The Li7P3S11 glass-ceramic is a promising superionic conductor electrolyte (SCE) with an extremely high Li(+) conductivity that exceeds that of even traditional organic electrolytes. In this work, we present a combined computational and experimental investigation of the material performance limitations in terms of its phase and electrochemical stability, and Li(+) conductivity. We find that Li7P3S11 is metastable at 0 K but becomes stable at above 630 K (∼360 °C) when vibrational entropy contributions are accounted for, in agreement with differential scanning calorimetry measurements. Both scanning electron microscopy and the calculated Wulff shape show that Li7P3S11 tends to form relatively isotropic crystals. In terms of electrochemical stability, first-principles calculations predict that, unlike the LiCoO2 cathode, the olivine LiFePO4 and spinel LiMn2O4 cathodes are likely to form stable passivation interfaces with the Li7P3S11 SCE. This finding underscores the importance of considering multicomponent integration in developing an all-solid-state architecture. To probe the fundamental limit of its bulk Li(+) conductivity, a comparison of conventional cold-press sintered versus spark-plasma sintering (SPS) Li7P3S11 was done in conjunction with ab initio molecular dynamics (AIMD) simulations. Though the measured diffusion activation barriers are in excellent agreement, the AIMD-predicted room-temperature Li(+) conductivity of 57 mS cm(-1) is much higher than the experimental values. The optimized SPS sample exhibits a room-temperature Li(+) conductivity of 11.6 mS cm(-1), significantly higher than that of the cold-pressed sample (1.3 mS cm(-1)) due to the reduction of grain boundary resistance by densification. We conclude that grain boundary conductivity is limiting the overall Li(+) conductivity in Li7P3S11, and further optimization of overall conductivities should be possible. Finally, we show that Li(+) motions in this material are highly collective, and the flexing of the P2S7 ditetrahedra facilitates fast Li(+) diffusion.
We present a characterization of Florida lightning return stroke electric and magnetic fields derived from simultaneous measurements of the fields at two separate stations, one station being within 15 km of the lightning, the other at either about 50 or 200 km from the lightning. We give (1) examples of correlated wave forms, (2) typical first and subsequent stroke wave forms over the distance range 1.0–200 km, and (3) the following statistical data from which the typical wave forms were derived: for electric field, rise time, initial peak value, ramp starting time, ramp slope, value at 170 μs, ratio of value at 170 μs to initial peak, zero‐crossing time for 50 and 200 km wave forms; for magnetic fields, time of hump following initial peak, ratio of hump value to initial peak value, zero‐crossing time for 50 and 200 km wave forms. Return stroke electric and magnetic field characteristics appear to be independent of location in Florida.
UV photodetector fabricated using a single ZnO nanobelt (NB) has shown a photoresponse enhancement up to 750 times higher than that of a bare ZnO NB after coating with ∼20nm plasma polymerized acrylonitrile (PP-AN) nanoscale film. The mechanism for this colossal photoconductivity is suggested as a consequence of the efficient exciton dissociation under UV illumination due to enhanced electron transfer from valence band of ZnO NB to the PP-AN and then back to the conduction band of ZnO. This process has demonstrated an easy and effective method for improving the performance of the nanowire∕NB-based devices, possibly leading to supersensitive UV detector for applications in imaging, photosensing, and intrachip optical interconnects.
In this work, we demonstrate the stable cycling of more than one Li in solid-state-synthesized ε-LiVOPO4 over more than 20 cycles for the first time. Using a combination of density functional theory (DFT) calculations, X-ray pair distribution function (PDF) analysis and X-ray absorption near edge structure (XANES) measurements, we present a comprehensive analysis of the thermodynamics, kinetics, and structural evolution of ε-Li x VOPO4 over the entire lithiation range. We identify two intermediate phases at x = 1.5 and 1.75 in the low-voltage regime using DFT calculations, and the computed and electrochemical voltage profiles are in excellent agreement. Operando PDF and EXAFS techniques show a reversible hysteretic change in the short (<2 Å) VO bond lengths coupled with an irreversible extension of the long VO bond (>2.4 Å) during low-voltage cycling. Hydrogen intercalation from electrolyte decomposition is a possible explanation for the ∼2.4 Å VO bond and its irreversible extension. Finally, we show that ε-Li x VOPO4 is likely a pseudo-1D ionic diffuser with low electronic conductivity using DFT calculations, which suggests that nanosizing and carbon coating is necessary to achieve good electrochemical performance in this material.
The thermal stability of electrochemically delithiated Li0.1Ni0.8Co0.15Al0.05O2 (NCA), FePO4 (FP), Mn0.8Fe0.2PO4 (MFP), hydrothermally synthesized VOPO4, LiVOPO4, and electrochemically lithiated Li2VOPO4 is investigated by differential scanning calorimetry (DSC) and thermogravimetric analysis, coupled with mass spectrometry (TGA-MS). The thermal stability of the delithiated materials is found to be in the order of NCA < VOPO4 < MFP < FP. Unlike the layered oxides and MFP, VOPO4 does not evolve O2 on heating. Thus, VOPO4 is less likely to cause a thermal run-away phenomenon in batteries at elevated temperature and so is inherently safer. The lithiated materials LiVOPO4, Li2VOPO4, and LiNi0.8Co0.15Al0.05O2 are found to be stable in the presence of electrolyte, but sealed-capsule high-pressure experiments show a phase transformation of VOPO4 → HVOPO4 → H2VOPO4 when VOPO4 reacts with electrolyte (1 M LiPF6 in EC/DMC = 1:1) between 200 and 300 °C. Using first-principles calculations, we confirm that the charged VOPO4 cathode is indeed predicted to be marginally less stable than FP but significantly more stable than NCA in the absence of electrolyte. An analysis of the reaction equilibria between VOPO4 and EC using a multicomponent phase diagram approach yields products and reaction enthalpies that are highly consistent with the experiment results.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
customersupport@researchsolutions.com
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
This site is protected by reCAPTCHA and the Google Privacy Policy and Terms of Service apply.
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.