锂离子电池用非晶硅薄膜负极材料的研究

采用磁控溅射法在铜箔集流体上沉积得到了厚度约2 μm的非晶硅薄膜。X-射线衍射(XRD)、高分辨率透射电镜(HRTEM)和选区电子衍射(SAED)分析表明，该薄膜为非晶态。扫描电镜(SEM)结果表明，该硅电极在电化学吸、放锂循环后体积膨胀率为300%，但电池依然保持良好的循环寿命。在1.5～0.005 V (vs Li⁺/Li)和0.1 mA·cm^-2条件下，该薄膜电极循环100 次后容量仍能保持在0.47 mAh·cm^-2以上，为初始容量的84%。每周容量衰减率仅为初周的0.16%。HRTEM和SAED结果表明，该薄膜在电化学吸、放锂循环后仍为非晶态，这可能是其具有良好电化学循环寿命的主要原因。     

多孔锂-硅薄膜锂离子电池负极材料的电沉积制备及其电化学性能

采用多步恒电流沉积技术, 在铜箔上电沉积制备了多孔锂-硅薄膜电极(LSF). 用X射线衍射(XRD)和扫描电镜(SEM)测试手段研究了该电极的结构和表面形貌. 作为锂离子电池负极材料, 电化学测试结果表明锂-硅薄膜电极具有较好的循环稳定性, 通过改变电沉积条件, 可有效调控该电极的嵌脱锂容量及首次循环效率. 譬如, 在0.5 mol·L^-1四氯化硅+0.7 mo·L^-1高氯酸锂的碳酸丙烯酯电解液中, 首先以-3.82 mA·cm^-2的恒定电流密度沉积600 s, 再将电流密度恒定为-1.27 mA·cm^-2, 继续电沉积7200 s, 制得锂-硅薄膜电极(LSF^-3), 该电极以12.7 μA·cm^-2的电流密度预循环2次, 其首次循环库仑效率高达97.1%. 预循环2次后, 电流密度增加到25.5 μA·cm^-2, 此时,锂-硅薄膜电极充电质量比容量和面积比容量分别为1410 mAh·g^-1及240.6 μAh·cm^-2; 50次循环后充电比容量为179 μAh·cm^-2 (1049 mAh·g^-1), 容量保持率为74.4%. 锂-硅薄膜电极中的活性锂组分可补偿首次循环时不可逆容量损失, 同时薄膜电极中的多孔结构可缓解电极材料的体积效应并改善其循环性能.     

Co金属有机骨架模板制备NiCo水滑石/泡沫镍复合材料及电容性能

通过两步法先在泡沫镍(nickel foam,NF)上原位生长Co金属有机骨架(Co metal-organic framework,Co-MOF)纳米片阵列,再浸入不同浓度Ni²⁺离子溶液刻蚀Co-MOF纳米片,在NF表面得到NiCo水滑石(NiCo layered double hydroxide,NiCo-LDH)。NiCo-LDH/NF继承了Co-MOF纳米片结构形成一级纳米片阵列,并在一级纳米片表面形成次级纳米片褶皱。在2 mmol Ni(NO₃)₂·6H₂O溶液中刻蚀得到的NiCo-LDH/NF表现出高容量、高倍率性能,在电流密度为5 mA·cm^-2时比电容为7 764.5 mF·cm^-2,电流密度为20 mA·cm^-2时比电容为6 098.2 mF·cm^-2,容量保持率为78.5%,在20 A·g^-1电流密度下经过5 000次长循环后,容量保持率为85.9%。与活性炭组装的混合电容器达到38.9 Wh·kg^-1的最大能量密度和8 000.0 W·kg^-1的最大功率密度。     

脉冲激光沉积NiCo2S4薄膜及其电化学特征

采用脉冲激光沉积法制备了NiCo₂S₄薄膜,利用恒流充放电和循环伏安测试研究了NiCo₂S₄薄膜作为锂离子电池负极材料的电化学性能和充放电机理。采用高分辨电子显微镜和选区电子衍射(TEM&SAED)表征了NiCo₂S₄薄膜首次循环过程中的组成与结构变化。恒流充放电测试结果显示NiCo₂S₄薄膜在3 μA·cm^-2的放电电流下,0~3 V(vs Li⁺/Li)范围内,薄膜的首次放电容量为698 mAh·g^-1,经过200次循环之后的放电容量为365 mAh·g^-1;在循环伏安测试中得到了分步反应的可逆氧化还原峰。TEM和SAED分析结果揭示了NiCo₂S₄薄膜与Li的电化学反应机理：首次放电过程中NiCo₂S₄与Li发生转化反应生成了Li₂S、Ni和Co,充电后生成了CoS和NiS复合薄膜。后续循环为CoS和NiS复合薄膜的可逆分解与形成。研究表明NiCo₂S₄是一种有潜在应用价值的锂离子电池负极材料。     

脉冲激光沉积NiCo2S4薄膜及其电化学特征研究

采用脉冲激光沉积法制备了NiCo₂S₄薄膜,利用恒流充放电和循环伏安测试研究了NiCo₂S₄薄膜作为锂离子电池负极材料的电化学性能和充放电机理。采用高分辨电子显微镜和选区电子衍射(TEM&SAED)表征了NiCo₂S₄薄膜首次循环过程中的组成与结构变化。恒流充放电测试结果显示NiCo₂S₄薄膜在3 μA·cm^-2的放电电流下,0~3 V(vs Li⁺/Li)范围内,薄膜的首次放电容量为698 mAh·g^-1,经过200次循环之后的放电容量为365 mAh·g^-1;在循环伏安测试中得到了分步反应的可逆氧化还原峰。TEM和SAED分析结果揭示了NiCo₂S₄薄膜与Li的电化学反应机理：首次放电过程中NiCo₂S₄与Li发生转化反应生成了Li₂S、Ni和Co,充电后生成了CoS和NiS复合薄膜。后续循环为CoS和NiS复合薄膜的可逆分解与形成。研究表明NiCo₂S₄是一种有潜在应用价值的锂离子电池负极材料。     

基于导电基底的多孔银耳状氧化镍的电化学行为

采用化学沉淀法, 在导电基底上原位生长多孔状氧化镍。采用X射线衍射(XRD)、扫描电镜(SEM)和透射电子显微镜(TEM)对其结构和形貌进行了表征。采用循环伏安、恒流充放电技术和交流阻抗对其电化学性能进行了测试。结果表明, 由于泡沫镍导电基底增强了电极的导电性, 充分利用各组成单元的多孔特性, 在电流密度为0.5 A·g^-1时, 电极的比容量达到3.5 F·cm^-2 (705 F·g^-1), 同时电极具有较好的倍率特性(电容保持率68.1%)和稳定的长循环寿命(3 000次循环后电极比容量增加17.6%)。     

基于导电基底的多孔银耳状氧化镍的电化学行为

采用化学沉淀法,在导电基底上原位生长多孔状氧化镍.采用X射线衍射(XRD)、扫描电镜(SEM)和透射电子显微镜(TEM)对其结构和形貌进行了表征.采用循环伏安、恒流充放电技术和交流阻抗对其电化学性能进行了测试.结果表明,由于泡沫镍导电基底增强了电极的导电性,充分利用各组成单元的多孔特性,在电流密度为0.5 A·g^-1时,电极的比容量达到3.5 F·cm^-2 (705 F·g^-1),同时电极具有较好的倍率特性(电容保持率68.1%)和稳定的长循环寿命(3 000次循环后电极比容量增加17.6%).     

基于有机溶剂原位制备的致密疏水铜金属层在保护锌负极中的应用

通过在 N-甲基吡咯烷酮(NMP)有机溶剂中锌电极与 CuI之间的置换反应,在锌电极上原位构建了一层致密且疏水的铜金属保护层(Cu@Zn)。铜金属保护层能有效地隔离锌电极与电解液的接触,减少锌电极-电解液界面的析氢和腐蚀等副反应。同时,铜金属保护层还具有较好的亲锌性,更小的界面电阻,更低的成核能垒,有利于锌离子均匀沉积,从而有效抑制了锌枝晶的生成。Cu@Zn对称电池实现了超过 1 700 h(1 mA·cm^-2)和 1 330 h(3 mA·cm^-2)的循环寿命。采用商用 MnO₂与之匹配得到的Cu@Zn||MnO₂全电池不仅在1 A·g^-1下具有168.5 mAh·g^-1的可逆比容量,还可稳定循环2 000次以上。     

基于有机溶剂原位制备的致密疏水铜金属层在保护锌负极中的应用

通过在 N-甲基吡咯烷酮(NMP)有机溶剂中锌电极与 CuI之间的置换反应,在锌电极上原位构建了一层致密且疏水的铜金属保护层(Cu@Zn)。铜金属保护层能有效地隔离锌电极与电解液的接触,减少锌电极-电解液界面的析氢和腐蚀等副反应。同时,铜金属保护层还具有较好的亲锌性,更小的界面电阻,更低的成核能垒,有利于锌离子均匀沉积,从而有效抑制了锌枝晶的生成。Cu@Zn对称电池实现了超过 1 700 h(1 mA·cm^-2)和 1 330 h(3 mA·cm^-2)的循环寿命。采用商用 MnO₂与之匹配得到的Cu@Zn||MnO₂全电池不仅在1 A·g^-1下具有168.5 mAh·g^-1的可逆比容量,还可稳定循环2 000次以上     

正极材料LiAl0.08Mn1.92O4单晶颗粒形貌演变及电化学性能

联合元素掺杂和形貌调控策略,采用固相燃烧法和不同焙烧温度处理合成LiAl_0.08Mn_1.92O₄正极材料。实验结果表明,Al掺杂和焙烧温度的变化未改变LiMn₂O₄的相结构,随着温度的升高结晶性增强,颗粒尺寸增大,其中焙烧温度650 ℃是形成截断八面体单晶颗粒形貌的关键点温度,750 ℃是颗粒突然变大的突变温度。650 ℃优化焙烧温度下焙烧的LiAl_0.08Mn_1.92O₄形成了较完整的包含(111)、(110)和(100)晶面的截断八面体单晶颗粒形貌,表现出优良的电化学和动力学性能。在1C下其首次放电比容量为 112.0 mAh·g^-1,循环 500 次后容量保持率为 72.9%,在 5C 和 10C 倍率下,其首次放电比容量可达到 107.1 和 100.4mAh·g^-1,经 2 000次长循环后,容量保持率为 52.2% 和 53.5%。并且具有最小氧化还原峰电位差(ΔE_p2,循环前后分别为 0.109和 0.114 V)、最小电荷转移电阻(R_ct,循环前后分别 106.49和 125.49 Ω)及较大的锂离子扩散系数(D_Li⁺ =1.72×10^-16 cm²·s^-1),表现出较好的电化学可逆性和较快的锂离子扩散速率。Al掺杂和单晶截断八面体颗粒形貌既有效抑制了LiMn₂O₄的Jahn-Teller畸变,又降低了Mn溶解,提高了材料的倍率性能和长循环寿命。     

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.     

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.     

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.     

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.     

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.