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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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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Printable high-performance iontronic power source based on osmotic effects

Energy Materials, Journal Year: 2025, Volume and Issue: 5(6)

Published: Feb. 26, 2025

Iontronic power sources have attracted widespread attention in the field of energy harvesting and storage. However, conventional devices only generate an output voltage ~1.0 V. Herein, we developed units with ultra-high ~2.0 V per unit based on osmotic effects fine-tuning interfacial redox reactions. These systems are designed to harness efficient ion dynamics K+ within graphene oxide nanofluidic channels tailor Faradaic processes at interfaces. Printable, scalable, optimized through fractal design, these miniaturized capable directly powering commercial electronics, presenting a transformative paradigm for salinity gradient-based generation. This approach offers safe, ultra-thin, portable solution next-generation systems.

Language: Английский

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Solvent Descriptors Guided Wide‐Temperature Electrolyte Design for High‐Voltage Lithium‐Ion Batteries

Advanced Energy Materials, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 25, 2024

Abstract Lithium‐ion batteries are increasingly required to operate under harsh conditions, particularly at high temperatures above 55 °C. However, existing electrolytes suffer from inadequate thermal stability and significant interphasial side reactions. Moreover, there is a lack of clear guidelines for developing that can withstand temperatures. Here solvent screening descriptor introduced based on dual local softness dielectric constant. The findings indicate solvents with moderate constants low reactivity ideal candidates high‐temperature electrolytes. Among the evaluated, tetraethyl orthosilicate (TEOS) identified as suitable option utilized formulate localized high‐concentration electrolyte (TEOS‐based LHCE). Remarkably, 1‐Ah LiNi 0.8 Co 0.1 Mn ||graphite pouch cell utilizing this TEOS‐based LHCE demonstrates 95.8% capacity retention after 300 cycles 60 Interphasial analysis reveals promotes formation thin, uniform LiF‐rich interphases, effectively suppressing interfacial reactions elevated This strategy not only enhances understanding performance but also paves way high‐throughput wide‐temperature lithium‐ion batteries.

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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Unraveling Inherent Degradation Mechanism of Electrolyte at High-Voltage and the d2sp3 Hybridization Strategy for Non-Flammable 4.8 V LiCoO2 Battery

Published: Jan. 1, 2025

The potential risk of transition metal (TM) ion dissolution is a prevalent issue in nearly all layered oxide cathodes. While the detrimental effects this are widely discussed context cathode material design, implications for electrolyte design receive comparatively less attention. In fact, severe decomposition frequently occurs after TM ions. This phenomenon typically attributed to catalytic However, there lack research that clearly explains destabilization electrolyte. study delves into different interface behaviors between Co3+ and Li+. Near anode surface, significant proportion solvent molecules PF6- ions escape from Li+ solvation sheath, with only small portion contributing formation electrode/electrolyte interface. Subsequently, free reduced, interpolated or deposited anode. contrast, exhibit stronger binding ability than ions, leading challenges desolvation. sheaths demonstrate reduction instability, trapped must be reduced. order mitigate hazard dissolution, fluorinated cathode/electrolyte was applied inhibit Isobutyronitrile (IBN) used capture harmful electrolyte, resulting d2sp3 hybrid orbitals when IBN combines Co3+. stable chelated complex effectively eliminated associated sheaths. developed through hybridization strategy addresses dissolved Co, even 0.1M Co intentionally added LCO batteries utilizing an impressive increase capacity retention, rising 56.6% 84.5% 300 cycles at 4.7 V. Additionally, retention battery 73.3% 200 4.8

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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Improving Low‐Temperature Tolerance of a Lithium‐Ion Battery by a Localized High‐Concentration Electrolyte Based on the Weak Solvation Effect

Battery energy, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 30, 2025

ABSTRACT Due to the strong affinity between solvent and Li + , desolvation process of at interface as a rate‐controlling step slows down, which greatly reduces low‐temperature electrochemical performance lithium‐ion batteries (LIBs) thus limits its wide application in energy storage. Herein, improve tolerance, localized high‐concentration electrolyte based on weak solvation (Wb‐LHCE) has been designed by adding diluent hexafluorobenzene (FB) solvating tetrahydrofuran (THF). Combining theoretical calculations with characterization tests, it is found that addition FB, dipole–dipole interaction causes FB compete for THF. This competition move away from weakening binding THF, whereas anions are transported into shell forming an anion‐rich structure. In accelerating process, this unique structure optimizes composition CEI film, making thin, dense, homogeneous, rich inorganic components, improving interfacial stability battery. As result, assembled LiFePO 4 /Li half‐cell shows excellent performances low temperature. That is, can maintain high discharge specific capacity 124.2 mAh g −1 after 100 cycles rate 0.2C −20°C. provides attractive avenue design advanced electrolytes improvement battery tolerance harsh conditions.

Language: Английский

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Asymmetric ether solvents for high-rate lithium metal batteries

Nature Energy, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 14, 2025

Language: Английский

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A Compact‐Solvation Electrolyte Under Low Concentration for High‐Energy Density and Stable Potassium‐Ion Batteries

Angewandte Chemie International Edition, Journal Year: 2025, Volume and Issue: unknown

Published: March 11, 2025

The development of potassium-ion batteries (PIBs) faces significant challenges due to the lack suitable electrolytes achieve satisfactory energy density and long-term stability. This work reports an innovative compact-solvation electrolyte (CSE) strategy leveraging ionic liquid-induced manipulation solvation structures under low concentration for high-performance PIBs. CSE, formulated with a low-salt 0.8 M, simultaneously exhibits compact abundant F-rich anions, high-ionic conductivity, low-desolvation energy. These features lead enhanced K-storage thermodynamics kinetics through formation robust KF-rich solid interphase (SEI) as well accelerated K+ transport kinetics. Consequently, graphite electrode in CSE delivers high-reversible capacity 252 mAh g-1 average Coulombic efficiency 99.5% after 300 cycles at 50 mA g. Furthermore, designed enables Prussian blue||graphite full cell operate over 1450 g-1, maintaining impressive retention 88%. represents advance safe compatible advanced

Language: Английский

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