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Lithium-sulfur (Li-S) batteries are highly considered as next-generation energy storage techniques. Weakly solvating electrolyte with low lithium polysulfide (LiPS) solvating power promises Li anode protection and improved cycling stability. However, the cathodic LiPS kinetics is inevitably deteriorated, resulting in severe cathodic polarization and limited energy density. Herein, the LiPS kinetic degradation mechanism in weakly solvating electrolytes is disclosed to construct high-energy-density Li-S batteries. Activation polarization instead of concentration or ohmic polarization is identified as the dominant kinetic limitation, which originates from higher charge-transfer activation energy and a changed rate-determining step. To solve the kinetic issue, a titanium nitride (TiN) electrocatalyst is introduced and corresponding Li-S batteries exhibit reduced polarization, prolonged cycling lifespan, and high actual energy density of 381 Wh kg in 2.5 Ah-level pouch cells. This work clarifies the LiPS reaction mechanism in protective weakly solvating electrolytes and highlights the electrocatalytic regulation strategy toward high-energy-density and long-cycling Li-S batteries.
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http://dx.doi.org/10.1021/jacs.4c02603 | DOI Listing |
J Colloid Interface Sci
September 2025
School of Energy and Environmental Engineering, Hebei University of Technology, Tianjin 300401, China; Hebei Engineering Research Center of Advanced Energy Storage Technology and Equipment, Hebei University of Technology, Tianjin 300401, China; State Key Laboratory of Reliability and Intelligence of
High-voltage lithium metal batteries (LMBs) have emerged as ideal candidates for achieving high-energy-density energy storage devices. Notably, high-reactive lithium metal and high-voltage transition metal oxide cathodes require electrolytes with superior electrochemical stability and interfacial compatibility. Herein, a solvent chemistry electrolyte design strategy is proposed that a weakly-solvated fluorinated bis(2,2,2-trifluoroethyl) carbonate (TFEC) was introduced into carbonate electrolyte for enhanced high voltage performance.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
August 2025
School of Chemical Engineering, The University of Adelaide, Adelaide, SA, 5005, Australia.
Gel polymer electrolytes (GPEs) show practical potential in lithium metal batteries (LMBs), but their development is hindered by insufficient understanding of Li solvation chemistry and its impact on ion transport and solid electrolyte interphase (SEI) formation. By regulating the solvation abilities of polymer and solvent, this work explores the relationships between GPE composition, Li coordination structures, Li transference number, and interphase chemistry. The GPE combining weakly coordinated solvents with strongly coordinating polymer results in strong Li-polymer attachment, leading to sluggish ion transport.
View Article and Find Full Text PDFMater Horiz
August 2025
College of Materials Science and Engineering, Fuzhou University, Fuzhou, Fujian, 350108, China.
Traditional ether-based electrolytes of Lithium metal batteries (LMBs), while enabling stable lithium deposition and low-temperature operation, suffer from insufficient oxidative stability under extreme conditions. Here, we propose a spatially decoupled solvation-shell strategy to construct weakly oriented fluorinated-ether-ester hybrid electrolytes with outer-shell fluorination protection. A spatially decoupled solvation structure is constructed where ether dominates the inner shell for stable Li coordination, while fluorinated solvents form an oxidation-resistant outer shield.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
August 2025
Chair for Functional Materials, Department of Physics, TUM School of Natural Sciences, Technical University of Munich, James-Franck-Str. 1, 85748, Garching, Germany.
Lithium metal batteries (LMBs) face challenges from unstable and fragile solid electrolyte interphases (SEIs). In this work, we successfully develop a novel electrolyte by effectively modulating the competitive solvation process in LMBs. In this formulation, the C─O─C motifs of glymes are competitively substituted by other anions and solvents to achieve single oxygen site coordination, thereby facilitating a weak solvation effect.
View Article and Find Full Text PDFACS Nano
August 2025
Department of Materials Science and Engineering, College of Aerospace Science and Engineering, National University of Defense Technology, Changsha 410000, P. R. China.
Lithium metal batteries (LMBs) offer exceptional energy storage potential but suffer from dendrite growth, SEI instability, and thermal risks. To address these challenges, a multifunctional composite separator (GF@UiO-66-NH + HFP) combining a glass fiber with a metal-organic framework (MOF) layer and polymer coating is constructed to synergistically regulate ion transport, thermal behavior, and interfacial chemistry. The MOF selectively adsorbs PF anions and solvent species, disrupting Li solvation to generate weakly solvated ions for uniform deposition, while poly(vinylidene difluoride)-HFP aligns polymer chains to homogenize Li flux, overcoming inherent limitations of porous substrates.
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