Confinement Effects on the Thermal and Conductivity Properties of LiPF<sub>6</sub>-Dimethyl Carbonate Solutions Relevant to Lithium Rechargeable Batteries

Butson, Eric D.; Atchley, Justin; Burba, Christopher M.

doi:10.1149/1.3647858

Cited by 2 publications

(1 citation statement)

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“…It is notable that fusion temperatures of dilute NaCl solutions confined within MCM-41 fall below the solidus temperature of the unconfined solution, suggesting that these solutions are unable to achieve the eutectic composition. LiBF 4 and LiPF 6 dimethyl carbonate solutions also experience concentration-dependent melting points when confined within MCM-41 and/or SBA-15 silicas, regardless of the presence or absence of an external reservoir. , …”

Section: Resultsmentioning

confidence: 97%

Nanoconfinement-Induced Phase Segregation of Binary Benzene–Cyclohexane Solutions within a Chemically Inert Matrix

et al. 2018

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Binary solutions provide a fertile arena to probe intermolecular and molecular/surface interactions under nanoconfinement. Here, the phase segregation of a solution comprising 0.80 mol fraction benzene and 0.20 mol fraction cyclohexane confined within SiO2 nanopores was evaluated using small-angle neutron scattering with hydrogen–deuterium contrast matching. It is demonstrated that benzene and cyclohexane are fully miscible at 303 K (30 °C), yet they unambiguously phase segregate by 153 K (−120 °C), which is below their respective freezing points and below the cubic-to-monoclinic phase transition of cyclohexane. Specifically, the cyclohexane and benzene separate into a core|shell morphology with cyclohexane concentrated toward the nanopore centers. Additionally, pure benzene is shown to form a frozen core of bulk density with a thin shell of slightly reduced density immediately adjacent to the SiO2 nanopore wall at 153 K. Because the SiO2 matrix is chemically inert to cyclohexane and benzene, the observed radially dependent phase segregation is strong evidence for the effects of confinement alone, with minimal host–wall attraction.

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Section: Resultsmentioning

confidence: 97%

Nanoconfinement-Induced Phase Segregation of Binary Benzene–Cyclohexane Solutions within a Chemically Inert Matrix

et al. 2018

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Thermal Properties and Ionic Conductivities of Confined LiBF₄Dimethyl Carbonate Solutions

et al. 2013

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Solutions of lithium tetrafluoroborate dissolved in dimethyl carbonate (DMC) are confined within MCM-41, a mesoporous silica matrix. Thermal measurements indicate that the melting points of pure DMC and the DMC solutions are significantly reduced when confined within the pores of MCM-41 compared to unconfined samples; this is an observation that is consistent with the Gibbs−Thomson equation. The melting point onsets of confined solutions are slightly lower than that of pure DMC, suggesting the dissolved salts impact the phase-transition temperature of DMC when confined within mesoporous silica. Rotational dynamics of the confined solutions are explored by doping DMC with small quantities of Tempone, an electron paramagnetic resonance (EPR)-active spin probe. Tempone rotational correlation times are an order of magnitude slower for confined liquids compared to unconfined solutions. Temperature-dependent conductivity measurements of the composite materials suggest that the liquid electrolyte solution is distributed among the MCM-41 pores and the intergrain voids between individual MCM-41 particles. Ionic conductivities of confined electrolyte solutions remain above 0.01 mS•cm −1 for temperatures greater than −50 °C. However, the ionic conductivity of the unconfined solutions (i.e., solution occupying the spaces between the MCM-41 particles) rapidly decreases over subzero temperatures. Limitations associated with directly implementing these materials as low-temperature ion conductors are discussed.

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Confinement Effects on the Thermal and Conductivity Properties of LiPF₆-Dimethyl Carbonate Solutions Relevant to Lithium Rechargeable Batteries

Cited by 2 publications

References 32 publications

Nanoconfinement-Induced Phase Segregation of Binary Benzene–Cyclohexane Solutions within a Chemically Inert Matrix

Nanoconfinement-Induced Phase Segregation of Binary Benzene–Cyclohexane Solutions within a Chemically Inert Matrix

Thermal Properties and Ionic Conductivities of Confined LiBF₄Dimethyl Carbonate Solutions

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Confinement Effects on the Thermal and Conductivity Properties of LiPF6-Dimethyl Carbonate Solutions Relevant to Lithium Rechargeable Batteries

Cited by 2 publications

References 32 publications

Nanoconfinement-Induced Phase Segregation of Binary Benzene–Cyclohexane Solutions within a Chemically Inert Matrix

Nanoconfinement-Induced Phase Segregation of Binary Benzene–Cyclohexane Solutions within a Chemically Inert Matrix

Thermal Properties and Ionic Conductivities of Confined LiBF4Dimethyl Carbonate Solutions

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Confinement Effects on the Thermal and Conductivity Properties of LiPF₆-Dimethyl Carbonate Solutions Relevant to Lithium Rechargeable Batteries

Thermal Properties and Ionic Conductivities of Confined LiBF₄Dimethyl Carbonate Solutions