Structure Design and Performance of LiNixCoyMn1‐x‐yO2 Cathode Materials for Lithium‐ion Batteries: A Review

Lithium‐ion batteries are now considered to be the technology of choice for future hybrid electric and full electric vehicles to address global warming. One of the challenges for improving the performance of lithium ion batteries to meet increasingly demanding requirements for energy storage is the development of suitable cathode materials. The recent advancement of lithium nickel cobalt manganese oxides are investigated as advanced positive cathode materials for lithium‐ion batteries. This review aims at providing the reader with an understanding of the critical scientific challenges facing the development of LiNi_xCo_yMn_1‐x‐yO₂ materials, the latest developments in crystal structure, synthesis methods, and structure designs to unravel the mechanisms of charge and mass transport processes associated with battery performance, and the outlook for future‐generation batteries that exploit gradient structures materials for significantly improved performance to meet the ever‐increasing demands of emerging technologies.     

A Core–Shell Fe/Fe2O3 Nanowire as a High‐Performance Anode Material for Lithium‐Ion Batteries

The preparation of novel one‐dimensional core–shell Fe/Fe₂O₃ nanowires as anodes for high‐performance lithium‐ion batteries (LIBs) is reported. The nanowires are prepared in a facile synthetic process in aqueous solution under ambient conditions with subsequent annealing treatment that could tune the capacity for lithium storage. When this hybrid is used as an anode material for LIBs, the outer Fe₂O₃ shell can act as an electrochemically active material to store and release lithium ions, whereas the highly conductive and inactive Fe core functions as nothing more than an efficient electrical conducting pathway and a remarkable buffer to tolerate volume changes of the electrode materials during the insertion and extraction of lithium ions. The core–shell Fe/Fe₂O₃ nanowire maintains an excellent reversible capacity of over 767 mA h g^?1 at 500 mA g^?1 after 200 cycles with a high average Coulombic efficiency of 98.6 %. Even at 2000 mA g^?1, a stable capacity as high as 538 mA h g^?1 could be obtained. The unique composition and nanostructure of this electrode material contribute to this enhanced electrochemical performance. Due to the ease of large‐scale fabrication and superior electrochemical performance, these hybrid nanowires are promising anode materials for the next generation of high‐performance LIBs.     

氧化石墨烯浓度对还原氧化石墨烯/ZnS电化学性能的影响

以氧化石墨烯(GO)、乙酸锌(Zn(CH₃COO)₂)和硫脲为原料,采用水热法成功制备了还原氧化石墨烯/ZnS(rGO/ZnS)复合材料,并将该材料用作锂离子电池负极。高导电性的 rGO可以为锂离子和电子的传输提供有效的路径,ZnS可以提供较高的理论比容量。rGO/ZnS复合材料在rGO与纳米级高度分散的类球形ZnS颗粒协同作用下展现了较好的嵌锂容量和循环性能。当GO质量浓度为2 mg·mL^-1时制备的rGO/ZnS复合材料的倍率性能最好,循环稳定性最佳。     

氧化石墨烯浓度对还原氧化石墨烯/ZnS电化学性能的影响

以氧化石墨烯(GO)、乙酸锌(Zn(CH₃COO)₂)和硫脲为原料,采用水热法成功制备了还原氧化石墨烯/ZnS(rGO/ZnS)复合材料,并将该材料用作锂离子电池负极。高导电性的 rGO可以为锂离子和电子的传输提供有效的路径,ZnS可以提供较高的理论比容量。rGO/ZnS复合材料在rGO与纳米级高度分散的类球形ZnS颗粒协同作用下展现了较好的嵌锂容量和循环性能。当GO质量浓度为2 mg·mL^-1时制备的rGO/ZnS复合材料的倍率性能最好,循环稳定性最佳。     

Coated/Sandwiched rGO/CoSx Composites Derived from Metal–Organic Frameworks/GO as Advanced Anode Materials for Lithium‐Ion Batteries

Rational composite materials made from transition metal sulfides and reduced graphene oxide (rGO) are highly desirable for designing high‐performance lithium‐ion batteries (LIBs). Here, rGO‐coated or sandwiched CoS_x composites are fabricated through facile thermal sulfurization of metal–organic framework/GO precursors. By scrupulously changing the proportion of Co²⁺ and organic ligands and the solvent of the reaction system, we can tune the forms of GO as either a coating or a supporting layer. Upon testing as anode materials for LIBs, the as‐prepared CoS_x‐rGO‐CoS_x and rGO@CoS_x composites demonstrate brilliant electrochemical performances such as high initial specific capacities of 1248 and 1320 mA h g^?1, respectively, at a current density of 100 mA g^?1, and stable cycling abilities of 670 and 613 mA h g^?1, respectively, after 100 charge/discharge cycles, as well as superior rate capabilities. The excellent electrical conductivity and porous structure of the CoS_x/rGO composites can promote Li⁺ transfer and mitigate internal stress during the charge/discharge process, thus significantly improving the electrochemical performance of electrode materials.     

Hierarchical SnO2 with double carbon coating composites as anode materials for lithium ion batteries

Hierarchical SnO₂ with double carbon coating (polypyrrole-derived carbon and reduced graphene oxide in order) composites have been successfully synthesized as anode materials for lithium ion batteries. The composites were characterized and examined by X-ray diffraction, scanning electron microscopy, thermogravimetric analysis, cyclic voltammetry, and galvanostatic discharge/charge tests. Such a novel nanostructure can not only provide a high conductivity but also prevent aggregation of SnO₂ nanoparticles, leading to the improvement of the cycling performance. Comparing with pure hierarchical SnO₂ and polypyrrole-derived carbon-coated hierarchical SnO₂, hierarchical SnO₂ with double carbon coating composite exhibits higher lithium storage capacities and better cycling performance, 554.8 mAh g^?1 after 50 cycles at a current density of 250 mA g^?1. In addition, the rate performance of hierarchical SnO₂ with double carbon coating composite is also very well. For all the improved performances, this double carbon coating architecture may provide some references for other electrode materials of lithium ion batteries.     

Vanadium oxide gels as electrode materials for lithium batteries

Electrochemical lithium insertion has been studied in a large number of vanadium oxides with three dimensional framework structure. Several of these oxides have shown high capacities for lithium insertion and good reversibility.Pure solutions of decavanadic acid have shown to undergo spontaneous polycondensation reaction forming sols or gels of highly polymerized vanadium oxides, M _w 10⁶. After dehydration a series of xerogels with varying amounts of water, V₂O₅ · nH₂O, can be obtained. The structure of these xerogels consists of ribbons of corner and edge sharing VO₆ octahedra stabilized by interlayer water molecules. Under ambient conditions the water content corresponds to n=1.8, but this value can be reversibly changed under mild drying conditions.This report deals with the electrochemical insertion of lithium in dried vanadium oxide xerogels, with special regard to the use of these materials as electrodes in rechargeable lithium batteries.     

锰氧化物负载碳氮三维网络结构复合材料的制备及锂电性能

通过硝酸锰和乙醇的水热反应在三聚氰胺泡棉（MF）上生成三氧化二锰颗粒,氮气下高温处理后形成锰氧化物负载碳氮三维网络结构的复合物。碳氮网络结构提高了充放电过程中材料结构的稳定性及导电性,且烧结过程中产生的孔道结构有利于锂离子传输,使得该复合材料作为负极在锂离子电池中表现出优异的充放电性能和循环稳定性。材料的比容量和循环稳定性大大提高,经500℃处理后的MnO/CNnws-500材料在160次循环后仍然保留590 mAh·g^-1的比容量,达到氧化亚锰理论容量755 mAh·g^-1的78%。     

锰氧化物/碳氮三维网络结构复合材料的制备及锂电性能

通过硝酸锰和乙醇的水热反应在三聚氰胺泡棉(MF)上生成三氧化二锰颗粒,氮气下高温处理后形成锰氧化物负载碳氮三维网络结构的复合物。碳氮网络结构提高了充放电过程中材料结构的稳定性及导电性,且烧结过程中产生的孔道结构有利于锂离子传输,使得该复合材料作为负极在锂离子电池中表现出优异的充放电性能和循环稳定性。材料的比容量和循环稳定性大大提高,经500℃处理后的MnO/CNnws-500材料在160次循环后仍然保留590 m Ah·g~(-1)的比容量,达到氧化亚锰理论容量755 m Ah·g~(-1)的78%。     

Cathode materials for lithium ion batteries prepared by sol-gel methods

Improving the preparation technology and electrochemical performance of cathode materials for lithium ion batteries is a current major focus of research and development in the areas of materials, power sources and chemistry. Sol-gel methods are promising candidates to prepare cathode materials owing to their evident advantages over traditional methods. In this paper, the latest progress on the preparation of cathode materials such as lithium cobalt oxides, lithium nickel oxides, lithium manganese oxides, vanadium oxides and other compounds by sol-gel methods is reviewed, and further directions are pointed out. The prepared products provide better electrochemical performance, including reversible capacity, cycling behavior and rate capability in comparison with those from traditional solid-state reactions. The main reasons are due to the following several factors: homogeneous mixing at the atomic or molecular level, lower synthesis temperature, shorter heating time, better crystallinity, uniform particle distribution and smaller particle size at the nanometer level. As a result, the structural stability of the cathode materials and lithium intercalation and deintercalation behavior are much improved. These methods can also be used to prepare novel types of cathode materials such as nanowires of LiCoO₂ and nanotubes of V₂O₅, which cannot be easily obtained by traditional methods. With further development and application of sol-gel methods, better and new cathode materials will become available and the advance of lithium ion batteries will be greatly promoted.     

Wintersweet‐Flower‐Like CoFe2O4/MWCNTs Hybrid Material for High‐Capacity Reversible Lithium Storage

CoFe₂O₄/multiwalled carbon nanotubes (MWCNTs) hybrid materials were synthesized by a hydrothermal method. Field emission scanning electron microscopy and transmission electron microscopy analysis confirmed the morphology of the as‐prepared hybrid material resembling wintersweet flower “buds on branches”, in which CoFe₂O₄ nanoclusters, consisting of nanocrystals with a size of 5–10 nm, are anchored along carbon nanotubes. When applied as an anode material in lithium ion batteries, the CoFe₂O₄/MWCNTs hybrid material exhibited a high performance for reversible lithium storage. In particular, the hybrid anode material delivered reversible lithium storage capacities of 809, 765, 539, and 359 mA h g^?1 at current densities of 180, 450, 900, and 1800 mA g^?1, respectively. The superior performance of CoFe₂O₄/MWCNTs hybrid materials could be ascribed to the synergistic pinning effect of the wintersweet‐flower‐like nanoarchitecture. This strategy could also be applied to synthesize other metal oxide/CNTs hybrid materials as high‐capacity anode materials for lithium ion batteries.     

Facile Preparation and Lithium Storage Properties of TiO2@Graphene Composite Electrodes with Low Carbon Content

Over the past decade, TiO₂/graphene composites as electrodes for lithium ion batteries have attracted a great deal of attention for reasons of safety and environmental friendliness. However, most of the TiO₂/graphene electrodes have large graphene content (9–40 %), which is bound to increase the cost of the battery. Logically, reducing the amount of graphene is a necessary part to achieve a green battery. The synthesis of TiO₂ nanosheets under solvothermal conditions without additives is now demonstrated. Through mechanical mixing TiO₂ nanosheets with different amount of reduced graphene (rGO), a series of TiO₂@graphene composites was prepared with low graphene content (rGO content 1, 2, 3, and 5 wt %). When these composites were evaluated as anodes for lithium ion batteries, it was found that TiO₂+3 wt % rGO manifested excellent cycling stability and a high specific capacity (243.7 mAh g^?1 at 1 C; 1 C=167.5 mA g^?1), and demonstrated superior high‐rate discharge/charge capability at 20 C.     

纳米级锂离子电池正极材料LiFePO4

LiFePO₄以其价格便宜,稳定性好,无毒等优点而倍受关注。但是非纳米LiFePO₄的电子导电率低及扩散系数小限制了其在锂离子电池领域的大规模应用。而纳米电极材料以其特有的优点很好的解决了这些问题。本文主要综述了国内外合成纳米级LiFePO₄ 的不同方法及所得材料的对电化学性能和相关机理,以及纳米LiFePO₄作为锂离子正极材料存在的问题。     

Facile simultaneous polymerization enabled in-situ confinement of size-tailored GeO2 nanocrystals in continuous S-Doped carbons for lithium storage

GeO₂ is a promising anode material for lithium ion batteries due to its high theoretical capacity (1126 mAh g^?1 for reversibly storing 4.4 Li⁺), and moderately low operating voltage (<1.5 V). Nevertheless, the fabrication of truly durable GeO₂ anode with satisfactory rate capability and cycling stability remains a big challenge because of its inherent low conductivity, and the large volume expansion upon charge-discharge that causes severe capacity fading. In this study, an innovative nanostructure with size-adjustable GeO₂ nanoparticles (16–26 nm) embedded in continuous S-doped carbon (GeO₂/S-doped carbon, GSC) has been successfully fabricated via a facile in-situ simultaneous polymerization method followed by heat treatment. The electrochemical results indicate that the as-prepared GSC composites show high reversible capacity (672.9 mAh g^?1 at 50 mA g^?1), superior rate capability (332.9 mAh g^?1 at 1000 mA g^?1), and long-term cycle life (179 mAh g^?1 after 500 cycles at 1000 mA g^?1) as anode materials for lithium ion batteries. The excellent electrochemical performance of GSC nanocomposites could be ascribed to the homogeneous and continuous S-doped carbon matrix, which provides shortened ion diffusion pathway, increased electrical conductivity, enhanced structural stability, and introduced surface/interface property.     

Amorphous cobalt silicate nanobelts@carbon composites as a stable anode material for lithium ion batteries

During the past decade, tremendous attention has been given to the development of new electrode materials with high capacity to meet the requirements of electrode materials with high energy density in lithium ion batteries. Very recently, cobalt silicate has been proposed as a new type of high capacity anode material for lithium ion batteries. However, the bulky cobalt silicate demonstrates limited electrochemical performance. Nanostructure engineering and carbon coating represent two promising strategies to improve the electrochemical performance of electrode materials. Herein, we developed a template method for the synthesis of amorphous cobalt silicate nanobelts which can be coated with carbon through the deposition and thermal decomposition of phenol formaldehyde resin. Tested as an anode material, the amorphous cobalt silicate nanobelts@carbon composites exhibit a reversible high capacity of 745 mA h g^–1 at a current density of 100 mA g^–1, and a long life span of up to 1000 cycles with a stable capacity retention of 480 mA h g^–1 at a current density of 500 mA g^–1. The outstanding electrochemical performance of the composites indicates their high potential as an anode material for lithium ion batteries. The results here are expected to stimulate further research into transition metal silicate nanostructures for lithium ion battery applications.     

Electrospun porous SnO2 nanotubes as high capacity anode materials for lithium ion batteries

Porous SnO₂ nanotubes were prepared via electrospinning followed by calcination in air. As anode materials for lithium ion batteries, the porous nanotubes delivered a high discharge capacity of 807 mAh g^? 1 after 50 cycles. Even after cycled at high rates, the electrode still retained a high fraction of its theoretical capacity. Such excellent performances of porous SnO₂ nanotubes could be attributed to the porous and hollow structure which facilitated liquid electrolyte diffusion into the bulk materials and buffered large volume changes during lithium ions insertion/extraction. Furthermore, the nanoparticles of nanotubes provided the shorter diffusion length for lithium ions insertion which benefited in retaining the structural stability and good rate performance. Our results demonstrated that this simple method could be extended for the synthesis of porous metal oxide nanotubes with high performances in the applications of lithium ion batteries and other fields.     

Direct Observation of Defect-Aided Structural Evolution in a Nickel-Rich Layered Cathode

Ni-rich LiNi_1−x−yMn_xCo_yO₂ (NMC) layered compounds are the dominant cathode for lithium ion batteries. The role of crystallographic defects on structure evolution and performance degradation during electrochemical cycling is not yet fully understood. Here, we investigated the structural evolution of a Ni-rich NMC cathode in a solid-state cell by in situ transmission electron microscopy. Antiphase boundary (APB) and twin boundary (TB) separating layered phases played an important role on phase change. Upon Li depletion, the APB extended across the layered structure, while Li/transition metal (TM) ion mixing in the layered phases was detected to induce the rock-salt phase formation along the coherent TB. According to DFT calculations, Li/TM mixing and phase transition were aided by the low diffusion barriers of TM ions at planar defects. This work reveals the dynamical scenario of secondary phase evolution, helping unveil the origin of performance fading in Ni-rich NMC.     

花瓣状微球MoS2/石墨烯复合材料的制备及其电化学性能

采用有利于二维层状结构形成的L-半胱氨酸作为硫源,钼酸钠作为钼源,制备聚乙烯基吡咯烷酮（PVP）辅助水热合成花瓣状微球形貌的MoS₂/还原氧化石墨烯复合电极材料（PVP-MoS₂/RGO）. X射线衍射（XRD）及透射电子显微镜（TEM）证实,经过PVP的适量添加,MoS₂有序堆垛结构的片层数目明显减少. 扫描电子显微镜（SEM）显示,添加适量PVP的MoS₂/石墨烯材料具有分散性更好的花瓣状微球形貌. 上述的少层有序堆垛结构及复合材料的良好分散性缩短了MoS₂中锂离子的嵌入/脱出路径,使其具有更高的容量、循环稳定性和倍率性能.     

An Approach towards Synthesis of Nanoarchitectured LiNi1/3Co1/3Mn1/3O2 Cathode Material for Lithium Ion Batteries

To explore advanced cathode materials for lithium ion batteries (LIBs), a nanoarchitectured LiNi_1/3Co_1/3Mn_1/3O₂ (LNCM) material is developed using a modified carbonate coprecipitation method in combination with a vacuum distillation‐crystallisation process. Compared with the LNCM materials produced by a traditional carbonate coprecipitation method, the prepared LNCM material synthesized through this modified method reveals a better hexagonal layered structure, smaller particle sizes (ca. 110.5 nm), and higher specific surface areas. Because of its unique structural characteristics, the as‐prepared LNCM material demonstrates excellent electrochemical properties including high rate capability and good cycleability when it is utilized as a cathode in the lithium ion battery (LIB).     

Breaking Mass Transport Limitations by Iodized Polyacrylonitrile Anodes for Extremely Fast-Charging Lithium-Ion Batteries

The fast-charging capability of rechargeable batteries is greatly limited by the sluggish ion transport kinetics in anode materials. Here we develop an iodized polyacrylonitrile (I-PAN) anode that can boost the bulk/interphase lithium (Li)-ion diffusion kinetics and accelerate Li-ion desolvation process to realize high-performance fast-charging Li-ion batteries. The iodine immobilized in I-PAN framework expands ion transport channels, compresses the electric double layer, and changes the inner Helmholtz plane to form LiF/LiI-rich solid electrolyte interphase layer. The dissolved iodine ions in the electrolyte self-induced by the interfacial nucleophilic substitution of PF₆⁻ not only promote the Li-ion desolvation process, but also reuse the plated/dead Li formed on the anode under fast-charging conditions. Consequently, the I-PAN anode exhibits a high capacity of 228.5 mAh g⁻¹ (39 % of capacity at 0.5 A g⁻¹ delivered in 18 seconds) and negligible capacity decay for 10000 cycles at 20 A g⁻¹. The I-PAN||LiNi_0.8Co_0.1Mn_0.1O₂ full cell shows excellent fast-charging performance with attractive capacities and negligible capacity decay for 1000 cycles at extremely high rates of 5 C and 10 C (1 C=180 mA g⁻¹). We also demonstrate high-performance fast-charging sodium-ion batteries using I-PAN anodes.