Coupling effect of the conductivities of Li ions and electrons by introducing LLTO@C fibers in the LiNi_(0.8)Co_(0.15)Al_(0.05)O_2 cathode

To probe the coupling effect of the electron and Li ion conductivities in Ni-rich layered materials(LiNi_(0.8)Co_(0.1)5 Al_(0.05)O_2,NCA),lithium lanthanum titanate(LLTO) nanofiber and carbon-coated LLTO fiber(LLTO@C) materials were introduced to polyvinylidene difluoride in a cathode.The enhancement of the conductivity was indicated by the suppressed impedance and polarization.At 1 and 5 C,the cathodes with coupling conductive paths had a more stable cycling performance.The coupling mechanism was analyzed based on the chemical state and structure evolution of NCA after cycling for 200 cycles at 5 C.In the pristine cathode,the propagation of lattice damaged regions,which consist of high-density edge-dislocation walls,destroyed the bulk integrity of NCA.In addition,the formation of a rock-salt phase on the surface of NCA caused a capacity loss.In contrast,in the LLTO@C modified cathode,although the formation of dislocation-driven atomic lattice broken regions and cation mixing occurred,they were limited to a scale of several atoms,which retarded the generation of the rock-salt phase and resulted in a pre-eminent capacity retention.Only NiO phase "pitting" occurred.A mechanism based on the synergistic transport of Li ions and electrons was proposed.     

Investigation on the electrochemical activation process of Li1.20Ni 0.32Co0.004Mn0.476O2

The lithium-rich layered oxides are one of the most attractive cathode materials for lithium-ion batteries.Here,two types of Li1.20Ni0.32Co0.004Mn0.476O2 were synthesized using Li2CO3 and LiOH as lithium sources.An electrochemical activation process occurs in Li1.2Ni0.32Co0.004Mn0.476O2 prepared from Li2CO3(LLO-1),while no obvious activation in Li1.2Ni0.32Co0.004Mn0.476O2 prepared from LiOH(LLO-2) is observed.Via advanced scanning transmission electron microscopy(STEM),we found that Li2MnO3-like structure is rich in the surface region of LLO-2.The study provides a direct explanation for the electrochemical activation of lithium-rich materials.The sample with more LiMO2-like phase at the surface region shows a better cycling performance.It is likely that more LiMO2-like phase at the surface region could stabilize the interface and improve the cycling performance of the Li-rich cathode materials.     

锂离子电池正极材料Li2FeSiO4的改性

采用高温固相反应法在氩气气氛下合成锂离子电池正极材料Li2FeSiO4、Li2FeSiO4/C和Li2Fe0.9Mn0.1SiO4/C,并采用X线衍射、扫描电镜和电化学方法研究材料的结构与性能.研究结果表明:改性后的Li2FeSiO4/C和Li2Fe0.9Mn0.1SiO4/C材料与Li2FeSiO4具有相同的晶体结构,锰离子掺杂和表面碳包覆有效地提高了材料的比容量和循环性能.以C/16倍率充放电,Li2FeSiO4/C的首次放电容量为112mA·h/g,Li2Fe0.9Mn0.1SiO4/C材料首次放电容量达122 mA·h/g,充放电循环30次后容量衰减仅为9％.     

高能量密度锂离子电池层状锰基正极材料研究进展

层状锰基材料Li[Lix(MnM)1-x]O2(M=Ni,Co,Cr,…)以高比容量成为最具应用前景的正极体系之一,近年来成为研究热点而倍受关注,尤其借助原位测试分析等先进表征手段,对Li[Lix(MnM)1-x]O2的结构及其高容量获取机理的研究取得显著进展.本文概括介绍了高能量密度层状正极材料的结构与充放电机理,重点针对其目前依然存在的问题,详细归纳了Li[Lix(MnM)1-x]O2正极材料充放电循环过程中电压衰减机理、界面/表面特征以及性能改善的研究新进展,而且对高能量密度层状正极材料的未来研究方向也进行了探讨.     

醋酸盐体系无焰燃烧合成LiMn_2O_4及性能研究

以醋酸锂和醋酸锰为原料,浓硝酸为辅助氧化剂,在温度600℃、时间3 h下采用无焰燃烧合成尖晶石型Li Mn2O4锂离子电池正极材料,研究了不同浓度硝酸对制备尖晶石型Li Mn2O4的影响.通过XRD和SEM分别研究了产物的物相组成及微观形貌;通过电性能测试研究了产物的比容量变化.实验结果表明,当n(Li)∶n(Mn)=1∶2(mol/mol)时,可得到Li Mn2O4单相,硝酸浓度对燃烧产物颗粒影响也较大;硝酸浓度为15 mol/L时产物初始放电比容量为112.1 m Ah/g,40次充放电循环后,放电比容量为99.0 m Ah/g,容量保持率为88.3%,具有较好的容量及存储性能.     

锂离子电池正极材料Li［CoxLi 1/3-x/3Mn2/3-2x/3］O2的制备与表征

采用柠檬酸盐法合成了Li［Co_xLi _{1/3-x/3}Mn_2/3-2x/3］O₂（x=0.1,0.2,0.3,0.4,0.5）正极材料. 利用X射线衍射(XRD), Raman光谱和红外光谱(FTIR)等方法研究不同质量分数的Co对材料晶体结构的影响, 并分析了原因. 对不同组分的材料进行了电化学性能测试, 结果表明, 当x=0.5时, 样品充放电容量高, 循环性能优良.      

Ce-doped LiNi1/3Co（1/3-x/3）Mn1/3Cex/3O2 cathode materials for use in lithium ion batteries

LiNi1/3Co1/3Mn1/3O2 and Ce-doped LiNi1/3Co1/3Mn1/3O2 cathode materials were synthesized by a co-precipitation method and solid phase synthesis and characterized using X-ray diffraction(XRD) and scanning electron microscopy(SEM).The results indicated that the resultant cathode materials with different Ce content all had a good layer structure and high crystallinity.Electrochemical performance testing of the cathode materials showed that the discharge capacity increased with increasing Ce content while the initial reversible capacity attenuation decreased with Ce doping.When the Ce content of the cathode materials is x=0.2,and the current charge and discharge rate is a constant 0.2 C,the discharge capacity maintained 91% of its initial capacity after cycling 50 times.     

锂插入TiS_2的阴极反应过程及其相应的结构变化研究

本文从 ＴｉＳ２和 ＬｉｘＴｉＳ２的电子衍射花样和 Ｘ－射线衍射谱分析得出 Ｌｉ＋插入ＴｉＳ２的阴极反应过程。 Ｌｉ＋先插入 ＴｉＳ２，而后有序化形成 ＬｉＴｉＳ２相。由 Ｘ－射线衍射数据分析得出，新相 ＬｉＴｉＳ２的重复周期 Ｉｃ＝１８．４０Ａ。电子衍射花样表明过量 Ｔｉ形成了超点阵，Ｔｉ在点阵中形成钉扎。伏安循环曲线表明过量Ｔｉ阻止Ｌｉ的插入和移出 ＴｉＳ２本文否定了 Ｌｉ＋插入 ＴｉＳ２只形成一级的 ＬｉｘＴｉＳ２的结论。     

锰含量对LiNi0.85-xCo0.15MnxO2结构及形貌的影响

采用共沉淀法先合成出氢氧化物前驱体Ni0.85-xCo0.15Mnx(OH)2,其中X=0、0.1、0.2和0.4,前驱体与Li2CO3在空气气氛中固相烧结制得正极材料LiNi0.85-xCo0.15MnxO2。用XRD、SEM研究了锰含量对材料结构和形貌的影响。研究发现,LiNi0.85Co0.15O2的X射线衍射图中存在微量第二相,而锰掺杂有利于减小反应过程中锂离子损失和镍离子占据锂位,容易形成有序层状结构材料。随着Mn离子替代Ni离子量的增加,晶胞参数a减小,晶胞参数c、c/a及I003/I104值增大。SEM结果表明前驱体和最终产物形貌均随锰含量增加颗粒均匀性增强,粒子尺寸变小,粒径分布变窄。     

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.     

High-performance lithium–sulfur battery based on porous N-rich g-C3N4 nan-otubes via a self-template method

The commercial development of lithium–sulfur batteries (Li–S) is severely limited by the shuttle effect of lithium polysulfides (LPSs) and the non-conductivity of sulfur. Herein, porous g-C3N4 nanotubes (PCNNTs) are synthesized via a self-template method and util-ized as an efficient sulfur host material. The one-dimensional PCNNTs have a high specific surface area (143.47 m2·g?1) and an abundance of macro-/mesopores, which could achieve a high sulfur loading rate of 74.7wt%. A Li–S battery bearing the PCNNTs/S composite as a cathode displays a low capacity decay of 0.021% per cycle over 800 cycles at 0.5 C with an initial capacity of 704.8 mAh·g?1. PCNNTs with a tubular structure could alleviate the volume expansion caused by sulfur and lithium sulfide during charge/discharge cycling. High N contents could greatly enhance the adsorption capacity of the carbon nitride for LPSs. These synergistic effects contribute to the excellent cycling stability and rate performance of the PCNNTs/S composite electrode.     

Preparation and electrochemical properties of carbon-coated LiFePO4 hollow nanofibers

Carbon-coated LiFePO4 hollow nanofibers as cathode materials for Li-ion batteries were obtained by coaxial electrospinning. X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Brunauer–Emmett–Teller specific surface area analysis, galvanostatic charge–discharge, and electrochemical impedance spectroscopy (EIS) were employed to investigate the crystalline structure, morphology, and electrochemical performance of the as-prepared hollow nanofibers. The results indicate that the carbon-coated LiFePO4 hollow nanofibers have good long-term cycling performance and good rate capability:at a current density of 0.2C (1.0C=170 mA·g?1) in the voltage range of 2.5–4.2 V, the cathode materials achieve an initial discharge specific capacity of 153.16 mAh·g?1 with a first charge–discharge coulombic efficiency of more than 97%, as well as a high capacity retention of 99%after 10 cycles;moreover, the materi-als can retain a specific capacity of 135.68 mAh·g?1, even at 2C.     

A deformable spinel-type chloride cathode with high ionic conductivity for all-solid-state Li batteries

All-solid-state Li batteries (ASSLBs) are now considered to be next-generation energy storage devices due to their advantages in safety and energy density. With liquid electrolytes replaced by solid electrolytes, novel cathode active materials (CAMs) with different characteristics are needed. The solid-solid contact in ASSLBs requires CAMs to have good deformability. In addition, higher ionic conductivity is also essential to reduce the mass of the Li-ion conductive agent, thus accessing a higher overall capacity. Herein, we report a spinel-type chloride cathode Li_2?2xMn_1?xZr_xCl₄, which has good deformability and high ionic conductivity (up to 0.16 mS?cm?1 at 25 °C). The ASSLB using the optimal composition of LiMn_0.5Zr_0.5Cl₄ as the cathode exhibits promising cycling stability for 200 cycles at room temperature.     

Application prospects of high-voltage cathode materials in all-solid-state lithium-ion batteries

All-solid-state lithium-ion batteries are lithiumion batteries with solid-state electrolytes instead of liquid electrolytes.They are hopeful in solving the safety problems of lithium-ion batteries,once their large capacity and long life are achieved,they will have broad application prospects in the field of electric vehicles and large-scale energy storage.The working potential window of solid electrolytes is wider than that of liquid electrolytes,so high-voltage cathode materials could be used in all-solidstate lithium-ion batteries to get higher energy density and larger capacity by elevating the working voltage of the batteries.The spinel LiNi0.5Mn1.5O4material,layered Li–Ni–Co–Mn–O cathode materials and lithium-rich cathode materials can be expected to be applied to all-solid-state lithium-ion batteries as cathode materials due to their highvoltage platforms.In this review,the electrochemical properties and structures of spinel LiNi0.5Mn1.5O4material,layered Li–Ni–Co–Mn–O cathode materials and lithiumrich cathode materials are introduced.More attentions are paid on recent research progress of conductivity and interface stability of these materials,in order to improve their compatibility with solid electrolytes as cathode materials in all-solid-state lithium-ion batteries and fully improve the properties of all-solid-state batteries.Finally,the existing problems of their application in all-solid-state lithium-ion batteries are summarized,the main research directions are put forward and their application prospects in all-solid-state lithium-ion batteries are discussed.     

Tuning Li3PO4 modification on the electrochemical performance of nickel-rich LiNi0.6Co0.2Mn0.2O2

Surface deterioration occurs more easily in nickel-rich cathode materials with the increase of nickel content. To simultaneously pre-vent deterioration of active cathode materials and improve the electrochemical performance of the nickel-rich cathode material, the surface of nickel-rich LiNi0.6Co0.2Mn0.2O2 cathode material is decorated with the stable structure and conductive Li3PO4 by a facile method. The LiNi0.6Co0.2Mn0.2O2–1wt％, 2wt％, 3wt％Li 3PO4 samples deliver a high-capacity retention of more than 85％ after 100 cycles at 1 C under a high voltage of 4.5 V. The effect of different coating amounts (0–5wt％) for the LiNi0.6Co0.2Mn0.2O2 cathode is analyzed in detail. Results show that 2wt％ coating of Li3PO4 gives better performance compared to other coating concentrations. Detailed analysis of the structure of the samples during the charge?discharge process is performed by in-situ X-ray diffraction. It is indicated that the modification for LiNi0.6Co0.2Mn0.2O2 cathode could protect the well-layered structure under high voltages. In consequence, the electrochemical performance of modified samples is greatly improved.     

锂离子电池正极材料LiFePO4/C的制备与表征

采用溶胶-凝胶法合成了LiFePO₄/C复合材料,利用元素分析、X射线衍射（XRD）、扫描电镜（SEM）等方法对其进行了表征,将其组装成模拟电池测试了其电化学性能.结果表明：LiFePO₄/C具有单一的橄榄石型晶体结构,碳粒子平均颗粒大小在1μm左右.LiFePO₄/C复合材料在3.4 V处具有很好的充放电电压平台,与LiFePO₄相比,具有更高的放电比容量和更好的循环性能,在60 ℃时的首次放电容量达到133 mAh/g,经20次循环后的容量保持率为93.8%.     

结晶态FePO4在锂电池中的应用

在不同的温度、物质的量比和煅烧时间等条件下,分别制备FePO4正极材料,并进行X射线衍射(XRD)测试、准开路电压(QOCV)和恒流充放电(CCV)等电化学测试.经湿法研磨后,结晶态FePO4的充放电容量有很大提高,有良好循环特性,表明结晶态FePO4可以通过控制颗粒特性提高比容量,可成为低成本环保型锂电池正极材料.     

尖晶石LiMn2O4掺杂改性研究进展

尖晶石型LiMn2O4是一种极有前途的锂离子电池正极材料，具有原材料资源丰富、价格低、环境污染小、合成工艺简单等优点，但在循环及存放的过程中，存在容量衰减，在高温情况下尤为严重．对尖晶石型LiMn2O4材料的容量衰减机理进行了探讨，并对该正极材料的金属离子掺杂改性研究进行了综述．     

Preparation and electrochemical properties of carbon-coated LiFePO4 hollow nanofibers

Carbon-coated LiFePO₄ hollow nanofibers as cathode materials for Li-ion batteries were obtained by coaxial electrospinning. X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Brunauer–Emmett–Teller specific surface area analysis, galvanostatic charge–discharge, and electrochemical impedance spectroscopy (EIS) were employed to investigate the crystalline structure, morphology, and electrochemical performance of the as-prepared hollow nanofibers. The results indicate that the carbon-coated LiFePO₄ hollow nanofibers have good long-term cycling performance and good rate capability: at a current density of 0.2C (1.0C = 170 mA·g-1) in the voltage range of 2.5–4.2 V, the cathode materials achieve an initial discharge specific capacity of 153.16 mAh·g-1 with a first charge–discharge coulombic efficiency of more than 97%, as well as a high capacity retention of 99% after 10 cycles; moreover, the materials can retain a specific capacity of 135.68 mAh·g-1, even at 2C.     

锂离子电池正极材料LiW_xV_3O_8的合成与性质研究

以LiOH.H2O,V2O5,WO3以及柠檬酸为原料采用流变相法合成了锂钒氧化合物LiWxV3O8(x=0,0.01,0.03,0.05).利用XRD对目标产物的结构进行表征,结果表明:掺杂前后LiWxV3O8均为单斜结构,但掺杂后晶胞参数a和c值与纯相LiV3O8相比略有增加,有利于锂离子在晶体结构中的迁移.同时,对该材料的电化学性质进行测试,结果发现:掺杂后样品的循环性能相对纯相LiV3O8均有所提高,尤其是LiW0.01V3O8电化学性能最为优异,首次放电比容量达238 mAh/g,经过40次循环后容量为185 mAh/g.交流阻抗谱也表明了LiW0.01V3O8具有较小的电荷传输阻抗.对LiW0.01V3O8具有较好电化学性能的原因进行了初步讨论.