Promotive effect of multi-walled carbon nanotubes on Co3O4 nanosheets and their application in lithium-ion battery

Co3O4/MWCNTs composites have been synthesized by a simple hydrothermal method using a surfactant(CTAB) and a precipitation agent(urea). The samples were characterized by XRD, SEM and BET methods. The electrochemical properties of the samples as anode materials for lithium batteries were studied by EIS and Galvanostatic measurements. The Co3O4/MWCNTs composites displayed higher capacity and better cycle performance in comparison with the Co3O4 nanosheets. The remarkable improvement of electrochemical performance within the hybrid composites is probably related to the addition of MWCNTs that possesses improved properties such as excellent electric conductivity and large surface area, which helps to alleviate the effect of volume change, shorten the distance of lithium ion diffusion, facilitate the transmission of electron and keep the structure stable.     

Three-dimensionally macroporous graphene-supported Fe3O4 composite as anode material for Li-ion batteries with long cycling life and ultrahigh rate capability

Fe3O4 is an attractive conversion reaction- based anode material with high theoretical capacity （928 mA h g^-1）. However, the poor cycling and rate per- formance hinder its applications in Li-ion batteries. In this work, we report an effective strategy to synthesize three- dimensionally macroporous graphene-supported Fe3O4 hybrid composite. Benefiting from advantage of the special structure, the hybrid composite exhibits excellent Li^＋ stor- age performance, delivering a high reversible capacity of 980 mA h g^-1at the current density of 4 A g^-1 even after 470 cycles and ultrahigh rate capability （293 mA h g^- 1 even at current density of 20 A g^-1）.     

Development and application of phase diagrams for Li-ion batteries using CALPHAD approach

Phase diagrams provide fundamental knowledge about design map of new electrode materials for Li-ion batteries. The CALPHAD (CALculation of PHAse Diagrams) approach is widely applied to the development of phase diagrams and property diagrams in a thermodynamic language. Within the CALPHAD framework, the theoretical modeling can be performed to predict phase equilibria, thermodynamics, electrochemical and physical properties of electrodes. This review provides the successful application of high quality calculated phase diagrams and thermodynamic property diagrams in CALPHAD investigation to both cathodes and anodes of Li-ion batteries, including Li–Co–O, Li–Ni–O, Li–Co–Ni–O, Li–Mn–O, Li–Cu–O, Li–Si, Li–Sb and Li–Sn systems with. The intensive CALPHAD-type research may also predict electrochemical properties, cell performance of the Li-ion batteries to achieve more efficient development of electrode materials.     

Nanostructured TiO2（B）:the effect of size and shape on anode properties for Li-ion batteries

Reducing the dimensions of electrode materials from the micron to the nanoscale can have a profound influence on their properties and hence on the performance of electrochemical devices,e.g.Li-ion batteries,that employ such electrodes.TiO2(B) has received growing interest as a possible anode for Li-ion batteries in recent years.It offers the possibility of higher energy storage compared with the commercialized Li4Ti5O12.Bulk,nanowire,nanotube,and nanoparticle morphologies have been prepared and studied.However,to date these materials have not be compared in one article.In the current review we first summarize the different synthesis methods for the preparation of nanostructured TiO2(B);then present the effects of size and shape on the electrochemical properties.Finally TiO2(B) with nanometer dimensions exhibit a higher capacity to store Li,regardless of rate,due to structural distortions inherent at the nanoscale.     

Sn/C复合材料的制备及作为锂离子电池负极材料的性能

采用SnCl2.2H2O乙醇溶液浸渍竹炭和NaBH4还原方法制备出一种锂二次电池负极用Sn/C复合材料。考察了复合材料中Sn含量对产物收率、微观结构及电化学性能的影响。结果表明,Sn2+大部分进入到竹炭的孔道中,并被还原为单质Sn;当单质Sn与复合材料质量比为42.5∶100时,复合电极材料具有555.1mAh/g的可逆容量,循环20次后容量保持在423.8 mAh/g,显示出较好的实用性能。     

Composite cathode and anode films for rechargeable lithium batteries

Recently the rechargeable Li and Li-ion polymer batteries have improved due to development of Li-ion conductive gel electrolytes and of high energe granting intercalation compounds. In our laboratory the composite cathodic film, the composite carbon anode film and PVC-based electralyte film were successfully prepared by casting procedures. Cycling experiments of the cells with Li or composite carbon anode in contact with PVC-based electrolyte and composite cathode were performed. Relatively good performance of the cell with Li anode, the composite cathode and LiPF₆-EC-DEC electrolyte was achieved in that over 50 cycles were possible with minimal capacity loss upon cycling. The same cell with PVC-based electrolyte was cycled over 20 cycles. Replacing Li anode by composite carbon anode, the cell behaved like the latter. It is found that appropriate amount of carbon content is helpful to improving specific capacity.     

电动汽车动力电池技术研究进展

 从锂离子电池材料技术、单体电池、电池系统等几个方面对锂离子动力电池的发展进行了评述。锰酸锂一般应用于轻型电动车辆,也可与三元材料混合提升新能源车辆用电池的安全性和倍率性能;磷酸铁锂适用于中等比能量要求的动力电池;三元材料通过材料、隔膜涂层和电池技术的改进提升安全性后适用于高比能量型电池;石墨负极目前仍然是广泛应用的负极材料,在碳负极材料中添加硅等高容量材料的努力仍在进行中,液体电解液在向高电压和宽工作温区方向发展;小圆柱电池、方形金属壳电池和软包电池各有特点,适应了多元化的电动汽车应用需求,国产制造设备技术水平持续提升,电池系统技术方面需要整车和电池方面合作努力以提升安全性和可靠性。锂离子动力电池是目前最具实用价值的动力电池,预期其比能量在不久的将来可提升至300 (W·h)/kg,满足新能源汽车产业未来10年的发展需求。     

Facile ball-milled synthesis of SnS2-carbon nanocomposites with superior lithium storage

A facile high-energy ball-milling method was developed to synthesize SnS_2-carbon(SnS_2/C-x(x = 40, 50, 60 wt%)) nanocomposites. The results showed that as anode materials for lithium-ion batteries(LIBs), the SnS_2-C nanocomposites exhibited high discharge capacity and excellent cycling stability. For the optimized SnS_2/C-50 wt% nanocomposite, a discharge capacity as high as 700 mA h g~(-1) and the initial coulombic efficiency of 80.8% were achieved at a current density of 100 mA g~(-1). The unique structure with SnS_2 nanoparticles(NPs)embedded into carbon network provided abundant Li-ion storage sites, high electronic conductivity and fast ion diffusion. The ball-milled synthesis is applicable for large-scale preparation of new sulfide-based anode materials with good performance for LIBs.     

Facile hydrothermal and sol-gel synthesis of novel Sn-Co/C composite as superior anodes for Li-ion batteries

As an anode material in lithium ion battery, the Sn-Co/C composite electrode materials have been successfully synthesized by hydrothermal and solgel methods, respectively. The resultant composites were mainly composed of Snbased oxides, nanometer Sn-Co alloy and carbon. Carbon and Co, acting as buffer materials, can accommodate to the large volume change of active Sn during the discharge-charge process, thus improving the cycling stability. Although charge/discharge curves revealed the excellent cycle performance for samples synthesized by both methods, composites obtained by the sol-gel showed a better dispersion effect of nanoparticles on the carbon matrix and possessed much more improved stable capacity with 624.9 mAh g-1 over 100 cycles and that by hydrothermal method only exhibited ～299.3 mAh g-1. Therefore, the Sn-Co/C composites obtained by solgel synthesis method could be a perfect candidate for anode material of Liion storage battery.     

Safety characteristics of Li-ion batteries evaluated by in situ measurement techniques

Li-ion batteries hold an important place in the field of high power batteries because of their high open circuit voltage and associated high energy density. However, the safety is less satisfactory; therefore, the study of the factors that affect the safety of Li-ion batteries has much meaning to the safety design. In this paper, a set of apparatus was developed for in situ measurements, and several commercial materials including electrolyte, separator and electrode materials for Li-ion batteries were investigated by the in situ method. The results showed： 1） The electrolyte vapor pressure is influenced significantly by the component with low boiling point and increases rapidly with the increasing of temperature; 2） the shutdown of separator occurs at around 135℃ and the impedance increases approximately by two orders of magnitude; 3） carbon anode materials affect the most the volume changes of the cell, and the change for a graphite anode is much greater than that of a glassy carbon anode.     

新型蜂窝结构Si/Co3O4复合材料的研究

本文通过超声分散、水热生长和煅烧方法制备了新型蜂窝结构Si/Co3O4复合负极材料,在此基础上研究其复合结构与电化学性能的关系。采用X射线衍（XRD）、扫描电子显微镜（SEM）和透射电子显微镜（TEM）对复合材料的物相、微观形貌进行表征,并采用电化学手段对其性能进行测试。结果表明:硅纳米颗粒主要分布于Co3O4蜂窝孔洞结构的内层;相比于纯Si负极材料,蜂窝结构Si/Co3O4复合材料具有更好的结构稳定性、倍率性能和循环性能,首次放电比容量为1475 mAh g-1,第二次维持在851 mAh g-1,经过75 次循环后放电比容量仍有 802 mAh g-1,较第二次比容量损失率仅为0.17%/周,这主要是归因于硅纳米颗粒和Co3O4之间存的空隙为Si负极嵌锂过程中的体积膨胀提供了空间,有效缓冲Si负极的体积变化。     

纳米LiMn2O4的溶胶-凝胶合成及表征

LiMn2O4是一种优良的锂离子电池正极材料。本文利用溶胶一凝胶法制备了LiMn2O4纳米粉体，使用XRD、TEM和IR进行表征。结果表明纳米样品的平均粒度为32nm。     

用均相沉淀法制备NiO-石墨复合材料

为提高石墨作为负极材料的性能,首先以球形石墨为原料,KMnO4为氧化剂,浓H2SO4为插层剂制备氧化石墨;再分别以球形石墨、氧化石墨为原料,尿素为沉淀剂,采用均相沉淀法制备NiO/石墨复合材料。应用X射线衍射仪、扫描电子显微镜表征材料结构及形貌。结果表明,氧化后石墨的主特征峰发生了向左的大角度偏移,层面呈现片层结构。以球形石墨为原料制备的复合材料中NiO均匀性较差,团聚明显,特征峰半峰幅宽较小,晶粒较大;以氧化石墨为原料制备的复合材料中NiO均匀分布,无团聚,特征峰半峰宽较宽,晶粒较小。采用均相沉淀法对石墨进行NiO修饰有效提高了其容量及循环稳定性能。     

具有分级结构的Co_3O_4绣球花状微米球的构筑及其锂离子电池负极性能研究

采用溶剂热法合成了绣球花状Co_3O_4纳米材料,并利用扫描电子显微镜和X射线衍射仪进行了微观形貌和结构的表征,结果显示样品的形貌为4~6μm绣球花状分级结构微米球,结晶良好,无杂相生成。该绣球花状Co_3O_4纳米材料用做锂离子电池负极材料时表现出很高的可逆比容量和良好的循环性能。在300 m A/g电流密度下,首次放电比容量达1 508 m A·h/g,经过20次循环可逆比容量为1 300 m A·h/g。其良好的电化学性能归功于绣球花状Co_3O_4材料的独特形貌,其多级结构能够缩短锂离子的传输路径,并且拥有足够大的孔隙,来适应和缓解电极材料在循环过程的体积效应。     

球形多孔氧化钴/碳复合材料的制备及电容性能研究

采用水热合成和煅烧制备氧化钴/碳(Co3O4/C)复合材料,通过SEM、XRD、N2吸附实验等对该材料进行表征.制备的Co3O4/C复合材料为5μm大小,孔径约为30nm的多孔球形结构.在6mol/L的氢氧化钾溶液中进行电化学测试.结果表明,Co3O4/C复合材料具有良好的电容性能.在电流密度为1A/g时,比电容为143F/g.此外,Co3O4/C复合材料还表现出良好的循环稳定性,在1A/g的电流密度下,充放电循环1000次后,比电容保持率为77.8%.     

喷雾干燥法制备LiMn 1.5Ni 0.5O4及其电化学性能

采用喷雾干燥方法合成了高电压锂离子电池正极材料LiMn 1.5Ni 0.5O4,并研究了其电化学性能.研究发现,室温条件下,在3.20～4.95 V的充放电电压范围,LiMn 1.5Ni 0.5O4的首次可逆容量为132 mAh/g, 并显示出良好的循环性能,在3.20～4.50 V 和4.50～4.95 V两个电压区间内,首次可逆容量分别为25和100 mAh/g.而在高温下,该电极材料的电化学性能发生了明显的改变.     

以竹纤维为模板制备微米管状Li4Ti5O12负极材料

以竹纤维为模板,Ti(OC4H9)4和Li(Ac).2H2O为原料,用模板法制备锂离子电池微米管状Li4Ti5O12负极材料。采用XRD,SEM,BET,充放电实验和交流阻抗等对合成材料的结构、形貌和电化学性能进行表征。研究结果表明:制备的微米管状Li4Ti5O12负极材料由尖晶石型纳米Li4Ti5O12颗粒构成,具有较大的比表面积,该材料具有良好的电化学性能,在0.5~3.0 V,0.1C倍率下的首次放电比容量为178 mA.h/g,充放电循环100次后放电比容量仍保留162 mA.h/g,且倍率性能优异。     

NiO超细粉末的均匀沉淀法制备与表征

以 Ni(NO₃)₂·6H₂O为主要原料,以尿素为沉淀剂,采用均匀沉淀法制备超细氧化镍,并通过热重-差重（TG/DTA）、X-射线衍射(XRD)、扫描电子显微镜（SEM）等分析手段对其进行了表征.采用此方法可以得到粒径在1~2 μm之间的超细氧化镍粉末.NiO的首次放电容量达到670.5 mAh/g,80次循环后每次循环的容量损失仅为0.031%,表明本法制备的NiO是一种优秀的锂离子电池负极材料.     

SnO2基锂离子电池负极材料研究进展

 作为一种N型半导体,二氧化锡基负极材料由于其拥有较高的理论比容量（782 mA·h·g^-1）、高能量密度等优势受到了广泛关注。然而,由于二氧化锡负极材料在充放电过程中的体积效应和本身导电性较差等导致的其循环性能和倍率性能较差,从而制约了其作为锂离子电池负极材料的应用。本文从二氧化锡的纳米化及复合化（包括其与金属氧化物、无定型碳、碳纳米管和石墨烯等复合）2 方面综述了二氧化锡基锂离子电池负极材料的研究进展,同时对SnO₂基锂离子电池负极材料的发展方向进行了展望。     

Practical development and challenges of garnet-structured Li7La3Zr2O12 electrolytes for all-solid-state lithium-ion batteries: A review

All-solid-state Li-ion batteries (ASSLIBs) have been widely studied to achieve Li-ion batteries (LIBs) with high safety and energy density. Recent reviews and experimental papers have focused on methods that improve the ionic conductivity, stabilize the electrochemical performance, and enhance the electrolyte/electrode interfacial compatibility of several solid-state electrolytes (SSEs), including oxides, sulf-ides, composite and gel electrolytes, and so on. Garnet-structured Li7La3Zr2O12 (LLZO) is highly regarded an SSE with excellent application potential. However, this type of electrolyte also possesses a number of disadvantages, such as low ionic conductivity, unstable cubic phase, and poor interfacial compatibility with anodes/cathodes. The benefits of LLZO have urged many researchers to explore effective solutions to over-come its inherent limitations. Herein, we review recent developments on garnet-structured LLZO and provide comprehensive insights to guide the development of garnet-structured LLZO-type electrolytes. We not only systematically and comprehensively discuss the preparation, ele-ment doping, structure, stability, and interfacial improvement of LLZOs but also provide future perspectives for these materials. This review expands the current understanding on advanced solid garnet electrolytes and provides meaningful guidance for the commercialization of ASSLIBs.