A solvent-anchored non-flammable electrolyte

Huang, Zhuojun; Lai, Jian‐Cheng; Kong, Xian; Rajković, Ivan; Xiao, Xin; Çelik, Hasan; Yan, Hongping; Gong, Huaxin; Rudnicki, Paul E.; Lin, Yangju; Ye, Yusheng; Li, Yanbin; Chen, Yuelang; Gao, Xin; Jiang, Yuanwen; Choudhury, Snehashis; Qin, Jian; Tok, Jeffrey B.‐H.; Cui, Yi; Bao, Zhenan

doi:10.1016/j.matt.2022.11.003

Cited by 16 publications

(9 citation statements)

References 47 publications

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“…These groups offer numerous binding sites for Li + anchoring, facilitating the migration of Li + along the molecular chains of the polymer host. [ 10a,21 ] Moreover, the QSE exhibits an extended electrochemical stability window of 4.5 V compared to that of LE (4.25 V, Figure 4e), which is due to the interaction between the solvent and fluoropolymer matrix. This property is promising for suppressing oxidative decomposition of the electrolyte and reducing the risk of cell overcharging.…”

Section: Resultsmentioning

confidence: 99%

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Nonflammable Polyfluorides‐Anchored Quasi‐Solid Electrolytes for Ultra‐Safe Anode‐Free Lithium Pouch Cells without Thermal Runaway

Hu,

Chen,

et al. 2023

Advanced Materials

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The safe operation of rechargeable batteries is crucial because of numerous instances of fire and explosion mishaps. However, battery chemistry involving metallic lithium (Li) as the anode is prone to thermal runaway in flammable organic electrolytes under abusive conditions. Herein, an in‐situ encapsulation strategy is proposed to construct nonflammable quasi‐solid electrolytes through the radical polymerization of a hexafluorobutyl acrylate (HFBA) monomer and a pentaerythritol tetraacrylate (PETEA) crosslinker. The quasi‐solid system eliminated the inherent flammability of ether electrolytes with zero self‐extinguishing time owing to the radical capturing ability of HFBA in the gas phase. Additionally, the graphitized carbon layer generated during the decomposition of PETEA at high temperatures obstructs the heat and oxygen required for combustion. When coupled with Au‐modified reduced graphene oxide anodic current collectors and lithium sulfide cathodes, the assembled anode‐free Li‐metal cell based on the QSE exhibited no signs of cell expansion or gas generation during cycling, and thermal runaway was eliminated under multiple mechanical, electrical, and thermal abuse scenarios and even rigorous strikes. This nonflammable quasi‐solid configuration with gas‐ and condensed‐phase flame‐retardant mechanisms can drive a technological leap in anode‐free Li‐metal pouch cells and secure the practical applications necessary to power our society in a safe manner.This article is protected by copyright. All rights reserved

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Section: Resultsmentioning

confidence: 99%

“…[ 9 ] Despite these benefits, there is still a potential safety hazard owing to the inherent volatilization and leakage risks associated with LE solvents. [ 10 ]…”

Section: Introductionmentioning

confidence: 99%

Nonflammable Polyfluorides‐Anchored Quasi‐Solid Electrolytes for Ultra‐Safe Anode‐Free Lithium Pouch Cells without Thermal Runaway

Hu,

Chen,

et al. 2023

Advanced Materials

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“…[34] The gradual upfield shift with increasing fluorination degree in 7 Li-NMR peak indicates the enhanced shielding effect from the nearest neighbors of Li + , which includes both solvents and anions in its inner solvation sheath (Figure 1d). [35][36][37] The solvation structure was further studied by Fourier transform infrared spectroscopy (FTIR) and Raman analysis (Figure 1e,f). The pure EA solvent exhibits the typical stretching vibration of carboxylic ester carbonyl group (C = O) at 1737 cm −1 with a weak peak at ≈1770 cm −1 pos-sibly arising from Fermi resonance.…”

Section: Spatial Arrangement and The Solvation Structure Characteriza...mentioning

confidence: 99%

Fluorinated Solvent Molecule Tuning Enables Fast‐Charging and Low‐Temperature Lithium‐Ion Batteries

Yi-min

Liu

Yin

et al. 2023

Advanced Energy Materials

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Popularly‐used fluorination can effectively weaken Li+‐solvent interaction to facilitate the desolvation process at low temperature; however, high fluorination degree sacrifices salt dissociation and ionic conductivity. Herein, functional fluorinations are well tuned with different amounts of F atoms to balance Li+‐solvent binding energy and ion movement, which reveals the fluorination effect on the solvation behavior and low‐temperature performance. Noteworthily, the moderately‐fluorinated ethyl difluoroacetate (EDFA) successfully favors a lower binding energy than less‐fluorinated ethyl fluoroacetateand superior salt dissociation more than highly‐fluorinated ethyl trifluoroacetate, realizing the trade‐off between weak affinity and sufficient ionic conductivity. The well‐formulated EDFA‐based electrolyte exhibits a unique solvation sheath and generates inorganic‐rich solid electrolyte interphase with low resistance for smooth Li+ diffusion, which enables graphite anodes with excellent fast‐charging capability (196 mAh g−1 at 6 C) and impressive low‐temperature performance with a reversible capacity of 279 mAh g−1 under −40 °C. Subsequently, the wide electrochemical potential window of EDFA‐based electrolyte endows the 1.2 Ah LiNi0.8Co0.1Mn0.1O2 (NCM811)||graphite pouch cells with a high reversible capacity retention of 58.3% at −30 °C and discharge capacity of 790 mAh at −40 °C. Such solvent molecules with a moderately‐fluorinated strategy promise advanced electrolyte design for lithium‐ion batteries operating under harsh conditions.

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“…[7b,13] Compared to small molecule additives, polymeric additives are relatively less explored in Zn ion batteries. Although polymers have been added for enhancing the stability of the anode and suppressing water splitting, [14] there is no report on exploiting polymeric additives for enhancing ion transport and electrochemical performance in aqueous electrolytes. It has been reported that attaching water molecules to the surrounding of polymers can enhance ion migration in hydrogels.…”

Section: Introductionmentioning

confidence: 99%

Polymer Chain‐Guided Ion Transport in Aqueous Electrolytes of Zn‐Ion Batteries

Wu,

Zhang,

Chen

et al. 2023

Advanced Energy Materials

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As a promising candidate for next‐generation energy storage devices, Zn metal battery excels with their good safety, high specific capacity, and economic attractiveness. However, it still suffers from a narrow electrochemical window, notorious dendrite formation, and sluggish Zn ion transfer. Aqueous electrolyte engineering has been regarded as an effective way to improve these. It is shown that by adding sodium polystyrene sulfonate (PSS) polymers into a dilute 1 m Zn(OTf)2 aqueous electrolyte, compact water shells with stronger hydrogen bonding and more ordered structures are formed around the polymer chains. As a result, a fast transport channel to the zinc ions is provided. The PSS chains also protect the zinc electrode from directly contacting the water molecules and thus suppress water decomposition. With these merits, a Zn//Cu cell demonstrates a high coulombic efficiency of ≈99% after 1500 h cycling. Meanwhile, a record‐high cumulative Zn plating capacity of 10 000 mA h cm−2 is obtained using a Zn||Zn cell. In addition, the Zn//C@V2O5 full cell achieves almost 100% capacity retention after 1000 cycles. This work provides a new strategy for designing advanced electrolyte systems excelling in ion transport kinetics.

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A solvent-anchored non-flammable electrolyte

Cited by 16 publications

References 47 publications

Nonflammable Polyfluorides‐Anchored Quasi‐Solid Electrolytes for Ultra‐Safe Anode‐Free Lithium Pouch Cells without Thermal Runaway

Nonflammable Polyfluorides‐Anchored Quasi‐Solid Electrolytes for Ultra‐Safe Anode‐Free Lithium Pouch Cells without Thermal Runaway

Fluorinated Solvent Molecule Tuning Enables Fast‐Charging and Low‐Temperature Lithium‐Ion Batteries

Polymer Chain‐Guided Ion Transport in Aqueous Electrolytes of Zn‐Ion Batteries

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