基于有机和组合电解液的锂空气电池研究进展

发展纯电动汽车与混合动力汽车是解决能源危机与环境问题的有效途径,这对新能源材料及储能设备提出了更高的要求. 其中以金属锂作为负极、以空气中的氧气作为正极活性物质组成的锂-空气二次电池具有很高的理论比能量,因在纯电动汽车、混合动力汽车方面有很好的应用前景而受到人们的广泛关注. 根据工作环境及介质条件,目前研究最多的锂-空气电池主要包括有机电解液、有机-水组合电解液及全固态电解质三种类型. 由于锂-空气电池的发展历史较短,目前仍处于起步阶段,在电池的正极、负极、电解液（质）及综合性能等方面均存在诸多的困难与挑战. 本文从作者课题组对有机电解液及组合电解液型锂-空气电池方面的研究出发,旨在向读者简单介绍锂-空气电池的发展历史,研究现状及未来努力的方向.     

非水体系锂-空气电池研究进展

锂-空气电池是目前已知具有最高能量密度的二次电池,有望成为未来电动汽车的动力电源。由于其能量密度高、环境友好以及成本较低,成为广大科研工作者研究的热点,在过去二十年间与之有关的研究已经在反应机理、电极结构、催化剂及电解液等各方面都取得了很大进展,但受诸多因素限制,其实用化仍然任重道远。本文总结了近几年来非水体系锂-空气电池在反应机理、正极材料、催化剂、电解液以及锂负极等方面的最新研究进展,并在此基础上展望其未来的发展方向。     

非水系锂空气电池的正极材料和电解液研究进展

锂空气电池的能量密度是传统锂离子电池的5~10倍, 可与汽油相媲美。近几年来, 锂空气电池因此受到了人们的广泛关注。本文概述了锂空气电池正极材料和电解液的最新研究进展。从商业碳、具有特定形态的碳材料、催化剂、导电聚合物几个方面阐述了正极材料;从物质结构的角度, 简要介绍了锂空气电池中常用的酯类、醚类、砜类、胺类和离子液体等电解液。最后指出了目前锂空气电池存在的问题, 并对其进行了展望。     

非水系锂空气电池的正极材料和电解液研究进展

锂空气电池的能量密度是传统锂离子电池的5~10倍,可与汽油相媲美。近几年来,锂空气电池因此受到了人们的广泛关注。本文概述了锂空气电池正极材料和电解液的最新研究进展。从商业碳、具有特定形态的碳材料、催化剂、导电聚合物等几个方面阐述了正极材料;从物质结构的角度,简要介绍了锂空气电池中常用的酯类、醚类、砜类、胺类和离子液体等电解液。最后指出了目前锂空气电池存在的问题,并对其进行了展望。     

锂空气电池研究述评

由于锂空气电池具有很高的理论能量密度因而引起了广泛关注和研究。本文较为全面地论述了各种电解质体系中的锂空气电池的进展,包括:有机体系、水体系、离子液体体系、有机-水双电解质体系和全固态体系的锂空气电池;详细阐述和归纳了它们的工作原理和最新研究现状。对最新提出的锂-空气-超级电容电池的原理和特点进行了较详细的论述。结合氧气在有机电解质中的电化学还原行为指出单一有机电解质锂空气电池存在的问题以及可能的解决办法;同时展示了这类电池中空气电极催化剂的发展现状。结合双电解质锂空气电池、固态电解质锂空气电池、锂-空气-超级电容电池的结构阐述了它们各自的优缺点。本文还展示了一些可望用于单一有机电解质锂空电池、有机-水双电解质体系锂空电池的新型碳材料。最后对锂空气电池的研究发展进行了总结与展望,提出新型电解液、催化剂以及改进锂空气电池构造将会成为今后的发展趋势。     

非水系锂空气电池碳基正极材料

锂空气电池因其极高的理论能量密度和环境友好等优点,有望成为下一代车用动力电源体系。然而,目前锂空气电池尚存在许多的问题和挑战,就正极而言,空气电极活性低的问题已成为制约锂空气电池技术发展最为重要的问题,因此,开发高性能锂空气电池正极催化剂一直以来都是该领域的重要研究课题。碳基催化剂(正极材料)是目前最具吸引力的锂空气电池正极材料之一,近年来得到了广泛的关注和研究。本文总结和介绍了近年来国内外在多孔碳基材料、石墨烯基材料、掺杂碳材料等碳材料作为锂空气电池正极材料方面的进展,包括本课题组在非水系锂空气电池正极材料方面的研究工作,并对碳基正极材料的发展及其在锂空气电池中的应用前景做了展望。     

基于含氧化还原中间体聚合物电解质的长寿命锂空气电池

正锂氧电池又被称为锂空气电池,由于其理论能量密度是普通锂离子电池的5-10倍,因而受到了人们的广泛关注~1。目前研究发现大多数基于无水电解液的锂空气电池的相关报道都是采用干燥的纯氧做为正极活性物质,这严重阻碍了锂空气电池的真正实用化发展~2。而要实现锂空气电池的高能量密度,其所需要的氧气应该来自于空气中,就像商业化的锌空气电池一样。然而空气中的水     

下一代能源存储技术及其关键电极材料

由于能源危机与环境问题,全球能源的消耗正逐渐从传统化石能源转向其它清洁高效能源。高效清洁能源的存储是电动汽车和智能电网的关键技术,对新能源、新材料和新能源汽车国家战略新兴产业的发展具有重要意义。锂离子电池是目前广泛应用的一种能源存储器件。电动汽车和智能电网对能量密度、功率密度、循环寿命和成本等方面的要求越来越高,传统的锂离子电池面临巨大挑战,发展下一代能源存储技术迫在眉睫。高能量密度的锂硫电池和锂空气电池,低成本、高安全性的室温钠离子电池受到了越来越多的关注。本文简要总结了近年来锂硫电池、锂空气电池和钠离子电池及其关键电极材料的研究进展,并对这些新型能源存储技术存在的问题和未来的前景做出了分析和展望。     

非水溶剂锂-空气电池中的氧气电极反应

基于锂-氧气反应的锂-空气电池在所有的锂电池体系中具有最大的理论容量和能量密度,认识锂-空气电池中的氧气电极反应对锂-空气电池的研发具有指导意义.本文以金电极/乙腈电解液为模型体系,介绍了锂-空气电池在放电和充电过程中的氧气电极反应机理.电池放电时,氧气还原成超氧自由基,超氧自由基与锂离子结合生成不稳定的超氧化锂;通过歧化反应,超氧化锂生成放电反应最终产物过氧化锂.电池充电时,过氧化锂通过一步两电子直接氧化生成氧气,不经过超氧化锂中间态.在阐述氧气电极反应机理的同时,还对研究氧气反应的各种电化学方法作了介绍.     

高能量密度锂二次电池电极材料研究进展

锂离子电池是目前广泛应用的高能量密度小型二次电池,但随着其应用领域突飞猛进的发展,迫切需要进一步提高其能量密度.本文介绍了近年来高能量密度锂离子电池正、负极材料及新型高能量密度锂二次电池体系方面的研究进展;结合本实验室的研究工作,着重介绍了高容量正、负极材料的选择、微纳结构设计、表面包覆和合成策略;讨论了锂硫电池、锂空气电池等高比能金属锂二次电池的未来发展方向.     

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%.     

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.     

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.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

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.