锂硫二次电池正极研究进展

综述了锂硫电池中硫基正极材料的制备方法、结构特征以及电化学性能. 简述了单质硫正极材料, 重点探讨了有机硫化物、碳/硫复合材料、聚合物/硫复合材料的结构设计、材料制备、反应机理以及充放电特性, 并对其中存在的问题进行了分析, 还介绍了硫化锂正极材料. 最后对硫基正极的进一步发展, 以及锂硫电池的商业化应用进行了展望.     

本征导电聚合物开发的最新进展

本征导电聚合物是一种新型功能高分子材料 ,因具有独特的化学、电化学和光学性能 ,在能源、电磁屏蔽和电致发光等领域有着广阔的应用前景 .本文扼要综述本征导电聚合物的开发现状和目前存在的问题 ,并对其今后的发展趋势进行了展望     

过渡金属及其化合物应用于锂硫电池的研究进展

锂硫电池因具有高理论比容量和性价比,被认为是具有发展潜力的新型二次电池。 但是,作为活性物质的单质硫和反应产物是电子绝缘体,充放电过程的中间产物多硫化锂在电解液中易于溶解和迁移引起“穿梭效应”和一系列的副反应,造成活性物质利用率低,电池的电化学稳定性变差。 本文综述了近年来过渡金属纳米材料应用于锂硫电池的研究进展,重点介绍了材料的合成方法以及其抑制多硫化锂溶解并促进其转化的反应机理,并对锂硫电池正极载体材料的发展方向进行了展望。     

导电含硫材料/聚苯胺复合物作为镁二次电池的正极材料

使用通过简单加热聚丙烯腈(PAN)和硫单质而得到的导电含硫材料(conductive sulfur-containing material, CSM)及其与聚苯胺(PAn)的复合物作为镁二次电池的正极材料. X射线衍射(XRD)和傅立叶红外光谱(FT-IR)测试表明, 导电含硫材料的结构由类似石墨的微晶相及无定形相所组成, 材料骨架为含有S—S键的脱水嘧啶型基质. 该导电含硫材料与聚苯胺复合并掺杂Cu(II)后, 其放电比容量和电化学可逆性大大提高, 放电比容量可达117.3 mAh·g-1, 22次循环后容量保持大约78％(相对于第二次放电容量). 聚苯胺不仅起到电化学催化剂的作用, 同时也是电极活性物质, 并且在分子水平上改善了活性材料的导电性能. 该复合物研究结果为镁二次电池正极材料结构设计的开发提供了新的思路.     

电化学沉积制备聚苯胺纳米阵列及性能研究的综合化学实验

为将导电聚合物超级电容器电极材料引入到本科教学实验中，设计了综合探究性高分子材料制备实验——电化学沉积制备聚苯胺纳米阵列及性能研究。首先采用电化学法构筑导电高分子聚苯胺纳米阵列；然后运用紫外光谱、拉曼光谱、扫描电子显微镜和电化学工作站等，分别对聚苯胺阵列的化学结构、形貌和电化学性能进行表征。从材料的合成角度来看，该实验可以使学生了解和掌握电化学合成导电聚合物的机理与方法；从材料的结构和性能表征方面来看，可以使学生学习和操作科研类的大型仪器设备，对学生的动手操作能力具有实质性的锻炼。此外，该综合性实验很好地将化学制备与材料的应用相结合，方法简单，耗时短，重复性好，可作为高分子类专业本科生综合探究性实验开设。     

硫化聚并苯导电材料结构的理论化学研究

采用量子化学从头算方法和AM1半经验方法,探讨了聚并苯导电聚合物硫掺杂前后结构和电子性质的变化,提出了硫化聚并苯导电材料的“双层夹心”分子结构模型.研究表明,硫化后的聚并苯材料,S原子位于两层聚并苯分子平面中间,并与两个聚并苯分子平面中相应的两个C原子相键合,形成C—S—C“桥式”共价单键;并解释了硫化聚并苯导电材料比本征态聚并苯材料作电极时可逆容量增大的原因.     

生物可降解电活性苯胺聚合物

导电聚合物通过其独特的电活性或导电性,可智能地传递或控制细胞电化学信号,从而定向诱导组织器官的再生修复,已成为神经和组织工程领域研究的热点.本文主要介绍了我们实验室生物可降解电活性苯胺聚合物的相关工作,介绍了以苯胺齐聚物与可降解高分子接枝或嵌段制备具有电活性、可生物降解的新型导电聚合物及其在细胞培养和组织工程方面的研究.介绍了静电纺丝制备电活性纳米纤维的概况.苯胺齐聚物与可降解聚合物的接枝和嵌段可同时赋予其电活性、生物相容性和生物可降解性.可生物降解的电活性聚合物是未来生物组织工程领域的发展趋势之一,具有广阔的应用前景.     

复合导电添加剂对全固态锂硫电池性能影响的研究

使用硫化物固体电解质的全固态锂硫电池由于多硫化物不溶于硫化物固体电解质及硫化物电解质不可燃的特性,得以完全避免穿梭效应并显著提高了电池的安全性能而被认为是极具潜力的下一代储能电池。如何建立并平衡复合正极中离子/电子导电网络且维持复合正极中较高活性物质含量对于全固态锂硫电池至关重要。本文以单质硫为活性物质研究了复合导电添加剂对全固态锂硫电池性能的影响,发现以乙炔黑（AB）为导电碳材料明显优于Super P和Ketjen Black;优化复合正极的组成,发现硫：乙炔黑：固体电解质的质量比为40:20:40时,全固态锂硫电池在室温和60℃下均具有良好的电化学性能。     

聚苯胺的图形化沉积

自1976年发现第一个有机聚合物聚乙炔掺杂后具有类似金属的导电性以来，先后发现了聚吡咯、聚噻吩和聚苯胺(PAn)等导电聚合物，其中聚苯胺以其合成方法简单、稳定性好、较高的电导率及良好的电化学性能等被预言为是最有应用前景的导电高分子材料之一。近年来，随着导电聚合物研究的广泛开展和不断深入，     

从导电聚吡咯到共轭聚合物光伏材料——我在中科院化学所30年共轭高分子研究历程

本文简要回顾了本人在中科院化学所30年的研究历程,重点介绍了在共轭高分子(包括导电聚吡咯电化学、聚合物发光电化学池(LEC)和共轭聚合物给体光伏材料)方面的研究成果。在导电聚吡咯电化学方面,对导电聚吡咯的电化学制备和电化学性质进行了深入研究,阐明了各种电化学聚合条件对制备的导电聚吡咯电导和力学强度等的影响,发现电解液溶剂给电子性(Donor number)对吡咯电化学聚合制备的导电聚吡咯电导的影响:溶剂Donor number越小制备的导电聚吡咯电导越高;使用非离子表面活性剂添加剂在水溶液中制备出表面非常光滑和高力学强度的导电聚吡咯薄膜;对于吡咯电化学聚合提出了电解液阴离子参与的阳离子自由基聚合机理,并推到出吡咯电化学聚合反应的动力学方程;发现在NaNO3水溶液中电化学聚合制备的导电聚吡咯除存在主链氧化、对阴离子掺杂结构外,还存在质子酸掺杂结构;阐明了导电聚吡咯在水溶液中电化学还原和再氧化的机理及其电化学过程的可逆性和稳定性,以及导电聚吡咯在有机电解液中特殊的第一次还原和再氧化的机理。在LEC方面,通过交流阻抗法确认了LEC的电化学掺杂机理和p-i-n结构,合成了多种适用于LEC的主链带离子导电单元的兼具离子导电性的发光嵌段共聚物,避免了LEC活性层中存在的发光聚合物和离子导电聚合物的分相问题;使用离子液体作为电解质制备了室温准冷冻p-i-n结LEC,改善了LEC的电致发光性能。在共轭聚合物给体光伏材料方面,我们提出了通过共轭侧链来拓宽聚合物吸收和提高空穴迁移率的分子设计思想,设计和合成了一系列带共轭侧链的二维共轭聚噻吩衍生物以及基于二噻吩取代苯并二噻吩的窄带隙高效二维共轭聚合物给体光伏材料。我们使用烷硫基取代进一步降低了这类二维共轭聚合物的HOMO能级从而进一步提高了其光伏性能。最后介绍了本组二维共轭聚合物给体光伏材料在非富勒烯聚合物太阳能电池方面的最新研究进展。     

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%.     

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.     

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.     

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.     

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.