Porous silicon based negative electrodes for lithium ion batteries

Various structures of macroporous silicon intended for the fabrication of lithium ion battery anodes have been studied. Macroporous membranes were prepared by the photoelectrochemical etching of n-type silicon wafers possessing various resistances, followed by the removal of the substrate. The porosity was increased via additional oxidation with the subsequent etching of oxide. The electric contacts on the membrane were fabricated by depositing copper with a titanium sublayer and soldering the structure to a supporting molybdenum disk. The electrochemical characteristics of anodes were studied in a cell with a lithium counterelectrode. These measurements showed that the obtained porous silicon electrodes possess a high capacity for lithium insertion (up to 50 mAh/cm²) and admit more than 20 charge/discharge cycles.     

锂离子电池用多孔电极结构设计及制备技术进展

随着人们对锂离子电池需求的日益增加, 高能量密度和高功率密度锂离子电池技术成为研究热点之一。材料改性及新材料开发能有效提高电池的能量密度, 除此以外, 孔隙率、孔径大小与分布、曲折度及电极组分分布等电极的微观结构参数也是决定电极及电池性能的关键因素。通过优化电极结构设计提升高比能电池的性能逐渐成为人们关注的焦点。本文综述了锂离子电池多孔电极结构设计优化的研究进展, 总结了多孔电极结构设计要素及制备方法, 最后对电极结构设计优化以及推动新型制备技术的规模化应用在高比能锂离子电池领域的未来发展前景进行展望。     

A comparative study on electrochemical performances of the electrodes with different nanocarbon conductive additives for lithium ion batteries

Three nanocarbon materials (0 D acetylene black (AB), 1 D carbon nanotubes (CNTs) and 2 D reduced graphene oxide (RGO)) were used as conductive additives (CAs) in the mesocarbon microbead anodes for lithium ion batteries. The electrochemical performances of the electrodes were investigated. The results show that the CAs have a significant impact on the electrode performance because they can influence the electron conduction and lithium ion transportation within the electrode. The electrode with RGO achieves a maximum capacity of 387 mAh g⁻¹ after 50 cycles at a current density of 50 mA g⁻¹, much higher than those of the electrodes with AB (334 mAh g⁻¹) and CNTs (319 mAh g⁻¹). The improvement should be mainly ascribed to the “plane-to-point” conducting network formed in the electrode with 2 D RGO which can favor the electron conduction and enhance the lithium ion transportation.     

锂离子电池电解质用含硼锂盐研究进展

电解质材料是锂离子电池的关键材料之一。LiBF4、双草酸硼酸锂(LiBOB)及草酸二氟硼酸锂(LiODFB)是极具应用前景的3种含硼锂盐。介绍了3种锂盐各自的优缺点及研究近况,重点综述了它们的离子传导特性及与电极材料的相容性能。     

Engineering the surface of LiCoO2 electrodes using atomic layer deposition for stable high-voltage lithium ion batteries

Developing advanced technologies to stabilize positive electrodes of lithium ion batteries under high-voltage operation is becoming increasingly important,owing to the potential to achieve substantially enhanced energy density for applications such as portable electronics and electrical vehicles.Here,we deposited chemically inert and ionically conductive LiAlO2 interfacial layers on LiCoO2 electrodes using the atomic layer deposition technique.During prolonged cycling at high-voltage,the LiAlO2 coating not only prevented interfacial reactions between the LiCoO2 electrode and electrolyte,as confirmed by electrochemical impedance spectroscopy and Raman characterizations,but also allowed lithium ions to freely diffuse into LiCoO2 without sacrificing the power density.As a result,a capacity value close to 200 mA·h·g-1 was achieved for the LiCoO2 electrodes with commercial level loading densities,cycled at the cut-off potential of 4.6 V vs.Li+/Li for 50 stable cycles;this represents a 40％ capacity gain,compared with the values obtained for commercial samples cycled at the cut-off potential of 4.2 V vs.Li+/Li.     

锂离子二次电池负极材料的研究综述

总结了在碳材料、合金材料和复合材料等3个锂离子电池负极材料研发的主导方向上的开发情况和它们各自特点,描述了目前的研究所面临难题,给出了锂离子电池负极材料研发取得重大突破的可能途径和建议.     

Evaluation of Si/Ge multi-layered negative film electrodes using magnetron sputtering for rechargeable lithium ion batteries

The capacity of a silicon anode diminishes during repeated lithium ion intercalation and extraction as the volume changes cause the active material to internally crack. In this study, electrodes are prepared by a deposition method, and silicon and germanium are deposited on the copper current collector in sequence. The number of layers is varied and we find evidence that a multi-layered structure is capable of improving cyclic ability. It is expected that germanium would act as a buffer against the volume change of the silicon and contribute to the elevating lithium ion diffusion. The morphologic changes and cyclic performances of the multi-layered electrodes prepared by the deposition method are observed. Deposited electrodes are verified by X-ray diffractometry, Raman spectroscopy, field-emission scanning electron microscopy and transmission electron microscopy. Si―Ge bonding at the interface is analyzed using extended X-ray absorption fine structure.     

锂离子电池硅基负极材料研究进展

由于硅负极不能在商业上大规模应用,研究者采用多种改性制备方法,提高硅基负极材料初始放电容量和循环性能。综述了近年来改善硅基负极材料性能的几种制备方法,指出了硅基材料作为锂离子电池负极材料的研究前景。     

Surface modification of cathode materials for lithium ion batteries

We have studied the effect of surface modification with aluminum hydroxide and alumina-boehmite mixtures on the electrochemical performance of an equimolar LiCoO₂/LiMn₂O₄ composite cathode material. A process has been developed for the deposition of aluminum hydroxide nanocoatings using ultrasonic processing. Al(OH)₃ nanocoatings, as well as alumina-boehmite nanocoatings, considerably improve the cyclability of the composite in an extended voltage range (up to 4.5 V) in comparison with the unmodified material, with an insignificant reduction in specific capacity in the first cycles. Both types of coatings markedly improve the cyclability of the composite at high current rates in comparison with the unmodified composite.     

锂离子电池用聚烯烃隔膜的改性

介绍了聚烯烃类隔膜在液态锂离子二次电池中的重要作用、制备方法及其优缺点和面对越来越广泛的应用需求该类隔膜所存在的主要不足;重点论述了针对目前聚烯烃隔膜低表面能、难以充分润湿及耐热性差的问题而进行改性的研究成果和现状;总结了所采用的物理涂覆、化学接枝、共混及凝胶填充等改性方法及其存在优缺点;最后提出了对于聚烯烃类隔膜改性未来发展趋势的展望.     

Electrodeposition of amorphous silicon anode for lithium ion batteries

Amorphous silicon has been successfully electrodeposited on copper using a SiCl₄ based organic electrolyte under galvanostatic conditions. The electrodeposited silicon films were characterized for their composition, morphology and structural characteristics using glancing angle X-ray diffraction (GAXRD), scanning electron microscopy (SEM), and Raman spectroscopy. GAXRD and Raman analyses clearly confirm the amorphous state of the deposited silicon film. The deposited films were tested for possible application as anodes for Li-ion battery. The results indicate that this binder free amorphous silicon anode exhibits a reversible capacity of ∼1300 mAh g⁻¹ with a columbic efficiency of >99.5% up to 100 cycles. Impedance measurements at the end of each charge cycle show a non-variable charge transfer resistance which contributes to the excellent cyclability over 100 cycles observed for the films. This approach of developing thin amorphous silicon films directly on copper eliminates the use of binders and conducting additives, rendering the process simple, facile and easily amenable for large scale manufacturing.     

Hollow iron oxide nanoparticles for application in lithium ion batteries

Material design in terms of their morphologies other than solid nanoparticles can lead to more advanced properties. At the example of iron oxide, we explored the electrochemical properties of hollow nanoparticles with an application as a cathode and anode. Such nanoparticles contain very high concentration of cation vacancies that can be efficiently utilized for reversible Li ion intercalation without structural change. Cycling in high voltage range results in high capacity (～132 mAh/g at 2.5 V), 99.7% Coulombic efficiency, superior rate performance (133 mAh/g at 3000 mA/g) and excellent stability (no fading at fast rate during more than 500 cycles). Cation vacancies in hollow iron oxide nanoparticles are also found to be responsible for the enhanced capacity in the conversion reactions. We monitored in situ structural transformation of hollow iron oxide nanoparticles by synchrotron X-ray absorption and diffraction techniques that provided us clear understanding of the lithium intercalation processes during electrochemical cycling.     

软包锂电池铝塑复合膜制作工艺途径

本文介绍了软包锂离子电池铝塑复合膜的典型结构及制作工艺途径与产品质量指标,并简要论述市场需求前景。     

正极材料磷酸铁锂的改性研究进展

介绍了锂离子电池正极材料磷酸铁锂的改性方法,综述了近年来锂离子电池正极材料磷酸铁锂的研究进展.重点叙述了金属粒子掺杂改性及碳包覆改性方面的研究成果.在综述各改性方式方面进展的基础上,指出了现阶段研究上对改性方式的理论体系建立方面所存在的问题,并结合作者研究小组的研究,对磷酸铁锂材料的未来研究方向进行了展望.     

锂离子电池凝胶聚合物电解质制备技术进展

综述了近几年锂离子电池凝胶聚合物电解质的制备技术进展,主要介绍了溶液浇铸法、倒相法和现场聚合等工艺的优缺点。现场聚合工艺流程简单、产品成本低,有极其广阔的发展前景。通过添加无机纳米粒子改善凝胶聚合物电解质的性能是目前的研究热点和发展趋势。     

锂离子电池负极墨水的制备及性能研究

钛酸锂因零应变特性已成为性能优异的锂离子电池负极材料,在锂离子电极负极材料有良好的应用前景,确保后期3D打印出性能良好的微电池棒状电极.选取钛酸锂作为棒状电极的负极材料,与溶剂、增稠剂、分散剂和保湿剂等按一定比例制备打印墨水,随后通过以挤压为基础的3D打印技术打印电极,并在氮气保护下高温烧结获得的棒状电极。本文主要探究了钛酸锂掺杂石墨、钛酸锂质量分数以及烧结温度对棒状电极的性能影响,其次通过打印墨水的流变特性模拟分析来探究墨水黏度对挤压过程中流动速度的影响.结果表明:掺杂10%石墨的钛酸锂棒状电极相比未掺杂石墨的电极,其充放电容量提高了18%,表现出较好的循环性能;当钛酸锂质量分数为59%,打印墨水黏度为26.53 Pa·s,所制备棒状电极的电阻率为221 kΩ·cm,打印墨水具有良好的打印及导电性能;当烧结温度为950℃,棒状电极电阻率较小,为205 kΩ·cm,与基板有良好的附着力,膜层表面平整、致密且有许多孔洞,有助于电解液的渗透.对打印墨水的黏度进行模拟分析可知,随黏度的增减而使墨水流动速度变化明显.     

Quantitative and time-resolved detection of lithium plating on graphite anodes in lithium ion batteries

The ability of fast and safe charging is critical for the further success of lithium ion batteries in automotive applications. In state-of-the-art lithium ion batteries, the charging rate is limited by the onset of lithium plating on the graphite anode. Despite its high importance, so far no analytical technique has been available for directly measuring lithium plating during battery charge. Herein, we introduce operando electron paramagnetic resonance (EPR) spectroscopy as the first technique capable of time-resolved and quantitative detection of lithium metal plating in lithium ion batteries. In an exemplary study, the C-rate dependence of lithium metal plating during low-temperature charging at ?20?°C is investigated. It is possible to quantify the amount of ‘dead lithium’ and observe the chemical reintercalation of plated lithium metal. In this way, it is possible to deconvolute the coulombic inefficiency of the lithium plating/stripping process and quantify the contributions of both dead lithium and active lithium loss due to solid electrolyte interphase (SEI) formation. The time-resolved and quantitative information accessible with operando EPR spectroscopy will be very useful for the optimization of fast charging procedures, testing of electrolyte additives, and model validation.     

Electrochemical performance of modified synthetic graphite for lithium ion batteries

The carbon-coated composite has been manufactured and investigated as the negative electrode for Li-ion batteries. The carbon-coated composite powders are prepared by a simple mixing of two types of synthetic graphite particles (SFG6 and SFG44) with polyvinylchloride powders and heating to a temperature between 800 and 1100°C under an argon gas flow.As a result of the carbon-coating treatment, the flake particles of the original graphites changed into a bulky shape of carbon-coated composite with a largely increased particle size due to aggregation through the treatment. It is shown that carbon-coated composite electrodes for the two types of graphite have much lower irreversible loss than the original graphites and coulombic efficiency of 91% in the first cycle in a PC-based electrolyte. The carbon coating treatment improves the cycling performance. Despite their coarse morphology due to aggregation, carbon-coated composite electrodes show the enhanced high rate capabilities.