SiO的电化学性能及其电极过程动力学研究

本文采用恒流充放电考察SiO的电化学性能，并在0.5 MHz至0.001 Hz的频率范围内，通过交流阻抗技术研究SiO电极在首次嵌锂反应中的电极过程。对不同电压区间下测得的交流阻抗图谱，提出不同的等效电路模型并对结果进行了拟合。通过拟合结果，探讨了SiO电极过程动力学以及嵌锂过程中电极界面的变化特性。     

锂离子固相扩散控制下的材料放电过程

从理论上分析了在锂离子相扩散控制条件下,电极材料的恒流放电过程,数值计算的结果表明,Q值（放电时率和扩散时间常数之比）对材料的放电容量有非常重要的影响,模拟了LiMn2O4正极材料和石墨负极材料的恒流放电曲线,分析了颗粒粒径对这两种材料放电容量的影响。     

锂离子电池正极材料的第一性原理研究进展

锂离子电池的发展主要依赖于电极材料的突破,解决现有电极材料存在的问题和预测新型未知材料是提高锂离子电池性能的关键,而第一性原理计算的出现能够较好的满足这一需求。本文介绍了第一性原理计算在锂离子电池正极材料研究方面的原理和应用,并对该原理在正极材料的平均嵌锂电压计算,嵌/脱锂机理、结构稳定性研究及新材料预测等方面的应用进行了详细论述,并指出了这一理论计算工具在电池材料设计过程中的重要性和局限性。     

Determining the Diffusion Coefficient of Lithium Insertion Cathodes from GITT measurements: Theoretical Analysis for low Temperatures**

Accurate knowledge of transport properties of Li-insertion materials in application-relevant temperature ranges is of crucial importance for the targeted optimization of Li-ion batteries (LIBs). Galvanostatic intermittent titration technique (GITT) is a widely applied method to determine Li-ion diffusion coefficients of electrode materials. The well-known calculation formulas based on Weppner's and Huggins’ approach, imply a square-root time dependence of the potential during a GITT pulse. Charging the electrochemical double layer capacitance at the beginning of a GITT pulse usually takes less than one second. However, at lower temperatures down to −40 °C, the double layer charging time strongly increases due to an increase of the charge transfer resistance. The charging time can become comparable with the pulse duration, impeding the conventional GITT diffusion analysis. We propose a model to describe the potential change during a galvanostatic current pulse, which includes an initial, relatively long-lasting double layer charging, and analyze the accuracy of the lithium diffusion coefficient, derived by using the Weppner-Huggins method within a suitably chosen time interval of the pulse. Effects leading to an inaccurate determination of the diffusion coefficient are discussed and suggestions to improve GITT analyses at low temperature are derived.     

Electrodeposition and characterization of assembly of Sn on Cu nanorods for Li-ion microbattery application

Assembly of Sn on Cu Nanorods as anode for Li-ion microbatteries was prepared by a two-step electrodeposition design. Firstly, Cu nanorods arrays were grown on copper substrate by anodic aluminum oxide template-assisted growth method. Then, Sn was deposited onto Cu nanorods arrays by galvanostatic deposition. X-ray diffraction and scanning electron microscopy measurements reveal that Cu nanorod arrays are covered with Sn. Electrochemical performances of prepared electrodes were evaluated by charge/discharge cycle measurement. The assembly of Sn on Cu nanorods electrode exhibited highly reversible specific capacity and superior capacity retention resulting from the three-dimensionally nano-architectured design, which exhibits a large surface area, shortened Li-ion diffusion distance, Cu?CSn alloying, and can accommodate the volume expansion of Sn during cycling. Deposition time is an important parameter for fabricating the assembly of Sn on Cu nanorods electrode with suitable structure and morphology.     

Electrodeposition and characterization of assembly of Sn on Cu nanorods for Li-ion microbattery application

Assembly of Sn on Cu Nanorods as anode for Li-ion microbatteries was prepared by a two-step electrodeposition design. Firstly, Cu nanorods arrays were grown on copper substrate by anodic aluminum oxide template-assisted growth method. Then, Sn was deposited onto Cu nanorods arrays by galvanostatic deposition. X-ray diffraction and scanning electron microscopy measurements reveal that Cu nanorod arrays are covered with Sn. Electrochemical performances of prepared electrodes were evaluated by charge/discharge cycle measurement. The assembly of Sn on Cu nanorods electrode exhibited highly reversible specific capacity and superior capacity retention resulting from the three-dimensionally nano-architectured design, which exhibits a large surface area, shortened Li-ion diffusion distance, Cu–Sn alloying, and can accommodate the volume expansion of Sn during cycling. Deposition time is an important parameter for fabricating the assembly of Sn on Cu nanorods electrode with suitable structure and morphology.

     

Electrocatalytic properties of cobalt-molybdenum alloy deposits in the hydrogen evolution reaction

Electrocatalytic activity of cobalt-molybdenum deposits is studied in the hydrogen evolution reaction (HER) in an alkaline solution. The studied electrode materials were obtained electrochemically in the galvanostatic mode. It is shown that the rate of hydrogen evolution in 1 M NaOH at 293 K at the Co-Mo alloy is higher, as compared to pure cobalt deposits obtained in similar conditions, which is due both to the increase of the electrode true surface area and possibly to the electronic structure of the obtained alloys. It is established that the hydrogen reaction exchange current grows at the increase of molybdenum content in the electrode deposits in the range of 0–40 at %.     

基于转化反应机制的锂离子电池电极材料研究进展

基于转化反应机制实现储锂功能的电极材料的研究和开发是提高锂离子电池性能,尤其是其可逆循环容量的重要方法,对于锂离子电池未来的发展有着非常重要的意义。本文综述近年来基于转化反应机制实现储锂功能的锂离子电池电极材料的研究进展,介绍了转化反应机制等新概念,重点讨论了基于转化反应机制实现储锂功能的简单过渡金属化合物电极材料的电...     

壳聚糖单体溶胶凝胶煅烧合成LiFePO4/C正极

本文以壳聚糖单体为碳源兼凝胶剂,利用溶胶-凝胶煅烧合成了锂离子电池LiFePO₄/C正极材料,使用XRD和SEM对合成的材料进行表征. 用恒电流充放电测试了LiFePO₄/C电极的电化学性能,当壳聚糖单体与LiFePO4摩尔比为1:1.2时,600 ^oC煅烧的LiFePO4/C电极性能最佳,其粒径分布均匀（200 ～ 400 nm）,该电极0.2C倍率放电比容量为155 mAh.g^-1,30周期循环放电比容量仍保持152 mAh.g^-1,库仑效率为97.9 %.     

锂离子电池锡薄膜负极制备及电化学性能研究

应用真空蒸发法在泡沫铜基底上制备锡薄膜负极.XRD、SEM分析表征薄膜的物相结构及其微观形貌,并测试了材料的电化学性能.结果表明,泡沫铜基底的三维结构增强了活性物质与基底的结合力.在同一基底温度下,锡颗粒随蒸发时间延长逐渐增大,电池电化学性能降低;而在同一时间内,升高基底温度,颗粒无明显变化,电池循环寿命有了很大提高.样品A″电池(基底温度:200℃,蒸发时间:0.5 h)经100次充放电循环后比容量仍达407.3 mAh·g-1.     

The influence of size on phase morphology and Li-ion mobility in nanosized lithiated anatase TiO2

Sustainable energy storage in the form of Li-ion batteries requires new and advanced materials in particular with a higher power density. Nanostructuring appears to be a promising strategy, in which the higher power density in nanosized materials is related to the dramatically shortened Li-ion diffusion paths. However, nanosizing materials also changes intrinsic material properties, which influence both ionic and electronic conductivity. In this work neutron diffraction is used to show that in addition to these two aspects, nanostructuring changes the phase behavior and morphology. Lithiated 40-nm TiO(2) anatase crystallites become single phase, either having the Li-poor original anatase phase, or the Li-rich Li-titanate phase, in contrast to microsized crystallites where these two phases coexist in equilibrium within one crystal particle. In addition, Li(x)TiO(2) compositions occur with stoichiometries that are not stable in micron-sized crystallites, indicating enhanced solid solution behavior. Reduced conduction electron densities at the sites of the Li ions are observed by NMR spectroscopy. This is accompanied by reduced spontaneous Li-ion mobility, suggesting a correlation between the electron density at the Li-ion site and the Li-ion mobility. The present results show that in the case of lithiated anatase TiO(2), significant effects on phase composition, morphology, and electronic configurations are induced, as well as slower intracrystallite Li diffusion.     

复合金属氧化物Sn-Sb-Mn/陶瓷粒子电极体系的电催化性能

通过热分解法制备了复合金属氧化物Sn-Sb-Mn/陶瓷粒子电极, 分别采用扫描电子显微镜(SEM)、能量色散X 射线能谱(EDS)、X射线衍射(XRD)和N2吸附-脱附等技术对电极的形貌、晶相组成、比表面积和孔径分布进行了表征. 考察了该三维粒子电极系统的析氧特性, 采用循环伏安法分析了三维系统的电催化性能, 并且进行了电化学催化降解苯酚的试验. 结果表明, 制备的陶瓷粒子电极涂层比表面较大、孔结构发达, 有利于电催化反应; 电催化降解主要发生在电化学析氧区; 粒子电极系统对苯酚降解作用显著, 明显高于二维电极系统, 苯酚的去除率为92.3%, 总有机碳(TOC)的去除率为66.7%. 研究结果表明, 该三维粒子电极系统具有优良的电催化性能.     

锂离子电池锡基合金体系负极研究

综述了锂离子电池锡基金属间化合物和复合物负极的研究进展。介绍了锡基合金体系作锂离子电池负极的优势, 指出了锡金属负极的不足,提出了采用锡基合金及其复合物是克服锡金属负极主体材料尺寸稳定问题的解决办法。概述了各种锡基合金和其复合物的结构、电化学性能、相应的加工方法和某些反应机理,总结了这些材料的优点和缺点,提出了改进这些材料性能的一些建议,如采用分散形态的纳米颗粒结构或用非晶合金并控制形态结构的转变,着重指出多相锡基锂合金复合物是最有前景的负极材料。     

Enhancing the performances of Li-ion batteries by carbon-coating: present and future

With progress of knowledge of electrode materials, it has been found that their surface structures are of great importance to the electrochemical performance of Li-ion batteries. Carbon coating can effectively increase the electrode conductivity, improve the surface chemistry of the active material, and protect the electrode from direct contact with electrolyte, leading to enhanced cycle life of the batteries. Carbon coating together with nanotechnology provides good conductivity as well as fast Li-ion diffusion, and thus also results in good rate capabilities. The recent development of carbon coating techniques in lithium-ion batteries is discussed with detailed examples of typical cathode and anode materials. The limitation of current technology and future perspective of the new concept of "hybrid coating" are also pointed out.     

Electrochemical performance of Li4Ti5O12/carbon nanofibers composite prepared by an in situ route for Li-ion batteries

A Li₄Ti₅O₁₂/carbon nanofibers (LTO/CNFs) composite has been synthesized by solid-state reaction with the in situ growth of CNFs using the chemical vapor deposition method in N₂/C₂H₂. The nanocomposite is characterized by X-ray powder diffraction, field emission scanning electron microscopy, transmission electron microscopy, Raman spectrum, and nitrogen adsorption/desorption isotherms, and is investigated as an anode material for lithium-ion (Li-ion) batteries. The underlying mechanism for the improvement is analyzed by cyclic voltammetry and electrochemical impedance spectroscopy. The in situ synthesized composite shows better electrochemical performance than the bare LTO. The in situ formation of CNFs not only supply an efficient electronic conductive network but also reduce the particle size of LTO and increase in specific surface area, leading to increased electrical conductivity and rapider Li-ion diffusion in electrode/electrolyte interface and bulk electrode.     

Characterization of bi-material electrodes for electrochemical hybrid energy storage devices

The hybridization of an electrochemical double layer capacitor and a lithium-ion battery at the electrode level can be realized by combining lithium insertion materials and capacitive materials in bi-material electrodes. A bi-material electrode based on activated carbon and LiMn₂O₄ has been prepared and characterized in the present work. An experimental setup was developed in order to measure the current sharing between the two different active materials in a single segmented bi-material electrode. This setup allows distinguishing the contribution of each material to the overall electrode performance. The characterization consisted of cyclic voltammetry and galvanostatic charge discharge cycling. The behavior of the bi-material electrode is essentially a linear combination of the behaviors of the two materials.     

A review of transition metal chalcogenide/graphene nanocomposites for energy storage and conversion

Recent advances in the applications of transition metal chalcogenides/graphene (TMC/graphene) nanocomposites in future energy storage and conversion are reviewed. The synthesis processes and structures of TMC/graphene, workingpriciple of evergy energy device, and the electrochemical performances are summarized.     

Temperature effect on electrochemical properties of lithium manganese phosphate with carbon coating and decorating with MWCNT for lithium-ion battery

Journal of Solid State Electrochemistry - The increasing demands for higher energy density and higher power capacity of Li-ion secondary batteries have led to a search for electrode materials whose...     

3d-Transition metal doped spinels as high-voltage cathode materials for rechargeable lithium-ion batteries

Finding appropriate positive electrode materials for Li-ion batteries is the next big step for their application in emerging fields like stationary energy storage and electromobility. Among the potential materials 3d-transition metal doped spinels exhibit a high operating voltage and, therefore, are highly promising cathode materials which could meet the requirements regarding energy and power density to make Li-ion batteries the system of choice for the above mentioned applications. The compounds considered here include substituted Mn-based spinels such as LiM_0.5Mn_1.5O₄ (M = Ni, Co, Fe), LiCrMnO₄ and LiCrTiO₄. In this review, the recent researches conducted on these spinel materials are summarized. These include different routes of synthesis, structural studies, electrode preparation, electrochemical performance and mechanism of Li-extraction/insertion, thermal stability as well as degradation mechanisms. Note that even though the Ni-, Co-, and Fe-doped materials share the same chemical formula, the oxidation state distributions as well as the operating voltages are different among them. Furthermore, apart from the initial structural similarity, the Li-intercalation takes place through different mechanisms in different materials. In addition, this difference in mechanism is found to have considerable influence on the long-term cycling stability of the material. The routes to improve the electrochemical performance of some of the above candidates are discussed. Further emphasis is given to the parameters that limit their application in current technology, and strategies to overcome them are addressed.     

利用过硫酸钠化学抽取制备脱锂态电极材料

介绍了一种通过常规化学反应制备锂离子电池脱锂态电极材料的方法。首先将氧化剂Na₂S₂O₈与锂离子电池电极材料混合于去离子水中,对混合液进行振荡和搅拌,使脱锂反应充分进行,获得不溶于水的脱锂态电极材料和溶于水的其他生成物,然后将溶于水的生成物过滤掉,最后对不溶于水的脱锂态电极材料进行反复清洗并干燥,便获得所需材料。此方法操作简便,容易控制,计算锂含量方便准确,并且可以得到足够量和纯净的脱锂态电极材料,克服了充放电法制备和采用其他氧化剂进行化学