Beyond LiF: Tailoring Li₂O-Dominated Solid Electrolyte Interphase for Stable Lithium Metal Batteries

ACS Nano, Journal Year: 2024, Volume and Issue: 18(3), P. 1969 - 1981

Published: Jan. 11, 2024

The components and structures of the solid-electrolyte interphase (SEI) are critical for stable cycling lithium metal batteries (LMBs). LiF has been widely studied as dominant component SEI, but Li2O, which a much lower diffusion barrier Li+, rarely investigated SEI. effect Li2O-dominated SEI on electrochemical performance still remains elusive. Herein, an ultrastrong coordinated cosolvation diluent, 2,3-difluoroethoxybenzene (DFEB), is designed to modulate solvation structure tailor LMBs. In DFEB-based LHCE (DFEB-LHCE), DFEB intensively participates in first shell synergizes with FSI– inorganic-rich different from LiF-dominated formed conventional LHCE. Benefiting this special architecture, high Coulombic efficiency (CE) 99.58% Li||Cu half cells, voltage profiles, dense uniform deposition, well effective inhibition Li dendrite formation symmetrical cell, achieved. More importantly, DFEB-LHCE can be matched various cathodes such LFP, NCM811, S cathodes, Li||LFP full cell using possesses 85% capacity retention after 650 cycles 99.9% CE. Especially 1.5 Ah practical pouch achieves excellent 89% 250 superb average CE 99.93%. This work unravels superiority feasibility tailoring through modulation structures.

Language: Английский

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Tuning the Li⁺ Solvation Structure by a “Bulky Coordinating” Strategy Enables Nonflammable Electrolyte for Ultrahigh Voltage Lithium Metal Batteries

ACS Nano, Journal Year: 2023, Volume and Issue: 17(10), P. 9586 - 9599

Published: May 1, 2023

In battery electrolyte design principles, tuning Li+ solvation structure is an effective way to connect chemistry with interfacial chemistry. Although recent proposed strategies are able improve cyclability, a comprehensive strategy for remains imperative. Here, we report by utilizing molecular steric effect create "bulky coordinating" structure. Based on this strategy, the designed generates inorganic-rich solid interphase (SEI) and cathode-electrolyte (CEI), leading excellent compatibility both Li metal anodes high-voltage cathodes. Under ultrahigh voltage of 4.6 V, Li/NMC811 full-cells (N/P = 2.0) hold 84.1% capacity retention over 150 cycles industrial pouch cells realize energy density 495 Wh kg-1. This study provides innovative insights into engineering offers promising path toward developing high-energy batteries.

Language: Английский

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Fluorine Chemistry in Rechargeable Batteries: Challenges, Progress, and Perspectives

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(6), P. 3494 - 3589

Published: March 13, 2024

The renewable energy industry demands rechargeable batteries that can be manufactured at low cost using abundant resources while offering high density, good safety, wide operating temperature windows, and long lifespans. Utilizing fluorine chemistry to redesign battery configurations/components is considered a critical strategy fulfill these requirements due the natural abundance, robust bond strength, extraordinary electronegativity of free fluoride formation, which enables fluorinated components with effectiveness, nonflammability, intrinsic stability. In particular, materials electrode|electrolyte interphases have been demonstrated significantly affect reaction reversibility/kinetics, tolerance batteries. However, underlining principles governing material design mechanistic insights atomic level largely overlooked. This review covers range topics from exploration fluorine-containing electrodes, electrolyte constituents, other for metal-ion shuttle constructing fluoride-ion batteries, dual-ion new chemistries. doing so, this aims provide comprehensive understanding structure–property interactions, features interphases, cutting-edge techniques elucidating role in Further, we present current challenges promising strategies employing chemistry, aiming advance electrochemical performance, operation, safety attributes

Language: Английский

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Interfacial “Single‐Atom‐in‐Defects” Catalysts Accelerating Li⁺ Desolvation Kinetics for Long‐Lifespan Lithium‐Metal Batteries

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(39)

Published: June 21, 2023

Abstract The lithium‐metal anode is a promising candidate for realizing high‐energy‐density batteries owing to its high capacity and low potential. However, several rate‐limiting kinetic obstacles, such as the desolvation of Li + solvation structure liberate , 0 nucleation, atom diffusion, cause heterogeneous spatial Li‐ion distribution fractal plating morphology with dendrite formation, leading Coulombic efficiency depressive electrochemical stability. Herein, differing from pore sieving effect or electrolyte engineering, atomic iron anchors cation vacancy‐rich Co 1− x S embedded in 3D porous carbon (SAFe/CVRCS@3DPC) proposed demonstrated catalytic promoters. Numerous free ions are electrocatalytically dissociated complex uniform lateral diffusion by reducing barriers via SAFe/CVRCS@3DPC, smooth dendrite‐free morphologies, comprehensively understood combined situ/ex situ characterizations. Encouraged SAFe/CVRCS@3DPC promotor, modified Li‐metal anodes achieve long lifespan (1600 h) without any formation. Paired LiFePO 4 cathode, full cell (10.7 mg cm −2 ) stabilizes retention 90.3% after 300 cycles at 0.5 C, signifying feasibility using interfacial catalysts modulating behaviors toward practical applications.

Language: Английский

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Toward Low‐Temperature Zinc‐Ion Batteries: Strategy, Progress, and Prospect in Vanadium‐Based Cathodes

Advanced Energy Materials, Journal Year: 2023, Volume and Issue: 14(8)

Published: Dec. 28, 2023

Abstract Low‐temperature vanadium‐based zinc ion batteries (LT‐VZIBs) have attracted much attention in recent years due to their excellent theoretical specific capacities, low cost, and electrochemical structural stability. However, working temperature surrounding often results retarded transport not only the frozen aqueous electrolyte, but also at/across cathode/electrolyte interface inside cathode interior, significantly limiting performance of LT‐VZIBs for practical applications. In this review, a variety strategies solve these issues, mainly including interface/bulk structure engineering electrolyte optimizations, are categorially discussed systematically summarized from design principles in‐depth characterizations mechanisms. end, several issues about future research directions advancements characterization tools prospected, aiming facilitate scientific commercial development LT‐VZIBs.

Language: Английский

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Locally Concentrated Ionic Liquid Electrolytes for Lithium‐Metal Batteries

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(17)

Published: Feb. 2, 2023

Non-flammable ionic liquid electrolytes (ILEs) are well-known candidates for safer and long-lifespan lithium metal batteries (LMBs). However, the high viscosity insufficient Li+ transport limit their practical application. Recently, non-solvating low-viscosity co-solvents diluting ILEs without affecting local solvation structure employed to solve these problems. The diluted electrolytes, i.e., locally concentrated (LCILEs), exhibiting lower viscosity, faster transport, enhanced compatibility toward anodes, feasible options next-generation high-energy-density LMBs. Herein, progress of recently developed LCILEs summarised, including physicochemical properties, solution structures, applications in LMBs with a variety high-energy cathode materials. Lastly, perspective on future research directions further understanding achieve improved cell performances is outlined.

Language: Английский

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Recent progress in ionic liquid-based electrolytes for nonaqueous and aqueous metal batteries

eScience, Journal Year: 2023, Volume and Issue: 4(2), P. 100173 - 100173

Published: Aug. 5, 2023

Nonaqueous Li metal batteries (LMBs) and aqueous Zn (ZMBs) are promising next-generation secondary owing to their high energy density. Selecting an appropriate electrolyte is critical for addressing the safety issues nonaqueous can encounter. Ionic liquids (ILs) have been widely used in because they non-flammable, present good thermal stability, wide electrochemical windows. This review highlights research progress on IL-based electrolytes stable Li/Zn anodes. We focus particularly these electrolytes' electrochemistry functionalities at electrolyte/anode interface inhibiting dendrite growth, preventing side reactions, enhancing performance. It expected that this will shed some light development of ILs batteries.

Language: Английский

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Co-Intercalation-Free Ether-Based Weakly Solvating Electrolytes Enable Fast-Charging and Wide-Temperature Lithium-Ion Batteries

ACS Nano, Journal Year: 2023, Volume and Issue: 17(18), P. 18103 - 18113

Published: Sept. 7, 2023

Ether-based electrolytes are competitive choices to meet the growing requirements for fast-charging and low-temperature lithium-ion batteries (LIBs) due low viscosity melting point of ether solvents. Unfortunately, graphite (Gr) electrode is incompatible with commonly used solvents their irreversible co-intercalation into Gr interlayers. Here, we propose cyclopentyl methyl (CPME) as a co-intercalation-free solvent, which contains cyclopentane group large steric hindrance obtain weakly solvating power Li+ wide liquid-phase temperature range (-140 +106 °C). A electrolyte (WSE) based on CPME fluoroethylene carbonate (FEC) cosolvents can simultaneously achieve fast desolvation ability high ionic conductivity, also induces LiF-rich solid interphase (SEI) anode. Therefore, Gr/Li half-cell this WSE deliver outstanding rate capability, stable cycling performance, specific capacity (319 mAh g-1) at an ultralow -60 °C. Furthermore, practical LiFePO4 (loading ≈25 mg cm-2)/Gr ≈12 cm-2) pouch cell reveals capability long-term performance above 1000 cycles Coulombic efficiency (≈99.9%) achieves impressive application potential

Language: Английский

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Eco‐Friendly Tetrahydropyran Enables Weakly Solvating “4S” Electrolytes for Lithium‐Metal Batteries

Advanced Energy Materials, Journal Year: 2023, Volume and Issue: 13(32)

Published: July 6, 2023

Abstract The growth of lithium dendrites hinders the commercial applications lithium‐metal batteries. Electrolytes play a crucial role in influencing electrode/electrolyte interfacial chemistry. Traditional electrolytes adopt strongly solvating solvents to dissolve Li salts, creating an organic‐rich solid electrolyte interface (SEI). + conductivity and mechanical strength SEI are poor, so derived cannot effectively suppress dendrites. weakly (WSE) system can realize inorganic‐rich SEI, demonstrating improved compatibility with metal. However, design rules for WSE not clear. Here, four kinds “4S” (single salt single solvent) designed investigate thickness, pore volume, porosity revealed via reactive force field. results show heterocyclic symmetric tetrahydropyran has most suitable power best stability battery system. This research provides route bridging molecular thermodynamic chemistry gap.

Language: Английский

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Electrolytes Design for Extending the Temperature Adaptability of Lithium‐Ion Batteries: from Fundamentals to Strategies

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(21)

Published: Feb. 13, 2024

Abstract With the continuously growing demand for wide‐range applications, lithium‐ion batteries (LIBs) are increasingly required to work under conditions that deviate from room temperature (RT). However, commercial electrolytes exhibit low thermal stability at high temperatures (HT) and poor dynamic properties (LT), hindering operation of LIBs extreme conditions. The bottleneck restricting practical applications has promoted researchers pay more attention developing a series innovative electrolytes. This review primarily covers design adaptability perspective. First, fundamentals concerning temperature, including donor number (DN), dielectric constant, viscosity, conductivity, ionic transport, theoretical calculations elaborated. Second, prototypical examples, such as lithium salts, solvent structures, additives, interfacial layers in both liquid solid electrolytes, presented explain how these factors can affect electrochemical behavior or temperatures. Meanwhile, principles limitations electrolyte discussed corresponding Finally, summary outlook regarding extend proposed.

Language: Английский

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