arXiv subjects

Beniamin Zahiri

Publications and source records attributed to Beniamin Zahiri.

3 recordsLinked to original sources

arXiv2023

Ionic Peltier Effect in Li-Ion Electrolytes

The coupled transport of charge and heat provide fundamental insights into the microscopic thermodynamics and kinetics of materials. We describe a sensitive ac differential resistance bridge that enables measurements of the temperature difference on two sides of a coin cell with a resolution of better than 10 uK. We use this temperature difference metrology to determine the ionic Peltier coefficients of symmetric Li-ion electrochemical cells as a function of Li salt concentration, solvent composition, electrode material, and temperature. The Peltier coefficients Π are negative, i.e., heat flows in the direction opposite to the drift of Li ions in the applied electric field, large, 30 kJ mol-1, and increase with increasing temperature at T > 300 K. The Peltier coefficient is approximately constant on time scales that span the characteristic time for mass diffusion across the thickness of the electrolyte, suggesting that heat of transport plays a minor role in comparison to the changes in partial molar entropy of Li at the interface between the electrode and electrolyte. Our work demonstrates a new platform for studying the non-equilibrium thermodynamics of electrochemical cells and provides a window into the transport properties of electrochemical materials through measurements of temperature differences and heat currents that complement traditional measurements of voltages and charge currents.

cond-mat.mtrl-sci↗

arXiv2023

Temperature dependence of 7Li NMR relaxation rates in Li3InCl6, Li3YCl6, Li1.48Al0.48Ge1.52(PO4)3 and LiPS5Cl

Inorganic solid-state battery electrolytes show high ionic conductivities and enable the fabrication of all solid-state batteries. In this work, we present the temperature dependence of spin-lattice relaxation time (T1), spin-spin relaxation time (T2), and resonance linewidth of the 7Li nuclear magnetic resonance (NMR) for four solid-state battery electrolytes (Li3InCl6 (LIC), Li3YCl6 (LYC), Li1.48Al0.48Ge1.52(PO4)3 (LAGP) and LiPS5Cl (LPSC)) from 173 K to 403 K at a 7Li resonance frequency of 233 MHz, and from 253 K to 353 K at a 7Li resonance frequency of 291 MHz. Additionally, we measured the spin-lattice relaxation rates at an effective 7Li resonance frequency of 133 kHz using a spin-locking pulse sequence in the temperature range of 253 K to 353 K. In LPSC, the 7Li NMR relaxation is consistent with the Bloembergen-Pound-Purcell (BPP) theory of NMR relaxation of dipolar nuclei. In LIC, LYC and LAGP, the BPP theory does not describe the NMR relaxation rates for the temperature range and frequencies of our measurements. The presented NMR relaxation data assists in providing a complete picture of Li diffusion in the four solid-state battery electrolytes.

cond-mat.mtrl-sci↗

arXiv2021

Good Solid-State Electrolytes Have Low, Glass-like Thermal Conductivity

Management of heat during charging and discharging of Li-ion batteries is critical for their safety, reliability, and performance. Understanding the thermal conductivity of the materials comprising batteries is crucial for controlling the temperature and temperature distribution in batteries. This work provides systemic quantitative measurements of the thermal conductivity of three important classes of solid electrolytes (oxides, sulfides, and halides) over the temperature range 150-350 K. Studies include the oxides Li1.5Al0.5Ge1.5(PO4)3 and Li6.4La3Zr1.4Ta0.6O12, sulfides Li2S-P2S5, Li6PS5Cl, and Na3PS4, and halides Li3InCl6 and Li3YCl6. Thermal conductivities of sulfide and halide solid electrolytes are in the range 0.45-0.70 W m-1 K-1; thermal conductivities of Li6.4La3Zr1.4Ta0.6O12 and Li1.5Al0.5Ge1.5(PO4)3 are 1.4 W m-1 K-1 and 2.2 W m-1 K-1, respectively. For most of the solid electrolytes studied in this work, the thermal conductivity increases with increasing temperature; i.e., the thermal conductivity has a glass-like temperature dependence. The measured room-temperature thermal conductivities agree well with the calculated minimum thermal conductivities indicating the phonon mean-free-paths in these solid electrolytes are close to an atomic spacing. We attribute the low, glass-like thermal conductivity of the solid electrolytes investigated to the combination of their complex crystal structures and the atomic-scale disorder induced by the materials processing methods that are typically needed to produce high ionic conductivities.

cond-mat.mtrl-sci↗