Molecular‐Layer‐Deposited Zincone Films Induce the Formation of LiF‐Rich Interphase for Lithium Metal Anodes

Advanced Energy Materials, Год журнала: 2023, Номер 13(12)

Опубликована: Янв. 31, 2023

Abstract Lithium metal anodes suffer from low Coulombic efficiency and dendritic growth owing to an unstable solid electrolyte interphase (SEI), which limit the practical applications of lithium anodes. Here, zincone (ZnHQ) is conformally fabricated on 3D copper nanowires (CuNWs) via a molecular layer deposition (MLD) technology. Upon polarization, terminal oxygen ZnHQ serves as strong nucleophilic agent attack Li bis (trifluoromethanesulfonyl)imide, yielding LiF‐rich SEI. This SEI facilitates transport, shuts off electron conduction, inhibits dendrites. In addition, zinc atoms induce favorable their lithiophilicity. These advantages enabled by MLD make ZnHQ‐modified CuNW (CuNW@ZnHQ) ideal anode, demonstrates excellent cyclability. A symmetrical cell CuNW@ZnHQ shows high cycling stability for more than 7000 h at current density 1 mA cm −2 . When pairing with Ni/Co/Mn ternary oxide cathode (NCM523), resultant CuNW@ZnHQ||NCM full cycled 1000 cycles 90% capacity retention areal 3.2 mAh The technology brings new opportunities next‐generation high‐energy batteries.

Язык: Английский

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Liquid electrolyte chemistries for solid electrolyte interphase construction on silicon and lithium-metal anodes

Chemical Science, Год журнала: 2023, Номер 14(37), С. 9996 - 10024

Опубликована: Янв. 1, 2023

Next-generation battery development necessitates the coevolution of liquid electrolyte and electrode chemistries, as their erroneous combinations lead to failure. In this regard, priority should be given alleviation volumetric stress experienced by silicon lithium-metal anodes during cycling mitigation other problems hindering commercialization. This review summarizes advances in sacrificial compound-based stress-adaptable interfacial engineering, which has primarily driven electrolytes for high-performance lithium batteries. Besides, we discuss how regulation lithium-ion solvation structures helps expand range formulations thus enhance quality solid interphases (SEIs), improve desolvation kinetics, realize longer-lasting SEIs on high-capacity anodes. The presented insights are expected inspire design synthesis next-generation materials accelerate advanced industrial applications.

Язык: Английский

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Stable Harsh-Temperature Lithium Metal Batteries Enabled by Tailoring Solvation Structure in Ether Electrolytes

ACS Nano, Год журнала: 2023, Номер 17(20), С. 19625 - 19639

Опубликована: Окт. 11, 2023

For lithium metal batteries (LMBs), the elevated operating temperature results in severe capacity fading and safety issues due to unstable electrode-electrolyte interphases electrolyte solvation structures. Therefore, it is crucial construct advanced electrolytes capable of tolerating harsh environments ensure stable LMBs. Here, we proposed a localized high-concentration (LHCE) by introducing highly solvating power solvent diethylene glycol dimethyl ether (DGDME). Computational experimental evidence discloses that original DGDME-LHCE shows favorable features for high-temperature LMBs, including high Li+-binding stability, electro-oxidation resistance, thermal nonflammability. The tailored solvated sheath structure achieves preferred decomposition anions, inducing (cathode Li anode)/interphases simultaneously, which enables homogeneous plating-stripping behavior on anode side high-voltage tolerance cathode side. Li||Li cells coupled with DGDME-LHCE, they showcase outstanding reversibility (a long lifespan exceeding 1900 h). We demonstrate exceptional cyclic stability (∼95.59%, 250 cycles), Coulombic efficiency (>99.88%), impressive (4.5 V) (60 °C) performances Li||NCM523 using DGDME-LHCE. Our advances shed light an encouraging tactic Li-metal confronted stringent challenges.

Язык: Английский

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Nonflammable electrolyte with low exothermic design for safer lithium-based batteries

Nano Energy, Год журнала: 2023, Номер 114, С. 108639 - 108639

Опубликована: Июнь 25, 2023

Язык: Английский

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Hydrated solvation suppression of zinc ions for highly reversible zinc anodes

Chemical Engineering Journal, Год журнала: 2023, Номер 466, С. 143189 - 143189

Опубликована: Апрель 26, 2023

Язык: Английский

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Interfacial Chemistry of Perfluorinated-Anion Additives Deciphering Ether-Based Electrolytes for Sodium-Ion Batteries

ACS Energy Letters, Год журнала: 2024, Номер 9(2), С. 461 - 467

Опубликована: Янв. 12, 2024

Ether-based electrolytes with high reductive stability can be compatible multiple anodes. However, their low oxidative and flash point lead to restrictions for sodium-ion batteries. Here we report a rational coupling design between perfluorinated-anion additives cathode/solvent self-assemble protective cathode-electrolyte interphase (CEI) concurrently build −C–F···H–C– stable interaction network promote the of ethers. The preferential adsorption oxidization enable electrolyte restrain weak oxidation at voltage withstand up 4.5 V vs Na/Na+. Such also facilitate uniform Na deposition inhibit growth dendrites. pseudo hydrogen bond developed solvents contributes markedly elevated thermal 60 °C. These results highlight significance regulating interfacial environment solvation effect by sacrificial boosting electrochemical high-temperature performance.

Язык: Английский

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Reversible Carbon Dioxide/Lithium Oxalate Regulation toward Advanced Aprotic Lithium Carbon Dioxide Battery

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(17)

Опубликована: Фев. 27, 2024

Li-CO

Язык: Английский

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Two-Dimensional Electrolyte Design: Broadening the Horizons of Functional Electrolytes in Lithium Batteries

Accounts of Chemical Research, Год журнала: 2024, Номер 57(8), С. 1163 - 1173

Опубликована: Апрель 1, 2024

ConspectusSince their commercialization in the 1990s, lithium-ion batteries (LIBs) have been increasingly used applications such as portable electronics, electric vehicles, and large-scale energy storage. The increasing use of LIBs modern society has necessitated superior-performance LIB development, including electrochemical reversibility, interfacial stability, efficient kinetics, environmental adaptability, intrinsic safety, which is difficult to simultaneously achieve commercialized electrolytes. Current electrolyte systems contain a solution with Li salts (e.g., LiPF6) solvents ethylene carbonate dimethyl carbonate), latter dissolves strongly interacts Li+ (lithiophilic feature). Only lithiophilic agents can be functionally modified additives solvents), altering bulk behaviors solvates. However, approaches alter pristine solvation processes, making it strike balance between performance other desired functions. This common design shows strong coupling among formulation, coordination, electrochemistry, function. invention lithiophobic cosolvents multifluorinated ether fluoroaromatic hydrocarbons) expanded space (interacts Li+) but not dimensions. Functional modifications switch cosolvents, affording superior properties (carried by cosolvents) little impact on primary (dictated solvents). engineering technique based 2D (TDE) principle, decouples molecular-scale understanding TDEs expected accelerate innovations next-generation LIBs.This Account provides insights into recent advancements electrolytes for from perspective (i.e., cosolvents), establishing generalized TDE principle functional design. In electrolytes, microsolvating competition emerges because cosolvent-induced dipole–dipole ion–dipole interactions, forming loose shell kinetically favorable electrolyte. At electrode/electrolyte interface, cosolvent affords reliable passivation desolvation, compatibility reversibility even under harsh conditions. Based this unique coordination chemistry, are formulated without significantly sacrificing performance. First, tune Li+–solvent affinity anion mobility, promoting diffusion kinetics benefit high-rate low-temperature applications. Second, undergoes less thermally induced decomposition constructs stable interphase TDEs, high-temperature adaptability cycling stability. Third, modifies local Li+–solvent–anion topography, controlling afford numerous promising that cannot Finally, mitigates detrimental crosstalk flame retardants solvents, improving safety compromising performance, broadens horizons optimizing versatile inspiring new ideas liquid electrochemistry battery systems.

Язык: Английский

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Ether‐Based Electrolyte for High‐Temperature and High‐Voltage Lithium Metal Batteries

Advanced Functional Materials, Год журнала: 2024, Номер 34(19)

Опубликована: Янв. 9, 2024

Abstract The compatibility of lithium metal with organic solvents is the most crucial for batteries (LMBs). Even though ether show excellent toward metal, reactivity at elevated temperatures and high voltages hinders their utilization in battery systems. In this study, a high‐temperature electrolyte designed comprising oxalyldifluoroborate (LiODFB), diethylene glycol dibutyl (DGDE), 3‐methoxypropionitrile (MPN), fluorinated ethylene carbonate (FEC), which abbreviated as MDF electrolyte. presence MPN changes solvation structure, thereby facilitating increased redox reactions ODFB − synergizing FEC to build robust solid interface (SEI), effectively inhibiting dendrites growth solvent decomposition. Consequently, exhibits not only long cyclic stability coulombic efficiency Li||Cu Li||Li cells but also characteristics both Li||LiFePO 4 (LFP) Li||LiNi 0.8 Co 0.1 Mn O 2 (NCM811) cells. Remarkably, these demonstrate stable operation even when exposed higher up 80 °C, while Li||NCM811 cell maintains consistent an voltage level 4.5 V.

Язык: Английский

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Amide-Modulated Gel Electrolytes Enable Nickel-Rich Cathodes with Enhanced Interphase Stability at 90 °C

ACS Energy Letters, Год журнала: 2024, Номер 9(4), С. 1826 - 1834

Опубликована: Март 29, 2024

The safe and reliable operation of high-voltage lithium metal batteries (LMBs) at elevated temperatures is currently hindered by the lack electrolyte designs that exhibit a high thermal safety oxidation resistance. Here, an in situ gelation strategy, combining thermally stable sulfone-based with N,N-dimethylacrylamide monomer, proposed to fabricate wide-temperature gel up 235 °C maintains stability above 4.3 V 90 °C. An oxidation-resistant protective layer enables conformal coating LiNi0.6Co0.2Mn0.2O2 particles cathode, effectively preventing decomposition during temperatures. As result, Li/LiNi0.6Co0.2Mn0.2O2 resulting demonstrate exceptional cycle life °C, even under abusive conditions. This study paves new pathway development high-energy LMBs operating extremely high-temperature

Язык: Английский

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