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    University - Student Department: Chemical Engineering Position: Graduate

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  • Interfacial Lithium Redox Kinetics Regulated by Solvent Asymmetry and Moment of Inertia in Li Metal Batteries. Journal of the American Chemical Society Choi, I. R., Shah, A., Heo, J., Shuchi, S. B., Holoubek, J., Florian, J., Lee, J. K., Lyu, H., Zhang, E., Lee, J. H., Lin, Y., Cui, Y., Qin, J., Bao, Z. 2026; 148 (33): 35293-35306

    Abstract

    Lithium metal batteries (LMBs) offer high energy density, but interfacial charge-transfer kinetics remain a bottleneck for high-rate operation. In this work, we construct a library of 12 ether solvents with systematic variations in symmetry and fluorination, confirming that molecular asymmetry is an important feature that results in enhanced Li+ redox kinetics and more stable solid electrolyte interphases on Li0. Furthermore, we developed a mechanistic understanding of the underlying process. We show that more tilted dipoles and lower moments of inertia strongly correlate with higher exchange current densities. Among the solvents in our study, the asymmetric F5MPE (1-methoxy-2-(2,2,3,3,3-pentafluoropropoxy) ethane) molecule, a previously unreported solvent molecule, enabled >170 stable cycles in high-rate Li||NMC full cells, outperforming the previously reported best single-salt-single-solvent ether solvent, F5DEE molecule. Overall, this work links molecular-level information with the behavior at electrochemical interfaces and provides an understanding of molecular design considerations for next-generation electrolytes tailored for high-power, fast-charging LMBs.

    View details for DOI 10.1021/jacs.5c21712

    View details for PubMedID 42677567

  • Interfacial LithiumRedox Kinetics Regulated by SolventAsymmetry and Moment of Inertia in Li Metal Batteries JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Choi, I., Shah, A., Heo, J., Shuchi, S., Holoubek, J., Florian, J., Lee, J. K. J., Lyu, H., Zhang, E., Lee, J., Lin, Y., Cui, Y., Qin, J., Bao, Z. 2026

    View details for DOI 10.1021/jacs.5c21712

    View details for Web of Science ID 001850800900001

  • Spatiochemical Segregation in Porous Lithium-Metal Interphases. Journal of the American Chemical Society Yu, W., Lyu, H., Li, D., Lin, K. Y., Florian, J., Cho, Y., Xu, X., Chen, Y., Hao, H., Xu, C., Nordlund, D., Nanda, J., Qin, J., Cui, Y., Bao, Z. 2026

    Abstract

    The solid-electrolyte interphase (SEI) on lithium metal forms through electrolyte reduction at a dynamically evolving metal surface, yet how its chemistry and spatial organization develop during lithium plating and stripping remains poorly understood. Here, using a 1,2-dimethoxyethane (DME)/1 M lithium bis(fluorosulfonyl)imide (LiFSI) electrolyte system, we show that three-dimensional lithium growth drives spatiochemical segregation of interphase products into chemically heterogeneous domains that are mechanically reorganized during stripping into a porous electrolyte-retaining framework. Correlative X-ray photoelectron spectroscopy, scanning electron microscopy, nanoscale secondary ion mass spectrometry (NanoSIMS), and synchrotron X-ray absorption spectroscopy reveal that FSI--derived inorganic species, dominated by LiF, become enriched in regions spatially decoupled from oxygen-containing phases near the lithium surface. Stripping-induced contraction compacts these chemically distinct domains into confined intergranular volumes, where supersaturation promotes precipitation and consolidation, yielding a porous SEI that retains electrolyte-derived species within a buried pore network beyond the reach of surface-sensitive probes. Spatiochemical segregation thus couples interfacial reaction pathways to lithium chemo-mechanics, dictating interphase composition, architecture, and permeability. These findings establish a chemo-mechanical framework for SEI evolution and suggest strategies to mitigate electrolyte retention and interphase instability in lithium-metal batteries.

    View details for DOI 10.1021/jacs.6c04430

    View details for PubMedID 42224578

  • Field-Responsive Dynamic Monolayer Regulated Interphase for Enhanced Lithium Metal Batteries. Journal of the American Chemical Society Zhang, E., Holoubek, J., Lyu, H., Li, Y., Florian, J., Shuchi, S. B., Lee, J. K., Michalek, L., Chen, T., Chen, Z., Choi, I. R., Guo, X., Mondonico, L., Cui, Y., Bao, Z. 2026

    Abstract

    Lithium metal batteries offer high energy density but suffer from persistent interphase instability, where continuous corrosion, solid electrolyte interphase (SEI) growth and poor lithium deposition morphology remain key barriers to long cycle and calendar life. Here, we introduce a novel concept of dynamic monolayers on Li metal anodes, consisting of electric field-responsive molecules that assemble into packed, structured layers at the lithium interphase under an applied voltage. We employed electrochemical quartz crystal microbalance with dissipation monitoring for in situ verification of the field responsiveness and packing behavior of these molecules. Dynamic monolayers with stronger packing are found to promote more inorganic-rich SEI and chunkier lithium growth, as directly observed by cryogenic X-ray photoelectron spectroscopy and operando optical microscopy. Together, these interfacial improvements translate into enhanced Coulombic Efficiency, reduced overpotential, and improved long-term cycling stability across Li||Cu, Li||Li, ultrathin lithium (20 mum) and anode-free NMC811 configurations. Dynamic monolayers potentially provide a broadly applicable approach for tackling interfacial challenges across a range of alkali metal battery systems.

    View details for DOI 10.1021/jacs.5c19365

    View details for PubMedID 41649298

  • Stabilizing All-Solid-State Li-S Batteries by a Polysulfide-Repelling and Anode-Protecting Self-Segregated Trilayer Polymer Electrolyte. Journal of the American Chemical Society Lyu, H., Gao, X., Michalek, L., Chen, T., Yu, W., Lim, C. Y., Florian, J., Mondonico, L., Zhang, W., Sarkar, S., Zhang, P., Shi, Y., Lin, K., Liao, S., Zheng, X., Qin, J., Cui, Y., Bao, Z. 2026

    Abstract

    Rational management of lithium polysulfide (LiPS) transport is essential for stable, high-energy-density Li-S batteries. We introduce a freestanding, self-segregated trilayer polymer electrolyte (TLE) that forms two layers of nanometer-thin, ion-selective coatings at the cathode and anode interfaces by autonomous phase separation of two immiscible polymers while preserving a highly conductive bulk matrix. In Li-S cells, these coatings simultaneously repel dissolved LiPS at the sulfur cathode and stabilize lithium plating and stripping at the Li metal anode without sacrificing ion transport. Operando optical cell monitoring and theoretical modeling reveal that the dual-functional coatings are responsible for stable Li metal anode operation and effective shuttle suppression. The TLE enables an initial discharge capacity of 1369 mAh g-1 (81.7% of theoretical) and maintains a stable capacity over 50 cycles at 0.2C. Fabricated by a single-step casting process, this scalable electrolyte membrane offers a practical route to durable, all-solid-state Li-S batteries.

    View details for DOI 10.1021/jacs.5c18042

    View details for PubMedID 41622643

  • Simply Fabricatable Reference Electrode for Studying Li Metal Interfaces <i>Operando</i> ACS ENERGY LETTERS Florian, J., Lyu, H., Mondonico, L., Zhao, Y., Lee, J. K. J., Musgrove, A. L., Cui, Y., Sacci, R. L., Bao, Z. 2026

    View details for DOI 10.1021/acsenergylett.5c03496

    View details for Web of Science ID 001659662500001

  • Revealing Solvent-Assisted Li+ Transport in the Solid Electrolyte Interphase operando. Journal of the American Chemical Society Florian, J., Lyu, H., Choi, I. R., Mondonico, L., Lam, S., Zhao, Y., Kim, M. J., Westover, A., Cui, Y., Sacci, R. L., Bao, Z. 2025

    Abstract

    The performance of energy-dense lithium metal batteries is critically influenced by the properties of the solid electrolyte interphase (SEI). Yet, progress in understanding this layer has been limited by the lack of accurate operando characterization because the SEI evolves dynamically during cycling. Here, we apply dynamic electrochemical impedance spectroscopy (dEIS) to resolve the real-time evolution of the SEI on lithium metal in ether-based electrolytes with varying degrees of fluorination. We find that faster stabilization of the compact SEI resistance correlates with improved passivation and higher Coulombic efficiency. Unexpectedly, compact SEI resistance correlates directly with Li+ solvation energy, revealing that weaker Li+ solvation increases not only bulk but also interphase resistance. These findings challenge the conventional view of the SEI as a purely solid-phase conductor and instead support a solvent-assisted Li+ transport mechanism within the compact SEI. This framework emphasizes the need to balance SEI ionic conductivity with the Li+ solvation environment to maximize lithium metal battery performance.

    View details for DOI 10.1021/jacs.5c14284

    View details for PubMedID 41202327

  • Asymmetric ether solvents for high-rate lithium metal batteries NATURE ENERGY Choi, I., Chen, Y., Shah, A., Florian, J., Serrao, C., Holoubek, J., Lyu, H., Zhang, E., Lee, J., Lin, Y., Kim, S., Park, H., Zhang, P., Lee, J., Qin, J., Cui, Y., Bao, Z. 2025

    View details for DOI 10.1038/s41560-025-01716-w

    View details for Web of Science ID 001421539700001

  • Analyzing Structure-Activity Variations for Mn-Carbonyl Complexes in the Reduction of CO2 to CO INORGANIC CHEMISTRY Florian, J., Cole, J. M. 2022: 318-335

    Abstract

    Contemporary electrocatalysts for the reduction of CO2 often suffer from low stability, activity, and selectivity, or a combination thereof. Mn-carbonyl complexes represent a promising class of molecular electrocatalysts for the reduction of CO2 to CO as they are able to promote this reaction at relatively mild overpotentials, whereby rare-earth metals are not required. The electronic and geometric structure of the reaction center of these molecular electrocatalysts is precisely known and can be tuned via ligand modifications. However, ligand characteristics that are required to achieve high catalytic turnover at minimal overpotential remain unclear. We consider 55 Mn-carbonyl complexes, which have previously been synthesized and characterized experimentally. Four intermediates were identified that are common across all catalytic mechanisms proposed for Mn-carbonyl complexes, and their structures were used to calculate descriptors for each of the 55 Mn-carbonyl complexes. These electronic-structure-based descriptors encompass the binding energies, the highest occupied and lowest unoccupied molecular orbitals, and partial charges. Trends in turnover frequency and overpotential with these descriptors were analyzed to afford meaningful physical insights into what ligand characteristics lead to good catalytic performance, and how this is affected by the reaction conditions. These insights can be expected to significantly contribute to the rational design of more active Mn-carbonyl electrocatalysts.

    View details for DOI 10.1021/acs.inorgchem.2c03391

    View details for Web of Science ID 000904442000001

    View details for PubMedID 36541860

    View details for PubMedCentralID PMC9832541