电压区间对LiNi0.8Co0.1Mn0.1O2/MCMB全电池性能的影响

以LiNi_0.8Co_0.1Mn_0.1O₂（NCM811）为正极、中间相碳微球（MCMB）为负极构建锂离子全电池,研究了充放电电压区间对NCM811/MCMB全电池电化学性能的影响。研究结果表明：以4.3 V为充电截止电压,降低放电截止电压可提高全电池的容量,但高放电截止电压下全电池的循环性能更加稳定;在2.8~4.3 V电压区间下,NCM811/MCMB全电池不但具有高的比容量,同时还具有良好的循环性能和充放电可逆性。     

颗粒微观结构对LiNi0.8Co0.1Mn0.1O2正极材料电性能的影响研究

锂离子电池正极材料LiNi_0.8Co_0.1Mn_0.1O₂（简称NCM811）能量密度高,有望满足电动汽车长续航里程要求,近年来成为业内关注和研究的焦点。然而,NCM811存在表面碱度高,稳定性差,长循环下颗粒容易碎裂和粉化等问题,阻碍了其大规模应用。本文将三元材料进行单晶化研究,即将二次球颗粒熔融形成单晶颗粒,以期解决三元材料结构和表面稳定性差等问题,并探索在高电压体系使用可行性。实验结果表明,将锂与过渡金属配比设为1.05,在910°C下烧结12 h,可得到形貌较好的单晶NCM811材料,此时材料表面碱度和晶格Ni/Li阳离子混排度均较低,分别为0.288wt%和2.24%。电性能评估结果显示,该材料在3.0–4.3 V下克容量可达191.5mAh/g,同时高温和高电压下循环稳定性得到明显提升,在高温50°C下,3.0–4.4V电压区间内循环100周,容量保持率可达95.1%,而二次颗粒材料仅为88.5%。相比二次颗粒,单晶形态的NCM811材料虽然倍率性能会稍有下降,但结构和表面稳定性更佳,在高电压高能量密度体系具有较好的应用前景。     

纳米材料在锂离子电池中的研究进展

锂离子电池的核心是选择高能储锂电极材料,纳米材料以其独特的物理化学性能应用作为锂离子电池电极材料,具有减小极化,增大充放电电流密度,提高放电容量和循环稳定性等优点,有利于高性能、高容量和高功率电池的发展。纳米电极材料具有非常广阔的应用前景,但目前已有的研究基本处于实验开发阶段,且主要集中在制备方法上,其微观结构和电化学性能沿需进一步研究探讨。     

高性能复合固态电解质的制备及固态锂金属电池性能研究

固态锂金属电池相较于传统液态电池,其能量密度更高、安全性更好,具有巨大的应用前景。但聚合物固态电解质离子电导率低、强度低、电化学稳定性差,阻碍了其进一步发展。将丁二腈与聚碳酸丙烯酯通过无溶剂法加以玻璃纤维作为支撑制备了室温下高性能的复合固态电解质。所制备的复合固态电解质在室温下离子电导率达3.06×10^?4 S/cm,锂离子迁移数达0.47,电化学窗口最高达4.3 V;其锂金属对称电池在电流为0.1 mA/cm²的条件下,稳定循环超400 h;磷酸铁锂固态锂金属电池0.5 C循环100次的容量保持率为95.9%,展现出良好的循环稳定性。     

纳米硅@碳高性能锂离子电池负极材料

采用化学气相沉积法,通过在纳米硅表面原位制备碳层而获得具有坚固核壳结构的nano-Si@C锂离子电池负极材料,该材料能有效克服硅负极在充放电过程中出现的体积变化大和电导率低的问题.实验结果表明,nano-Si@C具有优良的电化学性能,首次库伦效率为87.0％,循环100次仍能保持高比容量(1133 mA·h·g-1)和高容量保持率.循环前后的透射电子显微镜(transmission electron microscopy,TEM)结果证明,紧密坚固的核壳结构使nano-Si@C在充放电过程中保持较好的结构稳定性,有利于电极的循环稳定.     

纳米硅@碳高性能锂离子电池负极材料

采用化学气相沉积法,通过在纳米硅表面原位制备碳层而获得具有坚固核壳结构的nano-Si@C锂离子电池负极材料,该材料能有效克服硅负极在充放电过程中出现的体积变化大和电导率低的问题.实验结果表明,nano-Si@C具有优良的电化学性能,首次库伦效率为87.0％,循环100次仍能保持高比容量(1133 mA·h·g-1)和高容量保持率.循环前后的透射电子显微镜(transmission electron microscopy,TEM)结果证明,紧密坚固的核壳结构使nano-Si@C在充放电过程中保持较好的结构稳定性,有利于电极的循环稳定.     

高能量密度全固态锂金属电池Li6.4La3Zr1.4Ta0.6O12基锂硼负极的制备及性能

采用熔融态金属锂与高纯硼粉复合制备了锂硼复合材料并应用于固态电解质(Li_6.4La₃Zr_1.4Ta_0.6O₁₂, LLZTO)制作对称电池，对比研究了锂硼复合固态对称电池与锂金属固态对称电池的电化学性能。结果表明:锂硼复合固态电池界面阻抗(约6 Ω/cm2)小于金属锂固态电池的界面阻抗(约103 Ω/cm2)，说明锂硼复合电极和固态电解质接触良好；在400 μA/cm2的电流密度下进行充放电测试，锂硼复合固态对称电池可以稳定循环250次以上，而金属锂固态电池很快失效；锂硼复合固态对称电池在0.1 mAh保持容量下的临界电流密度达到2 700 μA/cm2，在0.1 mA/cm2电流密度下的面容量可达12 mAh/cm2。研究表明该锂硼复合固态对称电池具有优异的循环性能。     

共溶剂对石墨电极界面SEI膜成膜机制和膜性能的影响

在锂离子电池负极材料中 ,石墨类炭材料具有优良的嵌脱锂性能、充放电电位平台低且平稳、循环性能稳定等突出优点 ,仍然是目前锂离子电池的首选负极材料 .本文选用具有良好贮锂结构的人工石墨为研究对象 ,组配了 6种常用的电解液体系 ,考察了石墨电极在不同化学组成的液体非水电解质体系中的电化学嵌脱锂性能 ,确定了电极界面SEI膜的化学组成 ,探讨了共溶剂对电极界面SEI膜成膜机制和膜性能的影响 .以碳酸乙烯酯 (EC)为主体溶剂 ,分别与共溶剂组分二甲基碳酸酯 (DMC)、二乙基碳酸酯 (DEC)、二甲氧基乙烷 (DME)按1∶1混合 ,使用无水L…     

水解法制备SnO_2纳米材料及作为锂离子电池负极的性能研究

分别使用十二烷基苯磺酸钠(SDBS)作为表面活性剂以及十二烷基苯磺酸钠(SDBS)和聚乙烯吡咯烷酮(PVP)作为双表面活性剂,采用水解法制备出SnO_2纳米材料,并研究了SnO_2纳米材料的形貌和作为锂离子电池负极时的电化学性能之间的关系.结果表明,所制备的SnO_2纳米颗粒均为球形,大小为45~75 nm,在双表面活性剂的调控下所制备的SnO_2纳米材料体积较大.所制备的SnO_2纳米颗粒均为具有金红石结构的锡石型,属于四方晶系.恒电流充放电循环测试结果表明,SnO_2纳米颗粒具有较高的放电比容量,首次放电比容量大约为1400~1600 m Ah/g,但是循环稳定性较差,循环5次以后样品的放电比容量衰减至400~700 m Ah/g.总之,双表面活性剂调控下,7h煅烧制备得到的SnO_2纳米材料相对较好,具有相对较大的比容量和相对较小的阻抗.     

微乳液法制备锂离子电池纳米铜锡合金负极材料

用反相微乳液法制备出了具有无定形结构的纳米铜锡合金,并将其用作锂离子电池的阳极材料.颗粒粒径为50-60nm的铜锡合金在0-1.2V之间充放电具有300mAh/g的稳定比容量,50次循环的容量保持率为93.3%.微乳液工艺中乳化剂的含量、热处理工艺中热处理的温度以及电极制备工艺中导电剂的含量对材料电化学性能有较大的影响.     

磷酸铁锂动力电池阻抗谱参数分析

以电动汽车用动力锂离子电池为测试对象,通过等效电路拟合实际测量的电化学阻抗曲线来分析电池电极系统的动力学过程,并选取等效电路模型在不同荷电状态下的参数分析不同交流阻抗组份及阻抗特性对电池充放电特性的影响。 结果表明:基于阻抗谱测试得到的等效电路模型参数有利于得出更高精度的电池电荷转移阻抗以及扩散阻抗,并且较好地区分电化学极化和浓差极化,可以用于分析不同温度和不同荷电状态的电池充放电性能。      

锂离子电池负极材料力学行为研究进展

 可充电锂离子电池被广泛应用于便携式电子设备、电动汽车等领域。随着其应用领域的快速发展,迫切需要进一步提高其能量密度。本文综述对目前广泛研究的高能量密度负极材料（如硅、锗）在充/放电过程中力学行为的研究进展;基于最新实验手段及数值模拟方法,介绍负极材料由于电化学-力学耦合所造成的变形和破坏,并讨论相关技术在其他电池系统研究中的应用。     

Capacity fading of spinel LiMn2O4 during cycling at elevated temperature

A normal spinel LiMn2O4 as cathode material for lithium-ion cells was cycled galvanostatically (0.2 C) at 55℃. To determine the contribution of each voltage plateau to the total capacity fading of the cathode upon repeated cycling, the capacities in each plateau were separated by differentiation of voltage vs. capacity. The results showthat the capacity fading in the upper voltage plateau is more rapidlythan that in the lower during discharging, while in charging process,it fades slower than that in the lower voltage range. The increased capacity shift and aggravated self-discharge/electrolyte oxidation during discharging contribute to a high fading rate in the upper step. Capacity shift also takes place during charging process, which again enhancing the fading rate of the lower voltage plateau. An increase in capacity shift, as a result of an increase in polarization of the cell, plays a major role in determining the fading rate in each voltage plateau, further reflecting the thickening of the passivation layer on the active particles, and the accumulation of electrolyte decomposition. The relative capacity loss for modified spinels is well correlated withthe relative increase in the polarization of the half-cells, confirming the above causes for capacity fade of this kind of cathode material.     

A pore-scale smoothed particle hydrodynamics model for lithium-ion batteries

A mesoscopic pore-scale model of multi-disciplinary processes coupled with electrochemical reactions in lithium-ion batteries is established via a relatively novel numerical method—smoothed particle hydrodynamics(SPH)method.This model is based on mesoscopic treatment to the electrode(including separator)micro-pore structures and solves a group of inter-coupled SPH equations,including charge(ion in electrolyte phase and electron in solid phase),species(Li?in electrolyte phase and lithium in solid active materials),and energy conservation equations.Model parameters,e.g.the physicochemical properties are location-dependent,directly associated with the local component of the medium.The electrochemical reactions are prescribed to occur exactly at the interface of solid active materials and electrolyte.Simulations to isothermal discharge processes of a battery of 2-dimensional idealized micro-pore structure in electrodes and separator preliminarily corroborate the reasonability and capability of the developed SPH model.     

Bi/Bi2O3复合碳纳米纤维的制备及其储锂性能研究

为提高Bi负极材料的循环性能,提出了一种Bi/Bi₂O₃碳纳米复合纤维(Bi/Bi₂O₃-CNFs)的合成方法。以Bi₂S₃纳米棒为模板,采用静电纺丝技术及后续高温热处理方法成功合成了具有纵孔结构的Bi/Bi₂O₃(w)-CNFs。采用扫描电子显微镜(SEM)、X射线衍射(XRD)、热重分析(TGA)、透射电子显微镜(TEM)和X-射线光电子能谱(XPS)对复合材料进行了表征。讨论了不同质量分数的Bi₂S₃对复合材料结构以及电化学性能的影响。结果表明:当添加8.7%(质量分数)的Bi₂S₃时,合成的Bi/Bi₂O₃(8.7%)-CNFs拥有最佳的电化学储锂性能。当充放电电流密度为0.1 A/g时,Bi/Bi₂O₃(8.7%)-CNFs复合材料首次放电比容量可达到806 mA·h/g,并能稳定循环1 000次,即使在5.0 A/g的大电流密度下,储锂容量仍有147 mA·h/g。Bi/Bi₂O₃(8.7%)-CNFs复合结构改善了充放电过程的动力学性能,提高了电化学性能。碳纤维及内部纵孔结构缓解了充放电过程中电极材料的体积膨胀,增强了电池的循环稳定性。     

Preparation and electrochemical properties of re-synthesized LiCoO2 from spent lithium-ion batteries

A new idea for reuse of the cathode materials of lithium-ion batteries(LIBs) is investigated to develop an environmentally friend-ly process for recycling spent batteries.LiCoO2 is re-synthesized from spent LIBs by leaching and a sol-gel method calcined at high temperature.Thermogravimetric analysis(TGA) and differential scanning calorimetry(DSC) are employed to study the re-actions occurring calcination that are responsible for the weight losses.X-ray diffraction(XRD) and scanning electron microscopy(SEM) are used to determine the structures of the LiCoO2 powders.It was found that a pure phase of LiCoO2 can be obtained by the re-synthesis process.Cyclic voltammetry(CV) and electrochemical impedance spectroscopy(EIS) are used to evaluate the electrochemical properties of the LiCoO2 powders.The discharge capacity of re-synthesized LiCoO2 is 137 mAh g-1 at the 0.1 C rate,and the capacity retention of the re-synthesized LiCoO2 is 97.98% after 20 cycles at the 0.1 C rate,and 88.14% after 40 cy-cles.The results indicate that the re-synthesized LiCoO2 displays good charge/discharge performance and cycling behavior.     

Changes of Some Capacities and Failure Mode of Ni/MH Batteries During Cycling

The changes of capacities of positive and negative electrodes,reserve capacities of charging and discharging, and the weight of batteries during cycling have been determined. The increase of the discharging reserve capacity due to the conjugated electrochemical reactions of the oxidation of hydrogen-storage alloy is estimated. The results show that the failure mode of Ni/MH batteries developed is as follows: during the increase of cycles, the hydrogen-storage alloy is oxidized continuously and the charging reserve capacity is decreased rapidly while the discharging reserve capacity is increased gradually, thus the internal pressure is increasing, first H2 leaks out from the battery, then the mixture of H2 and O2. The leakage of gases and the total reaction of oxidation of the alloy consume H2O, and the surface oxides on the alloy increase, so that the internal resistance of the battery increases.     

Nano-sized transition-metal oxides as negative-electrode materials for lithium-ion batteries

Rechargeable solid-state batteries have long been considered an attractive power source for a wide variety of applications, and in particular, lithium-ion batteries are emerging as the technology of choice for portable electronics. One of the main challenges in the design of these batteries is to ensure that the electrodes maintain their integrity over many discharge-recharge cycles. Although promising electrode systems have recently been proposed, their lifespans are limited by Li-alloying agglomeration or the growth of passivation layers, which prevent the fully reversible insertion of Li ions into the negative electrodes. Here we report that electrodes made of nanoparticles of transition-metal oxides (MO, where M is Co, Ni, Cu or Fe) demonstrate electrochemical capacities of 700 mA h g(-1), with 100% capacity retention for up to 100 cycles and high recharging rates. The mechanism of Li reactivity differs from the classical Li insertion/deinsertion or Li-alloying processes, and involves the formation and decomposition of Li2O, accompanying the reduction and oxidation of metal nanoparticles (in the range 1-5 nanometres) respectively. We expect that the use of transition-metal nanoparticles to enhance surface electrochemical reactivity will lead to further improvements in the performance of lithium-ion batteries.     

Nanostructure designing and hybridizing of high-capacity silicon-based anode for lithium-ion batteries

Lithium-ion batteries have long been used in electronic products and electric vehicles, but their energy density is slowly failing to keep up with demand. Because of its extraordinarily high theoretical specific capacity, silicon is regarded as the most potential next-generation anode material for practical lithium-ion batteries. However, its unavoidable volume expansion issue can cause electrode deformation and loss of electrical contact during cycling,resulting in significant performance reduc...     

晶态锂离子固体电解质的最新研究进展

锂离子电解质是高功率密度和能量密度、长循环寿命和安全性能良好的锂离子电池的关键材料之一,对锂电池的发展起着非常重要的作用。简单介绍了几种主要类型锂离子晶态固体电解质材料的研究情况,并详细概括了最近晶态锂离子固体电解质的研究热点材料——类石榴石结构的Li5La3M2O12（M=Ta,Nb）锂离子导体,最后对以Li5La3M2O12（M=Ta,Nb）锂离子导体为代表的晶态锂离子固体电解质的研究做出了展望。