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1. Calix[4]pyrrole‐Based Wavy Covalent Organic Framework: A Protective Layer for High Performance Lithium‐Metal Batteries

   https://doi.org/10.1002/smll.202506365  

   Tian, Jinya; Liao, Yaqi; Zhu, Yaling; Li, Yi; He, Yanlei; Zhou, Jianqiao; Yao, Yonggang; Yuan, Lixia; Sessler, Jonathan L; Huang, Yunhui; et al (September 2025, Small)

   Abstract Practical applications of lithium metal batteries are often limited by low cycling efficiencies and uncontrolled lithium dendrite growth caused by unstable and heterogeneous lithium‐electrolyte interfaces. To address this issue, a calix[4]pyrrole‐based wavy covalent organic framework (WCOF) is developed that acts as a protective layer to suppress Li dendrite growth and reduce side reactions on the Li anode. The presentWCOFis porous and contains calix[4]pyrrole units acting as “molecular traps” that allow efficient PF₆⁻anion capture while allowing for uniform Li⁺diffusion. This provides structurally stable artificial protective layers that permit high Li⁺transference numbers. The resulting solid electrolyte interphases permit ultralong‐term stable cycling at a current density of 1 mA cm⁻²and reversible lithium plating/stripping (over 2500 h) at an areal capacity of 2 mAh cm⁻². The protected anodes of this study also demonstrated excellent cell stability through 260 cycles when paired with high‐voltage cathodes (NCM811 with high mass loading: 20 mg cm⁻²). 

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2. Constructing Highly Ion‐Conductive Composite Solid Electrolytes via Crosslinking Strategy for Advanced Room‐Temperature Lithium Metal Battery

   https://doi.org/10.1002/aenm.202506534  

   Cai, Yuanyuan; Terlier, Tanguy; Smirnova, Alevtina L; Gu, Zhengrong (April 2026, Advanced Energy Materials)

   Designing and developing solid‐state electrolytes (SSEs) with excellent comprehensive performance is currently a key challenge in high‐performance all‐solid‐state batteries. Herein, a novel composite solid polymer electrolyte is fabricated by embedding both Li₁₀GeP₂S₁₂(LGPS) superionic conductors and cationic metal–organic frameworks (MOFs) in modified host poly(ethylene oxide) (PEO) utilizing mPEG‐silane coupling agent, which averts any phase separation between mPEG‐silane and PEO, enhances the polymers/fillers interface compatibility, and decreases the grain boundary resistance between all the particles, thus boosting the electrochemical properties of the SSEs. An exceptional room‐temperature Li⁺conductivity of 6.9 × 10⁻⁴S cm⁻¹, broad redox stability window of 5.36 V and high lithium‐ion transference number of 0.88 are obtained ascribed to the synergistic effect of polymer chains, LGPS and cationic MOFs. Accordingly, the Li symmetrical cell with the composite SSEs achieves an extremely long cycle stability of 11 000 h at 0.1 mA cm⁻². Additionally, the robust membrane structure and electrodes/SSEs interfacial compatibility enable the assembled LFP|Li solid battery to gain a discharge capacity of 130.7 mAh g⁻¹at 1 C over 1200 cycles. This work may open up a completely new path for the development of next‐generation high‐performance SSEs applied in the field of all‐solid‐state batteries. 

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3. Interrelation Between External Pressure, SEI Structure, and Electrodeposit Morphology in an Anode‐Free Lithium Metal Battery

   https://doi.org/10.1002/aenm.202302261  

   Liu, Wei; Luo, Yiteng; Hu, Yuhang; Chen, Zidong; Wang, Qiang; Chen, Yungui; Iqbal, Naseem; Mitlin, David (February 2024, Advanced Energy Materials)

   Abstract The interrelation is explored between external pressure (0.1, 1, and 10 MPa), solid electrolyte interphase (SEI) structure/morphology, and lithium metal plating/stripping behavior. To simulate anode‐free lithium metal batteries (AF‐LMBs) analysis is performed on “empty” Cu current collectors in standard carbonate electrolyte. Lower pressure promotes organic‐rich SEI and macroscopically heterogeneous, filament‐like Li electrodeposits interspersed with pores. Higher pressure promotes inorganic F‐rich SEI with more uniform and denser Li film. A “seeding layer” of lithiated pristine graphene (pG@Cu) favors an anion‐derived F‐rich SEI and promotes uniform metal electrodeposition, enabling extended electrochemical stability at a lower pressure. State‐of‐the‐art electrochemical performance is achieved at 1MPa: pG‐enabled half‐cell is stable after 300 h (50 cycles) at 1 mA cm⁻²rate −3 mAh cm⁻²capacity (17.5 µm plated/stripped), with cycling Coulombic efficiency (CE) of 99.8%. AF‐LMB cells with high mass loading NMC622 cathode (21 mg cm⁻²) undergo 200 cycles with a CE of 99.4% at C/5‐charge and C/2‐discharge (1C = 178 mAh g⁻¹). Density functional theory (DFT) highlights the differences in the adsorption energy of solvated‐Li⁺onto various crystal planes of Cu (100), (110), and (111), versus lithiated/delithiated (0001) graphene, giving insight regarding the role of support surface energetics in promoting SEI heterogeneity. 

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4. Regulating Li‐Ion Transport through Ultrathin Molecular Membrane to Enable High‐Performance All‐Solid‐State–Battery

   https://doi.org/10.1002/smll.202303625  

   Rajendran, Sathish; George, Antony; Tang, Zian; Neumann, Christof; Turchanin, Andrey; Arava, Leela Mohana (November 2023, Small)

   Abstract Solid‐state lithium metal batteries with garnet‐type electrolyte provide several advantages over conventional lithium‐ion batteries, especially for safety and energy density. However, a few grand challenges such as the propagation of Li dendrites, poor interfacial contact between the solid electrolyte and the electrodes, and formation of lithium carbonate during ambient exposure over the solid‐state electrolyte prevent the viability of such batteries. Herein, an ultrathin sub‐nanometer porous carbon nanomembrane (CNM) is employed on the surface of solid‐state electrolyte (SSE) that increases the adhesion of SSE with electrodes, prevents lithium carbonate formation over the surface, regulates the flow of Li‐ions, and blocks any electronic leakage. The sub‐nanometer scale pores in CNM allow rapid permeation of Li‐ions across the electrode–electrolyte interface without the presence of any liquid medium. Additionally, CNM suppresses the propagation of Li dendrites by over sevenfold up to a current density of 0.7 mA cm⁻²and enables the cycling of all‐solid‐state batteries at low stack pressure of 2 MPa using LiFePO₄cathode and Li metal anode. The CNM provides chemical stability to the solid electrolyte for over 4 weeks of ambient exposure with less than a 4% increase in surface impurities. 

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5. In Situ Engineering of Inorganic‐Rich Solid Electrolyte Interphases via Anion Choice Enables Stable, Lithium Anodes

   https://doi.org/10.1002/adma.202305645  

   Weeks, Jason A; Burrow, James N; Diao, Jiefeng; Paul‐Orecchio, Austin G; Srinivasan, Hrishikesh S; Vaidyula, Rinish Reddy; Dolocan, Andrei; Henkelman, Graeme; Mullins, C Buddie (March 2024, Advanced Materials)

   Abstract The discovery of liquid battery electrolytes that facilitate the formation of stable solid electrolyte interphases (SEIs) to mitigate dendrite formation is imperative to enable lithium anodes in next‐generation energy‐dense batteries. Compared to traditional electrolyte solvents, tetrahydrofuran (THF)‐based electrolyte systems have demonstrated great success in enabling high‐stability lithium anodes by encouraging the decomposition of anions (instead of organic solvent) and thus generating inorganic‐rich SEIs. Herein, by employing a variety of different lithium salts (i.e., LiPF_6,LiTFSI, LiFSI, and LiDFOB), it is demonstrated that electrolyte anions modulate the inorganic composition and resulting properties of the SEI. Through novel analytical time‐of‐flight secondary‐ion mass spectrometry methods, such as hierarchical clustering of depth profiles and compositional analysis using integrated yields, the chemical composition and morphology of the SEIs generated from each electrolyte system are examined. Notably, the LiDFOB electrolyte provides an exceptionally stable system to enable lithium anodes, delivering >1500 cycles at a current density of 0.5 mAh g⁻¹and a capacity of 0.5 mAh g⁻¹in symmetrical cells. Furthermore, Li//LFP cells using this electrolyte demonstrate high‐rate, reversible lithium storage, supplying 139 mAh g_(LFP)⁻¹at C/2 (≈0.991 mAh cm⁻², @ 0.61 mA cm⁻²) with 87.5% capacity retention over 300 cycles (average Coulombic efficiency >99.86%). 

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