Challenges and strategies of formulating low‐temperature electrolytes in lithium‐ion batteries

Qin, Mingsheng; Zeng, Ziqi; Cheng, Shijie; Xie, Jia

doi:10.1002/idm2.12077

Cited by 32 publications

(16 citation statements)

References 215 publications

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“…The low-temperature performance of LIBs is largely dictated by its electrochemical kinetics. , This section mainly discusses how to expedite desolvation from the perspective of lithiophilic solvents and lithiophobic cosolvents because bulk transport is discussed in the previous section. First, lithiophilic solvents are manipulated in TDEs for moderate Li + affinity and efficient kinetics.…”

Section: Applications Of Tdesmentioning

confidence: 99%

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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Section: Applications Of Tdesmentioning

confidence: 99%

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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“…Third, the formation of a LiF-rich SEI film by LMF145 facilitates the transport of Li + . [39][40][41] To give a better overview of the ultralow-temperature performance of this work, the comparison with recent reports is listed in Figure 6h and Table S2, Supporting Information, where this work shows superiority in capacity retention over the reports.…”

Section: Performance Of Ma-based Electrolyte At Low Temperaturementioning

confidence: 99%

Nonpolar Cosolvent Driving LUMO Energy Evolution of Methyl Acetate Electrolyte to Afford Lithium‐Ion Batteries Operating at −60 °C

Lei

Zeng

Yan

et al. 2023

Adv Funct Materials

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The operation of lithium‐ion batteries (LIBs) at low temperatures (<−20 °C) is hindered by the low conductivity and high viscosity of conventional carbonate electrolytes. Methyl acetate (MA) has proven to be a competitive low‐temperature electrolyte solvent with low viscosity and low freezing point, but its interfacial stability is poor and remains elusive until now. Here, it is revealed thaat the reductive stability of MA‐based electrolytes is fundamentally governed by the anion‐prevailed solvation structure. Based on this framework, fluorobenzene is employed in the electrolyte to promote the entry of anions into the solvation shell via dipole‐dipole interactions and the generation of free MA, thus enhancing the lowest unoccupied molecular orbital energy of MA. The designed electrolyte enables LiCoO2 (LCO)/graphite cells to exhibit excellent cycling performance at −20 °C (90% retention after 1000 cycles at 1 C) and to remain 91% of their room‐temperature capacity at a super‐low temperature of −60 °C at 0.05 C. Thanks to the plentiful free MA, this electrolyte has a high conductivity (2.61 mS cm−1) at −60 °C and allows LCO/graphite cell to charge at −60 °C. This study offers the possibility of practical applications for those solvents with poor reductive stability and provides new approaches to designing advanced electrolytes for low‐temperature applications.

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“…[58] By reducing the energy barrier associated with Li + , WSE can effectively promote the desolvation process of Li + from solvation structure before its intercalation into graphite. [59][60][61][62] Nevertheless, the weak solvation affinity with Li + also leads to the loss of ionic conductivity owing to insufficient dissociation ability of lithium salt. Therefore, it is of great importance to identify viable WSE with optimized physicochemical properties that well balance the desolvation energy and ionic conductivity at low temperature.…”

Section: Facilitating the Desolvation Process With Weakly Solvating E...mentioning

confidence: 99%

Electrolyte engineering and material modification for graphite‐based lithium‐ion batteries operated at low temperature

Yin

Dong

2023

Interdisciplinary Materials

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Graphite offers several advantages as an anode material, including its low cost, high theoretical capacity, extended lifespan, and low Li+‐intercalation potential. However, the performance of graphite‐based lithium‐ion batteries (LIBs) is limited at low temperatures due to several critical challenges, such as the decreased ionic conductivity of liquid electrolyte, sluggish Li+ desolvation process, poor Li+ diffusivity across the interphase layer and bulk graphite materials. Various approaches have therefore been explored to address these challenges. On the basis of graphite anode and corresponding LIBs, this review herein offers a comprehensive analysis of the latest advances in electrolyte engineering and electrode modification. First, electrolyte engineering is discussed in detail, highlighting the design of new electrolyte formula with broad liquid temperature range, optimized solvation structure, and well‐performed inorganic‐rich solid electrolyte interface. The advances in material modification have been then depicted with the view of improving the solid bulk diffusion rate to show general strategies with excellent performance at low temperatures. Finally, the corresponding challenges and opportunities have also been outlined to shed light on viable strategies for developing efficient and reliable graphite anode and graphite‐based LIBs under low‐temperature scenarios.

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Challenges and strategies of formulating low‐temperature electrolytes in lithium‐ion batteries

Cited by 32 publications

References 215 publications

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

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

Nonpolar Cosolvent Driving LUMO Energy Evolution of Methyl Acetate Electrolyte to Afford Lithium‐Ion Batteries Operating at −60 °C

Electrolyte engineering and material modification for graphite‐based lithium‐ion batteries operated at low temperature

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