Fluorinated Polyimide as a Novel High‐Voltage Binder for High‐Capacity Cathode of Lithium‐Ion Batteries

An increase in the energy density of lithium‐ion batteries has long been a competitive advantage for advanced wireless devices and long‐driving electric vehicles. Li‐rich layered oxide, xLi₂MnO₃?(1?x)LiMn_1?y?zNi_yCo_zO₂, is a promising high‐capacity cathode material for high‐energy batteries, whose capacity increases by increasing charge voltage to above 4.6 V versus Li. Li‐rich layered oxide cathode however suffers from a rapid capacity fade during the high‐voltage cycling because of instable cathode–electrolyte interface, and the occurrence of metal dissolution, particle cracking, and structural degradation, particularly, at elevated temperatures. Herein, this study reports the development of fluorinated polyimide as a novel high‐voltage binder, which mitigates the cathode degradation problems through superior binding ability to conventional polyvinylidenefluoride binder and the formation of robust surface structure at the cathode. A full‐cell consisting of fluorinated polyimide binder‐assisted Li‐rich layered oxide cathode and conventional electrolyte without any electrolyte additive exhibits significantly improved capacity retention to 89% at the 100th cycle and discharge capacity to 223–198 mA h g^?1 even under the harsh condition of 55 °C and high charge voltage of 4.7 V, in contrast to a rapid performance fade of the cathode coated with polyvinylidenefluoride binder.     

Understanding the Origin of Li2MnO3 Activation in Li‐Rich Cathode Materials for Lithium‐Ion Batteries

Li‐rich layered cathode materials have been considered as a family of promising high‐energy density cathode materials for next generation lithium‐ion batteries (LIBs). However, although activation of the Li₂MnO₃ phase is known to play an essential role in providing superior capacity, the mechanism of activation of the Li₂MnO₃ phase in Li‐rich cathode materials is still not fully understood. In this work, an interesting Li‐rich cathode material Li_1.87Mn_0.94Ni_0.19O₃ is reported where the Li₂MnO₃ phase activation process can be effectively controlled due to the relatively low level of Ni doping. Such a unique feature offers the possibility of investigating the detailed activation mechanism by examining the intermediate states and phases of the Li₂MnO₃ during the controlled activation process. Combining powerful synchrotron in situ X‐ray diffraction analysis and observations using advanced scanning transmission electron microscopy equipped with a high angle annular dark field detector, it has been revealed that the subreaction of O₂ generation may feature a much faster kinetics than the transition metal diffusion during the Li₂MnO₃ activation process, indicating that the latter plays a crucial role in determining the Li₂MnO₃ activation rate and leading to the unusual stepwise capacity increase over charging cycles.     

Tuning Anionic Redox Activity and Reversibility for a High‐Capacity Li‐Rich Mn‐Based Oxide Cathode via an Integrated Strategy

When fabricating Li‐rich layered oxide cathode materials, anionic redox chemistry plays a critical role in achieving a large specific capacity. Unfortunately, the release of lattice oxygen at the surface impedes the reversibility of the anionic redox reaction, which induces a large irreversible capacity loss, inferior thermal stability, and voltage decay. Therefore, methods for improving the anionic redox constitute a major challenge for the application of high‐energy‐density Li‐rich Mn‐based cathode materials. Herein, to enhance the oxygen redox activity and reversibility in Co‐free Li‐rich Mn‐based Li_1.2Mn_0.6Ni_0.2O₂ cathode materials by using an integrated strategy of Li₂SnO₃ coating‐induced Sn doping and spinel phase formation during synchronous lithiation is proposed. As an Li⁺ conductor, a Li₂SnO₃ nanocoating layer protects the lattice oxygen from exposure at the surface, thereby avoiding irreversible oxidation. The synergy of the formed spinel phase and Sn dopant not only improves the anionic redox activity, reversibility, and Li⁺ migration rate but also decreases Li/Ni mixing. The 1% Li₂SnO₃‐coated Li_1.2Mn_0.6Ni_0.2O₂ delivers a capacity of more than 300 mAh g^?1 with 92% Coulombic efficiency. Moreover, improved thermal stability and voltage retention are also observed. This synergic strategy may provide insights for understanding and designing new high‐performance materials with enhanced reversible anionic redox and stabilized surface lattice oxygen.     

Unveiling Nickel Chemistry in Stabilizing High‐Voltage Cobalt‐Rich Cathodes for Lithium‐Ion Batteries

A practical solution is presented to increase the stability of 4.45 V LiCoO₂ via high‐temperature Ni doping, without adding any extra synthesis step or cost. How a putative uniform bulk doping with highly soluble elements can profoundly modify the surface chemistry and structural stability is identified from systematic chemical and microstructural analyses. This modification has an electronic origin, where surface‐oxygen‐loss induced Co reduction that favors the tetrahedral site and causes damaging spinel phase formation is replaced by Ni reduction that favors octahedral site and creates a better cation‐mixed structure. The findings of this study point to previously unspecified surface effects on the electrochemical performance of battery electrode materials hidden behind an extensively practiced bulk doping strategy. The new understanding of complex surface chemistry is expected to help develop higher‐energy‐density cathode materials for rechargeable batteries.     

Understanding the Stability for Li‐Rich Layered Oxide Li2RuO3 Cathode

Lithium‐rich layered oxides are considered as promising cathode materials for Li‐ion batteries with high energy density due to their higher capacity as compared with the conventional LiMO₂ (e.g., LiCoO₂, LiNiO₂, and LiNi_1/3Co_1/3Mn_1/3O₂) layered oxides. However, why lithium‐rich layered oxides exhibit high capacities without undergoing a structural collapse for a certain number of cycles has attracted limited attention. Here, based on the model of Li₂RuO₃, it is uncovered that the mechanism responsible for the structural integrity shown by lithium‐rich layered oxides is realized by the flexible local structure due to the presence of lithium atoms in the transition metal layer, which favors the formation of O₂^2?‐like species, with the aid of in situ extended X‐ray absorption fine structure (EXAFS), in situ energy loss spectroscopy (EELS), and density functional theory (DFT) calculation. This finding will open new scope for the development of high‐capacity layered electrodes.     

Simultaneously Dual Modification of Ni‐Rich Layered Oxide Cathode for High‐Energy Lithium‐Ion Batteries

A critical challenge in the commercialization of layer‐structured Ni‐rich materials is the fast capacity drop and voltage fading due to the interfacial instability and bulk structural degradation of the cathodes during battery operation. Herein, with the guidance of theoretical calculations of migration energy difference between La and Ti from the surface to the inside of LiNi_0.8Co_0.1Mn_0.1O₂, for the first time, Ti‐doped and La₄NiLiO₈‐coated LiNi_0.8Co_0.1Mn_0.1O₂ cathodes are rationally designed and prepared, via a simple and convenient dual‐modification strategy of synchronous synthesis and in situ modification. Impressively, the dual modified materials show remarkably improved electrochemical performance and largely suppressed voltage fading, even under exertive operational conditions at elevated temperature and under extended cutoff voltage. Further studies reveal that the nanoscale structural degradation on material surfaces and the appearance of intergranular cracks associated with the inconsistent evolution of structural degradation at the particle level can be effectively suppressed by the synergetic effect of the conductive La₄NiLiO₈ coating layer and the strong Ti? O bond. The present work demonstrates that our strategy can simultaneously address the two issues with respect to interfacial instability and bulk structural degradation, and it represents a significant progress in the development of advanced cathode materials for high‐performance lithium‐ion batteries.     

Role of Ordered Ni Atoms in Li Layers for Li‐Rich Layered Cathode Materials

Li‐rich layered oxide materials are promising candidates for high‐energy Li‐ion batteries. They show high capacities of over 200 mAh g^?1 with the additional occupation of Li in their transition metal layers; however, the poor cycle performance induced by an irreversible phase transition limits their use in practical applications. In recent work, an atomic‐scale modified surface, in which Ni is ordered at 2c sites in the Li layers, significantly improves the performance in terms of reversible capacity and cycling stability. The role of the incorporated Ni on this performance, however, is not yet clearly understood. Here, the effects of the ordered Ni on Li battery performance are presented, based on first‐principles calculations and experimental observations. The Ni substitution suppresses the oxygen loss by moderating the oxidation of oxygen ions during the delithiation process and forms bonds with adjacent oxygen after the first deintercalation of Li ions. These Ni? O bonds contribute to the formation of a solid surface, resulting in the improved cycling stability. Moreover, the multivalent Ni suppresses Mn migration to the Li‐sites that causes the undesired phase transition. These findings from theoretical calculations and experimental observations provide insights to enhance the electrochemical performance of Li‐rich layered oxides.     

Microstructure Evolution of Concentration Gradient Li[Ni0.75Co0.10Mn0.15]O2 Cathode for Lithium‐Ion Batteries

Detailed analysis of the microstructural changes during lithiation of a full‐concentration‐gradient (FCG) cathode with an average composition of Li[Ni_0.75Co_0.10Mn_0.15]O₂ is performed starting from its hydroxide precursor, FCG [Ni_0.75Co_0.10Mn_0.15](OH)₂ prior to lithiation. Transmission electron microscopy (TEM) reveals that a unique rod‐shaped primary particle morphology and radial crystallographic texture are present in the prelithiation stage. In addition, TEM detected a two‐phase structure consisting of MnOOH and Ni(OH)₂, and crystallographic twins of MnOOH on the Mn‐rich precursor surface. The formation of numerous twins is driven by the lattice mismatch between MnOOH and Ni(OH)₂. Furthermore, the twins persist in the lithiated cathode; however, their density decrease with increasing lithiation temperature. Cation disordering, which influences cathode performance, is observed to continuously decrease with increasing lithiation temperature with a minimum observed at 790 °C. Consequently, lithiation at 790 °C (for 10 h) produced optimal discharge capacity and cycling stability. Above 790 °C, an increase in cation disordering and excessive coarsening of the primary particles lead to the deterioration of electrochemical properties. The twins in the FCG cathode precursor may promote the optimal primary particle morphology by retarding the random coalescence of primary particles during lithiation, effectively preserving both the morphology and crystallographic texture of the precursor.     

High‐Voltage Charging‐Induced Strain,Heterogeneity, and Micro‐Cracks in Secondary Particles of a Nickel‐Rich Layered Cathode Material

Nickel‐rich layered materials LiNi_1‐x‐yMn_xCo_yO₂ are promising candidates for high‐energy‐density lithium‐ion battery cathodes. Unfortunately, they suffer from capacity fading upon cycling, especially with high‐voltage charging. It is critical to have a mechanistic understanding of such fade. Herein, synchrotron‐based techniques (including scattering, spectroscopy, and microcopy) and finite element analysis are utilized to understand the LiNi_0.6Mn_0.2Co_0.2O₂ material from structural, chemical, morphological, and mechanical points of view. The lattice structural changes are shown to be relatively reversible during cycling, even when 4.9 V charging is applied. However, local disorder and strain are induced by high‐voltage charging. Nano‐resolution 3D transmission X‐ray microscopy data analyzed by machine learning methodology reveal that high‐voltage charging induced significant oxidation state inhomogeneities in the cycled particles. Regions at the surface have a rock salt–type structure with lower oxidation state and build up the impedance, while regions with higher oxidization state are scattered in the bulk and are likely deactivated during cycling. In addition, the development of micro‐cracks is highly dependent on the pristine state morphology and cycling conditions. Hollow particles seem to be more robust against stress‐induced cracks than the solid ones, suggesting that morphology engineering can be effective in mitigating the crack problem in these materials.     

A Review: Electrospun Nanofiber Materials for Lithium‐Sulfur Batteries

Lithium‐sulfur (Li‐S) batteries are in the spotlight because their outstanding theoretical specific energy is much higher than those of the commercial lithium ion (Li‐ion) batteries. Li‐S batteries are tough competitors for future‐developing energy storage in the fields of portable electronics and electric vehicles. However, the severe “shuttle effect” of the polysulfides and the serious damage of lithium dendrites are main factors blocking commercial production of Li‐S batteries. Owing to their superior nanostructure, electrospun nanofiber materials commonly show some unique characteristics that can simultaneously resolve these issues. So far, various novel cathodes, separators, and interlayers of electrospun nanofiber materials which are applied to resolve these challenges are researched. This review presents the fundamental research and technological development of multifarious electrospun nanofiber materials for Li‐S cells, including their processing methods, structures, morphology engineering, and electrochemical performance. Not only does the review article contain a summary of electrospun nanofiber materials in Li‐S batteries but also a proposal for designing electrospun nanofiber materials for Li‐S cells. These systematic discussions and proposed directions can enlighten thoughts and offer ways in the reasonable design of electrospun nanofiber materials for excellent Li‐S batteries in the near future.     

Nitrogen‐Doped Mesoporous Carbon Promoted Chemical Adsorption of Sulfur and Fabrication of High‐Areal‐Capacity Sulfur Cathode with Exceptional Cycling Stability for Lithium‐Sulfur Batteries

As one important component of sulfur cathodes, the carbon host plays a key role in the electrochemical performance of lithium‐sulfur (Li‐S) batteries. In this paper, a mesoporous nitrogen‐doped carbon (MPNC)‐sulfur nanocomposite is reported as a novel cathode for advanced Li‐S batteries. The nitrogen doping in the MPNC material can effectively promote chemical adsorption between sulfur atoms and oxygen functional groups on the carbon, as verified by X‐ray absorption near edge structure spectroscopy, and the mechanism by which nitrogen enables the behavior is further revealed by density functional theory calculations. Based on the advantages of the porous structure and nitrogen doping, the MPNC‐sulfur cathodes show excellent cycling stability (95% retention within 100 cycles) at a high current density of 0.7 mAh cm^‐2 with a high sulfur loading (4.2 mg S cm^‐2) and a sulfur content (70 wt%). A high areal capacity (≈3.3 mAh cm^‐2) is demonstrated by using the novel cathode, which is crucial for the practical application of Li‐S batteries. It is believed that the important role of nitrogen doping promoted chemical adsorption can be extended for development of other high performance carbon‐sulfur composite cathodes for Li‐S batteries.     

Lithium Accommodation in a Redox‐Active Covalent Triazine Framework for High Areal Capacity and Fast‐Charging Lithium‐Ion Batteries

The synthesis of a new type of redox‐active covalent triazine framework (rCTF) material, which is promising as an anode for Li‐ion batteries, is reported. After activation, it has a capacity up to ≈1190 mAh g^?1 at 0.5C with a current density of 300 mA g^?1 and a high cycling stability of over 1000 discharge/charge cycles with a stable Coulombic efficiency in an rCTF/Li half‐cell. This rCTF has a high rate performance, and at a charging rate of 20C with a current density of 12 A g^?1 and it functions well for over 1000 discharge/charge cycles with a reversible capacity of over 500 mAh g^?1. By electrochemical analysis and theoretical calculations, it is found that its lithium‐storage mechanism involves multi‐electron redox‐reactions at anthraquinone, triazine, and benzene rings by the accommodation of Li. The structural features and progressively increased structural disorder of the rCTF increase the kinetics of infiltration and significantly shortens the activation period, yielding fast‐charging Li‐ion half and full cells even at a high capacity loading.     

Synchronous Tailoring Surface Structure and Chemical Composition of Li‐Rich–Layered Oxide for High‐Energy Lithium‐Ion Batteries

Li‐rich–layered oxide is considered to be one of the most promising cathode materials for high‐energy lithium ion batteries. However, it suffers from poor rate capability, capacity loss, and voltage decay upon cycling that limits its utilization in practical applications. Surface properties of Li‐rich–layered oxide play a critical role in the function of batteries. Herein, a novel and successful strategy for synchronous tailoring surface structure and chemical composition of Li‐rich–layered oxide is proposed. Poor nickel content on the surface of carbonate precursor is initially prepared by a facile treatment of NH₃·H₂O, which can retain at a certain low amount on the surface in the final lithiated Li‐rich–layered oxide after a solid‐phase reaction process. Moreover, a phase‐gradient outer layer with “layered‐coexisting phase‐spinel” structure toward to the outside surface is self‐induced and formed synchronously based on poor nickel surface of the precursor. Electrochemical tests reveal this unique surface enables excellent cycling stability, improved rate capability, and slight voltage decay of cathodes. The finding here sheds light on a universal principle both for masterly tailoring surface structure and chemical composition at the same time for improving electrochemical performance of electrode materials.     

A Family of High‐Performance Cathode Materials for Na‐ion Batteries,Na3(VO1−xPO4)2 F1+2x (0 ≤ x ≤ 1): Combined First‐Principles and Experimental Study

Room‐temperature Na‐ion batteries (NIBs) have recently attracted attention as potential alternatives to current Li‐ion batteries (LIBs). The natural abundance of sodium and the similarity between the electrochemical properties of NIBs and LIBs make NIBs well suited for applications requiring low cost and long‐term reliability. Here, the first successful synthesis of a series of Na₃(VO_1?x PO₄)₂F_1+2x (0 ≤ x ≤ 1) compounds as a new family of high‐performance cathode materials for NIBs is reported. The Na₃(VO_1?x PO₄)₂F_1+2x series can function as high‐performance cathodes for NIBs with high energy density and good cycle life, although the redox mechanism varies depending on the composition. The combined first‐principles calculations and experimental analysis reveal the detailed structural and electrochemical mechanisms of the various compositions in solid solutions of Na₃(VOPO₄)₂F and Na₃V₂(PO₄)₂F₃. The comparative data for the Na _y (VO_1?x PO₄)₂F_1+2x electrodes show a clear relationship among V³⁺/V⁴⁺/V⁵⁺ redox reactions, Na⁺?Na⁺ interactions, and Na⁺ intercalation mechanisms in NIBs. The new family of high‐energy cathode materials reported here is expected to spur the development of low‐cost, high‐performance NIBs.     

Self‐Sacrifice Template Fabrication of Hierarchical Mesoporous Bi‐Component‐Active ZnO/ZnFe2O4 Sub‐Microcubes as Superior Anode Towards High‐Performance Lithium‐Ion Battery

In the work, a facile yet efficient self‐sacrifice strategy is smartly developed to scalably fabricate hierarchical mesoporous bi‐component‐active ZnO/ZnFe₂O₄ (ZZFO) sub‐microcubes (SMCs) by calcination of single‐resource Prussian blue analogue of Zn₃[Fe(CN)₆]₂ cubes. The hybrid ZZFO SCMs are homogeneously constructed from well‐dispersed nanocrstalline ZnO and ZnFe₂O₄ (ZFO) subunites at the nanoscale. After selectively etching of ZnO nanodomains from the hybrid, porously assembled ZFO SMCs with integrate architecture are obtained accordingly. When evaluated as anodes for LIBs, both hybrid ZZFO and ZFO samples exhibit appealing electrochemical performance. However, the as‐synthesized ZZFO SMCs demonstrate even better electrochemical Li‐storage performance, including even larger initial discharge capacity and reversible capacity, higher rate behavior and better cycling performance, particularly at high rates, compared with the single ZFO, which should be attributed to its unique microstructure characteristics and striking synergistic effect between the bi‐component‐active, well‐dispersed ZnO and ZFO nanophases. Of great significance, light is shed upon the insights into the correlation between the electrochemical Li‐storage property and the structure/component of the hybrid ZZFO SMCs, thus, it is strongly envisioned that the elegant design concept of the hybrid holds great promise for the efficient synthesis of advanced yet low‐cost anodes for next‐generation rechargeable Li‐ion batteries.     

Co3O4 Nanomaterials in Lithium‐Ion Batteries and Gas Sensors

Co₃O₄ nanotubes, nanorods, and nanoparticles are used as the anode materials of lithium‐ion batteries. The results show that the Co₃O₄ nanotubes prepared by a porous‐alumina‐template method display high discharge capacity and superior cycling reversibility. Furthermore, Co₃O₄ nanotubes exhibit excellent sensitivity to hydrogen and alcohol, owing to their hollow, nanostructured character.     

Engineering of Polyanion Type Cathode Materials for Sodium‐Ion Batteries: Toward Higher Energy/Power Density

The development of high energy/power density sodium‐ion batteries (SIBs) is still challenged by the high redox potential of Na/Na⁺ and large radius of Na⁺ ions, thus requiring extensive further improvement to, in particular, enhance the capacity and voltage of cathode materials. Among the various types of cathodes, the polyanion cathodes have emerged as the most pragmatic option due to their outstanding thermostability, unique inductive effect, and flexible structures. In this Review, a critical overview of the design principles and engineering strategies of polyanion cathodes that could have a pivotal role in developing high energy/power density SIBs are presented. Specifically, the engineering of polyanion cathode materials for higher voltage and specific capacity to increase energy density is discussed. The way in which morphology control, architectural design, and electrode processing have been developed to increase power density for SIBs is also analyzed. Finally, the remaining challenges and the future research direction of this field are presented.