锂离子电池用复合导电剂浆料制备与性能

采用超声波混合、抽滤的方法把多壁碳纳米管(MWCNTs)和乙炔黑混合制备了锂离子电池用复合导电剂浆料,用扫描电子显微镜(SEM)和恒流充放电测试考察了复合导电剂的结构和其作为导电剂对LiCoO2电极放电比容量的影响.SEM的分析结果表明MWCNTs和乙炔黑实现了纳米层次的均匀混合.复合导电剂悬浮液和浆料分别被用作导电剂制成了两种LiCoO2电极,前一种电极为Cathode A,后一种电极为Cathode B,考察了不同MWCNTs含量时,两种电极0.5 C第10次放电比容量的差异.实验结果表明,随着MWCNTs含量的增加,两种电极放电比容量的差值增大,说明低含量MWCNTs的复合导电剂浆料是一种理想的锂离子电池导电剂.     

碳纳米管和乙炔黑对LiCoO2阴极倍率放电性能的影响

分别以多壁碳纳米管(MWCNTs)和乙炔黑(AB)为导电剂,比较了它们对锂离子电池LiCoO2阴极的倍率放电性能的影响.结果表明:MWCNTs的粉体或水性悬浮物作导电剂时,LiCoO2阴极的倍率放电性能差别较大;MWCNTs结晶度高于AB,但团聚比AB严重,粉体在电极片中局部聚集,水性悬浮物在电极片中均匀分散.AB的粉...     

锂离子电池碳包覆锡负极性能研究

应用水热法分解葡萄糖制作锂离子电池碳包覆锡负极. 充放电测试表明,添加5%（by mass）乙炔黑导电剂的该电极初始放电比容量达967 mAh.g^-1,经50周循环其放电比容量仍保持362 mAh.g^-1,远高于锡电极的比容量（50周循环166 mAh.g^-1）. 碳包覆可防止锡粉团聚,降低锡的不可逆容量损失. 而添加乙炔黑可降低碳包覆电极与电解液间的交流阻抗,改善电极内部锂离子及电子的传导通道,从而也提高了该电极的初始放电比容量.     

磷酸铁锂离子电池正极材料掺碳纳米管的研究

应用球磨法于LiFePO4掺杂多壁碳纳米管,制成LiFePO4/MWCNTs复合电极,然后以其组装成锂离子电池.研究不同比例掺杂多壁碳纳米管对复合材料电极电化学性能的影响.XRD、SEM表征及电化学性能测试表明,多壁碳纳米管含量为10%(bymass)的LiFePO4/MWCNTs电极比其它比例的复合电极具有更优良的充放电性能,而且极化小、稳定性强、充放电平台更平稳,导电率更高.在常温0.1C下充放电,首次充、放电比容量分别为139和128.5mAh.g-1,库仑效率达92.4%,循环40次后,电极比容量损失率仅为5.3%.     

乙炔黑涂层对锂硫电池性能的影响

锂硫电池的循环放电稳定性较低,因此我们采用一种低成本的方法改善锂硫电池的性能,即在硫电极表面制备乙炔黑涂层并测试了材料的形貌结构及电化学性能。结果表明,在硫含量（质量分数）70%的硫-乙炔黑复合材料中,硫附着在乙炔黑颗粒表面。接着在硫电极表面制备了厚度15 μm左右的乙炔黑涂层,乙炔黑涂层-硫电极的氧化反应电位低于硫电极,说明乙炔黑涂层有助于硫电极氧化反应的进行。与硫电极相比,乙炔黑涂层-硫电极活性物质的聚集程度低于硫电极,乙炔黑涂层-硫电极具有更高的放电比容量和循环放电稳定性。在150次循环充放电后,乙炔黑涂层-硫电极的放电比容量为894 mAh·g^-1。     

锂离子电池正极材料(LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2)的流变相法合成及其电化学性能

以Li2CO3,Ni(NO3)2,Co2O3和Mn O2为原料,经流变相法合成了锂离子电池正极材料Li Ni1/3Co1/3Mn1/3O2(1),其结构和形貌经XRD和SEM表征。考察了煅烧温度(T)和煅烧时间(t)对1Tt电化学性能的影响。采用乙炔黑作导电剂,制备了1Tt的锂离子正极材料(2Tt)。电化学性能测试结果表明:于800℃煅烧12 h制备的280012电化学性能最好。在充放电条件[2.5 V~4.5 V,0.2 C倍率]下,280012首次放电比容量为180 m Ah·g-1,循环性较好。     

碳纳米管复合导电剂的应用研究

锂离子电池及其相关技术的发展对容量、充放电倍率特性、循环寿命和加工适用性等提出了更高的要求。目前最常用的负极和正极材料与电解液相容性差，充放电过程中结构变化大易剥落导致电池循环稳定性差。鉴于碳纳米管大的长径比、良好的导电性能、优异的力学性能和化学惰性，很适于用作导电剂提升电池性能。本文主要研究了碳纳米管复合材料用作导电剂，并制作成品锂离子电池检测其性能。主要取得了两项实用成果：（1）获得碳纳米管复合导电剂的制备方法，而且采用简单的机械搅拌就可以将复合导电剂进行有效均匀分散，易于进行规模化应用；（2）用碳纳米管复合材料作导电剂，与目前常用的导电剂导电碳黑相比，锂离子电池循环寿命提高一倍以上。     

锂浆料电池基础科学问题研究

锂浆料电池是一种低成本、长寿命、高安全性和易回收的容量型电化学储能技术。与传统锂电池的固定粘接电极不同,锂浆料电池的储锂活性颗粒分布在浆料态的三维导电网络中,具有厚电极和可维护再生的特征。目前制约锂浆料电池应用的关键科学问题主要包括：解析不同浆料电极厚度和配比下电子-离子的混合导电机制,获得低内阻、高能量密度和功率密度的电极浆料;解析活性材料表面及浆料-集流体界面的电化学反应机制与微观结构演化规律,降低界面内阻,稳定界面特性,减少极化和容量损失;解析电池性能衰减及失效机制,优化电池在线维护与回收再生方法等。本文将从锂浆料电池的工作原理与特点、浆料电极的关键材料与混合导电机制、浆料-集流体界面与厚电极设计以及电极浆料的维护再生等方面对锂浆料电池基础关键科学问题的研究进展进行介绍。     

数学模拟方法研究导电剂形貌对锂离子电池高倍率放电性能的影响

制备了正极中只含有一种导电剂(KS-6或Super-P)的锂离子电池,比较了它们的倍率放电性能并对放电过程进行了模拟。以Super-P为正极导电剂的电池15C放电容量为1C容量的84.3%,以KS-6为正极导电剂的电池15C放电容量为1C容量的21.8%,前者的倍率放电性能明显优于后者。数学模拟结果显示,以KS-6为导电剂的正极的Bruggeman系数为3.1,以Super-P为导电剂的正极的Bruggeman系数为2.76,前者明显大于后者,认为这是由于KS-6的片状形貌使其容易相互平行排列造成的。大电流放电时,以KS-6为导电剂的正极中出现了电解质耗竭而导致该区域内电化学反应停止的现象,从而导致电池放电容量急剧降低。     

碳纳米管复合导电剂的应用研究

锂离子电池及其相关技术的发展对容量、充放电倍率特性、循环寿命和加工适用性等提出了更高的要求.目前最常用的负极和正极材料与电解液相容性差,充放电过程中结构变化大易剥落导致电池循环稳定性差.鉴于碳纳米管大的长径比、良好的导电性能、优异的力学性能和化学惰性,很适于用作导电剂提升电池性能.本文主要研究了碳纳米管复合材料用作导电剂,并制作成品锂离子电池检测其性能.主要取得了两项实用成果:(1)获得碳纳米管复合导电剂的制备方法,而且采用简单的机械搅拌就可以将复合导电剂进行有效均匀分散,易于进行规模化应用;(2)用碳纳米管复合材料作导电剂,与目前常用的导电剂导电碳黑相比,锂离子电池循环寿命提高一倍以上.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

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.