Dynamic Heterogeneity of Solvent Motion and Ion Transport in Concentrated Electrolytes

Molecular-level understanding of the cation transference number t+0, an important property that characterizes the transport of working cations, is critical to the bottom-up design of battery electrolytes. We quantify t+0 in a model tetraglyme-based electrolyte using molecular dynamics simulation and the Onsager approach. t+0 exhibits a concentration dependence in three distinct regimes: dilute, intermediate, and concentrated. The cluster approximation uncovers dominant correlations and dynamic heterogeneity in each regime. In the dilute regime, t+0 decreases sharply as increasing numbers of solvent molecules become coordinated with Li+. The crossover to the intermediate regime, t+0 ≈ 0, occurs when all solvent molecules become coordinated, and a plateau is obtained because anions enter the Li+ solvation shell, resulting in ion pairs that do not contribute to t+0. Transference in concentrated electrolytes is dominated by the presence of cations in a variety of negatively charged and solvent-excluded clusters, resulting in t+0 < 0

Understanding the Impact of Multi-Chain Ion Coordination in Poly(ether-Acetal) Electrolytes

Performant solid polymer electrolytes for battery applications usually have a low glass transition temperature and good ion solvation. Recently, to understand the success of PEO for solid-sate battery applications and explore alternatives, we have studied a series of polyacetals along with PEO, both from an experimental and a computational standpoint. We observed that even though the mechanism of transport may be more optimal in polyacetals, the lower glass transition temperature of the PEO-salt electrolyte system still makes it the best option, in this class of polymers, for battery applications. In this work, we explored the free-energy landscape of PEO and P(EO-MO) at various compositions and temperatures using metadynamics simulations to gain deeper insights into the various factors that affect the glass transition temperatures in these systems. In particular, we study the competition between intra- and inter-chain coordination of the cation in these systems that we had hypothesized in our previous work was responsible for the differences in the glass transition temperature. We observe that in PEO, the single-chain binding motif is thermodynamically more stable than the multi-chain binding motif, unlike P(EO-MO), where the opposite is true. We also show that multi-chain coordination, and the associated higher glass transition temperature, in P(EO-MO) is due to a larger strain energy for single-chain coordination that originates in the introduced OCO linkages (relative to PEO’s consistent OCCO linkages). Furthermore, the type of pathways to move from one transition state to another in the various systems do not change at higher concentrations though the relative probability of cation–anion coordinated states increases. Calculations at different temperatures to understand the entropic effect on the stability of these coordination environments reveal that as we increase the temperature, single-chain coordination becomes relatively more stable due to the entropic cost of multi-chain coordination, reducing the number of accessible states for the polymer. The various insights into the factors that affect glass transition temperature in these systems suggest design principles for polymer electrolyte systems with lower glass transition temperatures that need further research to compete with PEO at the same absolute battery working temperatures

High-Temperature “Spectrochronopotentiometry”: Correlating Electrochemical Performance with In Situ Raman Spectroscopy in Solid Oxide Fuel Cells

Carbon formation or “coking” on solid oxide fuel cell (SOFC) anodes adversely affects performance by blocking catalytic sites and reducing electrochemical activity. Quantifying these effects, however, often requires correlating changes in SOFC electrochemical efficiency measured during operation with results from ex situ measurements performed after the SOFC has been cooled and disassembled. Experiments presented in this work couple vibrational Raman spectroscopy with chronopotentiometry to observe directly the relationship between graphite deposited on nickel cermet anodes and the electrochemical performance of SOFCs operating at 725 °C. Raman spectra from Ni cermet anodes at open circuit voltage exposed to methane show a strong vibrational band at 1556 cm^–1 assigned to the “G” mode of highly ordered graphite. When polarized in the absence of a gas-phase fuel, these carbon-loaded anodes operate stably, oxidizing graphite to form CO and CO₂. Disappearance of graphite intensity measured in the Raman spectra is accompanied by a steep ∼0.8 V rise in the cell potential needed to keep the SOFC operating under constant current conditions. Continued operation leads to spectroscopically observable Ni oxidation and another steep rise in cell potential. Time-dependent spectroscopic and electrochemical measurements pass through correlated equivalence points providing unequivocal, in situ evidence that identifies how SOFC performance depends on the chemical condition of its anode. Chronopotentiometric data are used to quantify the oxide flux necessary to eliminate the carbon initially present on the SOFC anode, and data show that the oxidation mechanisms responsible for graphite removal correlate directly with the electrochemical condition of the anode as evidenced by voltammetry and impedance measurements. Electrochemically oxidizing the Ni anode damages the SOFC significantly and irreversibly. Anodes that have been reconstituted following electrochemical oxidation of carbon and Ni show qualitatively different kinetics of carbon removal, and the electrochemical performance of these systems is characterized by low maximum currents and large polarization resistances

Understanding the Solvation Structure of Li-Ion Battery Electrolytes Using DFT-Based Computation and ¹H NMR Spectroscopy

Molecular dynamics (MD) simulations, density functional theory (DFT) calculations, and 1H NMR spectroscopy were performed to gain a complementary understanding of the concentrated Li-ion electrolyte system, lithium bis(trifluoro­methane­sulfonyl)imide (Li[TFSI]) dissolved in tetraglyme. The computational methods provided the concentration dependence of differing solvation structure motifs by reference to changes in the corresponding NMR spectra. By combining both the computational and experimental methodologies, we show that the various solvation structures, dominated by the coordination between the tetraglyme (G4) solvent and lithium cation, directly influence the chemical shift separation of resonances in the 1H NMR spectra of the solvent. Thus, the 1H NMR spectra can be used to predict the fraction of tetraglyme involved in the solvation process, with quantitative agreement with solvation fraction predictions from MD simulation snapshots. Overall, our results demonstrate the reliability of a hybrid computational and experimental methodology to understand the solvation structure and hence transport mechanism of LiTFSI-G4 electrolytes in the low concentration region

Characterizing Oxygen Local Environments in Paramagnetic Battery Materials via ¹⁷O NMR and DFT Calculations

Experimental techniques that probe the local environment around O in paramagnetic Li-ion cathode materials are essential in order to understand the complex phase transformations and O redox processes that can occur during electrochemical delithiation. While Li NMR is a well-established technique for studying the local environment of Li ions in paramagnetic battery materials, the use of ¹⁷O NMR in the same materials has not yet been reported. In this work, we present a combined ¹⁷O NMR and hybrid density functional theory study of the local O environments in Li₂MnO₃, a model compound for layered Li-ion batteries. After a simple ¹⁷O enrichment procedure, we observed five resonances with large ¹⁷O shifts ascribed to the Fermi contact interaction with directly bonded Mn⁴⁺ ions. The five peaks were separated into two groups with shifts at 1600 to 1950 ppm and 2100 to 2450 ppm, which, with the aid of first-principles calculations, were assigned to the ¹⁷O shifts of environments similar to the 4i and 8j sites in pristine Li₂MnO₃, respectively. The multiple O environments in each region were ascribed to the presence of stacking faults within the Li₂MnO₃ structure. From the ratio of the intensities of the different ¹⁷O environments, the percentage of stacking faults was found to be ca. 10%. The methodology for studying ¹⁷O shifts in paramagnetic solids described in this work will be useful for studying the local environments of O in a range of technologically interesting transition metal oxides

Exploring the Ion Solvation Environments in Solid-State Polymer Electrolytes through Free-Energy Sampling

The success of poly­(ethylene oxide) (PEO) in solid-state polymer electrolytes for lithium-ion batteries is well established. Recently, in order to understand this success and to explore possible alternatives, we studied polyacetal electrolytes to deepen the understanding of the effect of the local chemical structure on ion transport. Advanced molecular dynamics techniques using newly developed, tailored interaction potentials have helped elucidate the various coordination environments of ions in these systems. In particular, the competition between cation–anion pairing and coordination by the polymer has been explored using free-energy sampling (metadynamics). At equivalent reduced temperatures, with respect to the polymer-specific glass-transition temperature, two-dimensional free-energy plots reveal the existence of multiple coordination environments for the lithium (Li) ions in these systems and their relative stabilities. Furthermore, we observe that the Li-ion movement in PEO follows a serial, stepwise pathway when moving from one coordination state to another, whereas this happens in a more continuous and concerted fashion in a polyacetal such as poly­(1,3-dioxalane) [P­(EO-MO)]. The implication is that interconversion between coordination states of the Li ions may be easier in P­(EO-MO). However, the overarching observation from our free-energy analysis is that Li-ion coordination is dominated by the polymer (in either case) and contact-ion pairs are rare. We rationalize the observed higher increase in glass-transition temperature (Tg) with salt loading in polyacetals as due to intermolecular Li-ion coordination involving multiple polymer chains, rather than just one chain for PEO-based electrolytes. This interchain coupling in the polyacetals, resulting in the higher Tg, works against any gains due to variations in Li-ion coordination that might enhance transport processes over PEO. Further research is required to overcome the interdependence between local coordination and macroscopic properties to compete with PEO electrolytes at the same absolute working temperature

Endogenous ¹⁷O Dynamic Nuclear Polarization of Gd-Doped CeO₂ from 100 to 370 K

17O NMR is an invaluable tool to study the structure and dynamics of oxide materials but remains challenging to apply in many systems. Even with isotopic enrichment, studies of samples with low masses and/or concentrations of the active species, such as thin films or interfaces, are limited by low sensitivity. Here, we show how endogenous dynamic nuclear polarization (DNP) can dramatically improve the sensitivity in the oxide-ion conductor Gd-doped CeO2, with a 17O enhancement factor of 652 at 100 K. This is the highest enhancement observed so far by endogenous DNP or Gd3+ DNP, which is explained in terms of the electron paramagnetic resonance characteristics. The DNP properties are studied as a function of Gd concentration for both enriched and natural-abundance samples, and the buildup behavior shows that spin diffusion in 17O-enriched samples improves sensitivity by relaying hyperpolarization throughout the sample. Notably, efficient hyperpolarization could still be achieved at elevated temperatures, with enhancement factors of 320 at room temperature and 150 at 370 K, paving the way for the characterization of materials under operational conditions. Finally, the application of endogenous Gd3+ DNP is illustrated with the study of interfaces in vertically aligned nanocomposite thin films composed of Gd-CeO2 nanopillars embedded in a SrTiO3 matrix, where DNP affords selective enhancement of the different phases and enables a previously infeasible two-dimensional correlation experiment to be performed, showing spin diffusion between Gd-CeO2 and the solid–solid interface

Zn-Ion Transporting, <i>In Situ</i> Formed Robust Solid Electrolyte Interphase for Stable Zinc Metal Anodes over a Wide Temperature Range

Hydrogen evolution, corrosion, and dendrite formation in the Zn anodes limit their practical applications in aqueous Zn metal batteries. Herein, we propose an interfacial chemistry regulation strategy that uses hybrid electrolytes of water and a polar aprotic N,N-dimethylformamide to modify the Zn2+-solvation structure and in situ form a robust and Zn2+-conducting Zn5(CO3)2(OH)6 solid electrolyte interphase (SEI) on the Zn surface to achieve stable and dendrite-free Zn plating/stripping over a wide temperature range. As confirmed by 67Zn nuclear magnetic resonance relaxometry, electrochemical characterizations, and molecular dynamics simulation, the electrochemically and thermally stable Zn5(OH)6(CO3)2-contained SEI achieved a high ionic conductivity of 0.04 to 1.27 mS cm–1 from −30 to 70 °C and a thermally activated fast Zn2+ migration through the [010] plane. Consequently, extremely stable Zn-ion hybrid capacitors in hybrid electrolytes are demonstrated with high capacity retentions and Coulombic efficiencies over 14,000, 10,000, and 600 cycles at 25, −20, and 70 °C, respectively