锂离子电池硅基负极材料嵌锂行为的第一性原理研究

采用基于密度泛函理论的第一性原理平面波赝势方法,计算不同数量的锂离子引起的硅材料晶体结构的变化以及在嵌锂过程中形成Li_xSi(x=1、2、2.4、4.4)合金相的形成能与电子结构.采用LST/QST方法计算过渡态,模拟合金体相中的锂离子迁移过程.计算结果表明,随着嵌锂数量的增加,硅晶胞的体积在不断增大;Li_xSi合金相的形成能为负值,表明在嵌锂过程中锂离子和硅原子可以自发形成这些合金相,其中Li₇Si₃合金最容易形成;随着嵌锂量的增加,锂离子在费米能级处s轨道提供的电子数逐渐增加,锂硅合金在费米能级处的电子数量呈增大趋势,表明锂硅合金的导电性越来越优;常温下Li₂Si体相中很难直接形成锂离子空位,但锂离子空位的迁移过程很容易发生.     

Effects of nitrogen on the carbon anode of a lithium secondary battery

Nitrogen-containing carbons have been made from different polymer precursors at 600°C. Their composition and structure have been studied by chemical analysis, X-ray powder diffraction and X-ray photoelectron spectroscopy. These results show that this kind of carbon is disordered, and nitrogen exists as two kinds of forms in the polymeric carbons: graphene nitrogen (N_1s binding energy 398.5 eV) and conjugated nitrogen (N_1s binding energy 400.2 eV). The discharge and charge process suggests that these two kinds of nitrogen are bonded satisfactorily and could not result in irreversible reaction with Li. The increase of reversible capacity mainly results from the graphene nitrogen, and the higher the content of nitrogen, the higher the charge capacity. Part of the irreversible capacity is derived from the formed lithium carbide and lithium atoms which are intercalated and could not be deintercalated.     

Recent progress of computational investigation on anode materials in Li ion batteries

Computations have been widely used to explore new Li ion battery materials because of its remarkable advantages. In this review, we summarize the recent progress on computational investigation on anode materials in Li ion batteries. By introducing the computational studies on Li storage capability in carbon nanotubes, graphene, alloys and oxides, we reveal that computations have successfully addressed many fundamental problems and are powerful tools to understand and design new anode materials for Li ion batteries.     

Carbon anode thin films for lithium batteries

This paper describes a simple method to create carbon anode films for potential applications to the research field of lithium batteries. Carbon films were prepared using DC magneton sputtering with post-annealing process in the range from room temperature (RT) to 700 °C. Half cells assembled with lithium foils as the counter electrode and 1 M LiPF₆ in EC:DMC (1:1 v/v) electrolytic solution was used to evaluate the discharging capacity of prepared anode thin films. We showed that carbon film deposited at RT can be more suitable for an anode material than that of higher temperature annealed films above 400 °C. A variety of analysis methods including X-ray diffraction spectrometry (XRD), X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy were utilized to evaluate the defect density of the films; for example, the more defects on the film were identified when the carbon film was treated at a low temperature such as RT. It is envisioned that DC magnetron-sputtering with optimized process conditions can be useful for fabricating carbon based film anodes.     

Effects of binder content on manganese dissolution and electrochemical performances of spinel lithium manganese oxide cathodes for lithium ion batteries

In this study, the effects of the polyvinylidene fluoride (PVdF) binder on the Mn dissolution behavior and electrochemical performances of LiMn₂O₄ (LMO) electrodes are investigated. It is found that increasing the PVdF content (3, 5, 7, and 10 wt.%) leads to reduced Mn dissolution, and thus superior cycle performance at elevated temperature (60 °C). This can be ascribed to increased binder coverage on the LMO surface, as evidenced by X-ray photoelectron spectroscopy measurements, which acts a role as a passivation layer for Mn dissolution. The rate capability of the LMO electrode is hardly deteriorated as the PVdF content increases, despite the increasing surface coverage. Electrochemical impedance measurements reveal that the LMO electrode with higher binder loading exhibits lower electrode impedance, which is suggested to be due to enhanced electronic passage through the composite LMO electrode.     

锂离子电池负极材料CuSn的Li嵌入性质的研究

使用基于混合基表示的第一原理赝势法，研究了锂离子电池非碳类负极材料CuSn的Li嵌入时的形成能以及相应的电子结构.还给出了Li嵌入时的体积变化，能带结构、电子态密度以及电荷密度分布等性质, 并讨论了CuSn作为负极材料的特点.计算发现，Cu-Sn化合物在闪锌矿结构时，Li嵌入主体材料时的嵌入形成能大致在3.5eV附近. 关键词： 锂离子电池 负极材料 CuSn 电子结构     

Nanoporous carbon microspheres as anode material for enhanced capacity of lithium ion batteries

Nanoporous carbon microspheres (NCMs) are prepared by a one-step carbonizing and activating resorcinol?formaldehyde polymer spheres (RFs) in inert and CO₂ atmosphere for anode materials of lithium-ion batteries (LIBs). Compared with RFs carbon microspheres (RF-C), after activating with hot CO₂, the NCMs with porous structure and high BET surface area of 2798.8 m² g^?1, which provides abundant lithium-ion storage site as well as stable lithium-ion transport channel. When RF-C and NCM are used to anode material for LIBs, at the same current density of 210 mA g^?1, the initial specific discharge capacity are 482.4 and 2575.992 mA h g^?1, respectively; after 50 cycles, the maintain capacity are 429.379 and 926.654 mA h g^?1, respectively. The porous spherical structure of NCM possesses noticeably lithium-ion storage capability, which exhibits high discharge capacity and excellent cycling stability at different current density. The CO₂ activating carbonaceous materials used in anode materials can tremendously enhance the capacity storage, which provides a promising modification strategy to improve the storage capacity and cyclic stability of carbonaceous anode materials for LIBs.     

Lithium insertion studies on boron-doped diamond as a possible anode material for lithium batteries

Boron-doped diamond (BDD) was prepared by the hot filament chemical vapor deposition method. The prepared samples were subjected to X-ray diffraction, scanning electron microscopy, and Raman spectroscopy studies. The BDD composite electrode/Li cell has been assembled, and its cycling behavior was studied. The BDD possesses large sp² sites, which effectively participate in the lithium storage process. Furthermore, nanocrystalline tin (Sn) particles were prepared by the chemical reduction method. The addition of nanotin with the BDD-active material greatly enhances the cyclability of the cell. An erratum to this article can be found at     

锂离子电池中的物理问题及其研究进展

锂离子电池作为一种性能优越的新型可充放电池已经或将要在移动通信、手提式计算机和电动汽车等诸多领域获得广泛的应用 .然而与锂离子电池相关的物理问题却往往被人们忽视 .例如 ,如何从本质上来提高正极材料的体相电子电导率 ,而不是在正极活性物质中添加炭黑之类的电子导电材料 .文章将着重针对与锂离子电池相关的物理问题 ,介绍近年来的主要进展 ,以期待对锂离子电池有更深入的了解 .     

AA-stacked borophene-graphene bilayer as an anode material for alkali-metal ion batteries with a superhigh capacity

As the lightest two-dimensional material, monolayer borophene exhibits great potential as electrode materials, but it suffers from stability issues in the free-standing form. Here, the striped-borophene and graphene bilayer (sB/Gr) is found to be a high-performance anode material for rechargeable alkali-metal ion batteries. The first-principles results show that all the three alkali-metal atoms, Li, Na, and K, can be strongly adsorbed on sB/Gr with ultra-low diffusion barriers than that on pristine borophene/graphene, indicating good charge-discharge rates. Remarkably, high storage capacities are proposed for LIBs (1880 mA·h/g), NIBs (1648 mA·h/g), and KIBs (470 mA·h/g) with relatively small lattice change rate (<2.9%) in the process of alkali-metal atoms intercalations. These intriguing features of sB/Gr make it an excellent choice for batteries.     

Synthesis and characterization of LiMnBO3 cathode material for lithium ion batteries

LiMnBO₃ with enhanced powder density was successfully synthesized by a commercially available spray-drying process. A monoclinic-LiMnBO₃ single phase was experimentally substantiated by an X-ray diffractometer with crystallinity investigated by Rietveld refinement method (Bragg R-factor and RF-factor <10). The dense LiMnBO₃ powder prepared by the spray drying process showed spherical morphology. The electrochemical property of LiMnBO₃ was extensively investigated, positively revealing that 0.27 Li⁺ (Li_0.27MnBO₃) was stoichiometrically extracted from the host LiMnBO₃ material at first cycle.     

Chemically shortened multi-walled carbon nanotubes used as anode materials for lithium-ion batteries

An easy chemically cutting process, modified Hummers' method, was proposed to treat multi-walled carbon nanotubes, successfully cutting pristine long, entangled carbon nanotubes into hydrosoluble pieces, mostly less than 200 nm. This short, chemically oxidized carbon nanotube was then applied as an anode material for lithium-ion batteries. The as-prepared material possessed higher reversible capacity and coulombic efficiency. The intrinsic factors were explored by X-ray photoelectron spectroscopy and cyclic voltammetry.     

Synthesis and electrochemical performance of hole-rich Li4Ti5O12 anode material for lithium-ion secondary batteries

Hole-rich Li₄Ti₅O₁₂ composites are synthesized by spray drying using carbon nanotubes as additives in precursor solution, subsequently followed calcinated at high temperature in air. The structure, morphology, and texture of the as-prepared composites are characterized with XRD, Raman, BET and SEM techniques. The electrochemical properties of the as-prepared composites are investigated systematically by charge/discharge testing, cyclic voltammograms and AC impedance spectroscopy, respectively. In comparison with the pristine Li₄Ti₅O₁₂, the hole-rich Li₄Ti₅O₁₂ induced by carbon nanotubes exhibits superior electrochemical performance, especially at high rates. The obtained excellent electrochemical performances of should be attributed to the hole-rich structure of the materials, which offers more connection-area with the electrolyte, shorter diffusion-path length as well faster migration rate for both Li ions and electrons during the charge/discharge process.     

Electrochromic & magnetic properties of electrode materials for lithium ion batteries

Progress in electrochromic lithium ion batteries(LIBs) is reviewed, highlighting advances and possible research directions. Methods for using the LIB electrode materials' magnetic properties are also described, using several examples.Li_4Ti_5O_(12)(LTO) film is discussed as an electrochromic material and insertion compound. The opto-electrical properties of the LTO film have been characterized by electrical measurements and UV–Vis spectra. A prototype bi-functional electrochromic LIB, incorporating LTO as both electrochromic layer and anode, has also been characterized by charge–discharge measurements and UV–Vis transmittance. The results show that the bi-functional electrochromic LIB prototype works well. Magnetic measurement has proven to be a powerful tool to evaluate the quality of electrode materials. We introduce briefly the magnetism of solids in general, and then discuss the magnetic characteristics of layered oxides, spinel oxides, olivine phosphate Li Fe PO_4, and Nasicon-type Li_3Fe_2(PO_4)_3. We also discuss what kind of impurities can be detected, which will guide us to fabricate high quality films and high performance devices.     

Effect of carbon nanotubes on the anode performance of natural graphite for lithium ion batteries

A comparative investigation was carried out on carbon black and multiwalled carbon nanotubes as conductive additives in spherical natural graphite for lithium ion batteries. Scanning electron microscopy images showed that carbon nanotubes interlaced graphite particles in series to form a three-dimensional network. The constant current charge-discharge experiments showed that carbon nanotubes were more effective in improving reversible capacity and cycle stability. The reversible capacity was improved to 366 mAh/g and the cycle stability was improved effectively when carbon nanotubes were used. The research is of potential interest to the application of carbon nanotubes as conductive additives in anode materials for high-power lithium ion batteries.     

锂离子电池SnSb/C复合负极材料的热碳还原法制备及电化学性能研究

采用高温还原技术,以SnO2,SbO3为原料,分别以葡萄糖、中间相碳微球(MCMB)作为还原剂,制备了两种结构的SnSb/C复合材料,并对比了它们的形貌和电化学性能.采用X射线衍射技术、拉曼技术、扫描电子显微镜技术对材料的结构和形貌进行了表征,并且通过测试恒电流充放电曲线、循环伏安曲线和交流阻抗谱分析了材料的电化学性能.实验结果表明:葡萄糖作为还原剂时,形成以合金颗粒为内核,絮状碳壳均匀包裹的微米球状结构,首次放电比容量为793.379 mA·h·g-1,循环50周后仍维持在449.987 mA·h·g-1;而以MCMB作为还原剂时,形成合金颗粒与MCMB混合共存并部分包覆的结构,首次放电比容量为1164.938 mA·h·g-1,50周后的比容量仅有290.807 mA·h·g-1.     

Pyrolysed pitch-polysilane blends for use as anode materials in lithium ion batteries II: the effect of oxygen

As previously reported, blends of pitch and polysilanes, (Me₂Si)_x(PhMeSi)_y, with various pitch/polysilane ratios were pyrolysed at 1000 °C [W. Xing, A.M. Wilson, G. Zank, J.R. Dahn, Solid State Ionics 93 (1997) 239]. Some of the pyrolysed mixtures demonstrated large reversible capacities for lithium insertion (600 mA h g⁻¹), small irreversible capacities (150–200 mA h g⁻¹) and small hysteresis between charge and discharge cycles. Here, we investigate the role of the oxygen in these materials. The magnitude of the irreversible capacity and hysteresis are correlated to the oxygen content. This suggests that these materials are disordered carbons containing nanodispersed silicon oxycarbide clusters and not nanodispersed silicon, as was previously suggested. This does not change our opinion that pyrolysed pitch-polysilane blends are good alternatives to carbons for anode materials in lithium ion batteries.     

Brief overview of electrochemical potential in lithium ion batteries

The physical fundamentals and influences upon electrode materials' open-circuit voltage(OCV) and the spatial distribution of electrochemical potential in the full cell are briefly reviewed. We hope to illustrate that a better understanding of these scientific problems can help to develop and design high voltage cathodes and interfaces with low Ohmic drop. OCV is one of the main indices to evaluate the performance of lithium ion batteries(LIBs), and the enhancement of OCV shows promise as a way to increase the energy density. Besides, the severe potential drop at the interfaces indicates high resistance there, which is one of the key factors limiting power density.     

Density functional theory calculations for ethylene carbonate-based binary electrolyte mixtures in lithium ion batteries

The density functional theory (DFT) calculations have been performed to investigate the interaction of Li⁺ with various organic solvents widely used as Li ion rechargeable battery electrolytes such as ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC); and their EC-based binary mixtures at the level of B3LYP/6-31G (d). The interaction of Li⁺ with these solvents has been calculated in terms of electronic structures of clusters of the mixtures of organic solvents including a lithium ion. The main objective of our investigation is to help in understanding a stable and enhancing ionic transfer at graphite/electrolyte interface assisted by the mixtures of the solvents. The calculated results favor the stability of EC-based binary mixtures and high EC-content binary mixture systems. In infrared (IR) vibrational spectra, the IR active modes of the solvent show significant changes due to the cation-solvent interaction.     

Chitosan: A N-doped carbon source of silicon-based anode material for lithium ion batteries

Silicon/graphite/carbon (Si/G/CTS-C) composite, based on nano-silicon, flake graphite, and chitosan-derived carbon (CTS-C), was prepared by spray drying and subsequent pyrolysis. The results of X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, and transmission electron microscopy illustrate that chitosan is a good dispersion agent and chitosan-derived carbon is N-doped. The results indicate that the initial charge capacity of Si/G/CTS-C composite is 613.9 mAh g^?1 at a current density of 100 mA g^?1 corresponding to an initial coulombic efficiency of 81.89%. Besides, the Si/G/CTS-C composite exhibits higher specific capacity, more superior rate capability, better cycling performance, and lower impedance than that of silicon/graphite/phenolic resin-derived carbon (Si/G/P-C) composite.