离子扩散系数;包覆碳纳米管有更大的容量保持率,更有助于进一步提高钛酸锂钠电池电化学性能。     

液相共沉淀法制备磷酸亚铁锂研究进展

以磷酸亚铁锂为正极材料的锂离子电池以其高安全、高环保、低价格、长寿命、大容量等特点,将逐步取代现有铅酸电池市场,成为未来动力锂离子电池研究的热点材料。简述了几种常规合成磷酸亚铁锂方法的同时,较系统地介绍了磷酸亚铁锂材料在液相共沉淀制备方法中的研究进展,包括全液相共沉淀法和半液相共沉淀法。指出全液相法合成工艺比较简单、工艺路线较短,但是由于溶液体系中各组分沉淀速度存在差异,因而可能会导致组成的偏离和均匀性的丧失;半液相法虽然增加了工艺流程,但是可以通过控制pH、滴加速度等控制磷铁复合盐的形成,使产品呈球状,进而有助于提高磷酸亚铁锂的振实密度。     

锂离子电池用草酸亚铁的合成研究

采用扫描电镜、激光粒度仪、振实密度仪,研究了陈化时间、分散剂浓度、亚铁离子浓度对草酸亚铁产品形貌、振实密度和粒径的影响。优化的草酸亚铁制备工艺条件为:亚铁离子浓度为85 g/L,分散剂浓度为0. 65 mol/L,陈化时间为9 h。制备得到的草酸亚铁产品振实密度为1. 22 g/cm~3,粒度(D_(50))为3. 16μm;以制备的草酸亚铁为原料,采用高温固相法合成磷酸铁锂正极材料,得到的正极材料充放电性能良好。     

锂离子电池正极材料磷酸钒锂制备方法研究进展

单斜结构的磷酸钒锂[Li₃V₂（PO₄）₃]材料与其他锂离子电池正极材料相比具有较高的工作电压（3.0~4.8 V）、良好的离子迁移率和优良的热稳定性,是一种具有竞争优势和发展前景的大功率锂离子电池正极材料,成为了近年来研究的热点。综述了锂离子电池正极材料磷酸钒锂的结构特点及其充放电机理。磷酸钒锂的常用合成方法有碳热还原法、水热法、溶胶-凝胶法及流变相法等,着重阐述了磷酸钒锂的不同合成方法对所制备样品的形貌和电化学性能的影响。分析总结了不同合成方法的改进方法,以改善磷酸钒锂正极材料电子导电性和锂离子扩散系数较低的问题。最后,针对磷酸钒锂正极材料在锂离子电池的应用中所存在的问题展望了该材料未来可能的发展方向和研究热点。指出需要优化材料的制备方法以改善材料的颗粒形貌、提高电子导电率和扩散系数等,进而改善材料的循环性能、倍率性能和充放电性能等;需要改进制备流程、提高实验的安全性、简化反应流程和减少制备成本等,以实现磷酸钒锂正极材料的工业化应用。     

Microwave-assisted preparation of submicron-sized FeTiO3 powders

FeTiO₃ powders were prepared from (Fe+Ti) mixed carbonate precursor by the microwave-assisted calcination method. The thermal analysis of the precursor was conducted by TG/DSC. It is demonstrated that the calcination process can be divided into three different stages: the removal of water, the decomposition of precursor and the formation of FeTiO₃. A variety of techniques, such as XRD, FT-IR, SEM and EDS were utilized to characterize the samples. The results indicated that FeTiO₃ powders can be prepared by microwave-assisted calcination for 20 min at 450 °C, while those cannot be obtained by conventional one until reaction time exceeds 120 min at 600 °C. The FeTiO₃ powders prepared by microwave-assisted calcination are nearly spherical with limited aggregation and have a mean particle size of 400–500 nm.     

Performance of LiNi1/3Co1/3Mn1/3O2 prepared from spent lithium-ion batteries by a carbonate co-precipitation method

Spherical LiNi_1/3Co_1/3Mn_1/3O₂ cathode particles were resynthesized by a carbonate co-precipitation method using spent lithium-ion batteries (LIBs) as a raw material. The physical characteristics of the Ni_1/3Co_1/3Mn_1/3CO₃ precursor, the (Ni_1/3Co_1/3Mn_1/3)₃O₄ intermediate, and the regenerated LiNi_1/3Co_1/3Mn_1/3O₂ cathode material were investigated by laser particle-size analysis, scanning electron microscopy–energy-dispersive spectroscopy (SEM-EDS), thermogravimetry–differential scanning calorimetry (TG-DSC), X-ray diffraction (XRD), inductively coupled plasma–atomic emission spectroscopy (ICP-AES), and X-ray photoelectron spectroscopy (XPS). The electrochemical performance of the regenerated LiNi_1/3Co_1/3Mn_1/3O₂ was studied by continuous charge–discharge cycling and cyclic voltammetry. The results indicate that the regenerated Ni_1/3Co_1/3Mn_1/3CO₃ precursor comprises uniform spherical particles with a narrow particle-size distribution. The regenerated LiNi_1/3Co_1/3Mn_1/3O₂ comprises spherical particles similar to those of the Ni_1/3Co_1/3Mn_1/3CO₃ precursor, but with a narrower particle-size distribution. Moreover, it has a well-ordered layered structure and a low degree of cation mixing. The regenerated LiNi_1/3Co_1/3Mn_1/3O₂ shows an initial discharge capacity of 163.5 mA h g^?1 at 0.1 C, between 2.7 and 4.3 V; the discharge capacity at 1 C is 135.1 mA h g^?1, and the capacity retention ratio is 94.1% after 50 cycles. Even at the high rate of 5 C, LiNi_1/3Co_1/3Mn_1/3O₂ delivers the high capacity of 112.6 mA h g^?1. These results demonstrate that the electrochemical performance of the regenerated LiNi_1/3Co_1/3Mn_1/3O₂ is comparable to that of a cathode synthesized from fresh materials by carbonate co-precipitation.     

基于水热/溶剂热法制备不同形貌LiNi0.8Co0.1Mn0.1O2 锂离子电池正极材料

基于水热/溶剂热法制备LiNi_0.8Co_0.1Mn_0.1O₂电极材料,以镍、钴、锰乙酸盐为原料,以六亚甲基四胺为沉淀剂、水或乙醇为溶剂,通过调节溶剂组分控制Ni_0.8Co_0.1Mn_0.1（OH）₂（NCM）的成核与生长速率,从而合成两种形貌不同的Ni_0.8Co_0.1Mn_0.1（OH）₂前驱体,再经过混锂煅烧获得LiNi_0.8Co_0.1Mn_0.1O₂正极材料,研究比较了其电化学性能。以水为溶剂通过水热法合成的前驱体样品呈现出由一次片状颗粒紧密堆积组成的长方体状二次颗粒形貌,经混锂煅烧得到的产物表现出较高的放电比容量,在0.5C倍率下首次放电比容量可达到189.70 mA·h/g,循环200次容量保持率为69.72%。以乙醇为溶剂通过溶剂热法合成得到球形二次颗粒前驱体,最终得到的产物具有多孔球形结构,表现出了优异的循环性能,0.5C首次放电比容量为178.65 mA·h/g,循环200次容量保持率仍高达94.55%。     

Efficient decomposition of organic compounds with FeTiO3/TiO2 heterojunction under visible light irradiation

FeTiO₃/TiO₂, a new heterojunction-type photocatalyst working at visible light, was prepared by a simple sol–gel method. Not only did FeTiO₃/TiO₂ exhibit greatly enhanced photocatalytic activity in decomposing 2-propanol in gas phase and 4-chlorophenol in aqueous solution, but also it induced efficient mineralization of 2-propanol under visible light irradiation (λ ≥ 420 nm). Furthermore, it showed a good photochemical stability in repeated photocatalytic applications. FeTiO₃ showed a profound absorption over the entire visible range, and its valence band (VB) position is close to that of TiO₂. The unusually high photocatalytic efficiency of the FeTiO₃/TiO₂ composite was therefore deduced to be caused by hole transfer between the VB of FeTiO₃ and TiO₂.     

g-C3N4/泡沫陶瓷的光催化烟气脱硫性能

采用XRD和FT-IR对制备的g-C₃N₄光催化剂进行表征,使用气固光催化反应器考察60 ℃条件下g-C₃N₄/泡沫陶瓷的SO₂光催化氧化性能,包括吸附性能和光催化脱硫活性。结果表明,负载g-C₃N₄光催化剂的泡沫陶瓷,对SO₂的吸附容量性能大大提高;g-C₃N₄/泡沫陶瓷在H₂O和O₂同时存在时的光催化脱硫活性最好,脱硫率86.9%。     

Electrochemical performance of carbon-coated Li3V2(PO4)3 cathode materials derived from polystyrene-based carbon-thermal reduction synthesis

Li₃V₂(PO₄)₃ cathode materials were synthesized by a simple carbon-thermal reduction method using polystyrene as a carbon source. The residual carbon produced by the pyrolysis of polystyrene produced fine particle sizes and uniform carbon distribution on the Li₃V₂(PO₄)₃ particle surface. By increasing the amount of polystyrene added in the range of 0-16 wt.%, the thickness of the carbon coating increased, and the coating thickness was found to influence the electrochemical performance of the Li₃V₂(PO₄)₃ significantly. Our results indicate that the 6 wt.% polystyrene added Li₃V₂(PO₄)₃ with a 0.5-1 nm thick carbon coating possesses the highest initial discharge capacity of 132.7 mAh g⁻¹ between 3.0 and 4.3 V at 0.1 C. However, at high current densities, the higher polystyrene added Li₃V₂(PO₄)₃/C with a thicker carbon coating shows better performance in terms of the discharge capacity and cycling stability than that with the thin carbon coating. The improved cycling performance at higher current densities is attributed to the relatively small particle size and the suppressed impedance increase because of the thicker carbon coating.     

Effects of gradient concentration on the microstructure and electrochemical performance of LiNi0.6Co0.2Mn0.2O2 cathode materials

Nickel(Ni)-rich layered materials have attracted considerable interests as promising cathode materials for lithium ion batteries (LIBs) owing to their higher capacities and lower cost. Nevertheless, Mn-rich cathode materials usually suffer from poor cyclability caused by the unavoidable side-reactions between Ni⁴⁺ ions on the surface and electrolytes. The design of gradient concentration (GC) particles with Ni-rich inside and Mn-rich outside is proved to be an efficient way to address the issue. Herein, a series of LiNi_0.6Co_0.2Mn_0.2O₂ (LNCM622) materials with different GCs (the atomic ratio of Ni/Mn decreasing from the core to the outer layer) have been successfully synthesized via rationally designed co-precipitation process. Experimental results demonstrate that the GC of LNCM622 materials plays an important role in their microstructure and electrochemical properties. The as-prepared GC3.5 cathode material with optimal GC can provide a shorter pathway for lithium-ion diffusion and stabilize the near-surface region, and finally achieve excellent electrochemical performances, delivering a discharge capacity over 176 mAh·g⁻¹ at 0.2 C rate and exhibiting capacity retention up to 94% after 100 cycles at 1 C. The rationally-designed co-precipitation process for fabricating the Ni-rich layered cathode materials with gradient composition lays a solid foundation for the preparation of high-performance cathode materials for LIBs.     

Effects of synthetic route on structure and electrochemical performance of Li3V2(PO4)3/C cathode materials

Three different synthetic routes, including solid-state reaction, sol–gel and hydrothermal methods are successfully used for preparation of Li₃V₂(PO₄)₃/C. Ascorbic acid is used as a reducing agent and/or as a chelating agent. The Li₃V₂(PO₄)₃/C synthesized by hydrothermal method with fine particles exhibits lower impedance and smaller potential difference values between oxidation and reduction peaks than those by solid-state reaction and sol–gel methods. Thus as cathode material for Li-ion batteries, the Li₃V₂(PO₄)₃/C synthesized by hydrothermal method shows higher discharge capacity, better rate capability and cyclic performance. Even at a high charge–discharge rate of 10 C, it still can deliver a discharge capacity of 101.4 mAh g⁻¹ and 106.6 mAh g⁻¹ in the potential range of 3.0–4.3 V and 3.0–4.8 V, respectively. The hydrothermal synthesis has been considered to be a competitive process to prepare Li₃V₂(PO₄)₃/C cathode materials with excellent electrochemical performances.     

Electrochemical performance of Li3V2(PO4)3/C cathode materials using stearic acid as a carbon source

The Li₃V₂(PO₄)₃/C cathode materials are synthesized by a simple solid-state reaction process using stearic acid as both reduction agent and carbon source. Scanning electron microscopy and transmission electron microscopy observations show that the Li₃V₂(PO₄)₃/C composite synthesized at 700 °C has uniform particle size distribution and fine carbon coating. The Li₃V₂(PO₄)₃/C shows a high initial discharge capacity of 130.6 and 124.4 mAh g⁻¹ between 3.0 and 4.3 V, and 185.9 and 140.9 mAh g⁻¹ between 3.0 and 4.8 V at 0.1 and 5 C, respectively. Even at a charge–discharge rate of 15 C, the Li₃V₂(PO₄)₃/C still can deliver a discharge capacity of 103.3 and 112.1 mAh g⁻¹ in the potential region of 3.0–4.3 V and 3.0–4.8 V, respectively. Based on the analysis of cyclic voltammograms and electrochemical impedance spectra, the apparent diffusion coefficients of Li ions in the composites are in the region of 1.09 × 10⁻⁹ and 4.95 × 10⁻⁸ cm² s⁻¹.