Nano-sized copper tungstate thin films as positive electrodes for rechargeable Li batteries

Nano-sized CuWO₄ thin films have been fabricated by radio-frequency (R.F.) sputtering deposition, and are used as positive electrode with both LiClO₄ liquid electrolyte and LiPON solid electrolyte in rechargeable lithium batteries. An initial discharge capacity of 192 and 210 mAh/g is obtainable for CuWO₄ film electrode with and without coated LiPON in liquid electrolyte, respectively. An all-solid-state cell with Li/LiPON/CuWO₄ layers shows a high-volume rate capacity of 145 μAh/cm² μm in first discharge, and overcomes the unfavorable electrochemical degradation observed in liquid electrolyte system. A two-step reactive mechanism is investigated by both transmission electron microscopy and selected area electron diffraction techniques. Apart from the extrusion and injection of Cu²⁺/Cu⁰, additional capacity can be achieved by the reversible reactivity of (WO₄)²⁻ framework. The chemical diffusion coefficients of Li intercalation/deintercalation are estimated by cyclic voltammetry. Nano-CuWO₄ thin film is expected to be a promising positive electrode material for high-performance rechargeable thin-film lithium batteries.     

Interface control for high-performance all-solid-state Li thin-film batteries

We fabricated and evaluated four types of Li batteries, in this case a LTO/liquid electrolyte/Li battery, a LTO/LiPON/Li all-solid-state battery, and LTO/LiPON + liquid electrolyte/Li batteries with and without a separator to investigate and clarify the effects of each interface. Through the present research, it was found that a conventional polymer-based separator increases the impedance in the middle frequency region, resulting in an increase in the total cell resistance. After replacing the polymer-based separator with a thin-film solid electrolyte, the cycleability and capacity of the cell were comparable to those of a conventional Li-ion battery with a polymer separator. The all-solid-state Li thin-film battery without a liquid electrolyte exhibits the lowest capacity due to the large interfacial resistance between the Li metal and the LiPON solid electrolyte. However, we found that the insertion of an Al₂O₃ interlayer between the Li and LiPON improves the capacity.     

锂离子电池电极材料机械化学合成研究进展

简要介绍了机械化学合成的特性,着重论述了利用机械化学法合成锂离子电池电极材料的研究现状,以及利用机械化学法合成的这些电极材料的特点。展望了机械化学法在锂离子电池电极材料中的应用发展前景,并认为随着研究的深入,采用计算机模拟计算机械化学能量、粉末受力情况和机械化学进程,以指导新工艺、新材料的开发研究,从分子水平上设计出来的各种高性能的电极材料将有力地推动锂离子电池的研究和应用。     

从商业化角度看锂-空气电池的发展

锂-空气电池的完全商业化,一直是该研究领域的目标。但实现该目标,必须考虑到各方面的问题,任何小的影响因素都应该尽量考虑在内。负极需要保护其不受水分、二氧化碳、电解液中反应中间物等物质的侵蚀,并抑制枝晶的产生。正极中高效的电极反应催化剂及能容纳放电产物的高比表面积结构是维持电池稳定循环的基本要求。合理的添加剂对电解液性能的提高也非常有必要。电池整体需考虑各种外部因素,如电池构造、尺寸放大等。目前有关锂?空气电池的研究已经取得了很多进展,但仍然缺少决定性突破。以商业化为最终目的,本综述从锂?氧气电池各组成部分切入,对近几年的研究进展进行总结,着重于电池体系整体的研究报道,对未来锂?空气电池的发展进行了展望。     

Flower-like CuO film-electrode for lithium ion batteries and the effect of surface morphology on electrochemical performance

Nanostructured CuO films with flower-like architectures were fabricated by immersing copper foils in an aqueous solution of sodium hydroxide and sodium dodecylsulfate, and subsequent heat treatment at low temperature. The as-prepared CuO films exhibited not only higher reversible capacity but also better rate capability than those of network-like counterpart as negative-electrodes of lithium ion batteries. The effect of surface morphology on the electrochemical performance of the CuO electrodes was discussed. It was confirmed that the unique flower-like structures are mainly responsible for the difference in electrochemical performance between the two kinds of electrodes. The result of this study provides an attractive electrode with high energy-density for lithium ion batteries via a simple and green procedure.     

Interfacial structural stabilization on amorphous silicon anode for improved cycling performance in lithium-ion batteries

Interfacial structures of electrode-current collector and electrode-electrolyte have been designed to be stabilized for improved cycling performance of amorphous silicon (Si) that is considered as an alternative anode material to graphite for lithium-ion batteries. Interfacial structural stabilization involves the interdigitation of Si electrode-Cu current collector substrate by anodic Cu etching with thiol-induced self-assembly, and the formation of self-assembled siloxane on the surface of Si electrode using silane. The novel interfacial architecture possesses promoted interfacial contact area between Si and Cu, and a surface protective layer of siloxane that suppresses interfacial reactions with the electrolyte of 1 M LiPF₆/ethylene carbonate (EC):diethylene carbondate (DEC). FTIR spectroscopic analyses revealed that a stable solid electrolyte interphase (SEI) layer composed of lithium carbonate, organic compounds with carboxylate metal salt and ester functionalities, and PF-containing species formed when having siloxane on Si electrode. Interfacially stabilized Si electrode exhibited a high capacity retention 80% of the maximum discharge capacity after 200 cycles between 0.1 and 1.5 V vs. Li/Li⁺. The data contribute to a basic understanding of interfacial structural causes responsible for the cycling performance of Si-based alloy anodes in lithium-ion batteries.     

锂离子电池异构建模及内部传质机理探究：粒径分布的影响

锂离子电池是目前应用较广的储能设备,具有能量密度高、使用寿命长等特点。随着锂离子电池正极材料实际能量密度接近理论值,电池组装工艺参数的优化成了提升其性能的重要途径,其中电极颗粒粒径及分布是十分重要的参数。因此,本文针对石墨-LiFePO₄体系锂离子电池,利用异构模型构建单粒径和双粒径电极的几何结构,再结合Newman模型模拟其放电过程,定量研究了正极材料粒径分布对锂离子电池性能的影响,探究了存在粒径分布的电极中不同粒径的颗粒在充放电过程的作用机制。模拟结果表明,粒径的减小可以减小固相扩散系数对电池性能的影响,但会增加液相扩散阻力;而粒径的分布可以促进锂离子在电解液中的扩散,提高小粒径颗粒的锂嵌入量,但会引起极化增大,导致大颗粒的锂嵌入量降低。粒径分布宽度越大,总体粒度越大,锂离子电池的能量密度越小。选择合适的粒径分布宽度,适当减小总体粒度的大小,能有效提升电极的能量密度。研究结果对于锂离子电池电极活性材料颗粒粒径分布的选择提供了有益的基础知识和指导。     

Nano/micro-hybrid NiS cathodes for lithium ion batteries

The present study highlights a low temperature process by which 1D stacked 3D microstructures of nickel sulfide comprised of nanospikes have been synthesized and assembled as cathodes for lithium chalcogenide batteries. These micro/nano-clusters were synthesized hydrothermally under different conditions. These clusters exhibited a surface area of 15 m² g⁻¹. The present study also provides the first reports on the electrochemical performance of these NiS microclusters as cathode materials in lithium fluoro-Tris-sulfonimide electrolyte for lithium ion batteries. A detailed study has been performed to elucidate how surface morphology and redox reaction behaviors underlying these electrodes impact the cyclic behavior and specific capacity. This electrode−electrolyte combination showed minimal dissolution of the electrode in the electrolyte which was confirmed by inductively coupled plasma atomic emission spectroscopy. From the electrochemical analysis performed an intrinsic correlation between the capacity, self-discharge property and the surface morphology has been deduced and explained on the basis of relative contributions from the redox reactions of nickel sulfide in lithium fluoro-Tris-sulfonimide electrolyte. A working model of lithium battery in a coin cell form is also shown exhibiting a specific capacity of 550 mAh g⁻¹.     

Electrochemical characterization of amorphous LiFe(WO4)2 thin films as positive electrodes for rechargeable lithium batteries

Amorphous LiFe(WO₄)₂ thin films have been fabricated by radio-frequency (R.F.) sputtering deposition at room temperature. The as-deposited and electrochemically cycled thin films are, respectively, characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, selected area electron diffraction, and X-ray photoelectron spectra techniques. An initial discharge capacity of 198 mAh/g in Li/LiFe(WO₄)₂ cells is obtained, and the electrochemical behavior is mostly preserved in the following cycling. These results identified the electrochemical reactivity of two redox couples, Fe³⁺/Fe²⁺ and W⁶⁺/W^x+ (x = 4 or 5). The kinetic parameters and chemical diffusion coefficients of Li intercalation/deintercalation are estimated by cyclic voltammetry and alternate-current (AC) impedance measurements. All-solid-state thin film lithium batteries with Li/LiPON/LiFe(WO₄)₂ layers are fabricated and show high capacity of 104 μAh/cm² μm in the first discharge. As-deposited LiFe(WO₄)₂ thin film is expected to be a promising positive electrode material for future rechargeable thin film batteries due to its large volumetric rate capacity, low-temperature fabrication and good electrode/electrolyte interface.     

Effects of heteroatoms on electrochemical performance of electrode materials for lithium ion batteries

Recent studies of lithium ion batteries focus on improving electrochemical performance of electrode materials and/or lowering cost. Doping of active materials with heteroatoms is one promising method. This paper reviews the effects of heteroatoms on anode materials such as carbon- and tin-based materials, and cathode materials such as LiCoO₂, LiNiO₂, LiMn₂O₄ and V₂O₅. There are favorable and unfavorable effects, which depend on the species and physicochemical states of heteroatoms and the parent electrode materials. In the application of lithium ion batteries advantageous factors should be exploited, unwelcome side effects should be avoided as far as possible. Considerable gains towards improved electrochemical performance of the electrode materials have been achieved. Nevertheless, there are still problems needing further investigation including theoretical aspects, which will in the meanwhile stimulate the investigation for better electrode materials.     

金属-有机框架在二次电池中的储能机制研究进展

金属-有机框架（MOFs）具有多孔、大比表面积和结构与功能可调控等特点,已被广泛用作二次电池电极材料。本文重点介绍了MOFs作为二次电池电极材料的储能机制研究进展,主要分为转化储能机制、脱嵌储能机制、物理吸脱附储能机制等,并分析了各类储能机理的储能特点及对电化学性能的影响,探究了MOFs在较大离子半径的钠、钾离子电池中的应用特点及发展潜力。最后简要讨论了MOFs作为电极材料的设计思路为兼顾各类储能机制的优点,即选用较多储能位点的结构及较稳定的金属离子作为有机配体的连接点。     

钒酸镍锂离子电池负极材料的研究进展

综述了近年来国内外关于钒酸镍材料的合成方法、结构性质以及应用于锂离子电池新型负极材料的研究进展。钒酸镍(Ni3V2O8、NiV3O8等)电极材料具有成本低、环境友好、比容量高、倍率性能优异等优点,但其在充放电过程中体积的巨大变化、电导性差以及比表面积低等问题严重影响了其规模化应用。该文从三个方面阐述了近年来通过电极材料微纳米化、复合化、表面包覆等手段有针对性的进行钒酸镍电极材料改性的研究进展,积极探索了高性能钒酸镍材料的合成方法,展望了今后重点开展的研究方向,对于钒酸镍材料的广泛应用具有一定的学术价值和实用意义。     

中间相炭微球在锂离子电池负极材料的应用进展

中间相炭微球(MCMB)具有良好锂离子扩散性、导电性和机械稳定性等优势,是目前应用广泛、综合性能优异的锂离子电池负极材料,但较低理论比容量是制约其发展的关键因素。为了获得性能优良的MCMB基锂离子电池负极材料,改性修饰和复合材料已然成为目前研发重点。笔者论述了碳结构、表界面和复合材料等微观结构设计对MCMB负极材料电化学性能的影响。从碳堆积结构类型、有序性、层间距以及球体粒径大小等方面,论述了碳结构微观设计对MCMB电化学性能的影响。发现具有乱层结构的MCMB在充放电过程中内部产生应力较小,且碳结构较稳定,具有优异循环稳定性;内部具有大量微孔或碳层间距较大的MCMB,在充放电过程中可提高锂离子在电极中的迁移速率,并提供更多的储锂空间,一般具有优良的充放电比容量和倍率性能;小粒径MCMB具有较短的锂离子迁移路径和随之增加的比表面积,通常具有较好倍率性能,伴随着可逆比容量和充放电效率的衰减。从表界面碳层改性、包覆和掺杂改性等方面,论述了表界面改性对MCMB电化学性能的影响。表面碳层修饰可增加MCMB与电解液的相容性及其比表面积,提高了与电解液的接触面积及贮锂容量,改善了锂离子电池负极材料的电化学性能;另外,MCMB表面包覆一层无定型碳,可避免其表面与电解液直接接触,减少电化学副反应的产生,提升其可逆比容量。从碳活性物质复合材料、非碳活性物质复合材料等方面,论述了复合材料微观结构设计对MCMB电化学性能的影响。碳活性物质可降低MCMB内部碳层结构的有序性,减少锂离子嵌入过程中的内部应力,提升MCMB循环稳定性。非碳活性物质诱导MCMB生成更加有序的碳层结构,提高MCMB的比表面积,从而改善MCMB表面与电解液分子的接触能力及其嵌锂性能,有利于提升MCMB负极材料可逆比容量、循环性能和倍率性能。MCMB具有高碳层间距和多缺陷位点等结构特征,有利于钠离子自由脱嵌,应用于钠离子电池时具有良好的可逆比容量、循环稳定性和倍率性能。MCMB的不规则定向层状结构经活化等处理具有较高比表面积,可应用于超级电容器电极材料。最后提出在高性能锂离子电池电极材料快速发展的需求下,从微观结构角度设计MCMB纳米复合材料将是MCMB负极材料的研究重点。     

制备锂电池电解质六氟磷酸锂的工艺探讨

分析了目前国内外锂电池的发展状况,并对其中一种电解质六氟磷酸锂的制备工艺作了一些探讨。简要介绍了国外已经研究出的六氟磷酸锂的替代产品———氟烷基磷酸锂用作锂电池电解质。     

Recent progress in LiF materials for safe lithium metal anode of rechargeable batteries: Is LiF the key to commercializing Li metal batteries?

The lithium metal battery has attracted considerable attention as the ultimate lithium secondary battery for high energy density. However, safety issues and battery performance deterioration due to the growth of lithium dendrites have hampered the practical use of lithium metal batteries. Recently, lithium fluoride has been considered as a lithium metal protective layer to solve this problem. In this review, firstly, the results of the studies on dendrites and SEI that have been carried out to date are reviewed. Secondly, the results of studies on lithium fluoride are divided into additive, artificial SEI, and other methods and the possibilities of their practical use are discussed. Finally, the significance and limitations of the lithium fluoride studies are summarized, and general conclusions and prospects for recommended research directions to accelerate the commercialization of lithium metal batteries are presented.     

锂离子电池电极材料Li1+xV3O8研究进展

钒酸锂（Li_1+xV₃O₈）具有比容量大的优点,可用作传统锂离子电池正极材料及水溶液锂离子电池负极材料,是一种重要的锂离子电池活性材料。Li_1+xV₃O₈作为传统锂离子电池正极材料已被广泛研究,近年来Li_1+xV₃O₈作为水溶液锂离子电池负极材料的研究备受瞩目,成为了锂离子电池研究领域的热点与前沿。本文综述了Li_1+xV₃O₈作为传统锂离子电池正极材料的研究现状,从结构与充放电机理、合成方法及改性等方面进行了讨论,此外,综述了Li_1+xV₃O₈作为水溶液锂离子电池负极材料的研究现状并指出了其发展趋势。     

A brief review on hydrometallurgical technologies for recycling spent lithium‐ion batteries

Lithium‐ion battery is a mature technology that is used in various electronic devices. Nowadays, this technology is a good candidate as energy storage for electric vehicles. Therefore, much research is focused on the development of high‐density power lithium‐ion batteries. Government regulations force manufacturers to recycle the batteries for safety and health reasons but recycling could also be interesting from an economic viewpoint since cathodes in lithium‐ion batteries contain valuable metals. The electrodes in lithium‐ion batteries will evolve to provide more energy and the recycling processes will have to fit with this evolution. Leaching, bioleaching and solvent extraction are at the centre of these processes. In this paper, recent leaching and solvent extraction strategies for recovering valuable metals from spent lithium‐ion batteries are reviewed and the evolution of these processes is discussed. © 2013 Society of Chemical Industry     

硅酸盐基锂离子电池正极材料研究进展

硅酸盐基材料是一种锂离子电池的新型电极材料。本文简单综述了硅酸盐基材料的结构、合成方法及改性方法,并且对该材料目前存在的问题与应用前景进行了分析和探讨。该材料的开发对于锂离子电池的发展具有积极的推动作用。     

水性胶粘剂在锂离子电池电极中的应用

胶粘剂是锂离子电池中的重要辅助材料之一,它的合理选择和应用,直接影响着电池的电化学综合性能。由于良好的环保效应及性质,水性胶粘剂在电池中的应用及发展,已成为人们当前关注的一个技术热点。本文对不同类型水性胶粘剂,如水性天然高分子、水性半合成天然高分子及水性合成高分子等的应用及研究进展进行了简要综述。     

Anodically synthesized titania films for lithium batteries: Effect of titanium substrate and surface treatment

A number of titania films have been produced through anodising high purity titanium from different suppliers in either the as-received state or following polishing and etching. Anodising was carried out galvanostatically for a period of 10 min in 0.2 M H₂SO₄. The performance of the films was then evaluated as potential anode materials for lithium batteries. Raman spectroscopy showed these films had spectra characteristic of anatase with the presence of some rutile whilst the spectra of the lithiated state was characteristic of the orthorhombic phase of Li_xTiO₂.The surface condition in particular was found to have an effect on the electrochemical performance and properties of the films most notably on capacity fade. Whilst the electrodes produced from as-received titanium demonstrated stable cycle capacities after the initial few cycles, those on polished and etched substrates faded over 50 cycles. The best performing films offered a capacity of at least ∼48 μAh cm⁻² over the 50 cycles. All the electrodes examined however did show signs of the film having being damaged as a result of electrochemical cycling. With the wide range of anodising parameters that can be altered there is considerable scope for optimising the electrochemical performance of films produced through such a technique.