Additives-containing functional electrolytes for suppressing electrolyte decomposition in lithium-ion batteries

Several olefinic compounds such as vinyl acetate, divinyl adipate and allyl methyl carbonate were studied as additives for propylene carbonate (PC)-based electrolytes in lithium-ion battery, which kind of electrolytes always exfoliate graphitic carbon and decompose drastically to liberate organic gas. Three kinds of graphitic carbons commonly used in lithium-ion batteries, namely, natural graphite, MCMB 6-28 and MCF were chosen to test the decomposition-suppressing ability of additives. The effects of the type of graphitic anodes and the structure of additives on the electrolyte decomposition have been investigated in the terms solid electrolyte interface (SEI) formation, which was characterized by cyclic voltammetry (CV), ac impedance, SEM, XPS analyses, and auger electron spectroscopy (AES). The electrochemical performance of the additives-containing electrolytes in combination with LiCoO₂ cathode and graphitic carbon anode was also tested in coin cells.     

A review study on titanium niobium oxide-based composite anodes for Li-ion batteries: Synthesis,structure, and performance

The growing demands for Li-ion batteries (LIBs) in the electrification revolution, require the development of advanced electrode materials. Recently, intercalating titanium niobium oxide (TNO) anode materials with the general formula of TiNb_xO_2+2.5x have received lots of attention as an alternative to graphite and Li₄Ti₅O₁₂ commercial anodes. The desirability of this family of compounds stems from their high theoretical capacities (377–402 mAh/g), high safety, high working voltage, excellent cycling stability, and significant pseudocapacitive behavior. However, the rate performance of TNO-based anodes is poor owing to their low electronic and ionic conductivities. TNO-based composites generally are prepared with two aims of enhancing the conductivity of TNO and achieving a synergic effect between the TNO and the other component of the composite. Compositing with carbon matrices, such as graphene and carbon nanotubes (CNTs) are the most studied strategy for improving the conductivity of TNO and optimizing its high-rate performance. Also, for obtaining anode materials with high capacity and high long-term stability, the composites of TNO with transition metal dichalcogenides (TMDs) materials were proposed in previous literature. In this work, a comprehensive review of the TNO-based composites as the anodes for LIBs is presented which summarizes in detail the main recent literature from their synthesis procedure, optimum synthesis parameters, and the obtained morphology/structure to their electrochemical performance as the LIBs anode. Finally, the research gaps and the future perspective are proposed.     

Cyclability study of silicon–carbon composite anodes for lithium-ion batteries using electrochemical impedance spectroscopy

The effects of carbonization process and carbon nanofiber/nanotube additives on the cycling stability of silicon–carbon composite anodes were investigated by monitoring the impedance evolution during charge/discharge cycles with electrochemical impedance spectroscopy (EIS). Three types of Si–C anodes were investigated: the first type consisted of Si nanoparticles incorporated into a network of carbon nanofibers (CNFs) and multi-walled carbon nanotubes (MWNTs), with annealed polymer binder. The second type of Si–C anodes was prepared by further heat treatment of the first Si–C anodes to carbonize the polymer binder. The third Si–C anode was as same as the second one except no CNFs and MWNTs being added. Impedance analysis revealed that the carbonization process stabilized the Si–C anode structure and decreased the charge transfer resistance, thus improving the cycling stability. On the other hand, although the MWNTs/CNFs additives could enhance the electronic conductivity of the Si–C anodes, the induced inhomogeneous structure decreased the integrity of the electrode, resulting in a poor long term cycling stability.     

The effect of electrolytic oxidation on the electrochemical properties of multi-walled carbon nanotubes

Multi-walled carbon nanotubes (MWNTs) were electrochemically oxidized by a constant-potential electrolysis method and then investigated in detail using scanning electron microscope, transmission electron microscope, FT-IR, electrical impedance spectroscopy, and cyclic voltammetry. The FT-IR spectra showed that the amount of hydroxyl generated on the surface of MWNTs increased with increasing the electrochemical oxidation time of MWNTs. The CV results, being conducted in nitrobenzene solution, showed that the nitrobenzene reduction current increased with the increase in oxidation time of the MWNTs within the first 60 min of electrolysis. An electrical equivalent circuit model for electrical impedance spectroscopy was further established to analyze the surface capacitance and resistance of the MWNTs, and the model results showed that the capacitance of the oxidized MWNTs increased greatly while the charge transfer resistance decreased, suggesting electrochemical oxidized MWNTs modified pyrolytic carbon electrode being an effective electrochemical sensor for nitrobenzene determination.     

CNT@TiO2 nanohybrids for high-performance anode of lithium-ion batteries

This work describes a potential anode material for lithium-ion batteries (LIBs), namely, anatase TiO₂ nanoparticle-decorated carbon nanotubes (CNTs@TiO₂). The electrochemical properties of CNTs@TiO₂ were thoroughly investigated using various electrochemical techniques, including cyclic voltammetry, electrochemical impedance spectroscopy, galvanostatic cycling, and rate experiments. It was revealed that compared with pure TiO₂ nanoparticles and CNTs alone, the CNT@TiO₂ nanohybrids offered superior rate capability and achieved better cycling performance when used as anodes of LIBs. The CNT@TiO₂ nanohybrids exhibited a cycling stability with high reversible capacity of about 190 mAh g^-1 after 120 cycles at a current density of 100 mA g^-1 and an excellent rate capability (up to 100 mAh g^-1 at a current density of 1,000 mA g^-1).     

Improving the performance of silicon anode in lithium-ion batteries by Cu2O coating layer

The influence of a 200 nm Cu₂O coating layer on the electrochemical performance of an 800 nm Si thin-film anode was investigated by cyclic voltammetry, electrochemical impedance spectroscopy, and galvanostatic charge/discharge measurements. The electrochemical performance of the Si thin-film anode was improved by the coating layer. The coated Si anode exhibited higher values of conductivity in comparison with the pristine Si anode. Scanning electron microscopy images of the anodes after cycling test showed that the coated Si anode after cycling test had less cracks than the pristine Si anode. The galvanostatic charge/discharge measurements reveal that the cyclability and rate capability of the coated Si thin-film anode were better than the pristine Si thin-film anode.     

Performance of anaerobic fluidized bed microbial fuel cell with different porous anodes

Anode materials were used to construct microbial fuel cells(MFCs), and the characteristics of the anodes were important for successful applied performance of the MFCs. Via the cyclic voltammetry(CV) method, the experiments showed that 5 wt% multiwalled carbon nanotubes(MWNTs) were optimal for the PANI/MWNT film anodes prepared using 24 polymerization cycles. The maximum output voltage of the PANI/MWNT film anodes reached 967.7 mV with a power density of 286.63 mW·m~(-2). Stable output voltages of 860 mV, 850 mV, and870 mV were achieved when the anaerobic fluidized bed microbial fuel cell(AFBMFC) anodes consisted of carbon cloth with carbon black on one side, copper foam and carbon brushes, respectively. Pretreatment of the anodes before starting the AFBMFC by immersion in a stirred bacterial fluid significantly shortened the AFBMFC startup time. After the AFBMFC was continuously run, the anode surfaces generated active microbial catalytic material.     

木质素衍生炭在碱金属离子电池负极中的研究进展

碱金属离子在商品化石墨负极材料的嵌入/脱出过程中会发生较大的体积膨胀,导致容量衰减快、倍率性能差等问题。木质素衍生炭材料具有原料丰富、经济、制备工艺简单及结构可控等优点,作为碱金属离子电池负极表现出较高的容量、较好的倍率性能和循环稳定性。木质素衍生炭材料在过去十多年中取得了一些研究进展。基于此,简要介绍了碱金属离子电池碳材料负极的储能机理及特点,系统综述了木质素衍生炭材料在碱金属离子电池负极材料中的最新研究进展,重点总结了其合成策略、结构特征、储存机理以及其电化学性能等,指出了层间距调控、碳层排序和表面功能化与电化学性能之间的构效关系。此外,拓展概述了木质素衍生炭材料的发展前景和面临的挑战,为木质素衍生炭材料的下一步研究和开发提供参考。     

木质素衍生炭在碱金属离子电池负极中的研究进展

碱金属离子在商品化石墨负极材料的嵌入/脱出过程中会发生较大的体积膨胀,导致容量衰减快、倍率性能差等问题。木质素衍生炭材料具有原料丰富、经济、制备工艺简单及结构可控等优点,作为碱金属离子电池负极表现出较高的容量、较好的倍率性能和循环稳定性。木质素衍生炭材料在过去十多年中取得了一些研究进展。基于此,简要介绍了碱金属离子电池碳材料负极的储能机理及特点,系统综述了木质素衍生炭材料在碱金属离子电池负极材料中的最新研究进展,重点总结了其合成策略、结构特征、储存机理以及其电化学性能等,指出了层间距调控、碳层排序和表面功能化与电化学性能之间的构效关系。此外,拓展概述了木质素衍生炭材料的发展前景和面临的挑战,为木质素衍生炭材料的下一步研究和开发提供参考。     

MCMB/水性粘结剂体系锂离子电池负极制备工艺研究

在锂离子电池炭负极的制备中，粘结剂和导电炭黑用量、不同的碾压及封装条件都将影响电池的电化学性能。通过循环伏安及恒电流充放电测量技术，研究了中间相炭微球（MCMB）／水性粘结剂负极制备中上述因素的影响，发现水性粘结剂含量为2wt％（羰甲基纤维素钠：丁苯橡胶=1：1，质量比）、导电炭黑含量为3wt％、负极碾压压力为25MPa、封装压力50MPa时，MCMB作为负极材料时表现出了较好的充放电性能，可逆放电容量达到了320．3mAh／g。且水性粘结剂工艺性能良好，可以考虑代替成本高且对环境有污染的有机粘结荆。     

Electrochemical performance of La<Subscript>0.75</Subscript>Sr<Subscript>0.25</Subscript>Cr<Subscript>0.9</Subscript>M<Subscript>0.1</Subscript>O<Subscript>3</Subscript> perovskites as SOFC anodes in CO/CO<Subscript>2</Subscript> mixtures

The performance of La_0.75Sr_0.25Cr_0.9M_0.1O₃ (M = Mn, Fe, Co, and Ni) perovskitic materials as anodes was studied for a CO-fueled solid oxide fuel cell. The electrocatalytic performance and the tolerance to carbon deposition were investigated, while electrochemical characterization was carried out via AC impedance spectroscopy and cyclic voltammetry. The La_0.75Sr_0.25Cr_0.9Fe_0.1O₃ perovskite showed the best anode performance at temperatures above 900 °C; while at temperatures below 900 °C, the best performance was achieved with the La_0.75Sr_0.25Cr_0.9Co_0.1O₃ material. AC impedance spectroscopy was used for a semi-quantitative analysis of the LSC-M_0.1 anodes performance in view of total cell and charge transfer resistance. All anode materials exhibit high electronic conductivity and presumably do not substantially contribute to the overall cell resistance and concomitant ohmic losses.     

中间相炭微球在锂离子电池负极材料的应用进展

中间相炭微球(MCMB)具有良好锂离子扩散性、导电性和机械稳定性等优势,是目前应用广泛、综合性能优异的锂离子电池负极材料,但较低理论比容量是制约其发展的关键因素。为了获得性能优良的MCMB基锂离子电池负极材料,改性修饰和复合材料已然成为目前研发重点。笔者论述了碳结构、表界面和复合材料等微观结构设计对MCMB负极材料电化学性能的影响。从碳堆积结构类型、有序性、层间距以及球体粒径大小等方面,论述了碳结构微观设计对MCMB电化学性能的影响。发现具有乱层结构的MCMB在充放电过程中内部产生应力较小,且碳结构较稳定,具有优异循环稳定性;内部具有大量微孔或碳层间距较大的MCMB,在充放电过程中可提高锂离子在电极中的迁移速率,并提供更多的储锂空间,一般具有优良的充放电比容量和倍率性能;小粒径MCMB具有较短的锂离子迁移路径和随之增加的比表面积,通常具有较好倍率性能,伴随着可逆比容量和充放电效率的衰减。从表界面碳层改性、包覆和掺杂改性等方面,论述了表界面改性对MCMB电化学性能的影响。表面碳层修饰可增加MCMB与电解液的相容性及其比表面积,提高了与电解液的接触面积及贮锂容量,改善了锂离子电池负极材料的电化学性能;另外,MCMB表面包覆一层无定型碳,可避免其表面与电解液直接接触,减少电化学副反应的产生,提升其可逆比容量。从碳活性物质复合材料、非碳活性物质复合材料等方面,论述了复合材料微观结构设计对MCMB电化学性能的影响。碳活性物质可降低MCMB内部碳层结构的有序性,减少锂离子嵌入过程中的内部应力,提升MCMB循环稳定性。非碳活性物质诱导MCMB生成更加有序的碳层结构,提高MCMB的比表面积,从而改善MCMB表面与电解液分子的接触能力及其嵌锂性能,有利于提升MCMB负极材料可逆比容量、循环性能和倍率性能。MCMB具有高碳层间距和多缺陷位点等结构特征,有利于钠离子自由脱嵌,应用于钠离子电池时具有良好的可逆比容量、循环稳定性和倍率性能。MCMB的不规则定向层状结构经活化等处理具有较高比表面积,可应用于超级电容器电极材料。最后提出在高性能锂离子电池电极材料快速发展的需求下,从微观结构角度设计MCMB纳米复合材料将是MCMB负极材料的研究重点。     

以竹叶为碳源制备Li4Ti5O12/C复合材料

以钛酸四丁酯、醋酸锂、柠檬酸和竹炭为原料,采用两步煅烧和溶胶-凝胶法制备锂离子电池Li4Ti5O12/C负极材料。采用XRD、SEM表征材料的微观结构和形貌。采用恒流充放电、交流阻抗和循环伏安法研究材料的电化学性能。结果显示,Li4Ti5O12/C具有良好的结晶度,颗粒表面光滑,分散均匀,粒径为200~300 nm。10 C倍率下,Li4Ti5O12/C的首次放电比容量为180.4 mA•h/g,循环300圈后为167.5 mA•h/g,容量保持率为92.8%,远高于Li4Ti5O12的46.9%。在20 C大倍率下,Li4Ti5O12/C和Li4Ti5O12的容量保持率分别为68.9%和41.3%     

Si/VGCF复合材料的储锂性能

以纳米硅颗粒为原料,采用液相法制备了硅纳米粒子与气相生长碳纤维(VGCF)复合的材料(Si/VGCF)。考察了Si/VGCF制备工艺和VGCF的最佳含量,分别采用SEM和TEM表征了Si/VGCF材料形貌和晶体结构,测试和计算了材料电导、BET比表面积和孔尺寸数据。采用循环伏安、恒流充放电和交流阻抗等测试了Si/VGCF复合电极的电化学性能,并与其他碳材料进行了对比分析。结果表明,Si与VGCF形成了多级框架结构,丰富了离子和电子传输网络;同时发达的孔结构也缓解了Si粒子在嵌/脱锂过程中的体积效应,使电极活性材料的利用率和电化学稳定性显著提高。当m(Si)∶m(VGCF)为1:0.5时,Si/VGCF复合电极在500 mA/g的电流密度下,充放电循环100次后,可逆容量高达1470 mA·h/g。     

化学氧化改性微生物燃料电池阳极

浓HNO₃和酸性K₂Cr₂O₇都具有一定的氧化性,分别利用浓HNO₃和酸性K₂Cr₂O₇对阳极碳布进行氧化改性处理。通过红外光谱测试显示,碳布表面附着了羟基(-OH)和羧基(-COOH)。通过扫描电镜观察,碳布经过氧化改性后表面明显变粗糙。同时,循环伏安曲线(CV)和交流阻抗曲线(EIS)测试表明,经过改性后的碳布具有良好的电化学特性。分别以经过浓HNO₃和酸性K₂Cr₂O₇改性处理后的碳布作为微生物燃料电池(MFC)的阳极,获得的最大功率密度分别为291.11 mW·m^-2和438.08 mW·m^-2,比未经过改性处理的碳布阳极的功率密度分别提升了21%和82%。     

Electrochemical behavior of carbon-coated SnS2 for use as the anode in lithium-ion batteries

Carbon-coated SnS₂ nanoparticles were prepared by a simple solvothermal route at low temperature. A carbon coating with a thickness of about 5 nm was deposited on nano-sized SnS₂ particles to serve as the anode in lithium-ion batteries. Both the nanostructure and the morphology of the SnS₂ powders were characterized by X-ray diffraction (XRD), Raman spectroscopy, and transmission electron microscopy (TEM). The coated samples were used as active anode materials for lithium-ion batteries, and their electrochemical properties were examined by constant current charge-discharge cycling, cyclic voltammetry and electrochemical impedance spectroscopy. The reversible capacity of the carbon-coated SnS₂ after 50 cycles was 668 mAh/g, which was much higher than that of the uncoated SnS₂ (293 mAh/g). The carbon-coated SnS₂ also had a better rate capability than the uncoated SnS₂ in the range of 0.008-1 C. The capacity retention of the carbon-coated SnS₂ was improved due to its good conductivity and the effective buffer matrix that alleviated volume expansion during the charge-discharge process.     

中间相炭微球制备及应用概述

中间相炭微球（MCMB）是一种新型的炭材料,拥有杰出的化学稳定性、热稳定性、优良的导电导热性能,已引起人们的广泛关注。本文概述了MCMB的结构与形成机理、各种制备方法。以及在高密度各向同性炭材料、锂离子电池负极材料的应用研究及其最新研究进展;并展望了MCMB的应用和研究前景。     

Evaluation of the electrochemical activity of a Ti-RuO2-TiO2 permanent anode

Most of the hydrometallurgical processes use sulphuric acid solutions. The main anodic reaction is oxygen evolution by decomposition of water. Traditional anode materials have been lead alloys that have high overpotential towards oxygen evolution. Oxide type anodes are more active but they are also more expensive. In this work, the activities of binary RuO₂-TiO₂ anodes were measured using different electrochemical techniques. The activity measurements were based on the measurement of the redox reaction between Ru(III) and Ru(IV) in cyclic voltammetry and on the oxygen evolution reaction in potentiostatic tests and galvanostatic electrochemical impedance spectroscopy. Factors related to intrinsic electrocatalytic properties and electrochemically active surface area could be separated. Above 30 mol% no significant increase in activity towards oxygen evolution is gained by increasing the concentration of active oxide. With low amount of active oxide most of the active sites are inside the pores and cracks. This will cause anode failure by bubble formation inside the anode.     

Electrochemical lithiation and de-lithiation of MWNT-Sn/SnNi nanocomposites

Nanocrystalline multi-walled carbon nanotube (MWNT)-Sn and MWNT-SnNi composite anode materials were prepared by chemical reduction of SnCl₂ and NiCl₂ precursors in the presence of MWNTs. SEM and TEM observations showed that the Sn and SnNi particles are homogeneously dispersed on the MWNT surface and in the MWNT matrix. The electrochemical performance of MWNT-Sn and MWNT-SnNi nanocomposites has been investigated by charge/discharge tests, cyclic voltammetric experiments and the ac impedance technique. The MWNT-Sn and MWNT-SnNi anodes have demonstrated a high first discharge capacity (570 and 512 mA h/g for MWNT-Sn and MWNT-SnNi anodes, respectively), high charge/discharge efficiency in the first cycle (77.5% and 84.1% for MWNT-Sn and MWNT-SnNi anodes, respectively), and good cyclability (0.99 loss%/cycle for MWNT/SnNi anode). A reaction model has been proposed to explain the reaction mechanisms of lithium insertion and extraction in the MWNT-Sn and MWNT-SnNi electrodes.     

A review study on the recent advances in developing the heteroatom-doped graphene and porous graphene as superior anode materials for Li-ion batteries

Graphene materials, with their distinctively fascinating physicochemical properties, have been receiving great attention as favorable anode materials for use in Li-ion batteries (LIBs). However, the high affinity of graphene nanosheets to restack and agglomerate during electrode assembly reduces the deliverable specific capacity due to the limited available surface area and active sites for Li-ion storage. Furthermore, the high aspect ratio of graphene nanosheets could result in long transport pathways for Li-ions and consequently limiting the rate performance. These drawbacks can be significantly improved via the functionalization of graphene by various heteroatoms and also the formation of porous graphene, adding unique beneficial properties to the inherent characteristics of graphene. Here, a comprehensive review of porous and/or heteroatom doped graphene anode materials for LIBs is presented, which summarizes in detail the main recent literature from their procedure, optimum synthesis parameters, relevant mechanisms, and the obtained morphology/structure to their electrochemical performance as the LIBs anode. Finally, the research gaps are proposed. This review will promote the basic understanding and further development of porous and/or doped graphene materials as anodes for LIBs.