四氢呋喃预处理对吡咯修饰金属锂电极性能的影响

采用四氢呋喃对金属锂电极进行预处理, 以减少电极表面杂质和吡咯化锂钝化膜形成过程中产生的气体, 从而提高电极表面钝化膜的致密性和电极的充放电循环性能. 实验结果表明: 采用四氢呋喃对金属锂电极预处理后, 电极表面杂质显著减少, 能在电极表面形成一层更加均匀而致密的吡咯化锂钝化膜. 该钝化膜使得电极界面阻抗降低, 界面稳定, 金属锂溶解沉积过程的可逆性增加. 金属锂呈“海绵”状均匀沉积, 有效抑制或减少了锂枝晶或“死锂”的产生, 提高了金属锂的循环效率.     

富锂层状正极材料Li_2MnO_3的表面改性及其电化学性能研究（英文）

Li_2MnO_3正极材料具有较高的理论容量(459 m Ah·g~(-1)),不仅安全无毒还能够大大降低电池的制造成本,从而受到越来越多的关注.然而,较低的首圈库仑效率和较差的循环性能妨碍了其在锂电池中的实际应用.在此,作者研究了MgF_2涂层对Li_2MnO_3正极材料的电化学性能.结果表明,MgF_2涂层诱导部分层状Li_2MnO_3向尖晶石相转化,从而降低了首圈不可逆容量,提高库仑效率.重量比为0.5%、1.0%和2.0%的MgF_2涂层电极的初始库仑效率分别为70.1%、77.5%和84.9%,而原始电极仅为57.7%.充放电曲线表明,1.0wt.%MgF_2涂层改性的Li_2MnO_3具有最高的充放电容量和最佳的循环稳定性. 40个循环后1.0wt.%MgF_2涂层样品的容量保持率为81%,远高于原始样品的容量保持率(53.6%).电化学阻抗谱结果表明MgF_2涂层减少了不利成分的快速沉积,并改善了电极的循环稳定性.     

Li-CO_2电池机理、催化剂和性能研究进展（英文）

对化石能源依赖所造成的能源安全和环境污染等问题限制了人类社会的可持续发展.Li-CO_2电池能量密度高、原材料成本低廉且结构简单,因而被认为是开发和利用可再生清洁能源的有力技术,在住宅能量存储、电动汽车驱动和智能电网等领域具备良好的应用前景.此外,CO_2等温室气体的大量排放是全球变暖的主要原因,Li-CO_2电池放电时可将空气中的CO_2还原固定,生成的碳材料可用作燃料和化工原料,在资源利用化上提供了新途径.Li-CO_2电池是建立在锂-空气电池的基础上.相比大气中的其他成分,H2O与CO_2对该电池的影响很大.防水膜可以减少水的影响;而在放电过程中,CO_2的存在会生成Li_2CO_3,Li_2CO_3是可以分解的.由此可见,CO_2在可充放的锂电池中作为正极活性成分储能,从而被利用起来.目前Li-CO_2电池至少面临三个问题:(1)电池充放电的机理尚不完全清楚,并且以O2和CO_2混合气为活性气体的机理与以纯CO_2为活性气体的机理是有差别的,Li_2CO_3的生成与分解的机制仍在探索中;(2)电解液的稳定性;(3)寻找高效的正极催化剂材料.本文介绍了Li-CO_2电池的发展历程,讨论了Li-CO_2电池的充放电机理、电解液的影响以及正极催化材料的选取等.综述了活性气体为纯CO_2和CO_2-O2混合气时机理的差别,以及CO_2/O2混合比对电池性能的影响.选取电解液应考虑其粘度和介电性.高效能的正极催化材料大多具有高导电性、多孔结构和大的比表面积等特点.而温度也是影响Li-CO_2电池性能的因素之一.虽然Li-CO_2电池的概念相对较新,但可实现CO_2在能源储存与转化领域中的应用,并为Li-O2电池向锂空气电池飞跃提供了重要参考.本文以如何提高正极材料的催化性能和Li_2CO_3的生成和分解机理为重点,总结了正极材料所具有的导电性、比表面积、特殊结构等特点,以及相关机理.     

基于层析图像的磷酸铁锂电化学性能分析

为深入研究针磷酸铁锂电化学性能,减少实验过程中的破坏性,提出基于层析图像的磷酸铁锂电化学性能分析方法。通过前期准备的实验原料、试剂、仪器,制备了磷酸铁锂电极与其他材料电极的相同型号的电池,实验中对这两种类型的电池进行一定条件下的充放电测试,测试结果表明,磷酸铁锂电池的可用容量最大值为4.3Ah,存储过程中容量消耗慢;分析两种电池充放电后的纵向层析图得出结论,磷酸铁锂材料在电池电极中能够使电池中密度物质分布均匀,保证电池的容量不发生衰减。且在实验过程中,电化学性能分析所需时间短,不具有破坏性,为后续的研究提供一定的理论参考。     

锂离子电池纳米电极材料研究

采用ＸＲＤ，ＴＥＭ方法对纳米相电极材料的结构，形貌进行表征，并用循环伏安法，恒流充放电法对电极材料的嵌锂电化学行为进行研究。结果表明，由于纳米材料的微结构特性使萁 具有优越的嵌锂特性；１）锂离子嵌入电极材料内部的深度小，过程短，具 较大的比表面，有利于采用较大的电流对该电池进行充放电；２）具有较大的嵌锂空间位置，有利于增加电极的锂嵌容量。     

稻壳基活性炭对锰酸锂电池倍率性能的影响

稻壳基活性炭(RH-AC)具有天然的多级孔道结构,是由稻壳碳化和活化两步得到的。 用RH-AC和锰酸锂(LMO)混合制备复合电极,以锂片为对电极,组装半电池进行恒流充放电测试。 实验发现:含有质量分数为5%的RH-AC与90.5%的LMO的复合电极(RH-AC5)在5C电流密度循环100圈后比容量为89.3 mA·h/g,容量保持率高于89%,远优于纯锰酸锂电极。 采用循环伏安法计算出的锂离子扩散系数,及利用交流阻抗测试拟合后得到的结果进一步验证了该结论。     

金属锂二次电池锂负极改性

本文综述了金属锂二次电池中提高锂负极性能的研究进展。分别介绍了以下改性方法:对金属锂表面进行预处理,使其表面预先形成性能良好的固体电解质界面膜,或直接在其表面制备保护膜;在电解液中加入添加剂对锂电极进行表面改性;采用新型有机溶剂、离子液体、聚合物电解质、玻璃态固体电解质、塑晶固体电解质等电解质体系提高界面相容性;改进金属锂电极的制备工艺,如制备金属锂粉末多孔电极和电沉积锂电极、制备全固态薄膜锂电池以及利用物理方法处理锂电极。并在此基础上对今后的发展趋势进行了展望。     

Li3Fe2(PO4)3正极材料的制备及电化学性能研究

本文以本文通过高温固相反应合成了Nasicon型的Li_3Fe_2(PO_4)_3电极材料。XRD结果显示850℃烧结得到的Li_3Fe_2(PO_4)_3结晶性最好。为了优化Li_3Fe_2(PO_4)_3电极的性能,使用行星球磨将制备得到的Li_3Fe_2(PO_4)_3与乙炔炭黑混合均匀,得到了Li_3Fe_2(PO_4)_3/C复合正极材料。扫描电镜照片显示,球磨后活性材料的颗粒尺寸明显减小,而且更加均匀。对于Fe~(3 )/Fe~(2 )的氧化还原电对,恒电流充放电测试和伏安循环法揭示Li_3Fe_2(PO_4)_3/C复合正极材料再放电过程中在2.8和2.7V具有两个电压平台。样品球磨后,与800℃和900℃烧结得到的Li_3Fe_2(PO_4)_3相比,850℃烧结得到的材料具有更好的可逆性和更高的容量保持性,而且它的比容量在初始循环以C/20的倍率放电可以达到92 mAhg~(-1)以及在结束时的循环以C/10的倍率放电还具有62 mAhg~(-1)。     

锂离子电池富锂正极材料Li[NixLi1/3-2x/3Mn2/3-x/3]O2(x=1/5, 1/4, 1/3)的合成及电化学性能

通过共沉淀法制备了M(OH)2(M=Mn, Ni)前驱体, 并与LiOH混合, 合成了锂离子电池富锂正极材料Li[NixLi1/3-2x/3Mn2/3-x/3]O2, 采用XRD、SEM和充放电实验对其进行表征. 研究结果表明, Li, Ni, Mn原子在M层中呈有序分布, 形成超结构; 富锂正极材料由亚微米的一次粒子团聚组成1~3 μm颗粒; 在2.0~4.8 V电位范围内, 充放电电流密度为10 mA/g时, 富锂正极材料表现出很高的可逆比容量, 达到200~240 mA·h/g, 同时具有良好的循环可逆性能.     

嵌锂石墨充电机制的abinitio和DFT理论研究

用ab initio/HFt DFT/B3LYP方法探究了在锂离子二次电池中锂离子在石墨负 电极材料里可逆脱过程。理论计算结果表明，嵌锂石墨LIG充放电机制是锂在石黑 碳层间可闹乱子嵌脱，同时伴随着锂与碳层间发生电荷连续转移和碳层堆积方式改 变的协同过程；计算结果也明确证实，嵌锂石墨嵌入脱出锂离子的过程就是锂离子 二次电池储存与释放能量的过程，提出的嵌锂石墨充放电机制较好地丰富了固体电 解质相界面SEI机理和单电子还原机理。     

Computer simulation of negative electrode operation in lithium—ion battery: Galvanostatic discharg active intercalating agent grains,role of diffusion limitations

Computer simulation of the structure and methods of operation (galvanostatic discharge) of the negative electrode of a lithium-ion battery is performed. Two possible models of the active anode layer were compared. 1. The model of porous active layer (mixture of active substance grains with grains of electrolyte). Here, the electrochemical process occurs within a porous active layer. 2. The film model (constant-thickness layer) of pure active substance (intercalating agent) grains without admixture of grains of electrolyte. In this case, the electrochemical reaction occurs only on the planar active electrode layer/interelectrode space interface. In both cases, the optimum working parameters of anode active layers were calculated: porous active layer thickness (in the film model, this was the calculation parameter), duration of full anode discharge, specific electric capacitance and finite difference between the intercalating agent/electrolyte potentials at the active anode layer/interelectrode space interface. It is found that each of these two models has its advantages and faults. Specific electric capacitance C cannot exceed the values of the order of magnitude of 10 C/cm² when a porous active layer is used. Whereas in the film model, much higher values of C may be obtained: tens and even hundreds of C/cm². On the other hand, in the case of anode discharge, the reasonable discharge current density value, its maximum value, at which practically full recovery of lithium atoms from active intercalating agent grains is still possible, proves to be by orders of magnitude higher in the case of an anode with a porous active layer, as compared with a film-type anode. Thus, in the case of development of electrode active layers of lithium-ion batteries, there is a possibility of choosing from two variants. There is the variant of an active film-type layer providing high capacitance values, but low discharge current density. Or there is another variant: a porous active layer with limited capacitance but then much higher values of discharge current density.     

Thermokinetic and conductivity analyzes of the high CO_2 chemisorption on Li_5AlO_4 and alkaline carbonate impregnated Li_5AlO_4 samples: Effects produced by the use of CO_2 partial pressures and oxygen addition

The effect of CO_2 partial pressure was evaluated during the CO_2 chemisorption in penta lithium aluminate(Li_5AlO_4), using different CO_2 and O_2 partial pressures in the presence or absence of alkaline carbonates. Results showed that using low PO_2(0.1) did not affect the kinetic and final CO_2 chemisorption process. Moreover, small additions of oxygen(PO_2= 0.05) into the mixture flue gas, seemed to increase the CO_2 chemisorption. Additionally, the presence of alkaline carbonates modified the CO_2 capture temperature range. CO_2 chemisorption kinetic parameters were determined assuming a double exponential model where direct CO_2 chemisorption and CO_2 chemisorption controlled by diffusion processes are considered.Finally, ionic diffusion was analyzed by ionic conduction analysis, where all the gravimetric and ionic measurements were in good agreement showing different diffusion processes depending on temperature.Finally, the oxygen and alkaline carbonate additions have positive effects during the CO_2 chemisorption process in Li_5AlO_4, and a possible reaction mechanism is presented.     

Confining Li_2O_2 in tortuous pores of mesoporous cathodes to facilitate low charge overpotentials for Li-O_2 batteries

Achieving low charge overpotentials represents one of the most critical challenges for pursuing highperformance lithium-oxygen(Li-O₂)batteries.Herein,we propose a strategy to realize low charge overpotentials by confining the growth of lithium peroxide(Li₂O₂)inside mesoporous channels of cathodes(CMK-8).The CMK-8 cathode with tortuous pore structures can extend the diffusion distance of lithium superoxide(LiO₂)in the mesoporous channels,facilitating the further reduction of LiO₂ to lithium peroxide(Li₂O₂)inside the pores and preventing them to be diffused out of the pores.Therefore,Li₂O₂ is trapped in the mesoporous channels of CMK-8 cathodes,ensuring a good Li₂O₂/CMK-8 contact interface.The CMK-8 electrode exhibits a low charge overpotential of 0.43 V and a good cycle life for 72 cycles with a fixed capacity of 500 m Ah g^-1 at 0.1 A g^-1.This study proposes a strategy to achieve a low charge overpotential by confining Li₂O₂ growth in the mesoporous channels of cathodes.     

Computer simulation of negative electrode operation in lithium—ion battery: Galvanostatic discharge,porous electrode model and film model

Computer simulation of the structure and methods of operation (galvanostatic discharge) of the negative electrode of a lithium-ion battery is performed. Two possible models of the active anode layer were compared. 1. The model of porous active layer (mixture of active substance grains with grains of electrolyte). Here, the electrochemical process occurs within a porous active layer. 2. The film model (constant-thickness layer) of pure active substance (intercalating agent) grains without admixture of grains of electrolyte. In this case, the electrochemical reaction occurs only on the planar active electrode layer/interelectrode space interface. In both cases, the optimum working parameters of anode active layers were calculated: porous active layer thickness (in the film model, this was the calculation parameter), duration of full anode discharge, specific electric capacitance and finite difference between the intercalating agent/electrolyte potentials at the active anode layer/interelectrode space interface. It is found that each of these two models has its advantages and faults. Specific electric capacitance C cannot exceed the values of the order of magnitude of 10 C/cm² when a porous active layer is used. Whereas in the film model, much higher values of C may be obtained: tens and even hundreds of C/cm². On the other hand, in the case of anode discharge, the reasonable discharge current density value, its maximum value, at which practically full recovery of lithium atoms from active intercalating agent grains is still possible, proves to be by orders of magnitude higher in the case of an anode with a porous active layer, as compared with a film-type anode. Thus, in the case of development of electrode active layers of lithium-ion batteries, there is a possibility of choosing from two variants. There is the variant of an active film-type layer providing high capacitance values, but low discharge current density. Or there is another variant: a porous active layer with limited capacitance but then much higher values of discharge current density.     

尖晶石锂锰氧化物电极首次脱锂过程的EIS研究

研究了尖晶石锂锰氧化物电极首次脱锂过程中的电化学阻抗特征. 通过选取适当的等效电路拟合实验所得的电化学阻抗谱数据, 获得了首次脱锂过程中固体电解质相界面膜(SEI膜)的电阻、电容以及电荷传递电阻、双电层电容等随电极极化电位的变化规律.     

LiCoO_2 electrode/electrolyte interface of Li-ion batteries investigated by electrochemical impedance spectroscopy

The storage behavior and the first delithiation of LiCoO2 electrode in 1 mol/L LiPF6-EC:DMC:DEC elec- trolyte were investigated by electrochemical impedance spectroscopy (EIS). It has found that, along with the increase of storage time, the thickness of SEI film increases, and some organic carbonate lithium compounds are formed due to spontaneous reactions occurring between the LiCoO2 electrode and the electrolyte. When electrode potential is changed from 3.8 to 3.95 V, the reversible breakdown of the resistive SEI film occurs, which is attributed to the reversible dissolution of the SEI film component. With the increase of electrode potential, the thickness of SEI film increases rapidly above 4.2 V, due to overcharge reactions. The inductive loop observed in impedance spectra of the LiCoO2 electrode in Li/LiCoO2 cells is attributed to the formation of a Li1-xCoO2/LiCoO2 concentration cell. Moreover, it has been demonstrated that the lithium-ion insertion-deinsertion in LiCoO2 hosts can be well described by both Langmuir and Frumkin insertion isotherms, and the symmetry factor of charge transfer has been evaluated at 0.5.     

The origin of potential rise during charging of Li-O_2 batteries

When aprotic Li-O_2 batteries recharge, the solid Li_2O_2 in the positive electrode is oxidized, which often exhibits a continuous or step increase in the charging potential as a function of the charging capacity, and its origin remains incompletely understood.Here, we report a model study of electro-oxidation of a Li_2O_2 film on an Au electrode using voltammetry coupled with in situ Raman spectroscopy. It was found that the charging reaction initializes at the positive electrode|Li_2O_2 interface, instead of the previously presumed Li_2O_2 surface, and consists of two temporally and spatially separated Li_2O_2 oxidation processes, accounting for the potential rise during charging of Li-O_2 batteries. Moreover, the electrode surface-initialized oxidation can disintegrate the Li_2O_2 film resulting in a loss of Li_2O_2 into electrolyte solution, which drastically decreases the charging efficiency and highlights the importance of using soluble electro-catalyst for the complete charging of Li-O_2 batteries.     

Site-Selective Synthesis and Concurrent Immobilization of Imine-Based Covalent Organic Frameworks on Electrodes Using an Electrogenerated Acid

Imine-based covalent organic frameworks (COFs) are crystalline porous materials with prospective uses in various devices. However, general bulk synthetic methods usually produce COFs as powders that are insoluble in most of the common organic solvents, arising challenges for the subsequent molding and fixing of these materials on substrates. Here, we report a novel synthetic methodology that utilizes an electrogenerated acid (EGA), which is produced at an electrode surface by electrochemical oxidation of a suitable precursor, acting as an effective Brønsted acid catalyst for imine bond formation from the corresponding amine and aldehyde monomers. Simultaneously, it provides the corresponding COF film deposited on the electrode surface. The COF structures obtained with this method exhibited high crystallinities and porosities, and the film thickness could be controlled. Furthermore, such process was applied for the synthesis of various imine-based COFs, including a three-dimensional (3D) COF structure.     

反应物分散条件对Li1+xV3O8电化学性能的影响

以Li₂CO₃和NH₄VO₃为原料,在不同条件下合成了锂离子电池正极材料用Li_1+xV₃O₈。研究了反应物的分散条件和煅烧温度对产物晶型结构、形貌及电化学性能的影响。 XRD、IR和SEM结果表明,用超声波在无水乙醇中分散反应物得到的前驱体于550 ℃下煅烧,所得产物Li_1+xV₃O₈结晶度低、粒径小、形貌均匀。 充放电、循环伏安等结果表明,该材料在充放电过程中极化低、嵌脱锂位置多、循环稳定性好。 在0.5 C放电条件下,第2次循环放电容量达到268 mA·h/g,100次循环后容量仍保持210 mA·h/g以上。     

Drying and nondrying layer-by-layer assembly for the fabrication of sodium silicate/TiO2 nanoparticle composite films

Influences of drying and nondrying steps on structures of layer-by-layer (LbL) assembled sodium silicate/TiO(2) nanoparticles films (donated as silicate/TiO(2) films) have been systematically investigated. The nondrying LbL assembly produces highly porous silicate/TiO(2) films with large thickness. In contrast, the silicate/TiO(2) films fabricated with a drying step after each layer deposition are flat and thin without porous structures. In situ atomic force microscopy (AFM) measurements confirm that the sodium silicate and TiO(2) nanoparticles are deposited in their aggregated forms. A N(2) drying step can disintegrate the aggregated silicate and TiO(2) nanoparticles to produce thin silicate/TiO(2) films with compact structures. Without the drying steps, the aggregated silicate and TiO(2) nanoparticles are well retained, and their LbL assembly produces highly porous silicate/TiO(2) films of large thickness. The highly porous silicate/TiO(2) films are demonstrated to be useful as reusable film adsorbents for dye removal from wastewater because they can adsorb a large amount of cationic organic dyes and decompose them under UV irradiation. The present study is meaningful for exploring drying/nondrying steps for tailoring structure and functions of LbL assembled films.