LiBOB基电解液成膜性及其循环性能

通过循环伏安(CV)、电化学阻抗谱(EIS)、扫描电子显微镜(SEM)、X射线光电子能谱(XPS)和傅立叶变换红外(FTIR)光谱研究了双乙二酸硼酸锂(LiBOB)基电解液在石墨表面的成膜性及其在常温(25 ℃)和高温(70 ℃)下对石墨循环性能的影响. 结果表明, LiBOB基电解液的成膜电位在1.7 V, 其中BOB-离子还原形成的草酸盐是固体电解质相界面(SEI)膜的有效成分之一. 电化学阻抗谱显示, 膜阻抗在循环过程中呈现减小趋势, 这有利于提高循环稳定性. 在常温和高温条件下, 石墨在该电解液体系中均表现出优于其在LiPF6基电解液体系中的循环性能.     

LixCoO2及其与LiPF6/EC+DEC电解液的热稳定性研究

使用C80微量量热仪对不同充电状态下LixCoO2的热稳定性、LixCoO2与1.0molLLiPF6EC DEC(质量比=11)电解液的热稳定性进行了研究。结果表明,LixCoO2的放热量和主放热峰温度随x值减小而增加,Li0.05CoO2在271.8℃达到放热峰,总放热量高达1575.5Jg。LixCoO2与电解液反应时,LixCoO2首先分解出的氧气使电解液氧化,同时电解液也发生分解等反应,放热峰温度随x的增大呈增大趋势,放热量随x的增大呈减少的趋势。此外,LixCoO2与电解液反应产生大量的CO2、HF等气体。     

量子化学方法在锂离子电池电解液研究中的应用

总结了近年来量子化学方法在锂离子电池电解液研究中的应用进展,阐述了量子化学方法在新型锂盐设计、功能添加剂作用机理分析和电极/电解液界面膜的形成过程研究中发挥的作用,对其用来设计锂离子电池电解液功能分子作出展望。     

锂离子电池电解液低温导电性能的研究

本文研究了用于锂电池的LiPF6＿乙烯碳酸酯(EC)＿甲基乙酸酯(MA)电解液体系,测定了该体系在不同的溶剂配比和盐浓度下于20℃～-50℃时的电导率,给出该体系性能最佳的溶剂配比和盐浓度,以此进行循环伏安和充放电测试,并与商用电解液(LiPF6 EC 二乙基碳酸酯(DEC)进行了比较.     

锂离子电池中电解液的热行为分析

以DSC方法研究分析了1M LiPF6 EC-DMC-EMC(1:1:1,质量比)电解液在锂离子电池中的热行为.锂离子电池中,电解液的热行为主要体现在三方面:电解液的热分解、参与充电态石墨负极的热分解反应、与Li0.5CoO2的热分解产物发生复杂的化学反应.电解液热分解反应是EMC分解生成DEC、DMC,而DEC、DMC与LiPF6的分解产物PF5发生系列的化学反应,释放大量热与气体.Li0.5CoO2分解释放的氧气导致电解液的分解产物及有机溶剂的燃烧,释放大量热与小分子气体.燃烧反应释放的大量热促使Li0.5CoO2的分解产物Co3O4的继续分解;当达到300℃以上时,由LI0.5CoO2分解生成的LiCoO2可能与燃烧产物CO2发生反应以及其他系列的化学反应.充电态的石墨电极的DSC结果表明,电极表面形成固体电解质膜(SEI膜)的碎裂反应是主要的放热反应,LiC6与粘结剂及电解液的放热反应相对较弱.     

锂离子电池有机硅电解液

有机硅电解液具有优良的热稳定性、低可燃性、无毒性、高电导率和高分解电压等优点,近年来成为了锂离子电池新型电解液的研究热点。本文综述了有机硅电解液的研究进展,重点介绍了聚醚有机硅电解液的设计合成、物理化学性能、与电解质盐和电极材料的匹配性关系及其在电池中的性能表现;简述了有机硅功能化电解液添加剂的研究进展,如成膜添加剂、阻燃添加剂、吸酸吸水添加剂等;最后对有机硅电解液的进一步研究趋势和应用前景进行了展望。     

高浓度锂盐电解液

基于1 mol ·dm^-3 LiPF₆/EC的传统非水型电解液已在锂离子电池中应用了20年。高功率、高比能锂离子电池以及锂金属电池（如Li-O₂和Li-S）的发展,对电解液提出了更高的要求,使得电解液的研究与开发到了一个革新换代的阶段。研究者们已经在离子液体、聚合物电解质和无机固态电解质等新型体系研究方面取得一定的研究成果,但是这些新体系存在的本征问题使其商业化应用面临一定的困难。研究者们也开始重新审视已优化的常规液态电解液体系,高浓度锂盐电解液（>3 mol ·dm^-3）再次引起广泛关注。本文综述了高浓度锂盐电解液的发展历程、溶液结构特征、分类标准及其特殊的物理化学性能、锂离子传输性质和电解液/电极相容性;对高浓度锂盐电解液存在的主要问题进行了简要分析,提出了相应的改进措施,展望了高浓度锂盐电解液未来的发展方向,为新型电解液的开发提供了一条新思路。     

锂离子电池有机硅功能电解液

高安全高电压电解液的开发是锂离子电池电解液发展的重要方向。有机硅化合物由于具有独特的理化性能,使其成为锂离子电池电解液领域的研究热点之一。本文综述了有机硅电解液的研究进展,重点从功能分子设计的角度介绍含碳酸酯基、氨基甲酸酯基、腈基、离子液体、含氟类的有机硅功能电解液溶剂制备及电池性能表现;详细阐述具有结构多样性的有机硅化合物用作高电压添加剂、高安全添加剂、高/低温添加剂、储存/耐自放电添加剂、吸酸吸水添加剂及其在不同电池材料体系中的应用。最后,对有机硅电解液的研究趋势和应用前景进行了展望。     

锂离子电池高压电解液

锂离子电池作为一种绿色可充电电池,具有较高能量密度以及功率密度,是便携式电子产品的首选,并逐渐应用于动力汽车领域.为了更好地满足其应用需求,需要进一步提高当前锂离子电池的能量密度.不同于高压正极材料的快速发展,传统电解液在较高工作电压下容易分解,很大程度上阻碍了高能量密度锂离子电池的商业化应用.作为锂离子电池的重要组分...     

锂离子电池有机电解液成膜添加剂研究进展

综述了锂离子电池有机电解液成膜添加剂的作用原理，从气体、液体、固体成膜添加剂三个方面综述了目前成膜添加剂的研究现状。重点论述了每一种添加剂的作用原理以及在碳负极上的还原机理，同时对它们的优缺点也作了适当的评述。     

Optimization of Electrolyte Conductivity for Li-ion Batteries Based on Mass Triangle Model

Mass triangle model was applied to lithium ion battery for electrolyte conductivity forecasting. Seven kinds of electrolytes with different proportions of 3 solvents were prepared. The solvent proportions of the seven electrolytes varied so as to make the seven coordinate points distribute in the ternary coordinate system to form a forcasting region by the connection of them. Their conductivities were tested and the conductivity value in the forecasting region was calculated based on the tested value by mass triangle model. Conductivity isolines formed in the region and blank area showing no forecasted value existed simultaneously. Optimized electrolyte with superior conductivity was selected according to conductivity variation trendency combined with the attention paid to the no-value-shown blank area. The conductivity of optimized electrolyte{m[ethyl carbonate(EC)]:m[propylene carbonate(PC)]:m[ethylmethyl carbonate(EMC)]=0.19:0.22:0.59} was 0.745 mS/cm at -40 ℃, increased by a factor of 51.4% compared to 0.492 mS/cm of common electrolyte[m(EC):m(PC):m(EMC)=1:1:1]. The accuracy of mass triangle model was demonstrated from the perspective that the maximum value existed in the blank area. Batteries with this optimized electrolyte exhibited a better performance.     

Properties of passivation film on carbon electrode in LiPF6/EC+DEC electrolytes

The co-solvent of ethylene carbonate (EC) and diethyl carbonate (DEC) was used to investigate the decomposition of electrolyte in Li-ion batteries. The electrolyte solutions were prepared by mixing in various volume ratios from pure DEC to 7:3 (EC:DEC). The potentials at which they are decomposed on the anodic electrode were examined using cyclic voltammetry. It was found that some kinds of reduction reactions proceeded and a film on the surface of the anode was formed. The film showed different properties, which were dependent on the mixing ratio of the solvents. From our results, we concluded that the best composition ratio of EC:DEC in 1 M LiPF₆/(EC+DEC) system was approximately 4:6 (EC:DEC, volume ratio).     

Enhanced Surface Interactions Enable Fast Li+ Conduction in Oxide/Polymer Composite Electrolyte

Li⁺‐conducting oxides are considered better ceramic fillers than Li⁺‐insulating oxides for improving Li⁺ conductivity in composite polymer electrolytes owing to their ability to conduct Li⁺ through the ceramic oxide as well as across the oxide/polymer interface. Here we use two Li⁺‐insulating oxides (fluorite Gd_0.1Ce_0.9O_1.95 and perovskite La_0.8Sr_0.2Ga_0.8Mg_0.2O_2.55) with a high concentration of oxygen vacancies to demonstrate two oxide/poly(ethylene oxide) (PEO)‐based polymer composite electrolytes, each with a Li⁺ conductivity above 10^?4 S cm^?1 at 30 °C. Li solid‐state NMR results show an increase in Li⁺ ions (>10 %) occupying the more mobile A2 environment in the composite electrolytes. This increase in A2‐site occupancy originates from the strong interaction between the O^2? of Li‐salt anion and the surface oxygen vacancies of each oxide and contributes to the more facile Li⁺ transport. All‐solid‐state Li‐metal cells with these composite electrolytes demonstrate a small interfacial resistance with good cycling performance at 35 °C.     

含FEC电解液的锂离子电池低温性能研究

研究含FEC溶剂电解液(FEC+EMC,EC,PC)的低温性能及其与磷酸铁锂正极或中间相碳微球(MCMB)负极的匹配.该电解液具有较高的低温电导率,FEC可在1.6 V与负极反应成膜,有效地提高负极稳定性.红外测试发现,FEC可抑制其它电解液溶剂在负极成膜过程中的分解,在常温(20℃)和低温(-20℃)下形成的SEI膜阻抗均较低.电化学测试表明,以该电解液装配的锂离子电池(电极)具有较高的低温放电容量和倍率性能.     

Electrolyte using blend salts of LiTFSI and LLZO for long-term high-safety lithium ion battery

It is crucial to obtain a reliable electrolyte system that is used for replacing thermally unstable and the moisture sensitive LiPF₆ salt in liquid electrolytes for developing excellent cycle stability lithium ion batteries with high safety. In this work, a kind of hybrid electrolytes, adding Ga–Bi co-doped Li₇La₃Zr₂O₁₂ (LLZO) into LiTFSI based commercial electrolyte, was successfully prepared. The results shows that adding Ga–Bi co-doped LLZO ceramic particles is benefit for enhancing conductivity of LiTFSI based commercial electrolyte, which is 3.14 mS cm⁻¹ from 3.02 mS cm⁻¹. Furthermore, the LiFePO₄| |Li cell assembling with LiTFSI based electrolyte with Ga–Bi co-doped LLZO ceramic particles shows good cycle performance and coulomb efficiency (100% except for the initial cycle value of 88%) due to a passivation multi-element film formed for preventing severe corrosion to the Al foil. The battery delivered a high first cycle discharge capacity of 144.2 mAh g⁻¹ (85% of theoretical LiFePO₄.) and a maximum value of 152.6 mAh g⁻¹ after the 69th cycle. After the 300 stable cycle, the capacity of 130.8 mAh g⁻¹ (85.7% of the maximum data) remained.     

Conductivity of LiBOB in various ternary solvent blends and the electrochemical performance of LiBOB-PC/EMC/DMC used in Li/MCMB and LiFePO4/Li cells

The solid-state reaction was employed to obtain LiBOB in vacuum dryer at 100°C, with the dryer of P₂O₅. The resulting LiBOB was employed in various ternary solvent blends to get the k, and its change with salt, solvent composition and temperature. 0.7 M LiBOB-PC/EMC/DMC (1: 1: 1, v: v: v) and 0.5 M LiBOB-EC/EMC/DMC (1: 1: 1, v: v: v) were observed to have better k at wide θ range, and the former was chosen to assemble Li/MCMB and LiFePO₄/Li cells. The results indicated that it can stabilize the MCMB anodes, and exhibit good stability in LiFePO₄/Li cell. Published in Russian in Elektrokhimiya, 2008, Vol. 44, No. 10, pp. 1231–1236. The text was submitted by the authors in English.     

Syntheses and Application of All-lithium Salts of Heteropolyacid as Electrolyte of Lithium-ion Battery

IntroductionThesecondarylithium ionbatterieshaverecentlybecomeoneofthechemicalenergysourceswhichhavebeenresearchedanddevelopedintheworldbecauseoftheirbiggerspecificcapacity ,lighterweight ,higheroperatingvoltage ,longercycliclifeandbettersecuri ty[1— 3] .LiClO4 ,LiAsF6 andLiPF6 aremainlyusedaselectrolytesinthecommercializedlithium ioncellsintheworldinspiteoftheirdisadvantages:LiClO4 isalittleunsafewhichwillbedetonablewhenbeingbumpedandishygroscopic ;LiAsF6 ispoisonousanditisanenvironment…