212 Search Results

Linear and quasilinear magnetohydrodynamic (MHD) modeling is carried out for two DIII-D discharges that both featured a transition from quiescent H-mode (QH) to wide-pedestal QH (WPQH). The MHD perturbations, associated with the edge harmonic oscillations (EHOs) observed during the QH-phase in both discharges, are identified as low-n (n is the toroidal mode number) resistive kink-peeling instabilities, with the ideal MHD counterpart remaining stable. The quasilinear model successfully simulates EHO-like perturbations during the QH phase in both discharges, confirming the experimental observations. A less intuitive finding is the EHO-like behavior involving the n = 2 perturbation, simulated for one of themore » discharges during the WPQH-phase. This result, while consistent with experimental observations, is obtained despite the fact that the initial perturbation is linearly stable. The eventual growth of the perturbation is solely due to nonlinear interaction between the MHD perturbation and the plasma toroidal flow. The occurrence of the EHO-like perturbation during the WPQH-phase is found to be sensitive to the initial profile of the plasma edge rotation. For DIII-D plasmas considered, the neoclassical toroidal viscosity, generated by three-dimensional low-n perturbations, is found to play a dominant role in modifying the edge flow during EHOs.« less

Dielectric polymer capacitors are essential for electrostatic energy storage but suffer from charge transport-induced energy losses, particularly at elevated temperatures where thermally activated charge carriers exacerbate conduction. Conventional mitigation strategies rely on introducing heterogeneous interfaces to create charge traps, complicating scalable film fabrication. A homogeneous molecular trapping mechanism would circumvent these complexities, yet remains underexplored. Herein, a charge trapping strategy is devised by modifying the lowest occupied molecular orbitals of dielectric polymers through Lewis acid-base adduct formation. The use of tris(pentafluorophenyl)boron (BCF) as a Lewis acidic molecular additive introduces deeper charge traps in commercial polyetherimide (PEI) while retaining homogeneity. Withmore » only 0.5 wt.% loading, the PEI-BCF film exhibits greatly improved breakdown strength, achieving an ultrahigh discharged energy density of 7.3 J cm-3 with excellent cycle stability at 200 °C. This work establishes a facile molecular approach to decoupling charge trapping from heterogeneous interfaces, enabling high-energy-density polymer capacitors operable under extreme thermal conditions.« less

Here, we use a combination of experiments and coarse-grained molecular dynamics simulations to elucidate the structure–property relationships in polymer electrolytes obtained by the copolymerization of poly(vinyl ethylene carbonate─lithium styrene bis(trifluoromethanesulfonyl)imide) or p(VEC-LiSTFSI). Experiments show that the conductivity reduces with increasing anion (i.e., STFSI) fraction on the chain, and the cation transference number (t₊) is found to be dependent on the anion fraction. Furthermore, a significant fraction of unpolymerized VEC monomers are observed. Since it is inherently difficult to experimentally control the chain architecture and the amount of unpolymerized VEC in these systems, we perform coarse-grained molecular dynamics simulations on modelmore » polymer systems with different chain architectures to mimic the plausible experimental systems. Specifically, we look at the differences in transference numbers arising from (i) a random copolymer of VEC and STFSI monomers; (ii) a blend of VEC-STFSI copolymer with VEC monomers; and (iii) a ternary blend of the VEC homopolymer, STFSI homopolymers, and VEC monomers. The ternary blend model demonstrates the closest resemblance with the experimental transference numbers and diffusivities. The lithium diffusivity obtained from the coarse-grained models with VEC monomers (plasticizers) is about 1.5 times that of the model without VEC monomers, showing that the plasticizing effect of VEC monomers is modest. We rationalize the experimental observations based on aggregate and cluster analyses obtained from molecular simulations. This work reveals that polymer electrolyte chain architecture and plasticizers can critically influence the transport properties, and these parameters should be considered when designing single ion conducting polymeric electrolytes.« less

Polymer electrolyte (PE)-based solid-state batteries (PE-SSBs) made with high-voltage cathodes are known to suffer from severe capacity fade, stemming primarily from the poor oxidative stability of most PEs under high-voltage cycling conditions. PEs also suffer from greater ion-transport limitations compared to liquid or solid electrolytes. However, often, these limitations are collectively stated to be responsible for the observed capacity fade, and it is challenging to decouple the contributions of different factors. Herein, a tunable cell fabrication platform was developed to systematically investigate and decouple the two primary capacity fade drivers (cell impedance growth and kinetic limitations), while keeping the othermore » cell parameters constant. Three PE types with distinct transport characteristics were compared. By utilizing a voltage profile analysis method, the contribution of the cell's internal impedance growth was quantitatively decoupled from the kinetic limitations stemming from the high concentration gradient in the polymer catholyte and slow charge transfer reactions. We demonstrate that the high interfacial impedance did not necessarily correlate with the high capacity fade rate. Kinetic limitations that are not reflected by impedance measurements can play a dominant role in causing cumulative capacity decay.« less

A central challenge in fusion energy is reconciling the high-confinement mode required for reactor performance with the intense intermittent relaxation events it produces, known as edge-localized modes. These instabilities arise in the steep pressure pedestal at the plasma edge when magnetohydrodynamic thresholds are crossed, inflicting damaging heat loads on reactor components. Here, we show that multiscale interactions between microscopic turbulence and macroscopic magnetohydrodynamic modes provide encouraging prospects for self-organized edge-localized modes regulation. Using direct quantitative measurements of multiscale modes, eddy dynamics, and turbulent flux, we show that small-scale electron drift wave turbulence actively scatters the large-scale peeling-ballooning modes. This scatteringmore » decorrelates the pressure and velocity fields of the instability, so arresting its growth. Our modeling and theoretical analysis confirm this suppression mechanism is effective even when conventional linear stability thresholds are exceeded. This work establishes a nonlinear principle for edge-localized modes stability, revealing how ambient micro-turbulence can be leveraged to maintain a macro-stable, high-performance pedestal for future fusion reactors.« less

The low-n (n is the toroidal mode number) magnetohydrodynamic (MHD) stability and plasma response are numerically investigated for various scenarios designed for STEP, that are relevant for the H-mode pedestal analysis. Control of the edge-localized modes (ELMs) with externally applied resonant magnetic perturbations (RMPs) is considered. Optimization of the ELM control coil current configuration, based on the computed plasma MHD response and well-established figures of merit validated on present-day experiments, finds reasonable robustness of a fixed coil phasing (for a given n-number) to control ELMs in all five STEP plasmas considered. Based on certain semi-empirical criteria, the required coil currentmore » to achieve ELM suppression is estimated to be about 10–20 kAt with the n = 1 or 2 RMP configuration and about 100–200 kAt for the n = 4 RMP. Systematic linear stability calculations are used to map out stability windows for the low-n kink-peeling modes, in terms of the ideal-wall location and variation of the edge safety factor q₉₅ with respect to the target design. The kink-peeling stability boundary is found to be generally sensitive to the q₉₅ variation, which has implications for achieving the quiescent H-mode regime in STEP. Full toroidal quasilinear initial-value simulations for these STEP plasmas find that generation of the edge-harmonic oscillations (EHOs) depends sensitively on the plasma scenario, the initial linear stability of the kink-peeling modes, the initial plasma toroidal flow and q₉₅. In general, it is easier (more robust) to access the EHO-regime for two of the cases considered with smaller plasma volume and higher on-axis safety factor. Finally, quasilinear simulations find robust density pumpout due to applied RMPs in these STEP plasmas, but the effect on the plasma toroidal flow varies among different cases.« less

Enabling the lithium metal anode has been the holy grail for improving the energy density for the next generation advanced batteries. Developing electrolytes that will suppress Li dendrite growth and provide sufficient ionic conductivity remains a major challenge in this field. In this study, we develop a polymer–ceramic composite electrolyte for lithium metal batteries. The polymer matrix is a vinyl ethylene carbonate (VEC) based single-ion-conducting polymer electrolyte. The ceramic filler is a Li₇La₃Zr_0.5Nb_0.5Ta_0.5Hf_0.5O₁₂ high-entropy Li-garnet (HE Li-garnet) ceramic, which is less prone to surface Li₂CO₃ formation compared to Al-doped Li garnets. The addition of HE Li-garnet leads to a 7-foldmore » increase in the ionic conductivity (8.6 × 10⁻⁵ S cm⁻¹ at 30 °C) compared to the pure polymer, while maintaining a high Li⁺ transference of 0.73. Proton nuclear magnetic resonance and thermogravimetric analysis results suggest that the addition of HE Li-garnet results in a lower degree of polymerization of VEC, leaving more unpolymerized VEC monomers in the matrix, serving as the governing mechanism for conductivity enhancement. The favorable interactions between HE Li-garnet particles and the polymer matrix lead to a stable and well-mixed composite with 2-fold enhancement of storage modulus at 40 °C. The simultaneous ion transport and mechanical property enhancement significantly improves the composite electrolyte's dendrite resistance and cycle life in Li symmetric cells. This work highlights the positive role HE Li-garnet can play in improving polymer electrolytes to enable lithium metal anodes.« less

Polymer-ceramic composites offer a path to enhance the transport and mechanical properties of solid electrolytes. However, an in-depth understanding of the extent and role of ion transport along and across polymer-ceramic interfaces in these systems is lacking. We have recently shown that Li-conducting Li_0.11Na_0.24K_0.02La_0.43TiO_2.82 (LMTO) nanorods can be prepared by a molten flux method, and the addition of 30–50 weight (wt.)% LMTO to a bis[(trifluoromethyl)sulfonyl]imide-vinyl ethylene carbonate-based single-ion conducting (SIC) polymer electrolyte leads to a two-fold enhancement in Li-ion conductivity, from 1.4 to 3.0 × 10⁻⁵ S/cm at 30 °C. In the present study, we use NMR methods to identifymore » the Li-ion transport pathways and determine the timescale of chemical exchange between the SIC polymer and LMTO ceramic components. Tracer exchange NMR indicates preferential transport through the polymer or polymer-interfacial regions, and exchange spectroscopy (EXSY) and a new isotope exchange method reveal negligible Li exchange between the SIC polymer and LMTO ceramic up to several days. Here, LMTO nanorods act as a passive filler. Our results further highlight that significant (e.g., 10- or 100-fold) conductivity enhancements in composite electrolytes can only be achieved 1) with ionically-conductive fillers, and 2) when both the ceramic and polymer components actively participate in long-range transport. For this, fast interfacial ion exchange is needed. In conclusion, this leads us to introduce a critical interfacial ion exchange time to evaluate whether a filler actively contributes to conduction in a composite electrolyte, and screen for promising polymer-ceramic pairings to accelerate the development of high conductivity solid electrolytes.« less

Understanding thermal transport in solid electrolytes is essential for improving the performance, reliability, and safety of all-solid-state batteries. Garnet-type lithium-ion conductors are promising candidates for solid electrolytes, yet their thermal-transport mechanisms remain poorly understood. Here, we connect the lattice and ion dynamics of single-crystal garnet-type Li_6.5La₃Zr_1.5Ta_0.5O₁₂ to its intrinsically low thermal conductivity. Our study reveals that the single crystals grown by the floating-zone method exhibit remarkably low glasslike thermal conductivity. Using first-principles calculations and inelastic-neutron-scattering measurements, we identify both the acoustic and numerous optical phonon modes, which stem from the complex crystal structure of the material. Notably, a low-energy opticalmore » branch exhibits an avoided crossing with acoustic phonons near 7 meV. These optical modes can enhance the scattering of heat-carrying acoustic phonons and reduce thermal conductivity. Furthermore, the calculated Grüneisen parameters are large, especially for the vibrational modes around 6 meV, indicating strong anharmonicity, with a noticeable contribution from lithium-ion vibrations. A two-channel thermal-transport model is employed to describe the weak temperature dependence of the thermal conductivity, which can be attributed to the substantial contribution of diffuson transport facilitated by the abundance of optical phonons and intrinsic anharmonicity. These results offer valuable insights into the thermal transport in a broad class of ionic conductors of interest for energy conversion and storage applications.« less

Solvent-free manufacturing of battery components is a promising alternative to traditional slurry processing for reducing the cost and environmental impact. In this work, we used twin-screw melt extrusion to fabricate a polymer-based high voltage composite cathode. The melt-processed cathode is dense (near zero porosity) and thick (65 μm) and has high active material loading (80 wt %). The active particles are distributed uniformly throughout the melt-processed cathode, unlike the traditional slurry-cast cathode, which exhibits inhomogeneous particle distribution. In the melt-processed cathode, polymer and carbon form separate phases, whereas in the slurry-cast cathode they blend into a single phase. Due tomore » these structural differences, the melt-processed cathode shows smooth charge–discharge profiles, while the slurry-cast cathode shows noisy charging and soft-shorting behavior. In conclusion, this work highlights that twin-screw extrusion as a scalable, solvent-free manufacturing method is advantageous in producing uniform cathodes, which mitigates anode instability.« less