Transformed Solvation Structure of Noncoordinating Flame‐Retardant Assisted Propylene Carbonate Enabling High Voltage Li‐Ion Batteries with High Safety and Long Cyclability

Lü, Di; Zhang, Shenghang; Li, Jiedong; Huang, Lang; Zhang, Xiaohu; Xie, Bin; Zhuang, Xiangchun; Cui, Zili; Fan, Xiulin; Xu, Gaojie; Du, Xiaofan; Cui, Guanglei

doi:10.1002/aenm.202300684

Cited by 23 publications

(9 citation statements)

References 72 publications

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“…Generally, the lower surface tension of electrolyte means better wettability. 30 It is found that with the increase of the amount of HFPN, the interfacial impedance of the Li–Li cells gradually increases (Fig. S3†), and the wettability of the electrolyte on separator gradually deteriorates (Fig.…”

Section: Resultsmentioning

confidence: 99%

Insight into the probability of ethoxy(pentafluoro)cyclotriphosphazene (PFPN) as the functional electrolyte additive in lithium–sulfur batteries

Li,

Zhang,

Zhang

et al. 2024

RSC Adv.

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Section: Resultsmentioning

confidence: 99%

Insight into the probability of ethoxy(pentafluoro)cyclotriphosphazene (PFPN) as the functional electrolyte additive in lithium–sulfur batteries

Li,

Zhang,

Zhang

et al. 2024

RSC Adv.

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Section: Applications Of Tdesmentioning

confidence: 99%

“…For example, lithiophobic pentafluoro(phenoxy)cyclotriphosphazene (FPPN) is directly used in PC electrolytes because it facilitates Li + desolvation and delays the thermal runaway temperature by passivating electrodes (Figure 7b). 48 Third, the crosstalk between carbonates and flame retardants is relieved by encapsulating the flame retardant in lithiophobic cosolvents. 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) interacts with carbonates by forming P−H bonds in common electrolytes, leading to interphase degradation.…”

Section: Intrinsic Safetymentioning

confidence: 99%

“…Second, the flame retardant–Li + interaction is removed using lithiophobic nonflammable cosolvents, which improves safety without destructing the primary Li + solvation structure. For example, lithiophobic pentafluoro(phenoxy)cyclotriphosphazene (FPPN) is directly used in PC electrolytes because it facilitates Li + desolvation and delays the thermal runaway temperature by passivating electrodes (Figure b) . Third, the crosstalk between carbonates and flame retardants is relieved by encapsulating the flame retardant in lithiophobic cosolvents.…”

Section: Applications Of Tdesmentioning

confidence: 99%

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

Qin,

Zeng,

Cheng

et al. 2024

Acc. Chem. Res.

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Metrics & MoreArticle Recommendations CONSPECTUS: Since their commercialization in the 1990s, lithium-ion batteries (LIBs) have been increasingly used in applications such as portable electronics, electric vehicles, and large-scale energy storage. The increasing use of LIBs in modern society has necessitated superior-performance LIB development, including electrochemical reversibility, interfacial stability, efficient kinetics, environmental adaptability, and intrinsic safety, which is difficult to simultaneously achieve in commercialized electrolytes.Current electrolyte systems contain a solution with Li salts (e.g., LiPF 6 ) and solvents (e.g., ethylene carbonate and dimethyl carbonate), in which the latter dissolves Li salts and strongly interacts with Li + (lithiophilic feature). Only lithiophilic agents can be functionally modified (e.g., additives and solvents), altering the bulk and interfacial behaviors of Li + solvates. However, such approaches alter pristine Li + solvation and electrochemical processes, making it difficult to strike a balance between the electrochemical performance and other desired electrolyte functions. This common electrolyte design in lithiophilic solvents shows strong coupling among formulation, coordination, electrochemistry, and electrolyte function. The invention of lithiophobic cosolvents (e.g., multifluorinated ether and fluoroaromatic hydrocarbons) has expanded the electrolyte design space to lithiophilic (interacts with Li + ) and lithiophobic (interacts with solvents but not with Li + ) dimensions. Functional modifications switch to lithiophobic cosolvents, affording superior properties (carried by lithiophobic cosolvents) with little impact on primary Li + solvation (dictated by lithiophilic solvents). This electrolyte engineering technique based on lithiophobic cosolvents is the 2D electrolyte (TDE) principle, which decouples formulation, coordination, electrochemistry, and function. The molecular-scale understanding of TDEs is expected to accelerate electrolyte innovations in next-generation LIBs. This Account provides insights into recent advancements in electrolytes for superior LIBs from the perspective of lithiophobic agents (i.e., lithiophobic additives and cosolvents), establishing a generalized TDE principle for functional electrolyte design. In bulk electrolytes, a microsolvating competition emerges because of cosolvent-induced dipole−dipole and ion−dipole interactions, forming a loose solvation shell and a kinetically favorable electrolyte. At the electrode/electrolyte interface, the lithiophobic cosolvent affords reliable passivation and efficient desolvation, with interfacial compatibility and electrochemical reversibility even under harsh conditions. Based on this unique coordination chemistry, functional electrolytes are formulated without significantly sacrificing their electrochemical performance. First, lithiophobic cosolvents are used to tune Li + −solvent affinity and anion mobility, promoting Li + diffusion and electrochemical kinetics of the electroly...

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“…Lithium-ion batteries have been widely used in 3C electronic products, energy storage devices, and power batteries due to their high operating voltage, environmental friendliness, and long cycle life. − The conventional liquid electrolyte used in Li-ion batteries makes it difficult to match high-voltage cathodes such as Li-rich Mn-based layered oxides due to its narrow electrochemical window, resulting in limited energy density. Moreover, flammable liquid electrolytes pose potential safety problems for Li batteries. − Given these concerns, significant effort has been devoted to exploring solid-state electrolytes (SSEs) with wider voltage windows and high safety, including perovskite , antiperovskite type, − sulfide type, − Na super ionic conductor (NASICON) type − and garnet type electrolytes. − Among these, garnet-type electrolytes have attracted much attention due to their excellent stability toward Li metal and air and fast ionic conduction. , However, the poor wettability and large interface resistance of garnet electrolytes and Li metal anode seriously obstruct the electrochemical performance of Li-ion batteries. ,− …”

Section: Introductionmentioning

confidence: 99%

In Situ Fabrication of High Ionic and Electronic Conductivity Interlayers Enabling Long-Life Garnet-Based Solid-State Lithium Batteries

Zeng,

Feng,

Shi

et al. 2024

ACS Appl. Mater. Interfaces

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Garnet-type Li6.75La3Zr1.75Ta0.25O12 (LLZTO) is a promising solid-state electrolyte (SSE) because of its fast ionic conduction and notable chemical/electrochemical stability toward the lithium (Li) metal. However, poor interface wettability and large interface resistance between LLZTO and Li anode greatly restrict its practical applications. In this work, we develop an in situ chemical conversion strategy to construct a highly conductive Li2S@C layer on the surface of LLZTO, enabling improved interfacial wettability between LLZTO and the Li anode. The Li/Li2S@C-LLZTO-Li2S@C/Li symmetric cell has a low interface impedance of 78.5 Ω cm2, much lower than the 970 Ω cm2 of a Li/LLZTO/Li cell. Moreover, the Li/Li2S@C-LLZTO-Li2S@C/Li cell exhibits a high critical current density of 1.4 mA cm–2 and an ultralong stability of 3000 h at 0.1 mA cm–2. When used in a LiFePO4 battery, the Li/Li2S@C-LLZTO/LiFePO4 battery exhibits a high initial discharge capacity of 150.8 mA h g–1 at 0.2 C without lithium storage capacity attenuation during 200 cycles. This work provides a novel and feasible strategy to address interface issues of SSEs and achieve lithium-dendrite-free solid-state batteries.

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Transformed Solvation Structure of Noncoordinating Flame‐Retardant Assisted Propylene Carbonate Enabling High Voltage Li‐Ion Batteries with High Safety and Long Cyclability

Cited by 23 publications

References 72 publications

Insight into the probability of ethoxy(pentafluoro)cyclotriphosphazene (PFPN) as the functional electrolyte additive in lithium–sulfur batteries

Insight into the probability of ethoxy(pentafluoro)cyclotriphosphazene (PFPN) as the functional electrolyte additive in lithium–sulfur batteries

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

In Situ Fabrication of High Ionic and Electronic Conductivity Interlayers Enabling Long-Life Garnet-Based Solid-State Lithium Batteries

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