中国锂二次电池正极材料的发展趋势和产业特点

一、锂离子电池正极材料发展对锂离子电池而言,其主要构成材料包括电解液、隔离膜、正负极材料等。一般来说,在锂离子电池产品组成成分中,正极材料占据着最重要的地位,正极材料的好坏,直接决定了最终二次电池产品的性能指标。而正极材料在电池成本中所占比例可高达40%左右。目前正极材料中,以过渡金属氧化物所表现出的性能最佳,主要有层状盐结构的锂钴氧化物(LiCoO2)、层状盐结构的锂镍氧化物(LiNiO2)以及尖晶石型(LiMn2O4)和层状盐结构(LiMnO2)的锂锰氧化物。从合成工艺上控制材料结构的规整性和稳定性是获得比能量高、循环寿命长的锂…     

富锂层状氧化物正极材料研究进展

富锂层状氧化物正极材料(xLi₂MnO₃·(1-x)LiMO₂(M=Ni_yMn_zCo_1-y-z….)理论容量高、价格低廉, 是新一代锂离子电池正极材料的候选之一。本文概述了该正极材料的结构, 分析了其在电化学活化过程与循环过程中结构的演变, 探讨了结构变化对正极材料电化学性能的影响规律, 并概括了目前针对该类正极材料电化学性能提升所开展的离子掺杂和表面改性的研究工作, 展望了未来富锂层状氧化物正极材料的发展方向。     

新一代高比能量锂离子电池富锂氧化物正极材料的研究进展

富锂氧化物xLi_2MnO_3·(1-x)LiMO_2(M为Co、Ni、Mn等)的比容量可达250~300mAh/g,是高比能量锂离子电池正极材料的首选之一。介绍了材料的晶体结构、嵌/脱锂机制和充放电过程中发生的结构相变,分析讨论了材料出现首次不可逆容量大、电压和容量衰减快、倍率性能和低温性能较差等问题的原因,阐述了材料的合成方法及改性技术,如表面包覆、离子掺杂、形貌和晶面调控以及合成层状相-尖晶石相共生结构的异质材料等。最后从基础研究和应用研究两个方面展望了富锂氧化物材料的发展前景。     

锂离子电池正极材料Li[Ni_(0.92)Co_(0.04)Mn_(0.04)]O_2的合成新方法

采用溶胶-凝胶法在球形Ni(OH)2颗粒表面包覆钴、锰氧化物,合成了核壳结构的镍钴锰酸锂复合正极材料Li[Ni0.92Co0.04Mn0.04]O2。用X射线衍射、扫描电镜、恒电流充放电测试等方法对材料的结构、表观形貌及电化学性能进行了表征。结果表明,与镍酸锂材料相比,该镍酸锂复合正极材料表现出了较高的比容量,较好的循环稳定性及更好的安全性。     

锂离子电池正极材料研究进展

锂离子电池(LIB)近年来受到了广泛的关注,与其他可充电电池相比,锂离子电池LIB具有更高的能量密度、功率和效率.正极作为LIB的关键部件,其特性会显著影响LIB的性能.本文分类综述了一些锂离子正极材料,包括一元、二元、三元金属锂氧化物和磷酸亚铁锂正极材料,并对其优缺点进行了介绍.此外,本文还对已商业化的正极材料物性数...     

锂离子电池正极材料研究进展以及水热法制备LiCoO2超细粉体

综述了近年来锂离子电池正极材料的研究情况.介绍了几种主要的锂离子二次电池正极材料,包括锂钴氧化物、锂镍氧化物、锂锰氧化物的结构、制备、电化学性能及改性方法等.并通过水热法合成获得均匀无杂相的、α-NaFeO2层状结构的HT-LiCoO2超细粉末.     

不同比例Cr_2O_3对硫正极材料导电性能的影响

解决单质硫导电性问题是提高锂硫电池性能的关键。纳米氧化物不仅能提高硫电极的孔隙度,还能吸附较多硫离子,另外对电池的氧化还原反应起到催化作用。常见纳米氧化物有:SiO2,TiO2,V2O5等。但很少有Cr2O3做添加剂的报道。本研究通过对锂硫电池正极材料单质硫的导电特性进行研究,研究添加不同比例的Cr2O3对单质硫电化学性能的影响,并采用XRD、SEM、粒度分析仪对电池材料物相、颗粒形貌和粒度分布进行表征。利用高精度电池性能分析测试系统等对正极材料、电池进行电性分析。     

石墨烯/富锂三元正极复合材料的制备及电化学性能研究

通过水热法制备了石墨烯包覆量不同的石墨烯/富锂三元正极复合材料。采用X射线衍射仪、扫描电子显微镜和电化学交流阻抗等对包覆后富锂三元正极复合材料的物相结构、形貌及电化学性能进行了研究。结果表明:石墨烯包覆量为2%(质量分数)时,包覆效果较好,石墨烯/富锂三元正极复合材料首次库仑效率为89.6%,比富锂三元正极材料提高了17.16%,放电比容量为226.41mAh/g,比原材料提高了21.38mAh/g;以0.5C循环100次后石墨烯/富锂三元正极复合材料放电比容量可保持在154mAh/g,容量保持率为88%,比富锂三元正极材料提高了5.3%;石墨烯/富锂三元正极复合材料阻抗为75Ω,比富锂三元正极材料阻抗低50Ω。     

锂离子电池正极材料的研究进展

介绍了不同正极材料的结构，电化学性能，研究现状，探讨了影响正极材料电化学性能的若干因素，比较了不同粉体合成方法的优缺点，说明了软化学法在锂离子电池正极材料制备中的优越性。     

锂离子电池富锂正极材料xLi2MnO3·（1-x）LiMO2(M=Co,Fe,Ni1/2Mn1/2…)的研究进展

新一代固溶体富锂正极材料xLi2MnO3.(1-x)LiMO2(M=Co,Fe,Ni1/2Mn1/2…)具有高比容量、优秀的循环能力以及新的电化学充放电机制,可能被用做新型高比能量锂离子电池正极材料.本文介绍了富锂正极材料的结构、合成方法、电化学性能研究,探讨了影响其电化学性能的若干因素.并对其进行的各种改性研究进行了概述,分析总结了不同富锂正极材料所具有的特性和发展趋势.     

锂离子二次电池正极材料氧化锰锂的研究进展

综述了最近几年对于锂离子二次电池正极材料氧化锰锂的研究。研究的氧化锰锂材料主要有尖晶石结构的ＬｉＭＮ２Ｏ４、Ｌｉ４Ｍｎ５Ｏ９和Ｌｉ４Ｍｎ５Ｏ１２以及层状结构的ＬｉＭｎＯ２。对于ＬｉＭＮ２Ｏ４,通过引入适当的杂原子和采用新的溶胶－凝胶法制备复相 可以有效地克服Ｊａｈｎ－Ｔｅｌｌｅｒ效应所造成的容量衰减现象。Ｌｉ４Ｍｎ５Ｏ９display structure     

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.     

Nano/micro lithium transitionmetal (Fe, Mn, Co and Ni) silicate cathode materials for lithium ion batteries

Lithium transitionmetal (Fe, Mn, Co, Ni) silicate cathode materials are new promising substituting cathode materials for lithium ion batteries. They had caught the researchers' eyes in the past several years. Nowadays, there are growing interests for silicate cathode materials in the field of lithium ion batteries. Among the silicate cathode materials, Li2FeSiO4 is the most promising cathode materials because of its high structure stability, high reversible capacity, high electronic conductivity and the abundant resource of iron and silicon. Although Li2MnSiO4 and Li2CoSiO4 have much higher theoretic specific capacity than Li2FeSiO4, they all have inferior electrochemical behaviours due to different reasons. There are only calculation results about Li2NiSiO4 till now. This brief critical review firstly discussed some papers about the first-principle calculation of Li2MSiO4 (M=Fe, Mn, Co Ni), and then collects and discusses relevant papers and recent patents about the fabrication, structure, particle size and electrochemical performance of nano/micro Li2MSiO4 (M=Fe, Mn, Co Ni) and their composites. Finally, the future challenges of Li2FeSiO4 are also discussed.     

Recent Advances in Energy Chemical Engineering of Next-Generation Lithium Batteries

Rechargeable lithium-ion batteries (LIBs) afford a profound impact on our modern daily life. However, LIBs are approaching the theoretical energy density, due to the inherent limitations of intercalation chemistry; thus, they cannot further satisfy the increasing demands of portable electronics, electric vehicles, and grids. Therefore, battery chemistries beyond LIBs are being widely investigated. Next-generation lithium (Li) batteries, which employ Li metal as the anode and intercalation or conversion materials as the cathode, receive the most intensive interest due to their high energy density and excellent potential for commercialization. Moreover, significant progress has been achieved in Li batteries attributed to the increasing fundamental understanding of the materials and reactions, as well as to technological improvement. This review starts by summarizing the electrolytes for next-generation Li batteries. Key challenges and recent progress in lithium-ion, lithium–sulfur, and lithium–oxygen batteries are then reviewed from the perspective of energy and chemical engineering science. Finally, possible directions for further development in Li batteries are presented. Next-generation Li batteries are expected to promote the sustainable development of human civilization.     

锂离子电池聚阴离子型硅酸盐正极材料的研究进展

综述了硅酸盐正极材料的设计、特性、制备及电化学性能,介绍了基于密度泛函理论的量子化学计算在锂离子电池材料设计中的方法和理论,认为进一步开展Li2MSiO4及其复合材料的理论和实验研究可以获得性能优异的高容量正极材料.     

Comprehensive understanding of Li/Ni intermixing in layered transition metal oxides

With the development of high energy density battery technology, layered transition metal oxide cathode materials, particularly Ni-rich layered cathodes of Li-ion batteries are urgently required due to its high energy density. However, Li/Ni intermixing inevitably occurs in Ni-rich cathode materials and affects the materials in terms of structure and performance. This review comprehensively summarizes the causes of Li/Ni intermixing and analyzes its inevitability due to ionic radius, Ni migration, magnetic interactions, and thermal stability. In addition, the effect of Li/Ni intermixing on materials is summarized, particularly its benefits, which have not yet been comprehensively examined. Finally, the methods for regulating Li/Ni intermixing that corresponds to its causes are presented in detail. This review can help researchers fully understand Li/Ni intermixing and propose solutions for the current shortcomings of Li/Ni intermixing research and directions for future studies.     

Research on Advanced Materials for Li‐ion Batteries

In order to address power and energy demands of mobile electronics and electric cars, Li‐ion technology is urgently being optimized by using alternative materials. This article presents a review of our recent progress dedicated to the anode and cathode materials that have the potential to fulfil the crucial factors of cost, safety, lifetime, durability, power density, and energy density. Nanostructured inorganic compounds have been extensively investigated. Size effects revealed in the storage of lithium through micropores (hard carbon spheres), alloys (Si, SnSb), and conversion reactions (Cr₂O₃, MnO) are studied. The formation of nano/micro core–shell, dispersed composite, and surface pinning structures can improve their cycling performance. Surface coating on LiCoO₂ and LiMn₂O₄ was found to be an effective way to enhance their thermal and chemical stability and the mechanisms are discussed. Theoretical simulations and experiments on LiFePO₄ reveal that alkali metal ions and nitrogen doping into the LiFePO₄ lattice are possible approaches to increase its electronic conductivity and does not block transport of lithium ion along the 1D channel.     

Lithium ion transport in a model of amorphous polyethylene oxide

Summary We have made a molecular dynamics study of transport of a single lithium ion in a previously reported model of amorphous polyethylene oxide. New ab initio calculations of the interaction of the lithium ion with 1,2-dimethoxyethane and with dimethyl ether are reported which are used to determine force fields for the simulation. We report preliminary calculations of solvation energies and hopping barriers and a calculation of the ionic conductivity which is independent of any assumptions about the mechanism of ion transport. We also report some details of a study of transport of the trapped lithium ion on intermediate time and length scales.     

Recent research progress of alloy-containing lithium anodes in lithium-metal batteries

Lithium metal is regarded as one of the most ideal anode materials for next-generation batteries, due to its high theoretical capacity of 3860 mAh g⁻¹ and low redox potential (−3.04 V vs standard hydrogen electrode). However, practical applications of lithium anodes are impeded by the uncontrollable growth of lithium dendrite and continuous reactions between lithium and electrolyte during cycling processes. According to reports for decades, artificial solid electrolyte interface (SEI), electrolyte additives, and construction of three-dimensional (3D) structures are demonstrated essential strategies. Among numerous approaches, metals that can alloy with lithium have been employed to homogenize lithium deposition and accelerate Li ion transportation, which attract more and more attention. This review aims to summarize the lithium alloying applied in lithium anodes including the fabricating approaches of alloy-containing lithium anodes, and the action mechanism and challenges of fabricated lithium anodes. Based on summarizing the literature, shortcomings and challenges as well as the prospects are also analyzed, to impel further research of lithium anodes and lithium-based batteries.