Anion reduced ionic conductivity in LiF

Geschwind, Gary

doi:10.1016/0022-3697(69)90225-x

Cited by 11 publications

(4 citation statements)

References 9 publications

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“…around 0.85 eV, which is slightly higher than the literature value for the cation vacancy migration enthalpy ΔH v ≠ (0.75 eV) 19. This activation energy value is close to that of most reported LiF single crystals in the corresponding extrinsic temperature range (∼1 eV) 20–22. The slight excess of E a over the migration energy can be attributed to the roughness of the assumptions, most probably to a temperature dependent core charge or to impurity association.…”

Section: Resultssupporting

confidence: 68%

Ionic Space‐Charge Depletion in Lithium Fluoride Thin Films on Sapphire (0001) Substrates

Guo

et al. 2011

Adv Funct Materials

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Section: Resultssupporting

confidence: 68%

Ionic Space‐Charge Depletion in Lithium Fluoride Thin Films on Sapphire (0001) Substrates

Guo

et al. 2011

Adv Funct Materials

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“…41 However, the LiF in the SEI is found to be crystalline in this work, which has a very low ionic conductivity (<10 −12 S cm −1 ). 42,43 In this regard, the functioning mechanism of the LiF should be doubted, but compounds such as Li x PO y F z need to be taken into account because the amorphous Li x PO y F z may have a higher ionic conductivity than the crystalline LiF, which will contribute to increasing the CE. (3) Relationship between CE and SEI: Although ultrathin (<1 nm) and thick (∼10 nm) SEIs were observed for the Cs + -and Zn 2+ -containing electrolytes, they showed comparable CE in the beginning, which indicates that the CE is not proportional to the SEI content.…”

Section: Nano Lettersmentioning

confidence: 99%

New Insights on the Structure of Electrochemically Deposited Lithium Metal and Its Solid Electrolyte Interphases via Cryogenic TEM

Wang¹,

Zhang²,

Alvarado³

et al. 2017

Nano Lett.

357

307

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Lithium metal has been considered the "holy grail" anode material for rechargeable batteries despite the fact that its dendritic growth and low Coulombic efficiency (CE) have crippled its practical use for decades. Its high chemical reactivity and low stability make it difficult to explore the intrinsic chemical and physical properties of the electrochemically deposited lithium (EDLi) and its accompanying solid electrolyte interphase (SEI). To prevent the dendritic growth and enhance the electrochemical reversibility, it is crucial to understand the nano- and mesostructures of EDLi. However, Li metal is very sensitive to beam damage and has low contrast for commonly used characterization techniques such as electron microscopy. Inspired by biological imaging techniques, this work demonstrates the power of cryogenic (cryo)-electron microscopy to reveal the detailed structure of EDLi and the SEI composition at the nanoscale while minimizing beam damage during imaging. Surprisingly, the results show that the nucleation-dominated EDLi (5 min at 0.5 mA cm) is amorphous, while there is some crystalline LiF present in the SEI. The EDLi grown from various electrolytes with different additives exhibits distinctive surface properties. Consequently, these results highlight the importance of the SEI and its relationship with the CE. Our findings not only illustrate the capabilities of cryogenic microscopy for beam (thermal)-sensitive materials but also yield crucial structural information on the EDLi evolution with and without electrolyte additives.

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“…It was revealed that the EDLi is amorphous with uneven SEIs containing amorphous organic species and crystalline LiF. Nevertheless, the crystalline LiF in the SEI layer possessed a low conductivity of <10 –12 S cm –1 , and the amorphous Li x PO y F z species could display a higher ionic conductivity, , which questioned the favorable effect and the working mechanism of LiF for high CEs. Soon after, using cryo-TEM, Cui and co-workers discovered the fundamental effects of SEI nanostructures (i.e., mosaic and multilayer) on the performance of a Li metal anode, pointing out that fluctuations in the crystalline grain distribution within the SEI played a vital role in differentiating the mosaic structure from the multilayer structure, thus dictating the battery performance .…”

Section: Understanding Fluorinated Interphases In Li-based Batteriesmentioning

confidence: 99%

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

Wang,

Yang,

Meng

et al. 2024

Chem. Rev.

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

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Anion reduced ionic conductivity in LiF

Cited by 11 publications

References 9 publications

Ionic Space‐Charge Depletion in Lithium Fluoride Thin Films on Sapphire (0001) Substrates

Ionic Space‐Charge Depletion in Lithium Fluoride Thin Films on Sapphire (0001) Substrates

New Insights on the Structure of Electrochemically Deposited Lithium Metal and Its Solid Electrolyte Interphases via Cryogenic TEM

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

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