控制结晶法制备球形锂离子电池正极材料的研究进展

球形材料具有堆积密度大、体积比容量高、加工性能好等突出优点. 球形化是锂离子电池正极材料的重要发展方向. 控制结晶法是制备球形材料的理想方法. 本文介绍了控制结晶法的原理, 综述了采用控制结晶法制备球形锂离子电池正极材料---LiCoO₂、LiNi_0.8Co_0.2O₂、LiMn₂O₄、LiNi_1/3Co_1/3Mn_1/3O₂、LiFePO₄的研究和发展, 并对球形材料在锂离子电池中的应用前景进行了分析.     

锂离子电池正极材料Li1+xV3O8的合成及性能研究

研究了一种新型制备锂离子电池正极材料Li_1+xV₃O₈的工艺方法.以NH₄VO₃为原料,通过淬火法制备出V₂O₅溶胶,加入LiOH溶液后,通过喷雾干燥法制备球形前驱体,再通过一定的热处理即制得锂离子电池正极材料Li_1+xV₃O₈.试验中,进行了前驱体的DTA/TGA分析;对产物进行了XRD、SEM及电化学性能测试研究.结果表明,经过350℃热处理24h后得到的样品颗粒细小、呈球形、粒径分布均匀、结晶度好,并且还表现出很好的电化学性能,其首次放电比容量高达378mAh·g^-1,经过10次充放电循环后,其放电比容量为312mAh·g^-1.     

SnO2-Sb2O3基压敏陶瓷致密化及脉冲电流耐受特性

实验研究了TiO₂、Co₃O₄、Cr₂O₃、Ni₂O₃和MnO掺杂对SnO₂-Sb₂O₃基压敏陶瓷材料微观结构和电性能的影响. 研究结果表明, TiO₂和Co₃O₄促进SnO₂陶瓷烧结致密化, 根据XRD图谱分析结果, Co₃O₄与SnO₂反应形成了Co₂SnO₄晶相, TiO₂则固溶于SnO₂晶相;Sb元素的引入能够促进SnO₂晶粒的半导化;复合添加Cr₂O₃、Ni₂O₃和MnO可以有效提高材料的电压非线性特性和脉冲电流冲击耐受能力. 获得电性能接近实用化的SnO₂压敏陶瓷样品, 其压敏电压V_1mA约为350V/mm, 非线性系数α达到50, 漏电流小于5μA, 并且在8/20μs脉冲电流冲击试验中,直径14mm的样品能够经受2kA的脉冲峰值电流.     

锂钒氧化物纳米管的合成与表征

利用溶胶凝胶法结合水热法, 以V₂O₅粉末和LiOH·H₂O为原料, 十六烷基胺（C₁₆H₃₃NH₂）为模板剂, 合成了锂钒氧化物纳米管正极材料. 对合成样品进行了SEM、TEM、XRD、FT-IR和XPS表征和分析, 并利用循环伏安测试研究了样品的电化学性能. 结果表明, 该法合成的锂钒氧化物为末端开口纳米管, 管壁为均匀有序的多层结构, 管长在1~3μm之间, 管内径约30nm左右, 外径约70nm左右. XPS分析表明样品中V、O、C、Li元素均由多种化学状态组成. 循环伏安测试表明, 锂钒氧化物纳米管具有良好的锂离子注入/退出可逆性.     

氧化钒纳米管的自组装合成机理

以V₂O₅和十六胺为原料在水热条件下合成了氧化钒纳米管, 采用XRD、SEM、TEM、FTIR、ESR等手段分析研究了氧化钒纳米管的形成机理. 结果表明, 氧化钒纳米管的形成主要基于“卷曲机理”, 其形成过程包括: 表面活性剂分子嵌入到钒氧化物层间, 形成新层状化合物前驱体; 水热驱动下层状化合物边缘松动, 并开始卷曲, 降低体系能量; 合适的水热反应时间下最终形成钒氧化物纳米管. 模板剂嵌入到钒氧化物层间形成一定大小的层间距以及V⁴⁺的存在对从层状化合物卷曲成纳米管起到了积极的作用.     

锂离子电池正极材料LiMn2O4的研究进展

具有尖晶石相的LiMn₂O₄因价格低、无毒、无环境污染、制备简单、研究较成熟,因此有着很好的应用前景,被看作最有可能成为新一代商用锂离子二次电池正极材料.由于LiMn₂O₄电化学循环稳定性能不好,表现在可逆容量衰减较大,尤其在高温下(>55℃)使用衰减更严重,从而限制了它的商业化应用.经过近十几年的研究,人们对其衰减机理有了比较清晰的了解,提出了造成容量衰减的几种可能原因如Jahn-Teller畸变效应、Mn²⁺在电解质中的溶解、出现稳定性较差的四方相以及电解质的分解等.通过掺杂、表面包覆、制备工艺的改进,人们已能制得循环稳定性能较好的尖晶相材料.本文结合我们研究小组的最新研究成果对锂离子二次电池正极材料LiMn₂O₄的最新研究进展进行综述和评论.     

LiNi0.9Co0.1O2正极材料的EDTA络合法合成及其性能研究

采用络合法制备了锂离子电池的活性正极材料LiNi_0.9Co_0.1O2粉体,实验表明合成的LiNi_0.9Co_0.1O₂粉体结晶良好,层状结构发育完善。电池充放电测试结果表明,其容量及循环性能与LiNi_0.9Co_0.1O₂粉体的合成温度有关,其中900℃合成得到的LiNi_0.9Co_0.1O₂材料具有最好的电化学性能,首次放电比容量高达120.5mAh/g,循环30次后可逆放电比容量仍高达118.8mAh/g,容量损失仅为1.4％。文中对容量退化的原因进行了分析。     

五种二元过渡金属氧化物界面上的相互作用、非晶相结构及催化性能(Ⅱ)—DSC、半导体气敏特性、催化活性与亚单层分散模

应用DSC、半导体气敏特性、催化活性及亚单(分子)层分散模型共四项表征技术,进一步研究了五种二元氧化物的界面结构及其特性,DSC曲线的放热峰及吸热峰分别与界面化学反应、晶格畸变和瓦解、熔化、烧结以及固溶体的形成相关,导电性能的测试证明这些二元氧化物属于N-型半导体,对邻二甲苯具有气敏特性,其灵敏度在化学吸附的初期阶段与邻二甲苯蒸气浓度呈线性关系,催化选择性及转化率的测定证明V₂O₅-MnO₃及WO₃-MoO₃体系对邻二甲苯选择性氧化为苯酐具有催化活性,其非晶相MoO₃及V₂O₅的活性较为显著,尤其当二元氧化物的组成接近分散阈值Dt时,选择性最佳,为了解释大的分散阈值Dt与小的比表面积之间的关系,经计算机编程计算,在分子水平及纳米尺度上提出了球形八面体密置的亚单层分散模型并求得了模型的七个参数,通过讨论亚单层分散与非晶相结构之间的关系,提出了晶相损失的机理以及作为催化剂的非晶相结构对热的亚稳特性。     

S-Co复合掺杂LiMn2O4的合成与性能

为了扩大锂离子电池正极材料Li_xMn₂O₄的工作电压范围,在保证良好循环性能的基础上提高材料的容量,本文对S-Co复合掺杂LiMn₂O₄的合成工艺和电化学性能进行了研究。溶胶-凝胶法合成的各试样均为纯的立方尖晶石相,且结晶状态良好。S-Co复合掺杂综合了S掺杂效应和Co掺杂效应,改善了LiMn₂O₄的电化学性能,在2.4～4.3V充放电压范围内,初始容量较高,达到170mAh/g,30次循环后容量不但没有衰减而且有一定增加。     

添加La2O3对Mg2TiO4陶瓷的显微结构与微波介电性能的影响

采用传统烧结工艺,制备了具有不同La₂O₃含量的镁钛镧陶瓷,并研究了La₂O₃组份对材料晶相构成、晶粒、晶界的演变、介电常数和品质因数的影响.结果表明,不含La₂O₃的钛酸镁陶瓷主晶相为Mg₂TiO₄,其平均晶粒尺寸>60μm;引入La₂O₃后,出现新晶相La_0.66Ti_O2.99,材料的晶粒尺寸明显下降;随La₂O₃含量的增加,材料的介电常数线性增加,材料的品质因数Q在10GHz出现最大值(16558).     

The possibility of intercalating alkali metals in a glass of the system V2O5 - P2O5

A semi-conducting phosphovanadate glass was tested as a possible material for positive electrode in solid state batteries.O.c. voltage with alkali metal (3.6 V/Li and 3.4 V/Na) is higher than for crystallized vanadium oxides and chemical intercalation of sodium or lithium is obtained using halogenated salts dissolved in organic solvents.     

Lithium incorporation into thin films of vanadium oxides

Thin-film electrodes based on vanadium oxides have been obtained using the thermal oxidation of vanadium films deposited in vacuum. It is established that these electrodes admit the reversible incorporation of lithium from aprotic electrolytes and possess an initial capacity exceeding 250 mA h/g. The electrodes have good prospects for use in thin-film lithium ion batteries.     

氧化钒作锂离子电池正极材料的研究进展

V_2O_5具有独特的层状结构,适合于锂离子的存储,与传统的锰酸锂、钴酸锂、磷酸铁锂等正极材料相比,具有高的理论比容量、功率密度以及价格低廉、原材料丰富等优势,在作为锂离子电池正极材料方面备受关注。但V_2O_5低的固有电导率及锂离子扩散系数,导致其容量保持率低和倍率性能差;此外,充放电过程中反复的相变会引起结构的不稳定,而且氧化钒会部分溶于电解液,因此表现出差的循环性能。正是由于这些制约因素的存在,对V_2O_5的固有缺陷进行改性研究以提高氧化钒正极材料的电化学性能成为重要的研究热点。将氧化钒进行纳米化以增大比表面积和缩短离子扩散距离,同时通过复合、掺杂改性等方法提高材料的导电性和循环稳定性,从而使V_2O_5正极材料表现出优异的电化学性能成为可能。文章从氧化钒电极材料纳米化,在纳米化的基础上复合导电材料,调节工作电压窗口,掺杂金属离子这四类方法阐述对氧化钒电化学性能的改善,以及各种方法对电极电化学性能的影响。     

Electrospun ultralong hierarchical vanadium oxide nanowires with high performance for lithium ion batteries

Ultralong hierarchical vanadium oxide nanowires with diameter of 100-200 nm and length up to several millimeters were synthesized using the low-cost starting materials by electrospinning combined with annealing. The hierarchical nanowires were constructed from attached vanadium oxide nanorods of diameter around 50 nm and length of 100 nm. The initial and 50th discharge capacities of the ultralong hierarchical vanadium oxide nanowire cathodes are up to 390 and 201 mAh/g when the lithium ion battery cycled between 1.75 and 4.0 V. When the battery was cycled between 2.0 and 4.0 V, the initial and 50th discharge capacities of the nanowire cathodes are 275 and 187 mAh/g. Compared with self-aggregated short nanorods synthesized by hydrothermal method, the ultralong hierarchical vanadium oxide nanowires exhibit much higher capacity. This is due to the fact that self-aggregation of the unique nanorod-in-nanowire structures have been greatly reduced because of the attachment of nanorods in the ultralong nanowires, which can keep the effective contact areas of active materials, conductive additives, and electrolyte large and fully realize the advantage of nanomaterial-based cathodes. This demonstrates that ultralong hierarchical vanadium oxide nanowire is one of the most favorable nanostructures as cathodes for improving cycling performance of lithium ion batteries.     

Developments in Nanostructured Cathode Materials for High‐Performance Lithium‐Ion Batteries

Nanostructured materials lie at the heart of fundamental advances in efficient energy storage and/or conversion, in which surface processes and transport kinetics play determining roles. This Review describes some recent developments in the synthesis and characterization of nanostructured cathode materials, including lithium transition metal oxides, vanadium oxides, manganese oxides, lithium phosphates, and various nanostructured composites. The major goal of this Review is to highlight some new progress in using these nanostructured materials as cathodes to develop lithium batteries with high energy density, high rate capability, and excellent cycling stability resulting from their huge surface area, short distance for mass and charge transport, and freedom for volume change in nanostructured materials.     

Polymer/Transitonal Metal Oxides Nanocomposites as Cathode Materials for Rechargeable Lithium/Lithium lon Batteries

The synthesis and properties of polymer/transition metal oxides nanocomposite material were reviewed.The new nanocomposite material(PPY)0.5/MoO3 prepared by a new method is described.The application of the nanocomposite materials as cathode material in rechargeable lithium/lithium ion batteries was explored.     

Electrode materials for lithium secondary batteries prepared by sol-gel methods

Since the commercialization of lithium secondary batteries in the early of 1990s, their development has been rapid. Nowadays, improving the preparation technology and electrochemical performance of their electrode materials is a major focus in research and development of the materials, power sources and chemistry. Sol-gel methods are a promising way to prepare electrode materials due to their evident advantages over traditional methods, for example, homogeneous mixing at the atomic or molecular level, lower synthesis temperature, shorter heating time, better crystallinity, uniform particle distribution and smaller particle size at nanometer level. In this paper, latest progress in the preparation of electrode materials by sol-gel methods is reviewed, including cathodic ones, e.g., lithium cobalt oxides, lithium nickel oxides, spinel and layered lithium manganese oxides, vanadium oxides and ferrous phosphates, and anodic ones, e.g., tin oxides and titanium oxides. Compared with those prepared by traditional solid-state reaction, the structure stability of the prepared electrode materials and the behavior of lithium intercalation and de-intercalation are much improved. As a result, the prepared products provide better electrochemical performance including reversible capacity, cycling behavior and rate capability. In addition, sol-gel methods can be used to prepare new kinds of electrode materials such as nanowires of LiCoO₂ and nanotubes of V₂O₅, which cannot be easily created by the traditional methods. Further development and application of sol-gel methods will bring about new and better electrode materials, meaning a great promotion to lithium secondary batteries.     

V2O5 nanofibre sheet actuators

Vanadium oxides, such as V2O5, are promising for lithium-ion batteries, catalysis, electrochromic devices and sensors. Vanadium oxides were proposed more than a decade ago for another redox-dependent application: the direct conversion of electrical energy to mechanical energy in actuators (artificial muscles). Although related conducting polymer and carbon nanotube actuators have been demonstrated, electromechanical actuators based on vanadium oxides have not be realized. V2O5 nanofibres and nanotubes provide the potential advantages of low-cost synthesis by sol-gel routes and high charging capacity and long cycle life. Here, we demonstrate electromechanical actuation for obtained high modulus V2O5 sheets comprising entangled V2O5 nanofibres. The high surface area of these V2O5 sheets facilitates electrochemical charge injection and intercalation that causes the electromechanical actuation. We show that the V2O5 sheets provide high Young's modulus, high actuator-generated stress, and high actuator stroke at low applied voltage.     

锂离子电池锡基负极材料研究进展

综述了锂离子电池锡基负极材料的研究进展,锡基钢极材料可分为氧化物,复合氧化物,合金三类,其储锂机理都为合金机理,对氧化物的丰重于电极反应的详细过程,对复合氧化物的研究重点则是储锂机理,而锡合金则是最有希望进入商业化市场的锡基钢极材料,其中锡与锂可逆形成合金,另一不与锂反应的金属作为导电基体与框架,容纳合金以改善循环性能。     

钒酸锂化合物的制备和性能

采用一种新的方法合成LiV₃O₈化合物,以LiOH、V₂O₅和NH₃H₂O为反应物质,先合成出含有Li和V的反应前驱物质,再用焙烧的方法生成最终产物.X射线试验结果发现,产物在(100)方向上的衍射峰强度与用传统方法得到的产物相比明显降低.充放电结果显示,当电流为0.3mA/cm²时,在1.8～4.0V区间内,产物的首次放电比容量达到264mAh/g,循环15次后仍能达到249mAh/g.