Synthesis of PAN/SnCl2 composite as Li-ion battery anode material

A novel process was proposed to synthesize the pyrolytic polyacrylonitrile (PAN)/SnCl₂ composite anode material for Li-ion batteries. The preparation started with the dissolution of PAN and SnCl₂ in dimethylformamide (DMF), followed by drying of the solution and pyrolysis of the dried mixture of PAN and SnCl₂ at 300 °C, leading to homogenous dispersal of SnCl₂ in pyrolytic PAN, which becomes conducting polymer matrix. The composite presented stable cycling capacity of about 490 mAh/g. It is demonstrated that SnCl₂, which has been considered to be an inactive electrode material, can become active by the proposed composite technique. This paves the promising way to prepare electrode materials for Li-ion batteries.     

Carbon-coated silicon/crumpled graphene composite as anode material for lithium-ion batteries

Silicon is a promising anode material for high-capacity Li-ion batteries (LIBs). However, its insulating property and large volume change during the lithiation/delithiation process result in poor cycling stability and in pulverization of Si. In this work, glucose-derived carbon-coated Si nanoparticles (C–Si NPs) are in conjunction with crumpled graphene (cGr) particles by a spray-drying method to prepare a novel composite (C–Si/cGr) material. The prepared C–Si NPs are uniformly embedded in the ridges of the cGr particles. The carbon layer of C–Si can make a good contact with the graphene sheet, resulting in enhanced electrical conductivity and fast charge transfer. In addition, the unique crumpled structure of the cGr can buffer the large volume change upon cycling process and facilitate the diffusion of electrolyte into the composite material. When employed as an anode electrode of LIBs, the C–Si/cGr composites deliver enhanced electrochemical performance, including stable cycling with a discharge capacity of 790 mAh·g⁻¹ after 100 cycles and a rate capability of 654 mAh·g⁻¹ at 2C. The synergistic effect of the carbon layer coating of Si NPs and the crumpled structure of the cGr particles results in a composite with improved the electrochemical performance, which is likely related to its high electrical conductivity and good mechanical stability of composite material.     

Carbon Nanostructures in Lithium Ion Batteries: Past,Present, and Future

Advent of nanotechnology has generated huge interest in application of carbon-based nanomaterials as a possible replacement for conventionally used graphite as anode of Li-ion batteries. Future Li-ion batteries demand high capacity, energy, power, and better safety, while graphite falls short of fulfilling all these necessities. Inspired by high conductivity, flexibility, surface area, and Li-ion insertion ability, a number of nano carbon materials, individually or as a composite, have been studied in detail to identify the best suitable material for next-generation energy storage devices. Many of these nano-C-based structures hold good promise, although issues like density of nanomaterials and scalability are yet to be addressed with confidence. This article aims to summarize the major research directions of nano-C materials in anodic application of Li-ion batteries and proposes possible future research directions in this widely studied field.     

Materials for Electrodes of Li-Ion Batteries: Issues Related to Stress Development

Presently, rechargeable Li-ion batteries, possessing highest energy densities among all batte-ries, are used in a major fraction of all portable electronic devices. However, for bestowing the Li-ion batteries suitable for such advanced applications, further improvements in the energy densities (Li-capacities) and in the cycle life are essential. In a broader sense, this can be achieved by replacing the presently used electrode materials by materials possessing higher Li-capacities and minimization of the degradation of such materials with electrochemical cycling. It has been realized that the major reason for degradation in battery performance in terms of capacity with cycling is the disintegration/fragmentation of the active electrode materials due to stresses generated during Li-intercalation/de-intercalation in every cycle. Such stresses arise from the reversible volume changes of the active electrode materials during Li-insertion and removal. In quest of higher energy densities, replacement of the presently used graphitic carbon by potentially higher capacity metallic anode materials (like Si, Sn, and Al) is likely to further accrue this stress related disintegration due to ～30 times higher volume changes experienced by such materials. It has also been recently realized that passivating layer formed on the surface of the electrodes also contributes toward the stress development. After briefly introducing the mechanistic aspects of Li-ion batteries, this article focuses on the reasons and consequences associated with stress developments in different electrode materials, highlighting the various strategies, in terms of designing new electrode com-positions or reducing the microstructural scale, that are being presently adopted to address the stress-related issues. Considering that experimental determination of such stresses is essential toward further progress in Li-ion battery research, this article introduces a recently reported technique developed for real-time measurement of such stresses. It finally concludes by raising some critical issues that need to be resolved through further research in this area.     

Nanocaging Silicon Nanoparticles into a Porous Carbon Framework toward Enhanced Lithium-Ion Storage

Silicon (Si) shows overwhelming promise as the high-capacity anode material of Li-ion batteries with high energy density. However, Si-based anodes are subjected to a limited electrochemical cycling lifetime due to their large volume change. Herein, a honeycomb-like biomass-derived carbon nanosheet framework is reported to encapsulate Si nanoparticles via a facile molten salt templating method. The carbon framework provides sufficient void space for effectively accommodating the large volume expansion of Si upon Li⁺ insertion. Moreover, the interconnected carbon skeletons afford fast electron/ion transport pathways for improving the reaction kinetics. Consequently, the porous Si/carbon composite could exhibit a high and stable Li storage capacity of 1022 mAh g⁻¹ at 0.2 A g⁻¹ over 100 cycles along with superior rate capability (555 mAh g⁻¹ at 5 A g⁻¹). This study demonstrates an effective structural design strategy for Si-based anodes toward stable lithium energy storage.     

Enhancement of the electrochemical performance of silicon/carbon composite material for lithium ion batteries

The silicon/carbon (Si/C) composite material was prepared, and the electrochemical performance was investigated as a promising anode material for lithium ion batteries. The results show that the binder in the electrode acts as an important role for improving the reversible capacity of the Si/C materials during cycling. The Si/C electrode with CMC/SBR binder possesses a better cycle performance than that with PVDF binder. The Si/C composite material shows an initial reversible capacity of more than 700 mAh∙g⁻¹ and remains a reversible capacity of 597 mAh g⁻¹ after 40 cycles.     

How M?ssbauer spectroscopy can improve Li-ion batteries

In the domain of Li-ion batteries, M?ssbauer spectroscopy is mainly used for the characterization of electrode materials and the analysis of electrochemical reactions. Depending on the properties under investigation, different approaches are often considered, which are based on ex situ, in situ and operando measurements. The specific electrochemical cells and sample preparations used for such measurements are described in this paper. Applications to selected examples of cathode and anode materials are presented in order to show how M?ssbauer spectroscopy, when associated with other techniques, provides essential information to understand the mechanisms and improves the performances of Li-ion batteries.     

Probing component contributions and internal polarization in silicon-graphite composite anode for lithium-ion batteries with an electrochemical-mechanical model

Silicon-graphite (Si-Gr) composite anodes are attractive alternatives to replace Gr anodes for lithium-ion batteries (LIBs) owing to their relatively high capacity and mild volume change. However, it is difficult to understand electrochemical interactions of Si and Gr in Si-Gr composite anodes and internal polarization of LIBs with regular experiment methods. Herein, we establish an electrochemical-mechanical coupled model to study the effect of rate and Si content on the electrochemical and stress behavior in a Si-Gr composite anode. The results show that the composites of Si and Gr not only improve the lithiation kinetics of Gr but also alleviate the voltage hysteresis of Si and decrease the risk of lithium plating in the negative electrode. What's more, the Si content is a tradeoff between electrode capacity and electrode volume variation. Further, various internal polarization contributions of cells using Si-Gr composite anodes are quantified by the voltage decomposition method. The results indicate that the electrochemical polarization of electrode materials and the electrolyte ohmic over-potential are dominant factors in the rate performance of cells, which provides theoretical guidance for improving the rate performance of LIBs using Si-Gr composite anodes.     

锂电池发展简史

由于具有很高的能量密度，锂金属在1958年被引入电池领域，1970年进入锂一次电池的商业研发阶段。自1990年以来，随着正极材料、负极材料与电解质的革新，可充放二次锂电池不断发展并实现商品化。如今锂电池技术仍在继续发展并将进一步改善人类生活。文章对40多年来锂电池技术发展历程进行了简单的回顾。     

Carbon-coated Si/graphite composites with combined electrochemical properties for high-energy-density lithium-ion batteries

Carbon-coated Si/graphite composites with different Si/graphite weight ratio have been fabricated using solid-state reaction with aim to improve the cyclic stability, coulombic efficiency, and rate capability simultaneously. Microstructural investigation reveals that the Si particles are covered by amorphous carbon and attached to the carbon-coated graphite surface. Electrochemical evaluation has been performed using cyclic voltammetry and charge/discharge cycling at different current densities, which indicate that addition of graphite can not only enhance the first-cycle coulombic efficiency to 90 % but also improve the cyclic stability drastically. The carbon-coated Si/graphite composite with appropriate contents of Si, graphite, and carbon is expected to be promising candidate as anode materials for high-energy-density lithium-ion batteries.     

Lithium titanate as anode material for lithium-ion cells: a review

Lithium titanate (Li₄Ti₅O₁₂) has emerged as a promising anode material for lithium-ion (Li-ion) batteries. The use of lithium titanate can improve the rate capability, cyclability, and safety features of Li-ion cells. This literature review deals with the features of Li₄Ti₅O₁₂, different methods for the synthesis of Li₄Ti₅O₁₂, theoretical studies on Li₄Ti₅O₁₂, recent advances in this area, and application in Li-ion batteries. A few commercial Li-ion cells which use lithium titanate anode are also highlighted.     

Theoretical prediction of honeycomb carbon as Li-ion batteries anode material

First principles calculations are performed to study the electronic properties and Li storage capability of honeycomb carbon. We find its right model consistent with the experimental result, the honeycomb carbon and its Li-intercalated configurations are all metallic which is beneficial to the electrode materials for lithium-ion batteries. The model 1 configuration shows fast Li diffusion and theoretical Li storage capacity of 319 mAh/g. Moreover, the average intercalation potentials for honeycomb carbon material is calculated to be low relatively. Our results suggest that the honeycomb carbon would be a new promising pure carbon anode material for Li-ion batteries.     

Nanoporous silicon flakes as anode active material for lithium-ion batteries

Nanoporous-silicon (np-Si) flakes were prepared using a combination of an electrochemical etching process and an ultra-sonication treatment and the electrochemical properties were studied as an anode active material for rechargeable lithium-ion batteries (LIBs). This fabrication method is a simple, reproducible, and cost effective way to make high-performance Si-based anode active materials in LIBs. The anode based on np-Si flakes exhibited a higher performances (lower capacity fade rate, stability and excellent rate capability at high C-rate) than the anode based on Si nanowires. The excellent performance of the np-Si flake anode was attributed to the hollowness (nanoporous structure) of the anode active material, which allowed it to accommodate a large volume change during cycling.     

A review of research on hematite as anode material for lithium-ion batteries

Hematite (α-Fe₂O₃) nanomaterials have been investigated intensively as a promising anode material for Li-ion batteries due to their advantages such as high theoretical capacity, low cost, environmental friendliness, high resistance to corrosion, etc. However, their practical application is hampered by poor capacity retention, low Coulombic efficiency, and poor high-rate capacity. To overcome these drawbacks, many effective works have been proposed. This review focuses first on the present status of α-Fe₂O₃ nanomaterials in the field of Li-ion batteries including their features, synthesized methods, modification, application and then on their near future development.     

Evolution of the negative electrode (tin/silicate) for Li-ion batteries studied by 119 Sn Mössbauer spectroscopy

A novel tin composite Sn/CaSiO₃ for the anode of Li-ion batteries was prepared by solid-state reaction. The CaSiO₃ matrix was synthesized by a sol-gel route. The crystalline structures and morphology were determined by X-ray diffraction (XRD) and ¹¹⁹Sn Mössbauer spectroscopy; the electrochemical properties were evaluated by galvanostatic charge and discharge. The results obtained show that the Sn/CaSiO₃ composite presents very interesting electrochemical performances in terms of specific capacity in the first discharge (591 mAh/g) and a good reversibility due to both the formation of an interface between active and inactive materials and the reversible formation of Li _x Sn alloys. We have also highlighted, by ¹¹⁹Sn Mössbauer spectroscopy, the various tin species constituting the material of the starting electrode, as well as the chemical evolutions occurring during the discharge and the charge of the electrode.     

Characterization of phospho-olivines as materials for Li-ion cell cathodes

Solid State Reaction was employed to prepare phospho-olivines LiMPO₄ (where M=Fe, Co) as pure phase and LiNiPO₄ in presence of foreign phases, as cathodic materials for lithiumions batteries. The relationship between structural, morphological and electrochemical properties were investigated in the case of LiFePO₄. Structural investigation has been carried out by means of X-ray powder diffraction (XRPD) and Rietveld refinement. The influence on the morphology of annealing temperature, different flowing gas mixture and addition of ascorbic acid during the synthesis, has been analysed via scanning electron microscopy. The electrochemical cycling performances on LiFePO₄ showed to be positively affected by the modifications of the experimental conditions. Cyclic voltammetry showed a good reversibility during insertion-extraction mechanism, in particular in presence of additives. LiCoPO₄ and LiNiPO₄ are interesting as high voltage cathode materials for Li-ion batteries and have been taken into account, but their electrochemical operating conditions are still to be optimised. In the case of LiNiPO₄ it is very difficult to obtain, by solid state synthesis, suitable purity powders, having a grain size small enough to exploit it usefully as cathodic material for Li-ion cells. Paper presented at the 8th EuroConference on Ionics, Carvoeiro, Algarve, Portugal, Sept. 16 – 22, 2000.     

The effect of S-functionalized and vacancies on V2C MXenes as anode materials for Na-ion and Li-ion batteries

The electrochemical properties of V₂C and V₂CT₂ (T = O, S) MXenes with and without vacancy as anode materials for Na-ion and Li-ion batteries, have been studied using first-principles calculation. The present results indicate that the adsorption strength of Li-ion and Na-ion on V₂CS₂ are less than that of O-functionalized, together with a lower diffusion barrier. Simultaneously, V₂CS₂ monolayer exhibits lower open-circuit voltage (OCV) values of 0.72 and 0.49 V for Li- and Na-ion, respectively. Interestingly, the presence of atomic vanadium vacancy on V₂CS₂ monolayer exerts more prominent effects on enhancing adsorption strength than that of carbon vacancy for Li-ion and Na-ion, but with an exception for the diffusion of Li-ion and Na-ion on V₂CS₂ monolayer. The finding suggests that the V₂CS₂ monolayer is expected to be a potential candidate as anode material for Li-ion and Na-ion battery due to its lower open-circuit voltages and diffusion barriers.     

Template-free synthesis of hierarchical NiO microtubes as high performance anode materials for Li-ion batteries

Hierarchical nanostructured NiO (h-NiO) microtubes were prepared by a simple wet-chemical synthesis without the use of template or surfactant, followed by the calcination of α-Ni(OH)₂ precursor. The structural characterization of the h-NiO microtubes were performed by scanning microscopy (SEM), transmission electron microscopy (TEM), and X-ray diffraction (XRD), the results of which indicated that the obtained h-NiO microtubes are covered by the nanosheet grown perpendicularly on the tube surface. The unique hierarchical nanostructure of h-NiO microtubes with high surface area and many voids facilitates the electrochemical reaction as well as the short ion and electron transport pathway. Therefore, as anode electrode of Li-ion batteries, the h-NiO microtubes deliver largely enhanced cycle capacity of 770 mAh·g⁻¹ at a current density of 0.5 C after 200 cycles with high columbic efficiency, compared to the NiO rods. These results suggest that the h-NiO microtubes can be a promising anode material for Li-ion batteries.     

Preparation of Si-PPy-Ag composites and their electrochemical performance as anode for lithium-ion batteries

The nanosilicon connected by polypyrrole (PPy) and silver (Ag) particles was simply synthesized by a chemical polymerization process in order to prepare Si-based anodes for Li-ion batteries. The phase structure, surface morphology, and electrochemical properties of the as-synthesized powders were analyzed by X-ray diffraction, FT-IR, scanning electron microscopy, and galvanostatic charge/discharge measurements. The cycle stability of the Si-PPy-Ag composites was greatly enhanced compared with the pure nanosilicon. A high capacity of more than 823 mA h g^?1 was maintained after 100 cycles. The improved electrochemical characteristics are attributed to the volume buffering effect as well as effective electronic conductivity of the polypyrrole and silver in the composite electrode.     

基于单粒子模型与偏微分方程的锂离子电池建模与故障监测

锂离子电池内部结构是一种复杂的分布参数系统, 如果为了降低计算难度而使用常微分方程描述锂离子电池, 可能会引入系统误差, 降低系统模型的可信度, 需要使用偏微分方程建立分布参数系统的精确模型. 本文提出了一种基于单粒子模型和抛物型偏微分方程的锂离子电池系统建模与故障监测系统设计方法, 当锂离子浓度实测值与理想值的残差大于预设门槛时判定分布参数系统处于故障状态. 通过一个仿真实例进行了锂离子电池系统建模和故障诊断实验, 实验证明基于单粒子模型和偏微分方程的锂离子电池故障监测系统具有更高的精确度和可信度.