锂离子电池高电压电解液的研究现状

目前提高锂离子电池能量密度的途径主要有提高锂离子电池的工作电压和应用高工作电压的正极材料,因此,锂离子电池高电压电解液的研究和开发势在必行。本文概述了锂离子电池电解液和高电压电解液的特点,介绍了前线轨道理论中的HOMO和LUMO对电解液设计的指导意义。尤其是结合日本知名企业和科研机构在高电压电解液方面的研究成果,阐述了两种实现电解质高电压化的途径,即提高溶剂本身的耐氧化性和使用添加剂,总结了氟代酯、氟化醚、硼酸酯、砜类和耐氧化添加剂等用于高电压电解液中的关键物质类型,并讨论了目前高电压电解液研究开发所带来的启示。     

锂离子电池高电压和耐燃电解液研究进展

电解液作为锂离子电池的重要组成部分,起着传输离子的作用,电解液的性质对电池的容量、循环性能及安全性能等影响巨大.近年来,随着高电压、高能量密度锂离子电池的开发应用,现有常规碳酸酯电解液存在正极稳定性差、闪点低、易燃烧等问题.因此,发展高电压耐燃电解液是应用高电压高容量正极材料、发展高电压高容量高安全性锂离子电池的迫切需要.主要综述了高电压电解液、耐燃性电解液及兼具抗氧化性和耐燃性的高浓度电解液的研究进展和现状.在此基础上,对锂离子电池新型电解液的发展方向进行了展望.     

锂离子电池高电压电解液

开发高电压正极材料是发展高能量密度锂离子电池的重要途径之一。常规电解液在高电压下容易与正极材料表面发生副反应,影响高电压正极材料性能的发挥,因此,高电压电解液引起了人们广泛的关注。本文主要从新型溶剂体系和常规碳酸酯溶剂体系两方面对锂离子电池高电压电解液进行综述与评价,提出了现有电解液的不足及面临的问题。从电解液溶剂分子设计理论入手,分析了砜类溶剂、腈基溶剂和离子液体等新型溶剂作为高压电解液溶剂的优缺点,同时探讨了不同种类添加剂在常规碳酸酯溶剂体系中的作用机理。此外,本文还介绍了理论计算方法在锂离子电池高电压电解液研究中的应用,并对其在设计新型高电压电解液中的应用前景进行了展望。     

含有氟代溶剂或含氟添加剂的锂离子电解液

随着大型移动设备（如新能源汽车等）、储能电站及其他便携式充电设备的日益普及,锂离子电池正逐步占领化学电源市场的主导地位。电解液是锂离子电池的重要组成部分,对电池的许多性能如输出电压、能量密度、输出功率、寿命、温度适用范围和安全性能等具有重要的影响。氟具有很强的电负性和弱极性,氟代溶剂或含氟添加剂具有低熔点、高闪点和高氧化分解电压等优点。氟代溶剂与电极材料之间的润湿性也较好,在高电压电解液、高安全性电解液、宽温度窗口电解液以及其他特殊功能电解液的开发中具有深入的研究和广泛的应用。本文综述了近年来氟代溶剂或添加剂在锂离子电池电解液中的不同应用,分析阐述了其对电池性能提升的机理,总结了以氟代碳酸乙烯酯（FEC）为代表的氟代溶剂的合成方法,最后对用于锂离子电池电解液的氟代溶剂或含氟添加剂的研发方向和发展趋势进行了展望。     

高能量密度的锂离子混合型电容器

锂离子混合型电容器兼有锂离子电池和超级电容器的优点,在电化学储能领域具有广泛的应用前景. 但其产业化仍存在一系列的基础及工艺方面的问题,具体包括器件结构设计、电极材料筛选、预嵌锂工艺和电解液与电极的界面等. 本文结合作者课题组的研究工作介绍了近年来高能量密度的锂离子混合型电容器的研究进展,内容涉及锂离子电容器正/负极材料的筛选、预嵌锂工艺的优化、内并联结构的锂离子电池型超级电容器复合正极组成材料的调控、隔膜的选择、电解液的组成、以及器件的高/低温性能,分析了锂离子电容器的容量衰减机制,探讨了锂离子电池型超级电容器的储能机制,提出了未来对高能量密度的锂离子混合型电容器研究的展望.     

石榴石Li7La3Zr2O12固态电解质电导率优化策略研究进展

近几年,应用碳材料负极和有机电解液的液态锂离子电池(LIBs)的弊端日益凸显,电解液泄漏和过热燃烧等安全事故频发。另外,传统的LIBs也无法满足当今社会对高能量密度电池的需求。由于上述LIBs存在的诸多缺点,市场急需开发兼顾高能量密度与高安全性能的新型电池,现已发现可通过引入固态电解质的途径来实现。固态锂电池(SSLBs)相较于传统的LIBs,具有较高的能量密度、较宽的工作温度范围和更高的安全性。其中,固态电解质作为固态电池的重要元件之一,对电池性能的影响至关重要。石榴石Li₇La₃Zr₂O₁₂凭借其高锂离子电导率(1×10^-4～1×10^-3 S/cm)、宽电化学窗口(9 V)以及对锂负极的高稳定性等优点,在众多固态电解质中脱颖而出。本综述就提高石榴石基电解质锂离子电导率的研究予以总结：首先,介绍了Li₇La₃Zr₂O₁₂晶体结构并分析了结构与电导率之间的关系;然后,综...     

锂离子电池低温性能改善研究进展

锂离子电池因其能量密度高,循环寿命长等优点已成为新型动力电池领域的研究热点,但其温度特性尤其是低温性能较差制约着锂离子电池的进一步使用. 本文综述了锂离子电池低温性能的研究进展,系统地分析了锂离子电池低温性能的主要限制因素. 从正极、电解液、负极三个方面讨论了近年来研究者们提高电池低温性能的改性方法. 并对提高锂离子电池低温性能的发展方向进行了展望.     

锂离子电池用高电位正极材料LiNi0.5Mn1.5O4

由于具有工作电压高、工作范围宽、比能量大、无污染、使用寿命长等优点,锂离子电池具有广阔的应用前景。 然而,目前商业化的锂离子电池仍无法满足电动汽车对电池低成本及高能量密度的要求。研发比能量更高、价格更低廉、寿命更长的锂离子电池成为电动汽车产业发展的关键。尖晶石结构的镍锰酸锂（LiNi_0.5Mn_1.5O₄）具有三维扩散通道,有利于锂离子的传输,且结构稳定;其理论放电比容量可达147 mAh ·g^-1。 更重要的是,其电压平台高达4.7 V,具有高的能量密度与功率密度,被认为是未来锂离子电池发展中最具前途与吸引力的正极材料之一。本文介绍了LiNi_0.5Mn_1.5O₄的结构、制备方法、掺杂与包覆改性研究及其应用前景,着重介绍了材料的改性方法并指出LiNi_0.5Mn_1.5O₄目前亟需解决的问题和研究重点。     

钠离子电池合金化负极材料研究及应用进展

钠离子电池凭借钠资源丰富、分布广泛、价格低廉的优势在大规模储能领域具有重要的应用前景,可与锂离子电池形成优势互补.负极材料是电池化学的关键组成,其能量密度、使用寿命等直接影响着电池性能.合金化材料具有理论比容量高、工作电压适宜等优势,被认为是一类有应用潜力的储钠负极.然而,这类材料发生合金化反应时体积膨胀严重,电极材料易粉化脱落,造成电化学稳定性欠佳.目前,主要通过材料微纳结构设计、界面化学调控、碳材料复合、表面包覆、电解液优化等方法来改善其电化学性能.本文综述了合金化负极材料的最新研究进展,探讨了其发展面临的瓶颈以及解决方案,介绍了基于合金化负极的钠离子全电池构筑策略和应用实例,为高性能钠离子电池的发展提供一定参考依据.     

锂离子电池安全性添加剂*

作为锂离子电池的一个重要组成部分,电解质对电池的性能有重要影响。有机电解液功能添加剂是近年来锂离子电池研究中的一个热点。本文介绍了锂离子电池有机电解液阻燃剂和过充电保护剂改善电池安全性的作用机理、特点以及它们的研究应用现状,并对各种添加剂的优缺点作了简要评价。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.