Numerical simulation of lithium‐ion battery performance considering electrode microstructure

A spatially resolved three‐dimensional microscale model of a lithium‐ion battery half‐cell is developed and applied to periodic electrode microstructures made up of spherical particles following a bidisperse particle size distribution. The geometries of the periodic unit cells are derived from discrete element simulations using periodic boundary conditions. Three different particle arrangements, which consist of two layered structures and one mixed particle array, as well as three different compression rates, are considered. In the study, the cathode is assumed to consist of LiMn₂O₄ as active material. Layered particle arrangements comprising the particle fraction of the smaller particle size in the region close to the separator are found to be beneficial especially for high‐rate applications. According to the simulation results, the high‐rate capability is reduced upon compression of the electrode microstructures. Copyright © 2015 John Wiley & Sons, Ltd.     

Polymer electrolytes and interfaces in solid-state lithium metal batteries

The polymer electrolyte based solid-state lithium metal batteries are the promising candidate for the high-energy electrochemical energy storage with high safety and stability. Moreover, the intrinsic properties of polymer electrolytes and interface contact between electrolyte and electrodes have played critical roles for determining the comprehensive performances of solid-state lithium metal batteries. In this review, the development of polymer electrolytes with the design strategies by functional units adjustments are firstly discussed. Then the interfaces between polymer electrolyte and cathode/anode, including the interface issues, remedy strategies for stabilizing the interface contact and reducing resistances, and the in-situ polymerization method for enhancing the compatibilities and assembling the batteries with favorable performances, have been introduced. Lastly, the perspectives on developing polymer electrolytes by functional units adjustment, and improving interface contact and stability by effective strategies for solid-state lithium metal batteries have been provided.     

Strain‐rate‐dependent mechanical properties of polypropylene separator for lithium‐ion batteries

The mechanical integrity of battery separators is critical for battery safety and durability. A comprehensive study of strain‐rate‐dependent tensile and puncture properties of a polypropylene lithium‐ion battery separator is presented here with a new model. Due to anisotropy of the polymeric membrane, tensile testing was conducted for different directions. Results showed that tensile strength and elastic modulus were increased 1000% and 500%, respectively, for different directions. It was also demonstrated that tensile strength changed 10 to 25% with strain rate (1.67 × 10^?4 to 1.67 × 10^?1 s^?1) for different directions. An equation was obtained for the first time for flow stress versus strain rate at varied tensile directions with respect to machine direction. Moreover, puncture testing was performed and it was shown that puncture strength was increased 140% with increasing strain rate from 0.25 to 250 mm min^?1. Two failure modes were also observed in puncture samples. Finally, Eyring's model was used to calculate activation enthalpy of the porous polypropylene separator. © 2020 Society of Chemical Industry     

Ca-Mg-Al复合氧化物催化尿素与1,2-丙二醇制碳酸丙烯酯

采用共沉淀法制备了系列Ca-Mg-Al复合氧化物催化剂，通过对沉淀剂配比、沉淀液pH值及焙烧温度等制备条件的考察，得到以Na₂CO₃为沉淀剂、pH=9.5、850℃下焙烧4h制备的Ca-Mg-Al催化活性最高。在 n(PG)∶n(urea)=1.5∶1、反应温度为145℃、绝压20kPa、反应时间4h、催化剂用量为尿素质量的5%时，碳酸丙烯酯收率达到84.6%。采用XRF、XRD、NH₃-TPD、SEM及BET对催化剂的组成、晶型及酸性进行了表征，发现随着沉淀剂中Na₂CO₃的含量增加，催化剂中CaO∶MgO的比例增大，碳酸丙烯酯的收率亦升高；经850℃焙烧后，催化剂中存在CaO和MgO两种活性中心，起协同催化作用；随着焙烧温度由700℃升高到850℃，NH₃-TPD脱附曲线向低温方向偏移，且强酸中心NH₃脱附峰面积比由81.14%明显下降为0，中强酸中心NH₃脱附峰面积比由0增加到78.07%，而碳酸丙烯酯收率由68%增加到84.6%，这表明催化剂强酸性位的减少是催化活性增加的主要原因。     

碳酸二甲酯液相音速测量与理论估算

生物燃料作为化石燃料的替代物越来越受到人们的重视，脂肪酸甲酯(FAEEs)是生物燃料中的重要组成成分。本文利用布里渊散射法，分别沿0.1、1、3、5、7和10 MPa六条等压线，在293.15 ~ 373.15 K的温度范围内，测量了碳酸二甲酯的液相音速。为方便工程应用，根据实验数据给出了碳酸二甲酯音速与温度和压力的关联式。在本文的p – T热力学区域内，实验值与关联计算值之间的平均绝对误差为0.20%。最后，结合碳酸二甲酯音速实验值和密度文献值，给出了碳酸根 (-CO3)、甲氧基(CH3O-)基团的Wada常数基团贡献值，分别为0.72769±103和0.66851±103。     

离子液体体系卤水提锂的洗涤工艺研究

溶剂萃取法是盐湖提锂的重要工艺方法。采用磷酸三丁酯（TBP）/1-丁基-3-甲基咪唑双三氟甲基磺酰亚胺盐（[C₄mim][NTf₂]）离子液体体系对高镁锂比盐湖卤水中的锂进行萃取分离提取实验,对负载有机相的洗涤和反萃过程进行了研究。萃取实验：在TBP与[C₄mim][NTf₂]体积比为9∶1、相比（有机相与水相的体积比）为2∶1条件下,锂离子与其他离子的分离系数分别为β（锂/钠）=94.70、β（锂/钾）=148.85、β（锂/镁）=131.81。洗涤实验：系统考察了洗涤剂种类及浓度、相比、洗涤次数等因素对杂质离子洗脱率的影响,结果发现氯化锂和盐酸的混合溶液是从负载有机相中洗涤除去杂质离子的有效洗涤剂。洗涤过程适宜条件：洗涤剂中氯化锂浓度为4 mol/L、盐酸浓度为0.5 mol/L,相比为5∶1,洗涤次数为2次。反萃实验：用稀盐酸（1.0 mol/L）对负载有机相进行反萃取,在相比为1∶1条件下,单级反萃率达到97.81%。研究表明,离子液体体系作为一种新型萃取体系,在高镁锂比盐湖卤水中提取锂具有较好的应用前景。     

用于盐湖卤水吸附法提锂的连续离子交换工艺研究

采用连续离子交换技术用于盐湖卤水的吸附法提锂。针对青海一里坪盐湖老卤体系,开发了连续离子交换吸附提锂工艺,研究了操作参数对连续离子交换系统提锂性能的影响,并在优化的工艺条件下进行了长周期的稳定性评价。结果表明,在转动步进周期为20 min、卤水进料量为3.2 BV/h、淋洗水量为2.9 BV/h、解吸水量为9.3 BV/h、解吸温度为15~25 ℃时,连续离子交换系统可以稳定获得镁锂质量浓度比（简称镁锂比）在3左右、锂质量浓度接近1.1 g/L的合格液,锂回收率为98.5%以上。     

酯交换法合成碳酸甲乙酯催化剂的研究进展

碳酸甲乙酯（EMC）是一种环境友好型的不对称碳酸酯，因其独特的结构性质被广泛用作溶剂或有机合成中间体，特别是随着锂离子电池的迅猛发展，其作为电池电解液主要成分市场需求量急增。文中简单介绍了光气法、氧化羰化法和酯交换法合成碳酸甲乙酯的研究进展。重点针对最具发展前景的酯交换法合成EMC工艺路线中所用催化剂进行了综述；讨论和分析了该路线所用催化剂的类型、结构、性质及性能，并对当前研究中存在的问题进行了归纳和分析总结。最后本文分析并展望了酯交换法合成EMC催化剂的研究方向及新型合成工艺发展趋势，提出研发经济、高效、稳定且制备工艺简单的非均相催化剂，并与反应精馏技术耦合是今后的主要发展趋势，期望为EMC的高效合成提供参考和借鉴。     

Superior lithium storage performance of hierarchical N-doped carbon encapsulated NaTi2(PO4)3 microflower

Na-superionic conductor (NASICON) structured NaTi₂(PO₄)₃ (NTP) as anode shows broad prospect in aqueous lithium ion battery. However, inherent low electrical conductivity of NaTi₂(PO₄)₃ remains a pivotal issue to be resolved. Herein, we report N-doped carbon encapsulated NaTi₂(PO₄)₃ microflower (NTP-CN) as anode for aqueous lithium ion battery, which is prepared via solvothermal way. NTP-CN with unique structural feature displays superb electrochemical performances. It delivers the discharge capacities of 131.2, 110.1, and 84.3 mAh g⁻¹ at 0.2, 3.0, and 15 C, respectively, 38.8, 33.8, and 51.1 mAh g⁻¹ higher than these of pristine NTP. NTP-CN also shows remarkable cycling stability at 6 C after 1000 cycles (capacity retention: 88.8%), superior to NTP (70.7%). The outstanding properties of NTP-CN may be due to that microflower structure can increase touching area between electrolyte and electrode, and carbon coating for electrode improves stability in aqueous electrolyte and ameliorates electrical conductivity. Moreover, nitrogen doping can further enhance hydrophilicity and conductivity of the sample, and also form lots of defects on electrode surface, which is beneficial for the intercalation/deintercalation of Li ions. This work reveals that the combination of microflower structure and N-doped carbon layer offers a promising method to improve electrochemical performances of NaTi₂(PO₄)₃.