Nanomaterials for lithium-ion rechargeable batteries

In lithium-ion batteries, nanocrystalline intermetallic alloys, nanosized composite materials, carbon nanotubes, and nanosized transition-metal oxides are all promising new anode materials, while nanosized LiCoO2, LiFePO4, LiMn2O4, and LiMn2O4 show higher capacity and better cycle life as cathode materials than their usual larger-particle equivalents. The addition of nanosized metal-oxide powders to polymer electrolyte improves the performance of the polymer electrolyte for all solid-state lithium rechargeable batteries. To meet the challenge of global warming, a new generation of lithium rechargeable batteries with excellent safety, reliability, and cycling life is needed, i.e., not only for applications in consumer electronics, but especially for clean energy storage and for use in hybrid electric vehicles and aerospace. Nanomaterials and nanotechnologies can lead to a new generation of lithium secondary batteries. The aim of this paper is to review the recent developments on nanomaterials and nanotechniques used for anode, cathode, and electrolyte materials, the impact of nanomaterials on the performance of lithium batteries, and the modes of action of the nanomaterials in lithium rechargeable batteries.     

固态离子学的新应用

固态离子学是研究固体中快离子输运规律及其应用的科学。它是上世纪70年代发展起来的一门新兴学科, 重点研究具有快离子传导特性的固体电解质材料以及具有离子/电子混合传导特性的电极材料。近年来, 固体离子及混合导电化合物在二次电池、燃料电池、传感器、超级电容器、电色器件、太阳能电池等方面的应用取得了突破性进展, 锂离子电池在各种电子器件中的大规模应用及其新材料体系的发现[1-2]、钠硫电池在大规模储能应用中的领先地位、ZEBRA电池在储能市场上的崛起、固体氧传感器在市场上的稳步发展以及SOFC逐步迈进市场成为固态离子学领域一个个闪光点, 极大地促进了新能源利用、电动汽车开发以及智能电网建设等重大任务的实施, 多领域的科学家和工程技术人员投身到固态离子学的研究中。
　　在众多的新能源技术研究方向中, 高比能量二次电池的研究是当前热点, 也是目前电动汽车开发和智能电网建设公认的瓶颈技术。近几年, 金属电极电池技术的发展使人们对二次电池的未来充满了信心。以金属为负极的二次电池得益于金属电极本身极高的比容量。金属负极主要以碱金属锂、钠和碱土金属镁为代表, 其中锂的重量和体积比容量分别高达3860 mAh/g和2062 mAh/cm3, 远高于目前商业化的碳类负极材料, 成为未来高比能量二次电池的目标。近期, 以金属锂负极活性材料的锂硫电池和锂空气电池的研究在国内外如火如荼, 并不断取得进展。
　　这些电池不仅具有高比能量的特点, 更有价格低廉的绝对优势, 同时也存在尚需改进之处。(1)在锂硫电池方面, 美国Sion Power公司利用PolyPlus公司的锂负极保护膜技术, 有望实现锂硫电池能量密度500 Wh/kg及循环500次的目标[3]。就在近期, 英国Oxis Energy公司报道其研制的200 Wh/kg的锂硫电池预计循环1700~1800次后的容量维持率仍达80%, 该公司计划明年早些时候实现量产[4], 这无疑是对锂硫电池的有力推动。国内有众多研究锂硫电池的机构, 如防化研究院、国防科技大学、北京理工大学、上海硅酸盐研究所、南开大学等均研制了软包装锂硫电池[5]。上海硅酸盐研究所研制的硫电极在2C倍率下循环500次后比容量达到900 mAh/g以上。不过目前看来, 锂硫电池虽然前景良好, 但要在市场上展现其价值尚需开展很多工作。(2)在锂空气电池方面, 针对电解质隔膜、催化剂、载体等核心材料有大量的文献报道, 通过无碳电极设计以及基于LATP锂离子固体电解质的电池设计, 很好地改进了锂空气电池的基本性能[6-8], 但离实际应用还差距甚远, 其电池反应机理方面尚存在争议, 电池技术还没有取得公认的突破。然而, 以锂空气电池为代表的金属空气电池由于其极高的比能量仍是未来电动汽车无法抗拒的追逐目标。
　　金属负极电池的开发在很大程度上取决于固体电解质新体系和新型电极材料的开发, 固态离子学成为高比能量二次电池研究与开发必须掌握的一门重要的科学, 无论是已经获得规模化应用的LiCoO2和LiFePO4等锂离子电池正极材料, Na-β/β″-Al2O3、ZrO2等离子导体, 还是新近突破的Li10GeP2S12和Li7La3Zr2O12[1-2]等锂离子导体新体系, 都为实现锂金属电池新的突破以及锂电池的全固体化、从而从根本上解决锂离子电池的安全性问题奠定了坚实的基础。正因为如此, 锂离子电池的企业界也在大力拓展市场的同时, 不断关注新型二次电池以及固态离子学的进展, 仅以我国两年一届的全国固态离子学学术会议为例, 其规模也从1980年的数十人发展到2012年第16届全国会议的与会代表400余人, 其中近20%代表来自电池与材料企业。可以说, 未来固态离子学将越来越发挥其重要作用, 为新能源技术的发展保驾护航。     

锂离子电池镍系正极材料的热稳定性研究进展

镍酸锂作为高性能、低成本的锂离子电池正极材料已倍受关注.但存在一些实用化的困难,热稳定性差即是主要的因素之一.本文综述了镍酸锂材料在全锂或电化学脱锂状态下的热行为和热分解机理的最新研究进展;概述了以解决镍酸锂用作锂离子电池正极材料的热稳定性问题所进行的各种改性研究情况.     

Polymer/Transitonal Metal Oxides Nanocomposites as Cathode Materials for Rechargeable Lithium/Lithium lon Batteries

The synthesis and properties of polymer/transition metal oxides nanocomposite material were reviewed.The new nanocomposite material(PPY)0.5/MoO3 prepared by a new method is described.The application of the nanocomposite materials as cathode material in rechargeable lithium/lithium ion batteries was explored.     

Oxygen Vacancy–Rich In‐Doped CoO/CoP Heterostructure as an Effective Air Cathode for Rechargeable Zn–Air Batteries

An efficient and low‐cost electrocatalyst for reversible oxygen electrocatalysis is crucial for improving the performance of rechargeable metal?air batteries. Herein, a novel oxygen vacancy–rich 2D porous In‐doped CoO/CoP heterostructure (In‐CoO/CoP FNS) is designed and developed by a facile free radicals–induced strategy as an effective bifunctional electrocatalyst for rechargeable Zn–air batteries. The electron spin resonance and X‐ray absorption near edge spectroscopy provide clear evidence that abundant oxygen vacancies are formed in the interface of In‐CoO/CoP FNS. Owing to abundant oxygen vacancies, porous heterostructure, and multiple components, In‐CoO/CoP FNS exhibits excellent oxygen reduction reaction activity with a positive half‐wave potential of 0.81 V and superior oxygen evolution reaction activity with a low overpotential of 365 mV at 10 mA cm^?2. Moreover, a home‐made Zn–air battery with In‐CoO/CoP FNS as an air cathode delivers a large power density of 139.4 mW cm^?2, a high energy density of 938 Wh kg_Zn^?1, and can be steadily cycled over 130 h at 10 mA cm^?2, demonstrating great application potential in rechargeable metal–air batteries.     

Electronically conductive phospho-olivines as lithium storage electrodes

Lithium transition metal phosphates have become of great interest as storage cathodes for rechargeable lithium batteries because of their high energy density, low raw materials cost, environmental friendliness and safety. Their key limitation has been extremely low electronic conductivity, until now believed to be intrinsic to this family of compounds. Here we show that controlled cation non-stoichiometry combined with solid-solution doping by metals supervalent to Li+ increases the electronic conductivity of LiFePO4 by a factor of approximately 10(8). The resulting materials show near-theoretical energy density at low charge/discharge rates, and retain significant capacity with little polarization at rates as high as 6,000 mA x g(-1). In a conventional cell design, they may allow development of lithium batteries with the highest power density yet.     

Lithiophilic 3D Nanoporous Nitrogen‐Doped Graphene for Dendrite‐Free and Ultrahigh‐Rate Lithium‐Metal Anodes

The key bottlenecks hindering the practical implementations of lithium‐metal anodes in high‐energy‐density rechargeable batteries are the uncontrolled dendrite growth and infinite volume changes during charging and discharging, which lead to short lifespan and catastrophic safety hazards. In principle, these problems can be mitigated or even solved by loading lithium into a high‐surface‐area, conductive, and lithiophilic porous scaffold. However, a suitable material that can synchronously host a large loading amount of lithium and endure a large current density has not been achieved. Here, a lithiophilic 3D nanoporous nitrogen‐doped graphene as the sought‐after scaffold material for lithium anodes is reported. The high surface area, large porosity, and high conductivity of the nanoporous graphene concede not only dendrite‐free stripping/plating but also abundant open space accommodating volume fluctuations of lithium. This ingenious scaffold endows the lithium composite anode with a long‐term cycling stability and ultrahigh rate capability, significantly improving the charge storage performance of high‐energy‐density rechargeable lithium batteries.     

Recent Progress in Multivalent Metal (Mg,Zn, Ca,and Al) and Metal‐Ion Rechargeable Batteries with Organic Materials as Promising Electrodes

The emerging demand for electronic and transportation technologies has driven the development of rechargeable batteries with enhanced capacity storage. Especially, multivalent metal (Mg, Zn, Ca, and Al) and metal‐ion batteries have recently attracted considerable interests as promising substitutes for future large‐scale energy storage devices, due to their natural abundance and multielectron redox capability. These metals are compatible with nonflammable aqueous electrolytes and are less reactive when exposed in ambient atmosphere as compared with Li metals, hence enabling potential safer battery systems. Luckily, green and sustainable organic compounds could be designed and tailored as universal host materials to accommodate multivalent metal ions. Considering these advantages, effective approaches toward achieving organic multivalent metal and metal‐ion rechargeable batteries are highlighted in this Review. Moreover, organic structures, cell configurations, and key relevant electrochemical parameters are presented. Hopefully, this Review will provide a fundamental guidance for future development of organic‐based multivalent metal and metal‐ion rechargeable batteries.     

Layered Transition Metal Dichalcogenide-Based Nanomaterials for Electrochemical Energy Storage

The rapid development of electrochemical energy storage (EES) systems requires novel electrode materials with high performance. A typical 2D nanomaterial, layered transition metal dichalcogenides (TMDs) are regarded as promising materials used for EES systems due to their large specific surface areas and layer structures benefiting fast ion transport. The typical methods for the preparation of TMDs and TMD-based nanohybrids are first summarized. Then, in order to improve the electrochemical performance of various kinds of rechargeable batteries, such as lithium-ion batteries, lithium–sulfur batteries, sodium-ion batteries, and other types of emerging batteries, the strategies for the design and fabrication of layered TMD-based electrode materials are discussed. Furthermore, the applications of layered TMD-based nanomaterials in supercapacitors, especially in untraditional supercapacitors, are presented. Finally, the existing challenges and promising future research directions in this field are proposed.     

锂离子电池炭负极材料结构及嵌锂机理研究进展

炭材料取代金属锂作为负极后,锂离子电池在商业应用上取得了成功,并以其高能量密度在各种电子设备上广泛使用.锂离子电池的性能很大程度上取决于炭负极材料的微观结构,不同种类的炭材料其电化学性能有很大差别.对近几年所研究的可逆储锂炭材料进行了综述,着重总结了炭负极材料的种类、结构及其嵌锂机理,并展望了锂离子电池炭负极材料的研究进展.     

A Flexible Film toward High‐Performance Lithium Storage: Designing Nanosheet‐Assembled Hollow Single‐Hole Ni–Co–Mn–O Spheres with Oxygen Vacancy Embedded in 3D Carbon Nanotube/Graphene Network

Ternary transition metal oxides (TMOs) are highly potential electrode materials for lithium ion batteries (LIBs) due to abundant defects and synergistic effects with various metal elements in a single structure. However, low electronic/ionic conductivity and severe volume change hamper their practical application for lithium storage. Herein, nanosheet‐assembled hollow single‐hole Ni–Co–Mn oxide (NHSNCM) spheres with oxygen vacancies can be obtained through a facile hydrothermal reaction, which makes both ends of each nanosheet exposed to sufficient free space for volume variation, electrolyte for extra active surface area, and dual ion diffusion paths compared with airtight hollow structures. Furthermore, oxygen vacancies could improve ion/electronic transport and ion insertion/extraction process of NHSNCM spheres. Thus, oxygen‐vacancy‐rich NHSNCM spheres embedded into a 3D porous carbon nanotube/graphene network as the anode film ensure efficient electrolyte infiltration into both the exterior and interior of porous and open spheres for a high utilization of the active material, showing an excellent electrochemical performance for LIBs (1595 mAh g^?1 over 300 cycles at 2 A g^?1, 441.6 mAh g^?1 over 4000 cycles at 10 A g^?1). Besides, this straightforward synthetic method opens an efficacious avenue for the construction of various nanosheet‐assembled hollow single‐hole TMO spheres for potential applications.     

Recent research progress on iron- and manganese-based positive electrode materials for rechargeable sodium batteries

Large-scale high-energy batteries with electrode materials made from the Earth-abundant elements are needed to achieve sustainable energy development. On the basis of material abundance, rechargeable sodium batteries with iron- and manganese-based positive electrode materials are the ideal candidates for large-scale batteries. In this review, iron- and manganese-based electrode materials, oxides, phosphates, fluorides, etc, as positive electrodes for rechargeable sodium batteries are reviewed. Iron and manganese compounds with sodium ions provide high structural flexibility. Two layered polymorphs, O3- and P2-type layered structures, show different electrode performance in Na cells related to the different phase transition and sodium migration processes on sodium extraction/insertion. Similar to layered oxides, iron/manganese phosphates and pyrophosphates also provide the different framework structures, which are used as sodium insertion host materials. Electrode performance and reaction mechanisms of the iron- and manganese-based electrode materials in Na cells are described and the similarities and differences with lithium counterparts are also discussed. Together with these results, the possibility of the high-energy battery system with electrode materials made from only Earth-abundant elements is reviewed.     

过渡金属离子掺杂对磷酸铁锂性能的影响

以碳酸锂、草酸亚铁、磷酸二氢铵、葡萄糖为原料,添加不同的过渡金属乙酸盐(乙酸锰、乙酸钴、乙酸镍、乙酸锌),在氩气保护下采用高温固相法制备LiFePO4/C复合材料.采用X射线衍射、扫描电子显微镜、同步热分析、恒电流充放电、电化学阻抗、循环伏安等方法研究掺杂金属离子及掺杂量对LiFePO4/C晶体结构和电化学性能的影响.结果表明,LiFe0.9M0.1PO4/C(M=Mn、Co、Ni、Zn)样品的晶体结构均与橄榄石型LiFePO4相同.掺杂过渡金属阳离子可以提高LiFeP04/C的还原电位,降低氧化电位,缩小氧化还原峰间距,提高化学反应的可逆性.掺杂后的样品在5C下的放电性能较好,以LiFe0.9Ni0.1PO4/C的放电容量最高,达到89 mAh/g.     

锂离子电池正负极材料的研究

锂离子电池作为新一代的充电电池,近年来得到了飞速的发展.它以高的性能被用于手机电池、笔记本电脑和其它便携式电器.不久的将来,它将会为电动汽车或大型储存电能的电池提供能量.本文阐述了锂离子电池技术发展的现状,其中包括正极材料、负极材料、电解质以及与之发展相关的问题的成因,并分析了它们的优缺点.     

Atomic‐Scale Structure Evolution in a Quasi‐Equilibrated Electrochemical Process of Electrode Materials for Rechargeable Batteries

Lithium‐ion batteries have proven to be extremely attractive candidates for applications in portable electronics, electric vehicles, and smart grid in terms of energy density, power density, and service life. Further performance optimization to satisfy ever‐increasing demands on energy storage of such applications is highly desired. In most of cases, the kinetics and stability of electrode materials are strongly correlated to the transport and storage behaviors of lithium ions in the lattice of the host. Therefore, information about structural evolution of electrode materials at an atomic scale is always helpful to explain the electrochemical performances of batteries at a macroscale. The annular‐bright‐field (ABF) imaging in aberration‐corrected scanning transmission electron microscopy (STEM) allows simultaneous imaging of light and heavy elements, providing an unprecedented opportunity to probe the nearly equilibrated local structure of electrode materials after electrochemical cycling at atomic resolution. Recent progress toward unraveling the atomic‐scale structure of selected electrode materials with different charge and/or discharge state to extend the current understanding of electrochemical reaction mechanism with the ABF and high angle annular dark field STEM imaging is presented here. Future research on the relationship between atomic‐level structure evolution and microscopic reaction mechanisms of electrode materials for rechargeable batteries is envisaged.     

Defect Engineering on Electrode Materials for Rechargeable Batteries

The reasonable design of electrode materials for rechargeable batteries plays an important role in promoting the development of renewable energy technology. With the in-depth understanding of the mechanisms underlying electrode reactions and the rapid development of advanced technology, the performance of batteries has significantly been optimized through the introduction of defect engineering on electrode materials. A large number of coordination unsaturated sites can be exposed by defect construction in electrode materials, which play a crucial role in electrochemical reactions. Herein, recent advances regarding defect engineering in electrode materials for rechargeable batteries are systematically summarized, with a special focus on the application of metal-ion batteries, lithium–sulfur batteries, and metal–air batteries. The defects can not only effectively promote ion diffusion and charge transfer but also provide more storage/adsorption/active sites for guest ions and intermediate species, thus improving the performance of batteries. Moreover, the existing challenges and future development prospects are forecast, and the electrode materials are further optimized through defect engineering to promote the development of the battery industry.     

Dual‐Layered Film Protected Lithium Metal Anode to Enable Dendrite‐Free Lithium Deposition

Lithium metal batteries (such as lithium–sulfur, lithium–air, solid state batteries with lithium metal anode) are highly considered as promising candidates for next‐generation energy storage systems. However, the unstable interfaces between lithium anode and electrolyte definitely induce the undesired and uncontrollable growth of lithium dendrites, which results in the short‐circuit and thermal runaway of the rechargeable batteries. Herein, a dual‐layered film is built on a Li metal anode by the immersion of lithium plates into the fluoroethylene carbonate solvent. The ionic conductive film exhibits a compact dual‐layered feature with organic components (ROCO₂Li and ROLi) on the top and abundant inorganic components (Li₂CO₃ and LiF) in the bottom. The dual‐layered interface can protect the Li metal anode from the corrosion of electrolytes and regulate the uniform deposition of Li to achieve a dendrite‐free Li metal anode. This work demonstrates the concept of rational construction of dual‐layered structured interfaces for safe rechargeable batteries through facile surface modification of Li metal anodes. This not only is critically helpful to comprehensively understand the functional mechanism of fluoroethylene carbonate but also affords a facile and efficient method to protect Li metal anodes.     

导电基质纳米复合电极材料的研究进展

在各种能源储存设备中,锂离子电池成为重要的首选储能器件,在便携电子设备、电动车、混合电动车及其它能源存储设备等方面都有广泛应用。如何提高锂离子电池用电极材料的锂离子储存性能,已经成为材料科学与工程领域的热点之一。利用导电基质构建纳米结构复合材料是提高锂离子储存性能的有效途径。简要介绍了碳基和金属基质纳米复合电极材料的研究进展,主要包括材料制备新方法、新工艺、锂离子电池改性及其发展趋势等内容。     

锂离子电池LiFeO2基材料研究进展

LiCoO2是目前商品锂离子电池中最广泛应用的正极材料,然而其价格昂贵且对环境有害,促使人们研究开发新型正极材料。由于Fe是地球上最丰富且无毒的金属,具有与LiCoO2相似岩盐结构的LiFeO2研究引起人们广泛关注。综述了LiFeO2基锂离子电池材料的研究进展,评述了制备与性能,展望了LiFeO2基锂离子电池材料未来的发展方向和应用前景。     

Reversible nanopore formation in Ge nanowires during lithiation-delithiation cycling: an in situ transmission electron microscopy study

Retaining the high energy density of rechargeable lithium ion batteries depends critically on the cycle stability of microstructures in electrode materials. We report the reversible formation of nanoporosity in individual germanium nanowires during lithiation-delithiation cycling by in situ transmission electron microscopy. Upon lithium insertion, the initial crystalline Ge underwent a two-step phase transformation process: forming the intermediate amorphous Li(x)Ge and final crystalline Li(15)Ge(4) phases. Nanopores developed only during delithiation, involving the aggregation of vacancies produced by lithium extraction, similar to the formation of porous metals in dealloying. A delithiation front was observed to separate a dense nanowire segment of crystalline Li(15)Ge(4) with a porous spongelike segment composed of interconnected ligaments of amorphous Ge. This front sweeps along the wire with a logarithmic time law. Intriguingly, the porous nanowires exhibited fast lithiation/delithiation rates and excellent mechanical robustness, attributed to the high rate of lithium diffusion and the porous network structure for facile stress relaxation, respectively. These results suggest that Ge, which can develop a reversible nanoporous network structure, is a promising anode material for lithium ion batteries with superior energy capacity, rate performance, and cycle stability.