Structure, ionic motion and conductivity in some solid-solutions of the LiClMCl2 systems (M=Mg,V,Mn)

Cros, C.; Hanebali, L.; Latie, L.; Villeneuve, Ge ́rard; Wang, Gang

doi:10.1016/0167-2738(83)90223-0

Cited by 33 publications

(8 citation statements)

References 9 publications

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“…Incorporation of these oxide electrolytes into solid-state batteries is typically difficult, as many suffer from high grain boundary resistance or require high temperature sintering to obtain good contact with the electrodes. The binary halides have extraordinarily wide stability windows, but ionic conductivity is prohibitively low for all but the lowest power applications unless a second cation is added. − Unfortunately, the addition of such a cation typically makes these materials unstable against reduction by low voltage anodes (Figure ).…”

Section: Discussionmentioning

confidence: 99%

Interface Stability in Solid-State Batteries

et al. 2015

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Development of high conductivity solid-state electrolytes for lithium ion batteries has proceeded rapidly in recent years, but incorporating these new materials into high-performing batteries has proven difficult. Interfacial resistance is now the limiting factor in many systems, but the exact mechanisms of this resistance have not been fully explained - in part because experimental evaluation of the interface can be very difficult. In this work, we develop a computational methodology to examine the thermodynamics of formation of resistive interfacial phases. The predicted interfacial phase formation is well correlated with experimental interfacial observations and battery performance. We calculate that thiophosphate electrolytes have especially high reactivity with high voltage cathodes and a narrow electrochemical stability window. We also find that a number of known electrolytes are not inherently stable but react in situ with the electrode to form passivating but ionically conducting barrier layers. As a reference for experimentalists, we tabulate the stability and expected decomposition products for a wide range of electrolyte, coating, and electrode materials including a number of high-performing combinations that have not yet been attempted experimentally.

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Section: Discussionmentioning

confidence: 99%

Interface Stability in Solid-State Batteries

et al. 2015

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“…This work opens up an interesting prospect for controlling surface chemistry by the choice of impurity. For instance, the Suzuki phase is known to be formed in NaCl by other divalent ions (e.g., Mn 2+ ,137, 138 Fe 2+ 130) as well as in other host lattices, such as LiCl (:Mg 2+ , V 2+ , Mn 2+ ),139 LiF:Mg 2+ ,140 MgO:Mn 4+ , and NiO:Mn 4+ 141, 142. An interesting challenge would be to create a Suzuki phase incorporating magnetic impurities, such as Mn 2+ and Fe 2+ 137; magnetic ordering in these structures could be studied by magnetic exchange force microscopy 60.…”

Section: Non‐contact Atomic Force Microscopymentioning

confidence: 99%

Recent Trends in Surface Characterization and Chemistry with High‐Resolution Scanning Force Methods

et al. 2010

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The current status and future prospects of non-contact atomic force microscopy (nc-AFM) and Kelvin probe force microscopy (KPFM) for studying insulating surfaces and thin insulating films in high resolution are discussed. The rapid development of these techniques and their use in combination with other scanning probe microscopy methods over the last few years has made them increasingly relevant for studying, controlling, and functionalizing the surfaces of many key materials. After introducing the instruments and the basic terminology associated with them, state-of-the-art experimental and theoretical studies of insulating surfaces and thin films are discussed, with specific focus on defects, atomic and molecular adsorbates, doping, and metallic nanoclusters. The latest achievements in atomic site-specific force spectroscopy and the identification of defects by crystal doping, work function, and surface charge imaging are reviewed and recent progress being made in high-resolution imaging in air and liquids is detailed. Finally, some of the key challenges for the future development of the considered fields are identified.

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“…Although we previously investigated the baseline kinetics for a variety of halide salts (X = F, Cl, Br), the complementary thermodynamic activation energies that provide the best insights into the reaction mechanism have not yet been resolved and thus motivate the present work. Due to the slow reaction rates when LiF is used as the salt source, these efforts focused on the salts LiCl and LiBr and their Mg 2+ -substituted variants (Li 1–2 x Mg x X) with engineered vacancies that are known to have higher ionic conductivities …”

Section: Resultsmentioning

confidence: 99%

“…Due to the slow reaction rates when LiF is used as the salt source, these efforts focused on the salts LiCl and LiBr and their Mg 2+ -substituted variants (Li 1−2x Mg x X) with engineered vacancies that are known to have higher ionic conductivities. 20 Extraction of Kinetic Data. The ion exchange of Li into Na 2 Mg 2 P 3 O 9 N (a = 9.2439 Å) is known to proceed through a three-stage process beginning with two distinct solid solutions and finishing with a two-phase reaction to form Li 2 Mg 2 P 3 O 9 N (a = 9.1118 Å).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Thermodynamic and Kinetic Barriers Limiting Solid-State Reactions Resolved through In Situ Synchrotron Studies of Lithium Halide Salts

et al. 2023

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Although halide salts such as LiCl and LiBr are routinely used as a source of Li ions during ion exchange reactions, a detailed understanding of the processes controlling the rates of these reactions is presently lacking. Recently, we discovered that the rate-limiting barriers for ion exchange are commonly associated with these salts rather than the ceramic target of ion exchange, making it important to quantitatively understand salt processes. Here, it is demonstrated that in situ synchrotron studies of ion exchange reactions can be used to precisely quantify the thermodynamic activation energies associated with these solid-state reactions in a manner that can be directly compared with predictions from density functional theory (DFT). While the temperature dependence of the LiCl reaction rate is found to be set by a barrier associated with ion hopping, it was discovered that for LiBr, the rate is also affected by the defect formation energy�an energy found to be substantially lower than predicted by DFT. Furthermore, it is shown that by varying the relative amounts of reactants, the resulting change in reaction rate can be used to identify the rate-limiting reagent and to elucidate an overall scaling relationship that controls the concentration dependence of the reaction rate. Also, it is demonstrated that global fits across doped and undoped salts can be used to probe both intrinsic and extrinsic vacancy concentrations. This improved understanding of ion exchange mechanisms can be used to predict reaction conditions that can accelerate ion exchange reaction rates by orders of magnitude. The techniques demonstrated here can be broadly applied to probe the kinetics and thermodynamics of solid-state reactions.

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Structure, ionic motion and conductivity in some solid-solutions of the LiClMCl2 systems (M=Mg,V,Mn)

Cited by 33 publications

References 9 publications

Interface Stability in Solid-State Batteries

Interface Stability in Solid-State Batteries

Recent Trends in Surface Characterization and Chemistry with High‐Resolution Scanning Force Methods

Thermodynamic and Kinetic Barriers Limiting Solid-State Reactions Resolved through In Situ Synchrotron Studies of Lithium Halide Salts

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