Mitigating detrimental chemical crosstalk between the cathode and anode is crucial for improving battery thermal stability and enabling the development of high-energy-density batteries. As the critical interlayer situated between the electrodes, the separator can be strategically designed to regulate the transport of transition metal ions, offering a direct and effective route to suppress chemical crosstalk and enhance battery safety. Herein, we demonstrate a covalent organic framework (COF) functional separator to alleviate this detrimental crosstalk in Li|LiNi0.6Co0.2Mn0.2O2 (NCM622) cells. The COF separator, featuring well-defined nanochannels and abundant functional groups, ensures a uniform Li+ flux and selectively captures dissolved transition metal ions. Moreover, COF cell delivers an initial discharge capacity of 169.3 mAh g-1 with 78% capacity retention after 700 cycles, substantially outperforming the PP-based cell (164.9 mAh g-1, 62%). The COF separator improves performance by suppressing parasitic reactions at both electrodes, promoting a stable SEI on the Li anode, and reducing electrolyte decomposition on the cathode. Furthermore, X-ray photoelectron spectroscopy (XPS) and Density Functional Theory (DFT) calculations confirm that the COF separator effectively inhibits the shuttling and deposition of Ni2+ ions. This work provides a viable strategy to address cathode anode crosstalk in high-energy-density batteries through rational separator design.

The pursuit of higher energy density has long dictated the development of cathode materials for lithium-ion batteries (LIBs). While the prevailing high-nickel, low-cobalt strategy effectively boosts specific capacity, it inevitably compromises structural stability, thermal safety, and manufacturing robustness. Here, a paradigm shift is proposed toward medium-nickel low-cobalt (MN-LC) cathodes with a composition of Ni 60−70%, Co ≤ 10%, and Mn ≥ 20%—a class of materials that has been historically underestimated but offers intrinsic advantages in cost efficiency, cycle life, and thermal safety. Through advanced modification strategies such as cut-off voltage extension, single-crystallization, and elemental doping, the specific capacity gap with high-nickel counterparts is effectively closed, enabling energy densities (active-material-level) exceeding 750 Wh kg−1 and cycle lives surpassing 2000 cycles with over 86% capacity retention in practical full cells. The synergy between these strategies is validated by both academic research and industrial pilot-scale production, demonstrating the strong potential for commercial adoption of optimized MN-LC cathodes. Future efforts should focus on composition refinement, electrolyte customization, multiscale failure analysis, manufacturing scale-up, and integration with solid-state battery platforms. Revitalizing the MN-LC cathode route represents a pragmatic and sustainable pathway toward next-generation LIBs that combine high safety, long durability, and supply-chain resilience.

Localized high-concentration electrolytes (LHCEs) exhibit excellent interfacial compatibility with lithium metal anodes and high-nickel cathodes, whereas the introduction of polymer networks during gelation may alter their intrinsic solvation structures. Here, we report a solvation-preserving gel electrolyte formed via in situ polymerization of a fluorinated polymer network within a 1,2-Dimethoxyethane (DME)-based LHCE. Unlike conventional gel polymer electrolytes, the fluorinated polymer exhibits limited Li+ coordination, thereby largely preserving the localized high-concentration solvation environment during gelation. This design couples the preserved LHCE solvation chemistry with a fluorinated polymer framework, enabling synergistic regulation of electrode-electrolyte interfaces and enhanced electrochemical performance. Meanwhile, the fluorinated polymer network further improves safety by reducing electrolyte flammability. Lithium symmetric cells achieve stable cycling over 2000 h, while LiNi0.9Co0.05Mn0.05O2 (NCM9)|Li full cells deliver 82.2% capacity retention after 300 cycles and operate stably up to 4.5 V. At the pouch-cell level, a gravimetric energy density of 394.3 Wh kg-1 is achieved under lean-electrolyte conditions, while no thermal runaway is observed up to 300°C. This work demonstrates that preserving solvation structure via rational polymer network design enables simultaneous improvements in interfacial stability, safety, and practical performance in quasi-solid-state lithium metal batteries.

The energy conversion and utilization of lithium sulfur batteries are inextricably linked to the adsorption- catalysis-conversion processes of polysulfide intermediates at the cathode side. Herein, we report novel carbon nanofibers (CNFs) bridged spatial reinforced multifunctional catalysts (Ni-CNFs-MnS) to accelerate the cascade adsorption-catalysis-conversion processes of carbon/sulfur cathodes prepared via vesicle reactors. The composite catalysts grow quasi-vertically on the carbon hosts, with CNFs acting as the bridges to connect top-end Ni nanoparticles (NPs) and bottom-end MnS NPs to achieve synergistic cascade desolvation-adsorption-catalysisconversion for lithium polysulfides. In situ Raman and theoretical calculation results reveal that the top-end Ni NPs can effectively enhance the desolvation/adsorption and catalytic conversion of long-chain polysulfides, while the bottom-end MnS NPs could preferentially adsorb and catalytically convert short-chain polysulfides. Meanwhile, CNFs serve as conductive bridges to offer rapid electron/ion transfer paths for polysulfide conversion, and simultaneously provide spatial confinement to suppress the shuttle effect of polysulfides. Accordingly, our cascade configuration combines multifunctional catalytic sites and carbon bridges with different spatial dimension to obtain fast adsorption-catalysis-conversion processes for polysulfides, endowing the carbon/sulfur cathodes with enhanced high-rate capacity and superior cycling stability. This work provides valuable insights into the design of high-efficiency spatially bridged cascade catalysts for multistage conversion reactions of sulfur.

The degradation of Ni-rich cathodes during long-term operation at high voltage has garnered significant attention from both academia and industry. Despite many post-mortem qualitative structural analyses, precise quantification of their individual and coupling contributions to the overall capacity degradation remains challenging. Here, by leveraging multiscale synchrotron X-ray probes, electron microscopy, and post-galvanostatic intermittent titration technique, the thermodynamically irreversible and kinetically reversible capacity loss is successfully deconvoluted in a polycrystalline LiNi0.83Mn0.1Co0.07O2 cathode during long-term charge/discharge cycling in full cell configuration. Contradicting the dramatic capacity loss, the layered structure remains highly alive even after 1000 cycles at 4.6 V while undergoing a three-order of magnitude reduction in the mass transfer kinetics, leading to almost fully recoverable capacity under kinetic-free conditions. Such kinetic dormant behavior after cycling is not simply ascribed to poor chemical diffusion by reconstructed cathode surface but highly synchronizes with the lattice strain evolution stemming from the structural heterogeneity between deeply delithiated layered and degraded rock-salt phases at high voltage. These findings deepen the degradation mechanism of high-voltage cathodes to achieve long-cycling and fast-charging performance.

Polar carbon materials play significant roles in electrochemical reactions in virtue of distinctive surface polarity, porous architecture sand multifunctional synergistic properties. In this study, we first propose steam puffing technology to construct versatile multi-doped porous carbon for sulfur hosts. In this design, maltose is utilized as the matrix which can be puffed by the internal moisture, thus endowing the carbon skeleton with hierarchical porous structure. Simultaneously, N, P, B heteroatoms are uniform-distributed in maltose-derived carbon matrix due to the co-puffing process. According to the density functional theory (DFT) calculations, these heteroatoms provide sufficient chemical adsorption and catalytic sites to soluble polysulfides, thus effectively impede the shuttling effect and accelerate the conversion kinetics of polysulfide intermediates. Beneficial from the synergistic effect of polar porous structure, the well-designed NPB-doped maltose derived carbon (NPB-MC) possess superior high-rate properties and long-time cycling stability. This research opens a new avenue for constructing polar carbon materials and high-performance sulfur cathodes in lithium sulfur batteries.

The construction of high-quality carbon-based energy materials through biotechnology has always been an eager goal of the scientific community. Herein, juice vesicles bioreactors (JVBs) bio-technology based on hesperidium (e.g., pomelo, waxberry, oranges) is first reported for preparation of carbon-based composites with controllable components, adjustable morphologies, and sizes. JVBs serve as miniature reaction vessels that enable sophisticated confined chemical reactions to take place, ultimately resulting in the formations of complex carbon composites. The newly developed approach is highly versatile and can be compatible with a wide range of materials including metals, alloys, and metal compounds. The growth and self-assembly mechanisms of carbon composites via JVBs are explained. For illustration, NiCo alloy nanoparticles are successfully in situ implanted into pomelo vesicles crosslinked carbon (PCC) by JVBs, and their applications as sulfur/carbon cathodes for lithium-sulfur batteries are explored. The well-designed PCC/NiCo-S electrode exhibits superior high-rate properties and enhanced long-term stability. Synergistic reinforcement mechanisms on transportation of ions/electrons of interface reactions and catalytic conversion of lithium polysulfides arising from metal alloy and carbon architecture are proposed with the aid of DFT calculations. The research provides a novel biosynthetic route to rational design and fabrication of carbon composites for advanced energy storage.

High energy-density Ni-rich layered cathodes suffer a long-standing challenge of severe performance deterioration at high potentials. Besides, it is of great challenge to develop a universal mitigation strategy to address numerous deterioration causes. Herein, to probe the dominant deterioration root for guiding rational development, we perform an in-depth investigation of LiNi 0.83 Mn 0.1 Co 0.07 O 2 in full cells with graphite anode for 1000 cycles at different state-of-charges. Intriguingly, severe capacity retention of harvest cathodes (like 54% at 4.6 V) is inconsistent with insignificant material degradation via synchrotron-based X-ray characterizations. To unpuzzle this, we deconvolute the overall performance deterioration of cycled cathode into irreversible and reversible losses. Our evaluation unveils Ni-rich cathodes are mostly alive (like 88% at 4.6 V) but kinetically inhibited in long-term cycling at high potentials. The evolution of Li + diffusion is of greater significance than that of electrical impedance. The exacerbated cathode-electrolyte interface, mainly rock-salt phase, is speculated experimentally and analytically as the predominant root for severe chemical diffusion and performance deterioration. Our findings highlight the upmost importance of stabilizing the cathode-electrolyte interface for deploying Ni-rich cathodes at higher potentials to awaken more energy and longer lifespan.

Biosynthesis methods are considered to be a promising technology for engineering new carbon‐based materials or redesigning the existing ones for specific purposes with the aid of synthetic biology. Lots of biosynthetic processes including metabolism, fermentation, biological mineralization, and gene editing have been adopted to prepare novel carbon‐based materials with exceptional properties that cannot be realized by traditional chemical methods, because microbes evolved to possess special abilities to modulate components/structure of materials. In this review, the recent development on carbon‐based materials prepared via different biosynthesis methods and various microbe factories (such as bacteria, yeasts, fungus, viruses, proteins) are systematically reviewed. The types of biotechniques and the corresponding mechanisms for the synthesis of carbon‐based materials are outlined. This review also focuses on the structural design and compositional engineering of carbon‐based nanostructures (e.g., metals, semiconductors, metal oxides, metal sulfides, phosphates, Mxenes) derived from biotechnology and their applications in electrochemical energy storage devices. Moreover, the relationship of the architecture–composition–electrochemical behavior and performance enhancement mechanism is also deeply discussed and analyzed. Finally, the development perspectives and challenges on the biosynthetic carbons are proposed and may pave a new avenue for rational design of advanced materials for the low‐carbon economy.

Nickel-rich transition-metal oxides are widely regarded as promising cathode materials for high-energy-density lithium-ion batteries for emerging electric vehicles. However, achieving high energy density in Ni-rich cathodes is accompanied by substantial safety and cycle-life obstacles. The major issues of Ni-rich cathodes at high working potentials are originated from the unstable cathode-electrolyte interface, while the underlying mechanism of parasitic reactions towards surface reconstructions of cathode materials is not well understood. In this work, we controlled the Li2CO3 impurity content on LiNi0.83Mn0.1Co0.07O2 cathodes using air, tank-air, and O2 synthesis environments. Home-built high-precision leakage current and on-line electrochemical mass spectroscopy experiments verify that Li2CO3 impurity is a significant promoter of parasitic reactions on Ni-rich cathodes. The rate of parasitic reactions is strongly correlated to Li2CO3 content and severe performance deterioration of Ni83 cathodes. The post-mortem characterizations via high-resolution transition electron microscope and X-ray photoelectron spectroscopy depth profiles reveal that parasitic reactions promote more Ni reduction and O deficiency and even rock-salt phase transformation at the surface of cathode materials. Our observation suggests that surface reconstructions have a strong affiliation to parasitic reactions that create chemically acidic environment to etch away the lattice oxygen and offer the electrical charge to reduce the valence state of transition metal. Thus, this study advances our understanding on surface reconstructions of Ni-rich cathodes and prepares us for searching for rational strategies.

为了在储能技术领域实现高能量密度和良好的安全性目标,全固态锂电池(ASSLBs)成为广泛研究的焦点.作为全固态锂电池的主要组成部分,无机固态电解质在全固态锂电池中起着至关重要的作用.在过去的几年里,无机固态电解质的研究已经取得了重大进展.经过几十年的研究努力,各种具有高离子导电性的锂固体电解质相继报道,硫化物固态电解质在高电位下的不稳定性限制了他在超过4.0 V(vs.Li+/Li)的高压正极材料中的应用;氧化物固态电解质在固固接触上的固有刚性限制了其机械加工性能;卤化物固态电解质同硫化物一并具有严重的空气湿度不稳定性,阻碍其大规模应用.针对电池循环过程中,固态电解质与电极匹配的界面副反应问题、材料本征的吸湿性(空气湿度稳定性差)的问题,以及固态电解质与电极界面物理接触失效问题等技术问题及其改进策略进行了总结和探讨,并提出了关于无机固态电解质自身与界面稳定性未来可行的研究方向.

Lithium (Li)-ion batteries using nickel (Ni)-rich layered oxide cathode have been pursued with interest due to high practical energy density. A fundamental understanding of the reaction pathways and structural evolution of the solid-phase synthesis of these materials is crucial for their rational design and process development for mass production. In this work, structural evolution during solid-state synthesis was traced via in situ technique, with a particular emphasis on the lithiation reaction and migration of transition metal (TM) ions. The sintering process is governed by the competitive relationship of decomposition and lithiation reactions, which can be regulated through temperature windows. Controlling the melting point of the Li sources, as well as their affinity to cathode precursors, is highly desired to maintain the layered ordering of TM ions throughout the whole synthesis process, which simplifies the manufacturing process and improves the quality of the manufactured cathode material.

过滤浓缩机能够增加锂电正极材料前驱体合成过程中反应釜内的固含量,改善前驱体的致密度、球形度.结合其在工业化中的生产情况,对其在锂电正极材料前驱体合成中的应用进行了介绍.

为了提高富锂锰基材料的循环稳定性,以Nb2 O5作为包覆剂,采用高温固相反应法对富锂锰基材料进行包覆改性.研究发现,Nb能够与材料表面的残存锂反应,生成LiNbO3;当Nb包覆量为0.2％ 时样品性能最佳:0.1C下放电比容量为285.6 m A·h/g,1C循环100次后的容量保持率为85.9％,且表现出较好的倍率性能和较低的电压衰减.富锂锰基材料的循环稳定性能的提升可能归因于高温热处理使Nb扩散进入材料表层晶格,形成了较强的Nb—O键,减缓了循环过程中晶格氧的流失,从而稳定结构;同时,表面生成的快离子导体LiNbO3不仅阻止了电解液对材料的侵蚀,而且促进了锂离子的扩散和电子的传导.

层状富锂锰基材料(LMR)凭借其高比容量(>250 mAh/g)和低成本等优点,有望成为新一代锂离子电池用正极材料.从该材料发现至今已有将近30年的时间,却始终没有实现真正商业化应用,主要原因包括:循环过程中,Mn3+迁移进入锂空位,使层状结构向尖晶石结构转变,导致平均放电电压持续降低,造成能量损失严重且给电池管理带来巨大的挑战;Li2MnO3低的电子电导率使LMR材料具有差的倍率性能;较低的电极密度,造成材料的体积能量密度较低;此外,LMR材料需要在高电压下(>4.55 V)才能发挥高容量,但高电压下电解液容易氧化分解,同时伴随着晶格氧被氧化为O2逸出,以上问题严重地影响了其商业化进程.本文基于多年来LMR材料的研究开发成果,综述了近年来LMR材料在充放电机理认识、前驱体工艺路线选择、体相掺杂、表面包覆、液相和气相后处理的作用效果和改性机理,以及O2/O3复合结构、单晶结构等新型特殊结构设计等方面的研究进展,并对LMR材料未来的发展方向和商业化前景进行展望,助力富锂锰基材料的产业化开发.

Current bottlenecks in cobalt (Co) supply have negatively impacted commercial battery application and inspired the development of Co-free cathodes with high energy density. Li-rich layered oxides (LLOs) are promising highenergy cathodes for lithium-ion batteries (LIBs), but the voltage decay and capacity fading are the main challenge for the commercialization. Herein, rich-Co Li1.140Mn0.575Co0.142Ni0.143O2+delta, middle-Co Li1.140Mn0.574Co0.074Ni0.212O2+delta, and Co-free Li1.140Mn0.572Ni0.287O2+delta cathodes were synthesized for investigating the function of Co on the electrochemical performance of LLOs. It is found that Co can promote the oxidation of O2- and contribute more capacity at above 4.5 V, which leads to oxygen release and irreversible structural transformations. As a result, Co-free cathode shows a better cycling stability but lower initial discharge capacity than the two Co-containing cathodes at a cutoff voltage of 4.6 V. Moreover, the Co-free cathode exhibits the highest average discharge voltage of 3.54 V at 0.5C and voltage retention of 95.0% compared with that of middle-Co material (3.47 V and 92.7%) and rich-Co material (3.43 V and 91.6%) after 80 cycles. This study not only provides fundamental insight in the role of Co in LLO cathodes, it also guides us to engineer the high energy and low-cost cathode materials for the rechargeable LIBs in the near future.

Ni-rich layered cathode is regarded as one of the most promising candidates to achieve lithium-ion batteries(LIBs) with high energy density. However, due to the irreversible phase transformation(IPT)and its eventual propagation from surface to the bulk of the material, Ni-rich layered cathode typically suffers from severe capacity fading, structure failure, and thermal instability, which greatly hinders its mass adoption. Hence, achieving an in-depth understanding of the IPT propagation mechanism in Ni-rich layered cathode is crucial in addressing these issues. Herein, the triggering factor of IPT propagation in Ni-rich cathode is verified to be the initial surface disordered cation mixing domain covered by a thin rock-salt phase, instead of the rock-salt phase itself. According to the density functional theory(DFT)results, it is further illustrated that the metastable cation mixing domain possesses a lower Ni migration energy barrier, which facilitates the migration of Ni ions towards the Li slab, and thus driving the propagation of IPT from surface to the bulk of the material. This finding clarifies a prevailing debate regarding the surface impurity phases of Ni-rich cathode material and reveals the origin of IPT propagation, which implies the principle and its effectiveness of tuning the surface microstructure to address the structural and thermal instability issue of Ni-rich layered cathode materials.

共沉淀法是工业化中制备多元材料前驱体的主流方法,介绍了沉淀反应、过滤洗涤和烘干三个工序的关键设备,为三元材料前驱体的产业化发展提供参考.

Herein, a distinctive dual-carbon-confined nanoarchitecture, composed of an inner highly conductive, robust carbon nanotube (CNT) support and outer well-designed porous carbon (PC) coating, was demonstrated to efficiently improve the electrochemical properties of CoO nanoparticles for the first time, and the CoO nanoparticles were confined between the CNTs and porous carbon. The welldesigned porous carbon coating showed significant superiority compared to common non-porous carbon coatings, due to its distinctive characteristics such as high flexibility, rich free space and open tunnel-like structure. Therefore, the synergistic effects of the CNT core and the porous carbon sheath endowed the CoO-based composite (CNTs@CoO@PC) with improved electrochemical reaction kinetics, large pseudocapacitive contribution and superior structural stability. As a result, the CNTs@CoO@PC showed outstanding performance with 1090, 571 and 242 mA h g(-1) at 200, 1000 and 5000 mA g(-1) after 300, 600 and 1000 cycles, respectively. Furthermore, this strategy may be used to improve other metal oxide anode materials for lithium storage.

镍钴锰三元材料Li(NixCoyMnz)O2(NCM)作为锂离子电池用正极材料,兼具了较高的可逆容量、优良的热稳定性、低成本等优点,成为笔记本电脑、电动工具、新能源汽车、储能等领域最具前景的锂离子电池正极材料之一.在三元正极材料的结构方面做了介绍,概括了Ni-Co-Mn比例对正极材料热稳定性、放电比容量和容量保持率的影响,并分析了掺杂、包覆与梯度材料的改善作用.最后对三元正极材料的改性、应用及发展前景进行了评价和展望.