Search arXivSearch

arXiv · 1911.09924

A Blessing and a Curse: How a Supercapacitor's Large Capacitance Causes its Slow Charging

Abstract

The development of novel electrolytes and electrodes for supercapacitors is hindered by a gap of several orders of magnitude between experimentally measured and theoretically predicted charging timescales. Here, we propose an electrode model, containing many parallel stacked electrodes, that explains the slow charging dynamics of supercapacitors. At low applied potentials, the charging behavior of this model is described well by an equivalent circuit model. Conversely, at high potentials, charging dynamics slow down and evolve on two relaxation time scales: a generalized $RC$ time and a diffusion time, which, interestingly, become similar for porous electrodes. The charging behavior of the stack-electrode model presented here helps to understand the charging dynamics of porous electrodes and qualitatively agrees with experimental time scales measured with porous electrodes.

Explore related subjects

Keep this discovery

Explore connections, maps & timelines

BibTeXRIS

Cheng Lian, Mathijs Janssen, Honglai Liu, René van Roij. 2020-02-25. A Blessing and a Curse: How a Supercapacitor's Large Capacitance Causes its Slow Charging. https://doi.org/10.1103/physrevlett.124.076001

Cite the original work for its findings. Save a collection to share your selection of sources.

KEEP EXPLORING

Related papers

Benchmarking Proton Tunneling Splittings with a Wavefunction-Based Double-Well Model: Application to the Formic Acid Dimer

Proton tunneling across hydrogen bonds is a fundamental quantum effect with implications for spectroscopy, catalysis, and biomolecular stability. While state-of-the-art instanton and path-integral methods provide accurate multidimensional tunneling splittings, simplified one-dimensional models remain valuable as conceptual and benchmarking tools. Here we develop a wavefunction-based framework for tunneling splittings using a Cornell-type double-well potential and apply it as a benchmark for hydrogen-bond tunneling. Analytical WKB estimates and numerical finite-difference solutions are compared across a range of barrier parameters, showing consistent agreement. As a test case, we map the formic acid dimer (FAD) barrier onto a quartic double-well model parameterized to reproduce the reported barrier height of $V_b \\approx 2848~\\text{cm}^{-1}$. The resulting tunneling splitting of about $0.037~\\text{cm}^{-1}$ matches the reduced-dimensional calculations of Qu and Bowman. The close agreement between numerical and semiclassical results highlights the pedagogical and diagnostic value of one-dimensional models, while comparison with molecular benchmarks clarifies their limitations relative to full multidimensional quantum treatments.

physics.chem-ph

A Physics-Regularized Neural Network and Kirchhoff Markov Random Field Framework for Inferring Internal Electrochemical States from Operando Spectromicroscopy

Quantitative understanding of coupled reaction-transport dynamics in lithium-ion battery (LIB) composite electrodes is limited by the inaccessibility of key internal electrochemical states. Here we present a physics-integrated, data-driven framework to reconstruct latent states from operando microscopic X-ray absorption fine structure ($μ$ -XAFS) hyperspectral data of LIB cathodes. Normalized-local-lithium-stoichiometry (NLLS) maps derived from Co K-edge spectra are refined using a physics-regularized neural network that enforces spatial continuity and current conservation to resolve ambiguities in the weak-sensitivity region. The reconstructed NLLS dynamics are embedded in a Kirchhoff-based Markov random field incorporating Kirchhoff's laws, Ohm's law, and Butler-Volmer kinetics to infer interfacial current density, ionic current, electrolyte potential, and effective ionic conductivity. Application to electrodes with differential initial electrolyte concentrations reveals distinct reaction-propagation modes that are consistent with a mechanism involving the non-monotonic concentration dependence of electrolyte conductivity. The inferred electrolyte concentration profiles qualitatively resemble the spatially extended concentration changes observed by independent operando X-ray transmission imaging using a 1 M LiAsF$_6$ electrolyte.

physics.chem-ph

Intracavity Photon Statistics from Correlated Molecular Electronic Structure

Quantum optics characterizes light through photon correlations, but ab initio cavity quantum electrodynamics (QED) has only calculated raw field moments at present. In this study, intracavity photon statistics of cavity-coupled molecules are computed from QED coupled-cluster (QED-CCSD-22) densities and validated against exact diagonalization of the Pauli-Fierz Hamiltonian. A change of coordinate origin or dipole convention displaces the ground state coherently, so second-order and higher cumulants of the cavity field are well defined even for molecular ions. The photon subsystem of QED Hartree-Fock is exactly coherent, so the invariant statistics measure electron-photon correlation. The field fluctuations are super-Poissonian, and their degree of second-order coherence is set by the cavity frequency rather than by the coupling strength, falling from 18.5 to 4.9 for H2 as the cavity is detuned from 5 to 20 eV. A parity selection rule makes the sign of the third cumulant a probe of the orientation of the molecular charge asymmetry along the cavity polarization.

physics.chem-ph