锂离子电池镍掺杂尖晶石LiMn2O4正极材料的电子结构

采用密度泛甬平面波赝势方法对LiMn2O4和LiNi0.5Mn1.5O4的几何结构进行了优化,并计算了相应的电子结构.计算的结果表明:在Li 脱嵌前后,LiMn2O4和LiNi0.5Mn1.5O4均为导体,且锂元素主要以离子形式存在于两种材料中,O2p轨道与Mn(Ni)的3d轨道形成了较强的共价键.Li 嵌入导致Mn(Ni)3d轨道的态密度峰发生移动.Ni的掺杂导致Mn(Ni)和O2p轨道的成键作用得以加强,电子在Mn(Ni)3d轨道的填充发生变化,从而提高了电池的充放电电压.     

Li(Ni0.5Co0.2Mn0.3)1-2xTixNbxO2的合成及电化学性能

采用共沉淀-高温固相烧结法在900oC空气中煅烧,合成了层状复合掺杂型正极材料Li(Ni0.5Co0.2Mn0.3)1-2xTixNbxO2(x=0,0.002,0.005,0.01,0.02).通过扫描电镜(SEM)、X-射线衍射(XRD)和电化学测试等观察与研究掺杂元素对Li(Ni0.5Co0.2Mn0.3)O2的形貌结构和电化学性能的影响.结果表明,适量Ti、Nb掺入Li(Ni0.5Co0.2Mn0.3)O2,降低了材料的阳离子混排程度,且晶胞参数随着掺杂量的增加而增加.与未掺杂材料相比,Ti-Nb复合掺杂的样品具有更好的电性能和高温性能.当x=0.005时,材料的综合性能最好,方型铝壳电池3.0~4.2 V电位区间首次1C放电比容165.9 mAh.g-1,常温循环100周期容量保持率96.5%,55oC循环300周期容量保持率为92.6%,80oC/6 h高温存储后冷却2 h电池厚度膨胀率9.8%.     

Li4Mn5O12包覆对三元正极材料结构和性能的影响

LiNi(1/3)Mn(1/3)Co(1/3)O2具有很高的理论比容量,但是三元正极材料在高电压下长循环时,其表面结构发生较大的衰退,导致电池的循环性能和倍率性能变差。本文采用耐高电压且结构稳定的富锂尖晶石Li4Mn5O(12)包覆LiNi(1/3)Mn(1/3)Co(1/3)O2可以有效改善材料的电化学性能。通过XRD、SEM、XPS和TEM等手段对包覆后的材料进行分析,证实了在LiNi(1/3)Mn(1/3)Co(1/3)O2的表面形成了10nm厚的均匀Li4Mn5O(12)的包覆层;在循环100圈后,包覆后的LiNi(1/3)Mn(1/3)Co(1/3)O2仍具有179.5m Ah/g的放电比容量和88.6%容量保持率,明显高于未包覆的LiNi(1/3)Mn(1/3)Co(1/3)O2的78.3%容量保持率。因此,利用富锂尖晶石Li4Mn5O(12)包覆LiNi(1/3)Mn(1/3)Co(1/3)O2为实现更高能量密度的锂离子电池提供了新的途径。     

LiNi0.5-xAl2xMn1.5-xO4的制备、结构及电化学特征

采用喷雾干燥法合成了LiNi0.5-xAl2xMn1.5-xO4(0≤2x≤0.15)正极材料,研究Al掺杂对LiNi0.5Mn1.5O4材料结构与电化学性能的影响.通过X射线衍射(XRD)、扫描电子显微镜(SEM)、电感耦合等离子体-原子发射光谱(ICP-AES)、傅里叶红外光谱(FTIR)、循环伏安(CV)和充放电测试等手段对其结构及电化学性能进行表征.结果表明,Al取代Ni和Mn使材料的晶体结构发生了转变,空间群由P4332转变为Fd3m,同时增大了锂离子的扩散速率,提高了材料的倍率性能.在室温下,LiNi0.4 5Al0.1Mn1.45O4表现了最好的倍率性能,当放电电流为0.5 C时,放电容量为126 mA.h/g,当放电电流增加到5 C时,放电容量为109 mA.h/g,保持率达到了87%.此外,Al取代Ni和Mn有效降低了材料在高温下的Mn溶解量,从而有效改善了材料在高温大倍率下的循环性能.LiNi0.45Al0.1Mn1.45O4材料在50℃,倍率为3 C时,放电容量为121.7mA.h/g,循环50次后,仍可保留初始容量的94%.     

锂离子电池正极材料LiNi0.5Co0.2Mn0.3O2的合成及其高温容量衰减研究

采用共沉淀-高温固相烧结法合成了富镍型三元复合正极材料LiNi0.5Co0.2Mn0.3O2.恒流充放电测试表明,材料在3.0～4.4 V下0.2C放电容量达到179.2 mAh.g-1,但在55℃下经历100次充放电循环后发生急剧的容量衰减.电化学交流阻抗谱、X射线光电子能谱和原子发射光谱等实验表明,在高温高电压下,电解液与LiNi0.5Co0.2Mn0.3O2电极材料之间的副反应加剧,导致过渡金属原子溶出,该材料局域结构被破坏.同时,电极材料表面还沉积了高阻抗的LiF/MFx层,使得在电极的充放电过程中电荷转移阻抗和Li+扩散阻抗不断增加,以致电池容量急剧衰减.     

层状LiNi0.5Mn0.5O2正极材料的优化合成及电化学性能

采用沉淀法首先得到了Ni0.5Mn0.5(OH)2沉淀物,以其为原料与LiOH反应制备了LiNi0.5Mn0.5O2正极材料。采用XRD、SEM、充放电测试等研究了其结构与电化学性能,同时研究了Li过量时对材料电化学性能和结构的影响。SEM分析表明,Ni0.5Mn0.5(OH)2与LiNi0.5Mn0.5O2产物均为微小晶粒团聚成的颗粒。LiNi0.5Mn0.5O2材料在2.5~4.4V电位区间内,首次放电容量为130mAh/g,0.2C倍率下,50次循环后的容量保持率为87.8%。锂过量有助于形成良好的层状结构材料,并能显著提高材料的比容量和循环性能,Li1.1Ni0.5Mn0.5O2的首次放电容量为149mAh/g,0.2C倍率下,50次循环后的容量保持率为92.6%。     

Ni-Mn共掺杂高电压钴酸锂锂离子电池正极材料

以金属硫酸盐为原料,Na OH和NH3·H2O为沉淀剂,用共沉淀法合成了Co0.9Ni0.05Mn0.05(OH)前驱体,再进行配锂并通过高温固相法合成了Ni-Mn共掺杂高电压钴酸锂锂离子电池正极材料Li(Co0.9Ni0.05Mn0.05)O2。用X射线衍射(XRD)、扫描电镜(SEM)、循环伏安(C-V)、交流阻抗(EIS)和充放电测试研究样品的晶体结构、形貌和电化学性能。结果表明Ni-Mn共掺杂正极材料Li(Co0.9Ni0.05Mn0.05)O2有优秀的电化学性能:在3.0~4.4 V和3.0~4.5 V区间,0.5C倍率下首次放电比容量分别为162.5 m Ah·g-1和185 m Ah·g-1,循环100次后容量保持率分别为94.4%和93.7%。     

锌掺杂提高LiNi1/3Co1/3Mn1/3O2正极材料的电化学稳定性

通过共沉淀法与固相法相结合制备了掺锌的高稳定性Li(Ni1/3Co1/3Mn1/3)1-xZnxO2(x=0,0.02,0.05)正极材料.循环伏安(CV)曲线表明Zn掺杂使氧化峰与还原峰的电势差减小到0.09 V,电化学阻抗谱(EIS)曲线表明Zn掺杂使电极的阻抗从266Ω减小到102Ω. Li+嵌入扩散系数从1.20×10-11 cm2·s-1增大到2.54×10-11 cm2· s-1. Li(Ni1/3Co1/3Mn1/3)0.98Zn0.02O2正极材料以0.3C充放电在较高的截止电压(4.6 V)下比其他两种材料的电化学循环性能更稳定,其第二周的放电比容量为176.2 mAh·g-1,室温下循环100周后容量几乎没衰减;高温(55°C)下充放电循环100周,其放电比容量平均每周仅衰减0.20%,远小于其他两种正极材料(LiNi1/3Co1/3Mn1/3O2平均每周衰减0.54%;Li(Ni1/3Co1/3Mn1/3)0.95Zn0.05O2平均每周衰减0.38%). Li(Ni1/3Co1/3Mn1/3)0.98Zn0.02O2正极材料以3C充放电时其放电比容量可达142 mAh·g-1,高于其他两种正极材料.电化学稳定性的提高归因于Zn掺杂后减小了电极的极化和阻抗,增大了锂离子扩散系数     

锂离子电池正极材料LixNi1／3Mn1／3及电化学性能研究CO1／3O2的合成及电化学性能研究

应用以氢氧化物共沉淀为前驱体的高温固相烧结法合成LiNi1/3Mn1/3Co1/3O2正极材料，研究了沉淀温度及烧结过程锂盐投入量对该材料的结构和电化学性能的影响．结果表明，以室温（-20℃）下合成的氢氧化物为前驱体制备的LiNi1/3Mn1/3Co1/3O2具有较好的电化学性能．高温固相烧结会导致部分LiOH损失，因而在合成过程中需加入过量的氢氧化锂，实验表明Li1.08Ni1/3Mn1/3Co1/3O2材料的电化学性能最优．     

LiNi0.49Mn1.49Y0.02O4的合成及其电化学性能研究

应用柠檬酸辅助溶胶-凝胶法.合成了Y3+掺杂的尖晶石LiNi0.49Mn1.49Y0.02O4材料.XRD、循环伏安、恒流充放电和交流阻抗测试结果表明,Y3+的掺杂能提高LiNi0.5Mn1.5O4的倍率和循环性能.在电压区间3.5～4.9V,1C倍率下,其初始放电比容量为114.9 mAh.g-1,100次循环后放电比容量仍可达113.0 mAh.g-1,容量保持率为98.3%.掺杂Y3+能减小材料界面阻抗.     

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.     

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.     

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.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

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.