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This work explores the effect of in situ electrochemical pretreatment of copper current collectors (CuCC), acting as anodes in anode‐free lithium‐metal battery (AFLMB) with sulfolane‐based localized high‐concentration electrolyte. Two electrochemical pretreatment methods, not involving lithium overpotential deposition are in focus. These strategies are investigated in terms of passive layer growth, surface morphology evolution, composition of the formed interphases, and electrochemical performance for AFLMBs. The passive layers formed on CuCC (Cu–solid‐electrolyte interphase [SEI]) are in situ characterized by means of electrochemical quartz crystal microbalance with damping monitoring, which indicates that the Cu–SEIs exhibit detectable viscoelastic properties. The morphological characterization of the modified CuCCs shows highly homogeneous Cu–SEI structure with low surface roughness. The composition and physical properties of the Cu–SEI layers are correlated with the electrochemical performance of the anodes. The observed positive effect of the procedures for SEI preformation is associated with the synergistic influence of balanced inorganic–organic composition, enhanced viscoelastic properties, and homogeneous morphology of the layer. The study demonstrates the positive impact of the designed pretreatments and provides an appropriate comparison between the proposed in situ approach and the state of the art. The effect of electrochemical in situ surface pretreatment of copper current collector, for anode‐free lithium‐metal batteries with sulfolane‐based localized high‐concentration electrolyte is explored. The constant potential and constant current pretreatment procedures benefit the anode performance. The observed effect is associated with the synergistic influence of balanced inorganic–organic structure, enhanced viscoelastic properties, and homogeneous morphology of the layer on the micro/nanoscale.

Lithium (Li) metal is a promising candidate for next‐generation high‐energy‐density rechargeable batteries. However, the solid electrolyte interphase (SEI) inevitably suffers from mechanical fracture owing to the large morphological change during Li cycling, leading to the uncontrollable growth of Li dendrites, low Coulombic efficiency, and short cycle life. The fabrication of an artificial interphase is an effective strategy for improving the performances of Li metal anodes. The ideal artificial interphase should provide sufficient mechanical robustness to suppress dendritic Li growth and accommodate large volume changes during Li deposition‐dissolution cycles. In this review, we focus on the fabrication of mechanically robust artificial interphases for stabilizing Li‐metal anodes, including the underlying mechanism of SEI fracture, quantitative requirements for mechanical properties, measurements of mechanical properties, and recent progress in the fabrication of mechanically stable artificial interphases. This review focuses on the fabrication of mechanically robust artificial interphases for stabilizing lithium metal anodes. It comprehensively covers the underlying mechanisms of solid electrolyte interface fracture, the quantitative requirements for mechanical properties, various measurement techniques, and recent advancements in the development of mechanically stable artificial interphases for improved performance of lithium metal anodes.

Lithium metal battery is a promising candidate for high‐energy‐density energy storage. Unfortunately, the strongly reducing nature of lithium metal has been an outstanding challenge causing poor stability and low coulombic efficiency in lithium batteries. For decades, there are significant research efforts to stabilize lithium metal anode. However, such efforts are greatly impeded by the lack of knowledge about lithium‐stable materials chemistry. So far, only a few materials are known to be stable against Li metal. To resolve this outstanding challenge, lithium‐stable materials have been uncovered out of chemistry across the periodic table using first‐principles calculations based on large materials database. It is found that most oxides, sulfides, and halides, commonly studied as protection materials, are reduced by lithium metal due to the reduction of metal cations. It is discovered that nitride anion chemistry exhibits unique stability against Li metal, which is either thermodynamically intrinsic or a result of stable passivation. The results here establish essential guidelines for selecting, designing, and discovering materials for lithium metal protection, and propose multiple novel strategies of using nitride materials and high nitrogen doping to form stable solid‐electrolyte‐interphase for lithium metal anode, paving the way for high‐energy rechargeable lithium batteries. Novel stabilization strategies for Li metal anode are proposed by uncovering lithium‐stable materials chemistry across the periodic table using first‐principles calculations. Nitride anion chemistry exhibits unique lithium stability, which is thermodynamically intrinsic or a result of stable passivation. Applying nitride interphase and nitrogen doping provides ultimate stability to protect lithium metal anode.

An elastic and safe electrolyte is demanded for flexible batteries. Herein, a stretchable solid electrolyte comprised of crosslinked elastic polymer matrix, poly(vinylidene fluoride‐hexafluoropropylene) (PVDF‐HFP), and flameproof triethyl phosphate (TEP) is fabricated, which exhibits ultrahigh elongation of 450%, nonflammability and ionic conductivity above 1 mS cm−1. In addition, in order to improve the interface compatibility between the electrolyte and Li anode and stabilize the solid‐electrolyte interphase (SEI), a protecting layer containing poly(ethylene oxide) (PEO) is designed to effectively prevent the anode from reacting with TEP and optimize the chemical composition in SEI, leading to a tougher and more stable SEI on the anode. The LiFePO4/Li cells employing this double‐layer electrolyte exhibit an 85.0% capacity retention after 300 cycles at 1 C. Moreover, a flexible battery based on this solid electrolyte is fabricated, which can work in stretched, folded, and twisted conditions. This design of a stretchable double‐layer solid electrolyte provides a new concept for safe and flexible solid‐state batteries. A stretchable polymer electrolyte is fabricated based on resilient copolymer and poly(vinylidene fluoride‐hexafluoropropylene) (PVDF‐HFP) with ultrahigh elasticity, nonflammability, and good ionic conductivity. A protective layer containing poly(ethylene oxide) (PEO) is designed to protect the electrolyte against the anode and stabilize the solid‐electrolyte interphase (SEI) during cycling. A flexible solid‐state battery is prepared using this double‐layer electrolyte, which can light a light emitting diode (LED) bulb under different deformed conditions.

Multi‐scale simulation is an important basis for constructing digital batteries to improve battery design and application. LiF‐rich solid electrolyte interphase (SEI) is experimentally proven to be crucial for the electrochemical performance of lithium metal batteries. However, the LiF‐rich SEI is sensitive to various electrolyte formulas and the fundamental mechanism is still unclear. Herein, the structure and formation mechanism of LiF‐rich SEI in different electrolyte formulas have been reviewed. On this basis, it further discussed the possible filming mechanism of LiF‐rich SEI determined by the initial adsorption of the electrolyte‐derived species on the lithium metal anode (LMA). It proposed that individual LiF species follow the Volmer–Weber mode of film growth due to its poor wettability on LMA. Whereas, the synergistic adsorption of additive‐derived species with LiF promotes the Frank‐Vander Merwe mode of film growth, resulting in uniform LiF deposition on the LMA surface. This perspective provides new insight into the correlation between high LiF content, wettability of LiF, and highperformance of uniform LiF‐rich SEI. It disclosed the importance of additive assistant synergistic adsorption on the uniform growth of LiF‐rich SEI, contributing to the reasonable design of electrolyte formulas and high‐performance LMA, and enlightening the way for multi‐scale simulation of SEI. The LiF wettable and lithiophilic additive‐derived species induce synergistic adsorption with LiF, promoting tiny LiF deposition on the lithium metal anode surface, which provides new insight into the correlation between high LiF content, wettability of LiF, and high‐performance LiF‐rich solid electrolyte interphase.

Zinc‐ion batteries (ZIBs) hold immense promise as next‐generation energy storage solutions, however, the practical application of zinc anodes is hindered by dendrite formation and parasitic side reactions. Engineering a stable solid‐ eletrolyte interphase (SEI) is crucial for addressing these issues. This study proposes a novel strategy to enhance Zn anode performance by incorporating a ZnSiF6 additive into a standard ZnSO4 (ZSO) electrolyte. The ZnSiF6 additive facilitates the formation of a stable, fluorine‐rich SEI on the Zn anode surface. Characterization reveals a hierarchical SEI structure, primarily composed of porous alkali zinc sulfate (ZHS) with embedded ZnF2. This unique architecture promotes rapid zinc ion desolvation and efficient transport, enhances corrosion resistance, and mitigates hydrogen evolution. Consequently, ZnSiF6‐modified cells exhibit exceptional cycling stability, exceeding 3000 hours at 0.5 mA cm−2 and 560 hours at 10 mA cm−2, significantly outperforming ZSO‐based cells. The modified cells also achieve high areal capacities (10 mAh cm−2), indicating superior zinc utilization. This work provides key insights for designing stable electrode/electrolyte interfaces, contributing to the development of high‐performance aqueous ZIBs. A ZnSiF6 additive in ZnSO4 (ZSO) electrolyte forms a fluorine‐rich, hierarchical solid‐electrolyte interphase (SEI) on Zn anodes, enhancing Zn‐ion battery (ZIB) performance. The SEI promotes uniform Zn deposition and suppresses side reactions, boosting cycling stability. Characterization reveals a porous ZHS framework with embedded ZnF2 within the SEI, contributing to high‐performance aqueous ZIBs.

Currently, lithium‐ion batteries (LIBs) are at the forefront of energy storage technologies. Silicon‐based anodes, with their high capacity and low cost, present a promising alternative to traditional graphite anodes in LIBs, offering the potential for substantial improvements in energy density. However, the significant volumetric changes that silicon‐based anodes undergo during charge and discharge cycles can lead to structural degradation. Furthermore, the formation of excessive solid‐electrolyte interphases (SEIs) during cycling impedes the efficient migration of ions and electrons. This comprehensive review focuses on the structural design and optimization of micron‐scale silicon‐based anodes from both materials and systems perspectives. Significant progress is made in the development of advanced electrolytes, binders, and conductive additives that complement micron‐scale silicon‐based anodes in both half and full‐cells. Moreover, advancements in system‐level technologies, such as pre‐lithiation techniques to mitigate irreversible Li+ loss, have enhanced the energy density and lifespan of micron‐scale silicon‐based full cells. This review concludes with a detailed classification of the underlying mechanisms, providing a comprehensive summary to guide the development of high‐energy‐density devices. It also offers strategic insights to address the challenges associated with the large‐scale deployment of silicon‐based LIBs. The significant volume change of the silicon‐based anode during cycling can lead to its structural degradation and the formation of excess solid‐electrolyte interphases. For the above problems, this review focuses on the structural design and optimization of micron‐sized silicon‐based anodes from the perspectives of materials and systems, providing a comprehensive summary to guide the development of high‐energy‐density devices.

Metallic anodes (lithium, sodium, and zinc) are attractive for rechargeable battery technologies but are plagued by an unfavorable metal–electrolyte interface that leads to nonuniform metal deposition and an unstable solid–electrolyte interphase (SEI). Here we report the use of electrochemically labile molecules to regulate the electrochemical interface and guide even lithium deposition and a stable SEI. The molecule, benzenesulfonyl fluoride, was bonded to the surface of a reduced graphene oxide aerogel. During metal deposition, this labile molecule not only generates a metal-coordinating benzenesulfonate anion that guides homogeneous metal deposition but also contributes lithium fluoride to the SEI to improve Li surface passivation. Consequently, high-efficiency lithium deposition with a low nucleation overpotential was achieved at a high current density of 6.0 mA cm−2. A Li|LiCoO₂ cell had a capacity retention of 85.3% after 400 cycles, and the cell also tolerated low-temperature (−10 °C) operation without additional capacity fading. This strategy was applied to sodium and zinc anodes as well.

The realization of lithium‐metal (Li) batteries faces challenges due to dendritic Li deposition causing internal short‐circuit and low Coulombic efficiency. In this regard, the Li‐deposition stability largely depends on the electrolyte, which reacts with Li to form a solid electrolyte interphase (SEI) with diverse physico‐chemical properties, and dictates the interphasial kinetics. Therefore, optimizing the electrolyte for stability and performance remains pivotal. Hereof, glyme ethers are an emerging class of electrolytes, showing improved compatibility with metallic Li and enhanced stability in Li─Air and Li─Sulfur batteries. Yet, the criteria for selecting glyme solvents, particularly concerning Li deposition and dissolution processes, remain unclear. The SEI characteristics and Li deposition/dissolution processes are investigated in glyme‐ether‐based electrolytes with varying chain lengths, using lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium nitrate (LiNO₃) salts under high capacity and limited electrolyte conditions. Longer glymes led to more homogeneous SEI, particularly pronounced with LiNO₃, minimizing surface roughness during stripping, and promoting compact Li deposits. Higher reductive stability, resulting in homogeneous interphasial properties, and slower kinetics due to high desolvation barrier and viscosity, underline stable Li growth in longer glymes. This study clarifies factors guiding the selection of glyme ether‐based electrolytes in Li metal batteries, offering insights for next‐generation energy storage systems. Although glyme ethers show enhanced compatibility with lithium (Li) electrode and better stability in Li─Air and Li─Sulfur batteries, the selection criteria for glyme solvents remain unclear. Investigation of Li deposition/dissolution in varying glyme ethers reveals that longer chain glymes lead to compact Li growth and homogeneous interphase, impacting battery performance. This study aids in glyme ether selection for advanced energy storage.

The fast charging‐discharging performance of power batteries has very practical significance. In terms of electrochemistry, this requires fast and stable kinetics for electrochemical reaction processes. Despite the great complexity of kinetics, it is clear that lithium‐ion desolvation and a subsequent step of crossing through cathode‐electrolyte interphase (CEI) are crucial to high‐rate performance, in which the two key steps depend heavily on the working electrolyte formula. In this work, a customized electrolyte is developed to coordinate ion desolvation and interphase formation by introducing vinylene carbonate (VC), triphenylboroxin (TPBX), and fluoroethylene carbonate (FEC) but excluding ethylene carbonate (EC). Serving Ni‐rich cathodes, the customized electrolyte generates a double‐layered CEI, LiF‐dominated inorganics inner layer, and ROCOOLi‐dominated organics outer layer, which is not only stable and very efficient for lithium ion transport. Meanwhile, a PF6− ${\\mathrm{PF}}_6^ - $ ‐dominated solvation structure is induced and effectively decreases the desolvation energy to 29.72 kJ mol−1, supporting fast lithium ion transport in the cathode interfacial processes. Consequently, the Ni‐rich lithium‐ion battery achieves a stable long cycle at a superior high rate of 10 C. A customized electrolyte for coordinating ion desolvation and interphase formation of superior high‐rate Ni‐rich lithium batteries is developed. A stable double‐layered CEI is generated, and a PF6− ${\\mathrm{PF}}_6^ - $ ‐dominated solvation structure is induced to effectively decrease the desolvation energy, both of which support fast lithium ion transport in the cathode interfacial processes.