A panoramic view of Li7P3S11 solid electrolytes synthesis,structural aspects and practical challenges for all-solid-state lithium batteries

The development of an inorganic electrochemical stable solid-state electrolyte is essentially responsible for future state-of-the-art all-solid-state lithium batteries (ASSLBs). Because of their advantages in safety, working temperature, high energy density, and packaging, ASSLBs can develop an ideal energy storage system for modern electric vehicles (EVs). A solid electrolyte (SE) model must have an economical synthesis approach, exhibit electrochemical and chemical stability, high ionic conductivity, and low interfacial resistance. Owing to its highest conductivity of 17 mS·cm^-1, and deformability, the sulfide-based Li₇P₃S₁₁ solid electrolyte is a promising contender for the high-performance bulk type of ASSLBs. Herein, we present a current glimpse of the progress of synthetic procedures, structural aspects, and ionic conductivity improvement strategies. Structural elucidation and mechanistic approaches have been extensively discussed by using various characterization techniques. The chemical stability of Li₇P₃S₁₁ could be enhanced via oxide doping, and hard and soft acid/base (HSAB) concepts are also discussed. The issues to be undertaken for designing the ideal solid electrolytes, interfacial challenges, and high energy density have been discoursed. This review aims to provide a bird's eye view of the recent development of Li₇P₃S₁₁-based solid-state electrolyte applications and explore the strategies for designing new solid electrolytes with a target-oriented approach to enhance the efficiency of high energy density all-solid-state lithium batteries.     

Room-Temperature Solid-State Lithium Metal Batteries Using Metal Organic Framework Composited Comb-Like Methoxy Poly(ethylene glycol) Acrylate Solid Polymer Electrolytes

Solid polymer electrolyte with good thermal stability and flexibility is an excellent candidate for solid-state lithium metal batteries, while its low ionic conductivity caused by high crystallinity limits its application at ambient temperature. Here a metal organic framework (zeolitic imidazolate framework-8, ZIF-8) composited comb-like methoxy poly(ethylene glycol) acrylate polymer electrolyte (MCPE) with high ionic conductivity (9.96 × 10⁻⁵ S cm⁻¹ at 30 °C) is prepared by an in situ UV polymerization method. The as-prepared MCPE exhibits improved mechanical property due to the introduction of porous ZIF-8 nanofillers, which is beneficial to suppress the growth of lithium dendrites. Consequently, the LiFePO₄||MCPE||Li cells show a high capacity of 116 mAh g⁻¹ at 30 °C and 0.5 C, and maintain 89.4% of initial capacity after 150 cycles with the average Coulombic efficiency of 99.9%. These results demonstrate that the MCPE shows great potential in solid-state lithium metal batteries near room temperature.     

高镍三元正极材料表面碱性物质研究进展

高镍三元正极材料表面形成的碱性物质容易导致电池容量衰减加快、寿命缩短,因而调控三元材料表面碱性物质对于提高锂离子二次电池的功能和安全性至关重要。综述了高镍锂离子电池三元正极材料表面碱性物质的形成机理及处理手段,从不同角度阐述了环境中的水、二氧化碳对表面碱性物质形成的影响。探讨了表面碱性物质形成过程中,由于锂离子和过渡金属的迁移与固化引发的表面结构的相变现象,造成了三元正极材料的加工储存性能的恶化。还对降碱工艺中的洗涤、干燥、低温烧结等过程进行了重点说明,阐述了洗涤工艺对三元材料表面碱性物质降低及对材料性质的影响,指出需选择合适的洗涤、干燥条件,减小材料表面发生的变异。最后结合目前降碱工艺对后续研究方向提出了建议。     

碳酸锂在水和NaCl-KCl溶液体系中溶解度的在线测定

碳酸锂溶解度在工业结晶生产中是十分重要的基础数据。采用浸入式红外探头和拉曼探头在线监测溶液体系中CO₃^2-和碳酸锂的特征峰峰强的变化,依据Lambert-Beer定律得出溶液体系中实时在线测定碳酸锂的溶解度。通过在线测定,测得碳酸锂在氯化钠-氯化钾溶液（c_NaCl=0.446 6 mol/L,c_KCl=0.015 8 mol/L）中的溶解度高于在水中的溶解度值。实验测试出的水中碳酸锂的溶解度数据还能与Van′t Hoff方程较好地关联,进一步测算碳酸锂在其他温度下水中的溶解度值。此外,该方法测定的碳酸锂在水中的溶解度数据比文献值中采用重量分析法测试出的溶解度数据偏小,是因为测试装置不同造成的。     

机械活化-湿化学合成LiMn2O4的组成、结构与表征

以MnO2和LiOH·H2O为原料,采用机械活化与湿化学集成的方法,在水溶液中直接合成了结晶态的尖晶石锂锰氧化物.当锂含量介于3.78%～4.35%之间时,所得锂锰氧化物为纳米级球形粉末,以尖晶石结构为主,含极少量的Mn3O4杂相;在300～800℃温度范围内热处理后,Mn3O4杂相消失,尖晶石结构更趋完善.所合成的含锂5.80%的高锂样品则以LiMnO2层状结构为主,含少量Mn3O4杂相,其SEM形貌为片状;在300～700℃下热处理8 h后,层状LiMnO2转变成尖晶石LiMn2O4,Mn3O4杂相峰明显减弱并随热处理温度的升高而消失;当温度升高至700～800℃时,开始出现缺锂的Li1-xMn2O4相.结果表明:该法制备锂锰氧化物可实现锂、锰、氧在原子级水平的均匀混合,所得产物的热稳定性能良好,其化学计量组成与结构易于调整和控制.     

LiNi1-xMxO2 (M =Co3+, Al3+)的制备与性能

采用球形Ni(OH)2和LiNO3、CoO、Al(OH)3为原料，在空气气氛条件下700℃恒温8h，合成了锂离子电池正极材料LiNixCo1-xO2和LiNi0.75Al0.25O2。X射线衍射分析表明合成的材料粉末结晶良好，具有规整的α-NaFeO2层状结构；SEM分析表明粉末颗粒呈球形，粒径约为7μm。充放电测试表明：合成的LiNixCo1-xO2正极材料的充电比容量为160mAh／g，放电比容量为152mAh／g；LiNi0.75Al0.25O2正极材料的充电比容量为140mAh／g，放电比容量为129mAh／g；这两种正极材料具有优良的电化学性能。     

基于容量参数的二次电池嵌入型电极材料固相扩散系数的测定方法

介绍了一种以容量参数为主变量的测定锂二次电池中电极材料固相扩散系数的方法.该方法只需颗粒半径这一辅助参数,通过球型扩散模型建立了恒流-恒压充电容量(RPG)比,进一步发展成为容量间歇滴定技术(CITT).采用RPG法可在较宽的电压范围内测定嵌入型电极材料的平均固相扩散系数,实验结果重现性好.由RPG法测得0～1.5 V时锂离子在石墨电极中的平均固相扩散系数值为1.055×10-10cm2/s.由CITT技术测得锂离子在LiMn2 O4中的固相扩散系数在3.95 V和4.12 V左右存在个两个极小峰,且随着循环次数的增加,扩散系数值逐渐增大.     

Phase transition of lithiated-spinel Li2Mn2O4 at high temperature

1 Introduction Lithium manganese oxides are the most attractive cathode materials for rechargeable lithium-ion batteries because of their low-cost and less toxicity when compared with either cobaltates or nickelates[1?3]. Among these oxides, the spinel-fr…     

锂离子电池正极材料第一原理计算研究

利用第一原理计算方法可分析和预测锂-金属氧化物电池正极材料在Li离子嵌入脱出过程中的电势和稳定性等性能。本文详细介绍了第一原理计算方法的理论背景以及目前LiCoO2正极材料计算研究的现状。利用此方法对LiNiO2及多组分材料掺杂进行研究是今后工作的重点。