锂离子电池的电化学阻抗谱分析研究进展

锂离子电池的电化学阻抗谱( EIS) 是研究电化学系统最有力的实验方法之一,在过去的20多年中,EIS被广泛应用于锂离子电池研究和生产领域,包括研究电极界面反应机理和容量衰减机制,测定相关电极过程动力学参数和电池的健康状态、荷电状态以及电池的内阻。本文分析了锂离子电池中电极极化过程包含的3个基本物理化学过程——电子输运、离子输运和电化学反应过程,探讨了每一基本物理化学过程包含的步骤及其EIS谱特征,详细论述了与电子输运相关的基本物理化学过程——接触阻抗和感抗产生的机制;介绍了多孔电极理论及其在锂离子电池中的应用,阐述了基于多孔电极理论进行阻抗谱数值模拟的建模原理与方法。综述了石墨、硅、二元3d过渡金属氧化物、LiCoO_2、尖晶石LiMn_2O_4、LiFePO_4、尖晶石Li_4Ti_5O_(12)、过渡金属氟化物材料等电极的典型阻抗谱特征和各时间常数的归属问题。最后讨论了EIS现存的问题及未来的发展方向。     

尖晶石LiMn2O4中锂离子嵌入脱出过程的电化学阻抗谱研究

运用电化学阻抗谱(EIS)研究了尖晶石LiMn2O4电极的首次充放电过程. 发现EIS谱高频区域拉长压扁的半圆是由两个半圆相互重叠而成的, 分别归属于与锂离子通过固体电解质相界面膜(SEI膜)的迁移和与尖晶石LiMn2O4材料的电子电导率相关的特征. 通过选取适当的等效电路, 对实验所得的电化学阻抗谱数据进行拟合, 获得尖晶石LiMn2O4电极首次充放电过程中SEI膜电阻、电子电阻和电荷传递电阻等随电极极化电位变化的规律. 根据研究结果提出了嵌锂物理机制模型.     

锂离子电池的电化学阻抗谱分析

电化学阻抗谱(EIS)是研究电极/电解质界面发生的电化学过程的最有力工具之一,广泛应用于研究锂离子在锂离子电池嵌合物电极活性材料中的嵌入和脱出过程。本文从分析嵌合物电极的EIS谱特征入手,探讨了电化学阻抗谱中各时间常数的归属问题,重点讨论了与锂离子嵌脱过程相关的动力学参数,如电荷传递电阻、活性材料的电子电阻、扩散以及锂离子扩散迁移通过固体电解质相界面膜(SEI膜)的电阻等,对电极极化电位和温度的依赖关系。     

电解液组成对尖晶石LiMn_2O_4中锂离子嵌脱过程的影响

运用电化学阻抗谱(EIS)研究了尖晶石LiMn2O4正极在1mol·L-1LiPF6-EC(碳酸乙烯酯)∶DEC(碳酸二乙酯)∶DMC(碳酸二甲酯),1mol·L-1LiPF6-EC∶DEC∶EMC(碳酸甲乙酯)和1mol·L-1LiPF6-EC∶DMC三种不同电解液中,-20-20℃范围内的阻抗谱特征随温度的变化.研究结果表明,温度强烈影响尖晶石LiMn2O4正极的阻抗谱特征,而电解液组成对尖晶石LiMn2O4正极阻抗谱特征的影响较小,但电解液组成对锂离子在尖晶石LiMn2O4正极中嵌入脱出过程相关动力学参数影响较大.测得尖晶石LiMn2O4正极在上述三种电解液中,锂离子迁移通过固体电解质相界面(SEI)膜的离子跳跃能垒平均值分别为7.60、16.40和18.40kJ·mol-1;电子电导率的热激活化能平均值分别为44.77、35.47和68.06kJ·mol-1;嵌入反应活化能平均值分别为52.19、46.19和69.86kJ·mol-1.     

对电极性能对染料敏化太阳电池动力学过程的影响

借助电化学阻抗谱(EIS)和强度调制光电流谱(IMPS)/强度调制光电压谱(IMVS)技术, 采用不同纳米TiO₂多孔薄膜对电极研究了染料敏化太阳电池(DSC)内部2个主要电荷输运过程的内在联系, 并探讨了载Pt材料对DSC界面动力学过程及电池宏观性能的影响机理. 借助等效电路模型分析了基于不同对电极材料电池的填充因子变化原因. 结果表明, 对电极材料的电极电荷交换过程制约光阳极膜内电子传输, 进而影响电池光伏性能; 同时对电极催化反应速率主要与催化剂活性、 载Pt材料电导率和催化反应面积有关.     

嵌入化合物电极的电化学阻抗谱: 模型与理论模拟

建立了单个嵌入化合物颗粒、混合颗粒、厚度均匀多孔电极层以及非均匀、多层多孔电极层的理论模型,模拟得了了上述模型的相对应电化学阻抗谱（EIS）特征.结果表明,单个颗粒和混合颗粒表现出相似的阻抗谱特征,均由高频区域内与锂离子通过固体电解质相界面（SEI）膜过程相关的R_SEI‖C_SRI半圆,与电荷传递过程相关的R_ct‖C_dl半圆以及锂离子在固体颗粒内部的扩散相关的斜线三部分组成.对于非均匀、多层多孔嵌入电极而言,一个个新奇的现象就是在阻抗谱中会出现三个半圆,影响第三个半圆现现并形成的因素主要为电极中的颗粒尺寸分布以及电极层的厚度分布,也就是说电极片中出现不同尺寸分布的颗粒以及形成薄厚两种电极层的时候,容易导致阻抗谱中出现第三个半圆.     

温度对尖晶石LiMn2O4中锂离子嵌脱过程的影响

运用电化学阻抗谱研究了商品化尖晶石LiMn₂O₄电极在1 mol/L LiPF₆-EC(碳酸乙烯酯):DEC(碳酸二乙酯)电解液中―10～30 ℃范围内的阻抗谱特征、固体电解质相界面(SEI)膜阻抗、电子电阻和电荷传递电阻等随温度的变化. 研究结果表明, 尖晶石LiMn₂O₄电极的阻抗谱特征与温度有关, 随温度的升高, 与活性材料电子电导率相关的半圆和与SEI膜相关的半圆会发生重叠而成为一个半圆. 通过选取适当的等效电路拟合了实验所得的电化学阻抗谱数据, 测得尖晶石LiMn₂O₄电极在1 mol/L LiPF₆-EC:DEC 电解液中, 锂离子迁移通过SEI膜的离子跳跃能垒平均值为15.49 kJ/mol; 电子电导率的热激活化能平均值为24.21 kJ/mol; 嵌入反应活化能平均值为53.07 kJ/mol.     

LiBOB对Li_(1.15)Ni_(0.68)Mn_(1.32)O_4电极电化学行为的影响

采用恒电流充放电技术研究了锂离子电池电解液添加剂双草酸硼酸锂(Li BOB)对Li1.15Ni0.68Mn1.32O4电极电化学性能的影响,用X射线衍射(XRD)、衰减全反射傅里叶变换红外光谱(FTIR-ATR)、电感耦合等离子体发射光谱(ICP)、扫描电子显微镜(SEM)和电化学阻抗谱(EIS)分析了Li BOB对Li1.15Ni0.68Mn1.32O4电极性能的影响.结果显示,Li BOB作为电解液添加剂能显著改善Li1.15Ni0.68Mn1.32O4电极的循环性能,原因是Li BOB在充放电过程中会在Li1.15Ni0.68Mn1.32O4电极表面发生分解,分解产物在电极表面沉积形成固体电解质界面(SEI)膜,SEI膜能够有效抑制Li1.15Ni0.68Mn1.32O4电极材料中Mn的溶解,确保其晶体结构的稳定性,从而提高Li1.15Ni0.68Mn1.32O4电极的循环性能.     

高倍率尖晶石型Li4Ti5O12/TiN锂离子电池负极材料的合成及其电化学性能

以乙酰丙酮(ACAC)螯合剂、聚乙二醇(PEG)为分散剂,采用溶胶-凝胶法合成了尖晶石型Li4Ti5O12/TiN材料.考察了TiN膜对尖晶石型Li4Ti5O12锂离子电池负极材料电化学性能的影响.利用X射线光电子能谱(XPS)对Li4Ti5O12表面的TiN膜进行了分析.X射线衍射(XRD)和扫描电子显微镜(SEM)分析表明,Li4Ti5O12/TiN材料为结晶良好的亚微米纯相尖晶石型钛酸锂.电化学性能测试表明,该材料的首次放电比容量为173.0mAh·g-1,并且具有良好的循环性能,以0.2C、1C、2C、5C倍率放电进行测试,10次循环后比容量分别为170.6、147.6、135.6、111.0 mAh·g-1,较之表面无TiN膜的钛酸锂材料表现出更好的倍率特性.循环伏安曲线(CV),交流阻抗图谱(EIS)进一步论证了TiN膜改善了尖晶石型Li4Ti5O12锂离子电池负极材料的电化学性能.     

电化学阻抗谱弛豫时间分布基础

电化学阻抗谱（EIS）是一种高效的原位/非原位电化学表征技术,已在电化学能源领域得到广泛应用,如用于锂离子电池、超级电容器、燃料电池等材料及器件性能的诊断和优化. 弛豫时间分布（DRT）是一种不依赖于研究对象先验知识的EIS解析技术,可用于分离和解析EIS中高度重叠的物理化学过程. 为了促进DRT解析技术的应用和推广,本文详细阐述了如下问题： 1） DRT解析原理、实现算法及重要扩展; 2） 典型电路基元的DRT解析分析; 3） DRT的具体实现及在电化学能源中的典型应用举例; 4）DRT解析技术研究进展、存在问题及发展趋势.     

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.