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1. Metal Organic Framework Derivative Improving Lithium Metal Anode Cycling

   https://doi.org/10.1002/adfm.201907579  

   Zhong, Yiren; Lin, Fang; Wang, Maoyu; Zhang, Yifang; Ma, Qing; Lin, Julia; Feng, Zhenxing; Wang, Hailiang (January 2020, Advanced Functional Materials)

   Abstract This work demonstrates a new approach in using metal organic framework (MOF) materials to improve Li metal batteries, a burgeoning rechargeable battery technology. Instead of using the MIL‐125‐Ti MOF structure directly, the material is decomposed into intimately‐mixed amorphous titanium dioxide and crystalline terephthalic acid. The resulting composite material outperforms the oxide alone, the organic component alone, and the parent MOF in suppressing Li dendrite growth and extending cycle life of Li metal electrodes. Coated on a commercial polypropylene separator, this material induces the formation of a desirable solid electrolyte interphase layer comprising mechanically flexible organic species and ionically conductive lithium nitride species, which in turn leads to Li||Cu and Li||Li cells that can stably operate for hundreds of charging–discharging cycles. In addition, this material strongly adsorbs lithium polysulfides and can also benefit the cathode of lithium–sulfur batteries. 

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2. Ultra‐Thin Lithium Silicide Interlayer for Solid‐State Lithium‐Metal Batteries

   https://doi.org/10.1002/adma.202210835  

   Sung, Jaekyung; Kim, So Yeon; Harutyunyan, Avetik; Amirmaleki, Maedeh; Lee, Yoonkwang; Son, Yeonguk; Li, Ju (April 2023, Advanced Materials)

   Abstract All‐solid‐state batteries with metallic lithium (Li_BCC) anode and solid electrolyte (SE) are under active development. However, an unstable SE/Li_BCCinterface due to electrochemical and mechanical instabilities hinders their operation. Herein, an ultra‐thin nanoporous mixed ionic and electronic conductor (MIEC) interlayer (≈3.25 µm), which regulates Li_BCCdeposition and stripping, serving as a 3D scaffold for Li⁰ad‐atom formation, Li_BCCnucleation, and long‐range transport of ions and electrons at SE/Li_BCCinterface is demonstrated. Consisting of lithium silicide and carbon nanotubes, the MIEC interlayer is thermodynamically stable against Li_BCCand highly lithiophilic. Moreover, its nanopores (<100 nm) confine the deposited Li_BCCto the size regime where Li_BCCexhibits “smaller is much softer” size‐dependent plasticity governed by diffusive deformation mechanisms. The Li_BCCthus remains soft enough not to mechanically penetrate SE in contact. Upon further plating, Li_BCCgrows in between the current collector and the MIEC interlayer, not directly contacting the SE. As a result, a full‐cell having Li_3.75Si‐CNT/Li_BCCfoil as an anode and LiNi_0.8Co_0.1Mn_0.1O₂as a cathode displays a high specific capacity of 207.8 mAh g⁻¹, 92.0% initial Coulombic efficiency, 88.9% capacity retention after 200 cycles (Coulombic efficiency reaches 99.9% after tens of cycles), and excellent rate capability (76% at 5 C). 

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3. Fluorination promotes lithium salt dissolution in borate esters for lithium metal batteries

   https://doi.org/10.1039/D3TA06228G  

   Ma, Peiyuan; Kumar, Ritesh; Vu, Minh Canh; Wang, Ke-Hsin; Mirmira, Priyadarshini; Amanchukwu, Chibueze V. (January 2024, Journal of Materials Chemistry A)

   Lithium metal batteries promise higher energy densities than current lithium-ion batteries but require novel electrolytes to extend their cycle life. Fluorinated solvents help stabilize the solid electrolyte interphase (SEI) with lithium metal, but are believed to have weaker solvation ability compared to their nonfluorinated counterparts and are deemed ‘poorer electrolytes’. In this work, we synthesize tris(2-fluoroethyl) borate (TFEB) as a new fluorinated borate ester solvent and show that TFEB unexpectedly has higher lithium salt solubility than its nonfluorinated counterpart (triethyl borate). Through experiments and simulations, we show that the partially fluorinated –CH2F group acts as the primary coordination site that promotes lithium salt dissolution. TFEB electrolyte has a higher lithium transference number and better rate capability compared to methoxy polyethyleneglycol borate esters reported in the literature. In addition, TFEB supports compact lithium deposition morphology, high lithium metal Coulombic efficiency, and stable cycling of lithium metal/LiFePO4 cells. This work ushers in a new electrolyte design paradigm where partially fluorinated moieties enable salt dissolution and can serve as primary ion coordination sites for next-generation electrolytes. 

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4. Ultrafine Silver Nanoparticles for Seeded Lithium Deposition toward Stable Lithium Metal Anode

   https://doi.org/10.1002/adma.201702714  

   Yang, Chunpeng; Yao, Yonggang; He, Shuaiming; Xie, Hua; Hitz, Emily; Hu, Liangbing (October 2017, Advanced Materials)
5. Cations Mediate Lithium Polysulfide Adsorption in Metal–Organic Frameworks for Lithium–Sulfur Batteries

   https://doi.org/10.1021/acs.jpcc.3c05539  

   Jarrín, Roberto A.; Bennett, Kevin; Thoi, V. Sara; Bukowski, Brandon C. (November 2023, The Journal of Physical Chemistry C)