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Zavadil, Kevin R.

Publications and source records attributed to Zavadil, Kevin R..

6 records
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DOE OSTI2024

From Bulk to Interface: Solvent Exchange Dynamics and Their Role in Ion Transport and the Interfacial Model of Rechargeable Magnesium Batteries

Multivalent battery chemistries have been explored in response to the increasing demand for high-energy rechargeable batteries utilizing sustainable resources. Solvation structures of working cations have been recognized as a key component in the design of electrolytes; however, most structure–property correlations of metal ions in organic electrolytes usually build upon favorable static solvation structures, often overlooking solvent exchange dynamics. We here report the ion solvation structures and solvent exchange rates of magnesium electrolytes in various solvents by using multimodal nuclear magnetic resonance (NMR) analysis and molecular dynamics/density functional theory (MD/DFT) calculations. These magnesium solvation structures and solvent exchange dynamics are correlated to the combined effects of several physicochemical properties of the solvents. Moreover, Mg 2+ transport and interfacial charge transfer efficiency are found to be closely correlated to the solvent exchange rate in the binary electrolytes where the solvent exchange is tunable by the fraction of diluent solvents. Our primary findings are (1) most battery-related solvents undergo ultraslow solvent exchange coordinating to Mg 2+ (with time scales ranging from 0.5 μs to 5 ms), (2) the cation transport mechanism is a mixture of vehicular and structural diffusion even at the ultraslow exchange limit (with faster solvent exchange leading to faster cation transport), and (3) an interfacial model wherein organic-rich regions facilitate desolvation and inorganic regions promote Mg 2+ transport is consistent with our NMR, electrochemistry, and cryogenic X-ray photoelectron spectroscopy (cryo-XPS) results. In conclusion, this observed ultraslow solvent exchange and its importance for ion transport and interfacial properties necessitate the judicious selection of solvents and informed design of electrolyte blends for multivalent electrolytes.

25 ENERGY STORAGE↗
DOE OSTI2023

Calcium Cosalt Addition to Alter the Cation Solvation Structure and Enhance the Ca Metal Anode Performance

Accessing the energy density and sustainability of calcium metal batteries requires mastering reversible calcium electrodeposition through electrolyte design. Several electrolytes support reversible, ambient temperature deposition but at utilization and rate too low for practical applications. These challenges stem from solvation structures characterized by either high barriers for cation desolvation or thermodynamic instability, leading to parasitic decomposition of the salt and solvent. The optimal solvation structure for the effective delivery of calcium to the electrode interface is not known. In this work, we show that adding a relatively small amount of a weakly associating calcium salt (calcium carba-closo-dodecaborate) to an otherwise strongly associated solution (calcium borohydride in tetrahydrofuran) produces a surprising population of fully solvent-coordinated Ca2+ cations in the form of solvent-separated ion pairs (SSIPs). We further demonstrate that the formation of these SSIPs beneficially impacts the kinetics and thermodynamics of calcium electrodeposition, revealing the unexpected finding that direct coordination of Ca2+ by the BH4– anion limits the electrodeposition process. These findings reveal how the competition between solvent and anion coordination to Ca2+ affects calcium deposition kinetics and cycling stability, setting the stage for a new calcium electrolyte design based on mixed anion electrolytes.

Landers, Alan T.↗
DOE OSTI2023

Evaluation of Lithium Metal Anode Volumetric Expansion through Laser Plasma Focused Ion Beam Cross-Sectional Imaging

Lithium metal is an ideal anode for high energy density batteries, however the implementation of lithium metal anodes remains challenging. Beyond the development of highly efficient electrolytes, degradation processes restrict cycle life and reduce practical energy density. Herein lithium volumetric expansion and degradation pathways are studied in half cells through coupling electrochemical analysis with cross-sectional imaging of the intact electrode stack using a cryogenic laser plasma focused ion beam and scanning electron microscope. Here, we find that the volumetric capacity is compromised as early as the first cycle, at best reaching values only half the theoretical capacity (1033 vs 2045 mAh cm -3 ). By the 101st electrodeposition, the practical volumetric capacity decreases to values ranging from 143 to 343 mAh cm -3 .

25 ENERGY STORAGE↗
DOE OSTI2023

Magnesium Battery Electrolytes with Improved Oxidative Stability Enabled by Selective Solvation in Fluorinated Solvents

Practical Mg batteries require electrolytes that are stable both toward reduction by Mg metal and oxidation by high voltage cathodes. State-of-the-art Mg electrolytes based on weakly-coordinating Mg salts utilize standard ether-type solvents (usually glymes) due to their reductive stability. However, the oxidative stabilities of these solvents are less than ideal, leading to difficulties in realizing the high oxidative stabilities of novel salts. On the other hand, alternative solvents with greater oxidative stability are typically unable to support Mg cycling. Here, in this work, we report a selective solvation approach involving the combination of glyme and hydrofluoroether solvents. Selective solvation of Mg 2+ by the glyme solvent component increases the oxidative stability of the glyme while maintaining sufficient reductive stability of the noncoordinating hydrofluoroether. We show that this approach enables the design of electrolytes with greater oxidative stability than glyme-only electrolytes while retaining enough reductive stability to cycle Mg metal. We also relate the influence of various coordination interactions among the solvents and anions with Mg 2+ to their electrochemical stabilities to better inform the design of future electrolytes.

25 ENERGY STORAGE↗