Electrolyte Solvent‐Ion Configuration Deciphering Lithium Plating/Stripping Chemistry for High‐Performance Lithium Metal Battery

Advanced Functional Materials, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 23, 2025

Abstract Electrolyte engineering plays a critical role in tuning lithium plating/stripping behaviors, thereby enabling safer operation of metal anodes batteries (LMBs). However, understanding how electrolyte microstructures influence the process at molecular level remains significant challenge. Herein, using commonly employed ether‐based as model, each component is elucidated and relationship between behavior established by investigating effects compositions, including solvents, salts, additives. The variations Li + deposition kinetics are not only analyzed characterizing overpotential exchange current density but it also identified that intermolecular interactions previously unexplored cause these 2D nuclear overhauser effect spectroscopy (NOESY). An interfacial model developed to explain solvent interactions, distinct roles anions, additives desolvation thermodynamic stability clusters during process. This clarifies configurations solvents ions related macroscopic properties chemistry. These findings contribute more uniform controllable deposition, providing valuable insights for designing advanced systems LMBs.

Language: Английский

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Revisiting the interfacial chemistry of calcium metal anodes: the importance of inorganic-rich solid/electrolyte interfaces derived from an aggregation-dominated electrolyte

Energy & Environmental Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

The degradation of Ca anode in ester/ether electrolytes is attached to an organic-rich SEI. On this basis, we propose a desirable 2+ solvation sheath rich AGG and obtain inorganic-rich SEI, achieving high reversible plating/striping.

Language: Английский

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Unveiling the Li/Electrolyte Interface Behavior for Dendrite‐Free All‐Solid‐State Lithium Metal Batteries by Operando Nano‐Focus WAXS

Advanced Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 31, 2025

Poly(ethylene oxide) (PEO)-based solid composite electrolytes suffer from poor conductivity and lithium dendrite growth, especially toward the metallic metal anode. In this study, succinonitrile (SN) is incorporated into a PEO electrolyte to fabricate an electrode-compatible with good electrochemical performance. The SN-doped successfully inhibits growth facilitates SEI layer formation, as determined by operando nanofocus wide-angle X-ray scattering (nWAXS), meanwhile, stably cycled over 500 h in Li/SN-PEO/Li cell. Apart observation of dendrite, robust formation mechanism first cycle investigated SN-enhanced nWAXS. inorganic reaction products, LiF Li3N, are found initially deposit on side, progressively extending This process effectively protected lithium, inhibited electron transfer, facilitated Li⁺ transport. study not only demonstrates high-performance interfacial-stable battery but also introduces novel strategy for real-time visualizing directing at interface area lithium.

Language: Английский

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Low-Concentration Electrolyte Design for Wide-Temperature Operation in Sodium Metal Batteries

Journal of The Electrochemical Society, Journal Year: 2025, Volume and Issue: 172(1), P. 010501 - 010501

Published: Jan. 1, 2025

Sodium metal batteries (SMBs) are cost-effective and environmentally sustainable alternative to lithium batteries. However, at present, limitations such as poor compatibility, low coulombic efficiency (CE), high electrolyte cost hinder their widespread application. Herein, we propose a non-flammable, low-concentration composed of 0.3 M NaPF 6 in propylene carbonate (PC), fluoroethylene (FEC), 1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether (TTE). This not only reduces but also delivers rapid ion diffusion superior wetting properties. While the Na||FePO 4 system with this demonstrates slightly reduced performance room temperature compared standard-concentration formulations (S-PFT), it excels both (55 °C) (−20 temperatures, showcasing its balanced performance. At 0.5 C (charge)/1 (discharge), capacity retention reaches 92.8% 98.5% elevated temperature, CE values surpassing 99% 99.63%, respectively, significant sustained −20 °C 0.2 C. development thus offers well-rounded, economically viable path high-performance SMBs for diverse environmental applications.

Language: Английский

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Multidentate ether-induced reconfiguration of solvation structure in non-flammable phosphate electrolytes for wide-temperature application in lithium-ion batteries

Research Square (Research Square), Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 13, 2025

Conventional carbonate electrolytes fail to meet the requirements for lithium-ion batteries (LIBs) with wide temperature range and high safety. Diethyl ethylphosphonate (DEEP) has excellent flame retardancy a (-83 198°C), which holds promise developing non-flammable electrolyte wide-temperature application in LIBs. However, its limited compatibility graphite electrodes slow ionic transport capability must be addressed effective application. Herein, we introduce diethylene glycol dimethyl ether (DEGDME) reconfigure solvation structure of DEEP-based further enhance ion capacity. The film-forming additives enable preserve 98% capacity retention after 150 cycles Li||Graphite cells modified DEGDME improved low-temperature performance achieving 71% 50th-cycle Graphite||LiFePO₄ at -20°C. This work introduces new strategy designing phosphate electrolytes, enabling reliable safe LIBs across range.

Language: Английский

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Trace NaBF₄ Modulated Ultralow‐Concentration Ether Electrolyte for Durable High‐Voltage Sodium‐Ion Batteries

Advanced Functional Materials, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 13, 2025

Abstract Ultralow‐concentration ether electrolytes hold great promise for cost‐effective sodium‐ion batteries (SIBs), while their inferior cycle stability under high voltages remains an awkward challenge. Herein, ultralow‐concentration diglyme (G2)‐based with single sodium salt are found to manifest high‐rate capability when employed high‐voltage Na 3 (VOPO 4 ) 2 F (NVOPF) cathode, but specific capacity rapidly depletes exhaustion during long‐term cycling. To address this issue, trace NaBF (0.03 m as electrolyte additive is introduced, which minimally affects ion conductivity of the pristine electrolyte, yet weakens coordination between + ions and G2 molecules. This allows more PF 6 − enter solvation sheath ions, forming a stable cathode interphase enhancing performance without sacrificing (up 20 C). As result, modulated G2‐based enables NVOPF steadily, retention 94.2% over 1000 cycles at low rate 1 C. work provides valuable insights into modulation use in durable SIBs.

Language: Английский

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Revealing the dissolution mechanism of organic carbonyl electrodes in lithium−organic batteries

Chemical Science, Journal Year: 2025, Volume and Issue: 16(10), P. 4335 - 4341

Published: Jan. 1, 2025

Organic carbonyl electrode materials (OCEMs) have shown great promise for high-performance lithium batteries due to their high capacity, renewability, and environmental friendliness. Nevertheless, the severe dissolution of these in conventional electrolytes results poor cycling stability, which hinders practical application. Herein, a unified model considering effects both ion-solvation structures electrolyte solvents is proposed elucidate mechanism OCEMs electrolytes. In this new model, driven by interactions with free (uncoordinated) non-polar electrolytes, strong between Li-anion aggregates accelerate OCEMs, leading anomalously solubility OCEMs. Conversely, strongly polar dominated interaction solvents. This transcends perspective that dissociation solely depends on solute-solvent interactions. Based we propose tuning altering solvent polarity could be an effective strategy inhibiting organic electrodes achieve long-cycle Li-organic batteries.

Language: Английский

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Development of PFAS-Free Locally Concentrated Ionic Liquid Electrolytes for High-Energy Lithium and Aluminum Metal Batteries

Accounts of Chemical Research, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 26, 2025

ConspectusLithium-ion batteries (LIBs) based on graphite anodes are a widely used state-of-the-art battery technology, but their energy density is approaching theoretical limits, prompting interest in lithium-metal (LMBs) that can achieve higher density. In addition, the limited availability of lithium reserves raises supply concerns; therefore, research postlithium metal underway. A major issue with these anodes, including lithium, dendritic formation and insufficient reversibility, which leads to safety risks due short circuits use flammable electrolytes.Ionic liquid electrolytes (ILEs), composed salts ionic liquids, offer safer alternative nonflammable nature high thermal stability. Moreover, they enable Coulombic efficiency (CE) for (LMAs) allow reversible stripping/plating various post-lithium metals application, e.g., aluminum (AMBs). Despite advantages, ILEs suffer from viscosity, impairs ion transport wettability. To resolve challenges, researchers have developed locally concentrated (LCILEs) by adding low-viscosity nonsolvating cosolvents, hydrofluoroether, ILEs. These cosolvents do not coordinate cationic charge carriers, thereby reducing viscosity improving without compromising compatibility anodes. However, inherent difference molecular organic solvents liquids full charged species, most i.e., less effective respect conventional solvents. hydrofluoroether contains environmentally problematic -CF3 and/or -CF2- groups, per- polyfluoroalkyl substances (PFAS), subject restrictions.In this Account, we provide an overview endeavors our group development PFAS-free LCILEs high-energy LMBs AMBs. First, aromatic cations less/nonfluorinated proposed weaken cation-anion interaction strengthen cation-cosolvent interaction, respectively. This consideration uncovered phase nanosegregation structure effectively reduces promotes Li+ ability nonaromatic highly fluorinated PFAS cosolvents. Then, effect electrolyte components Li+, SEI composition LMA reversibility presented, confirms feasibility reaching CE up 99.7% LCILEs. subsequent discussion cathode compatibility, present addition LiFePO4 cyclability inferior density, nickel-rich layered oxide sulfurized polyacrylonitrile (SPAN) be employed construct different anodic Additionally, feasible application LCILE strategy promote kinetics AMBs relying anode chemistry demonstrated. Lastly, future directions emphasis component optimization, dynamics, electrode/electrolyte interphase provided.

Language: Английский

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Non-Clusters Pseudo-Bilayer Solvation Sheaths for Driving Low Temperature High Power Lithium Ion Batteries

Energy storage materials, Journal Year: 2025, Volume and Issue: unknown, P. 104122 - 104122

Published: Feb. 1, 2025

Language: Английский

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Research progress on diluents of localized high-concentration electrolytes for high performance lithium metal batteries

Journal of Power Sources, Journal Year: 2025, Volume and Issue: 640, P. 236704 - 236704

Published: March 10, 2025

Language: Английский

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