Significant Enhancement of the Capacity and Cycling Stability of Lithium-Rich Manganese-Based Layered Cathode Materials via Molybdenum Surface Modification

Lithium-rich manganese-based layered cathode materials are considered to be one of the best options for next-generation lithium-ion batteries, owing to their ultra-high specific capacity (>250 mAh·g⁻¹) and platform voltage. However, their poor cycling stability, caused by the release of lattice oxygen as well as the electrode/electrolyte side reactions accompanying complex phase transformation, makes it difficult to use this material in practical applications. In this work, we suggest a molybdenum surface modification strategy to improve the electrochemical performance of Li_1.2Mn_0.54Ni_0.13Co_0.13O₂. The Mo-modified Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ material exhibits an enhanced discharge specific capacity of up to 290.5 mAh·g⁻¹ (20 mA·g⁻¹) and a capacity retention rate of 82% (300 cycles at 200 mA·g⁻¹), compared with 261.2 mAh·g⁻¹ and a 70% retention rate for the material without Mo modification. The significantly enhanced performance of the modified material can be ascribed to the formation of a Mo-compound-involved nanolayer on the surface of the materials, which effectively lessens the electrolyte corrosion of the cathode, as well as the activation of Mo⁶⁺ towards Ni²⁺/Ni⁴⁺ redox couples and the pre-activation of a Mo compound. This study offers a facile and effective strategy to address the poor cyclability of lithium-rich manganese-based layered cathode materials.     

Irreversible capacity of the amorphous silicon thin-film electrodes

Irreversible processes accompanying the lithium incorporation into amorphous thin-film silicon are investigated. It is shown that the irreversible processes occurred during the cathodic polarization result in the formation of passive film at the silicon surface. The passive film at silicon is close, in its composition, to the passive film at carbonaceous materials. However, unlike the carbonaceous electrodes, no effect of electrolyte composition on the irreversible capacity of the silicon electrodes is observed.     

Li3PO4包覆LiMn2O4正极材料的结构表征和电化学性能

采用共沉淀法在尖晶石LiMn2O4颗粒表面包覆Li3PO4.XRD、SEM研究结果表明,包覆后的材料仍为尖晶石结构,粒径均匀.电化学性能测试表明,Li3PO4包覆层的存在,减少了正极材料与电解液的直接接触,抑制了高温下电解液对LiMn2O4材料的侵蚀,从而有效改善了高温下材料的循环性能.在40℃时,包覆样品的比容量衰减率都低于未包覆样品,其中包覆1%Li3PO4的样品的初始比容量为110.4mAh/g,50次循环后比容量为84.1mAh/g.     

石墨基液流电池复合双极板

液流电池是一种安全性高、使用寿命长、可扩展的大规模储能系统,可以协助电网调峰储能,提高能源利用率,发展前景广阔。双极板是液流电池的重要组成部分。功能上起到了分隔、串联电池、传导电流、为电堆提供结构支撑等作用。从成本构成角度看,双极板的价格占电堆成本的比重也较大。开发高性能、低成本的双极板对加快液流电池的商业化应用具有重要意义,也是目前业界的迫切需求。虽然文献上报道了许多针对液流电池双极板开发的工作,但是目前高性能、低成本的液流电池双极板产品仍无法充分满足市场需求。本文着重介绍了石墨基复合双极板的研究现状,介绍了材料选择、工艺流程对关键性能的影响,对相关工作进行了评述,并为液流电池双极板的开发提出了建议。     

1,3-二氧戊环基LiCF3SO3电解液对锂硫电池正极材料单质硫的电化学性能影响

测试了二元和多元溶剂组分的1,3-二氧戊环基LiCF3SO3电解液的粘度、离子电导率和单质硫的溶解度. 研究结果表明, 由较强的给电子能力溶剂组成的低粘度电解液较容易提高单质硫的氧化还原反应活性和可逆性能, 有利于提高单质硫在2.10 V附近的低放电平台电位和放电比容量. DOL-DME LiCF3SO3电解液能够较好地改善单质硫电极的表面钝化层结构, 促进电活性物质离子扩散和降低界面电荷传递阻抗, 从而表现出很好的放电倍率特性. 在室温下充放电流密度分别为0.1和0.2 mA/cm2时, 单质硫的首次放电比容量为792 mA·h/g, 第29次放电比容量达到412 mA·h/g.     

层状LiMnO2的溶胶凝胶法合成及其改性

采用溶胶凝胶法合成了锂离子电池正极材料层状锰酸锂(o-L iMnO2),并对其进行了N i2+掺杂改性研究,优化了层状L iMnO2的合成路径及制备条件.采用XRD、充放电实验和交流阻抗测试方法研究了N i2+的掺入对o-L iMnO2充放电容量的影响.结果表明N i2+的掺入明显提高了锰酸锂的放电比容量和循环性能,抑制了循环过程中电池阻抗的增加.     

碳包覆LiFePO4的一步固相法制备及高温电化学性能

Carbon coated LiFePO₄ cathode material was synthesized by one-step solid-state reaction and characterized by X-ray diffraction (XRD), field-emission-scanning electron microscope (FESEM). Electrochemical performances of the material as cathode in lithium-ion battery were investigated at medium and elevated temperature (30 and 55 ℃) by galvanostatic charge-discharge and A.C. impedance tests. The results show that carbon coated LiFePO₄ powder exhibits a well-crystallized olivine structure and spherical morphology with an average particle size of about 500 nm. Galvanostatic charge-discharge tests show that the reversible discharge capacity at 1 C and 1.5 C rates was improved from 121 and 105 mAh·g^-1 at 30 ℃ to 136 and 123 mAh·g^-1 at 55℃, respectively, while the enhancement of high temperature on electrochemical performance is less obvious at a rate lower than 0.5 C. Impedance spectra analyses indicate that the cathode material has a remarkably higher lithium-ion diffusivity at 55 ℃ than that at 30 ℃, which improves the electrochemical performance at high temperature.     

低对称性硫代烃基四氮杂卟啉的合成、表征及电化学性质研究

合成了硫代烃基四氮杂卟啉2,3,7,8,12,13-六(甲硫基)-17,18-一(二噻英)四氮杂卟啉[H₂Pz(dtn)(mt)₆]及其过渡金属配合物MPz(dtn)(mt)₆,由元素分析、质谱、¹HNMR、UV-Vis和IR光谱对其组成和结构进行了表征,通过循环伏安测试结果讨论了H₂Pz(dtn)(mt)₆的电化学性质,证明H₂Pz(dtn)(mt)₆的还原过程为单电子连续传输过程,属于CE机理.研究了H₂Pz(dtn)(mt)₆对正极材料MnO₂在锂离子电池中的修饰作用.结果表明,H₂Pz(dtn)(mt)₆对改善锂离子电池的初始充放电容量和循环次数都有明显的增加.