arXiv subjects

Anis Allagui

Publications and source records attributed to Anis Allagui.

At least 19 recordsLinked to original sources

arXiv2026

Inversion of Electrochemical Immittance Spectra based on the Mellin Transform

In this work, we show that the Fredholm integral equations underlying the distribution of relaxation times (DRT), the distribution of capacitive times (DCT), and related frameworks share a common mathematical structure, namely that of a Mellin convolution. This comes from the fact that all standard immittance (impedance or admittance) kernels depend on the product $\omega\tau$ rather than on $\omega$ and $\tau$ independently. Exploiting this structure, we derive an exact algebraic inversion formula in Mellin space that converts the deconvolution problem into a closed-form relation between the Mellin transform of the measured immittance and that of the unknown distribution function. The framework is validated analytically on a set of examples including the constant phase element (CPE), the Davidson-Cole (DC) model, and the finite-length Warburg model with blocking boundary conditions. It is also validated numerically using the fast Mellin transform via the fast Fourier transform algorithm for both the CPE and the DC model, including their DRT and DCT recovery under clean and noisy conditions. The approach unifies the impedance- and admittance-based inversions under a single spectral framework, and provides a new approach for the characterization of electrochemical systems from immittance data.

physics.app-ph↗

arXiv2025

Energy-based interpretation of the dispersion coefficient of the constant phase element

The dispersion coefficient of the constant phase element (CPE) is typically treated as an empirical fitting parameter in the analysis of impedance spectroscopy data, with no clear physical meaning. Here we seek to establish a energy-based interpretation for this coefficient by linking it to the ratio of the dissipated or stored energy in the CPE relative to that supplied by the input source. Using the $RC$ network equivalency of a CPE, we decompose the total input energy into a contribution stored in the capacitive modes and another dissipated in the resistive modes. Analytical expressions are derived for three test examples: (i) a constant voltage, (ii) a voltage ramp, and (iii) a quadratic input of the form $v(t)=\lambda t^2$. In all cases we found that the ratios of any two of these energy quantities reduce to pure functions of the dispersion coefficient of the CPE, independent of excitation amplitude or material parameters. This result provides a new perspective of the CPE's dispersion coefficient from a thermodynamic/energetic basis, with direct implications for supercapacitor characterization, battery modeling, as well as for the analysis of other electrochemical systems and devices exhibiting the CPE behavior.

physics.app-ph↗

arXiv2025

On the behavior of a distributed network of capacitive constant phase elements

As a generalization of integer-order calculus, fractional calculus has seen tremendous applications in the past few years especially in the description of anomalous viscoelastic properties, transport processes in complex media as well as in dielectric and impedance spectroscopy of materials and electrode/electrolyte interfaces. The fractional-order capacitor or constant phase element (CPE) is a fractional-order model with impedance $z_c(s) = 1/(C_{\alpha} s^{\alpha})$ ($s=j \omega$, $C_{\alpha}>0$, $0<\alpha<1$) and is widely used in modeling impedance spectroscopy data in dispersive materials. In this study, we investigate the behavior of a network of distributed-order CPEs, each of which described by a Caputo-type time fractional differential equation relating the current on the CPE to its voltage, but with a non-negative, time-invariant weight function $\phi(\alpha)$. The behavior of the distributed-order network in terms of impedance and time-domain response to a constant current excitation is derived for two simple cases of $\phi(\alpha)$: (i) $\phi(\alpha)=1$ for $0 < \alpha < 1$ and zero otherwise, and $(ii)$ $\phi(\alpha) = \sum_i C_{\alpha_i}\, \delta(\alpha-\alpha_i)$ corresponding to the general case of parallel-connected elemental CPEs of different orders $\alpha$, and pseudocapacitances $C_{\alpha}$. Our results show that the overall network is not equivalent to a single CPE, contrary to what would of been expected with ideal capacitors.

physics.app-ph↗

arXiv2024

On the distributed resistor-constant phase element transmission line in a reflective bounded domain

In this work we derive and study the analytical solution of the voltage and current diffusion equation for the case of a finite-length resistor-constant phase element (CPE) transmission line (TL) network that can represent a model for porous electrodes in the absence of any Faradic processes. The energy storage component is considered to be an elemental CPE per unit length of impedance $z_c(s)={1}/{(c_{\alpha} s^{\alpha})}$ with constant parameters $(c_{\alpha},\alpha)$ instead of the ideal capacitor of impedance $z(s)={1}/{(c\, s)}$ usually assumed in TL modeling. The problem becomes a time-fractional diffusion equation for the voltage that we solve under galvanostatic charging, and derive from it a reduced impedance function of the form $z_{\alpha}(s_n)=s_n^{-\alpha/2}\coth({s_n^{\alpha/2}})$, where $s_n = j\omega_n$ is a normalized frequency. We also derive the system's step response, and the distribution function of relaxation times associated with it. The analysis can be viewed and used as a support for the fractal finite-length Warburg model.

cond-mat.mtrl-sci↗

arXiv2024

Power law susceptibility function for the analysis of anomalous spectral response

The extensions of the classical Debye model of susceptibility of dielectric materials to the well-known Cole-Cole, Davidson- Cole, or the Havriliak-Negami models is done by introducing non-integer power parameters to the frequency-domain function. This is very often necessary in order to account for anomalous deviations of the experimental data from the ideal case. The corresponding time-domain descriptions expressed in terms of the relaxation or response functions are in the form of first-order differential equations for the case of Debye model, but involves relatively complex integro-differential operators for the modified ones. In this work, we study the extension of the time-domain kinetic equation describing the Debye polarization function to include two extra degrees of freedom; one to transform the first-order time derivative of the polarization function to the Caputo fractional-order time derivative and another to change the linear term to a power term. From an electrical perspective, it results in a constant-phase element with two fractional parameters.

cond-mat.mtrl-sci↗

arXiv2024

Procedure for Obtaining the Analytical Distribution Function of Relaxation Times for the Analysis of Impedance Spectra using the Fox $H$-function

The interpretation of electrochemical impedance spectroscopy data by fitting it to equivalent circuit models has been a standard method of analysis in electrochemistry. However, the inversion of the data from the frequency domain to a distribution function of relaxation times (DFRT) has gained considerable attention for impedance data analysis, as it can reveal more detailed information about the underlying electrochemical processes without requiring a priori knowledge. The focus of this paper is to provide a general procedure for obtaining analytically the DFRT from an impedance model, assuming an elemental Debye relaxation model as the kernel. The procedure consists of first representing the impedance function in terms of the Fox $H$-function, which possesses many useful properties particularly that its Laplace transform is again an $H$-function. From there the DFRT is obtained by two successive iterations of inverse Laplace transforms. In the passage, one can easily obtain an expression for the response function to a step excitation. The procedure is tested and verified on some known impedance models.

physics.chem-ph↗

arXiv2024

Generalized Distribution Function of Relaxation Times with the Davidson-Cole Model as a Kernel

In this paper we propose a generalized distribution function of relaxation times (DFRT) considering the Davidson-Cole model as an elementary process instead of the standard Debye model. The distribution function is retrieved from the inverse of the generalized Stieltjes transform expressed in terms of iterated Laplace transforms. We derive computable analytical expressions of the generalized DFRT for some of the most known normalized impedance (or admittance) models including the constant phase element, the Davidson-Cole, Havriliak-Negami and the Kohlrausch-Williams-Watts models.

physics.chem-ph↗

arXiv2023

Time-space bi-fractional drift-diffusion equation for anomalous electrochemical transport

The Debye-Falkenhagen differential equation is commonly used as a mean-field macroscopic model for describing electrochemical ionic drift and diffusion in dilute binary electrolytes when subjected to a suddenly applied potential smaller than the thermal voltage. However, the ionic transport in most electrochemical systems, such as electrochemical capacitors, permeation through membranes, biosensors and capacitive desalination, the electrolytic medium is interfaced with porous, disordered, and fractal materials which makes the modeling of electrodiffusive transport with the simple planar electrode theory limited. Here we study a possible generalization of the traditional drift-diffusion equation of Debye and Falkenhagen by incorporating both fractional time and space derivatives for the charge density. The nonlocal (global) fractional time derivative takes into account the past dynamics of the variable such as charge trapping effects and thus subdiffusive transport, while the fractional space derivative allows to simulate superdiffusive transport.

physics.class-ph↗

arXiv2023

Theory and Application of the Fractional-order Delta Function Associated with the Inverse Laplace Transform of the Mittag-Leffler Function

This paper is devoted to the study of the $M$-Wright function ($M_{\alpha}(t)$) which is the inverse Laplace transform of the single-parameter Mittag-Leffler (ML) function ($E_{\alpha}(-s)$). Because $E_{\alpha}(-s)$ can be viewed as the fractional-order generalization of the exponential function for $0<\alpha<1$, to which it reduces for $\alpha=1$, i.e. $E_{1}(-s)=\exp(-s)$, its inverse Laplace transform, being $M_{\alpha}(t)$, can be viewed as a generalized fractional-order Dirac delta function. At the limiting case of $\alpha = 1$ the $M$-Wright function reduces to $M_{1}(t)=\delta(t-1)$. We investigate numerically the behavior of this fractional-order delta function as well as it integral, the fractional-order unit-step function. Subsequently, we validate our results with experimental data for the charging of a supercapacitive device.

physics.app-ph↗

arXiv2023

Tikhonov regularization for the deconvolution of capacitance from voltage-charge response of electrochemical capacitors

The capacitance of capacitive energy storage devices can not be directly measured, but can be estimated from the input and output signals expressed in the time or frequency domains. Here the time-domain voltage-charge relationship in non-ideal electrochemical capacitors is treated as an ill-conditioned convolution integral equation where the unknown capacitance kernel function is to be found. This comes from assuming \emph{a priori} that in the frequency domain the charge is equal to the product of capacitance by voltage. The computation of a stable solution to this problem particularly when dealing with experimental data is highly sensitive to noise as it may lead to an oscillating output even in the presence of small errors in the measurements. In this work, the problem is treated using Tikhonov's regularization method, where a degree of damping is added to each singular value decomposition (SVD) component of the solution, thus effectively filtering out the components corresponding to the small singular values.

physics.app-ph↗

arXiv2023

Fractional Marcus-Hush-Chidsey-Yakopcic current-voltage model for redox-based resistive memory devices

We propose a circuit-level model combining the Marcus-Hush-Chidsey electron current equation and the Yakopcic equation for the state variable for describing resistive switching memory devices of the structure metal-ionic conductor-metal. We extend the dynamics of the state variable originally described by a first-order time derivative by introducing a fractional derivative with an arbitrary order between zero and one. We show that the extended model fits with great fidelity the current-voltage characteristic data obtained on a Si electrochemical metallization memory device with Ag-Cu alloy.

cond-mat.mtrl-sci↗

arXiv2023

Observation of a Pinched-Loop in a Current-Excited Inductive Circuit

In this work, we show that a pinched-loop can be observed in the voltage-current plane when a series R-L circuit is current excited. Specifically, the resistance (R) in this circuit is variable and is voltage-controlled by the voltage developed across the inductor due to the exciting current. In this context, we confirm our previous results that the pinched-loop is not a characteristic of memrsitors or memrsitive systems and that it can be observed in many other nonlinear systems. Numerical simulations, circuit simulations and experimental results validate the theory.

physics.app-ph↗

arXiv2023

Time-domain Response of Supercapacitors using their Impedance Parameters and Fourier Series Decomposition of the Excitation Signal

Supercapacitors are mostly recognized for their high power density capabilities and fast response time when compared to secondary batteries. However, computing their power in response to a given excitation using the standard formul{\ae} of capacitors is misleading and erroneous because supercapacitors are actually non-ideal capacitive devices that cannot be characterized with a single constant capacitance. In this study we show how to estimate accurately the time-domain power and energy of supercapacitors in response to any excitation signal represented in terms of its Fourier series coefficients with the sole knowledge of the frequency-domain impedance parameters of device. The presented theory is first verified and validated with simulations conducted on an equivalent fifth-order RC circuit emulating the behavior of a fractional circuit consisting of a resistance (Rs) in series with a constant phase element (CPE) of fractional impedance ZCPE = 1/C{\alpha}s{\alpha}. Then we do the same for a commercial supercapacitor modeled as an Rs-CPE circuit, and subjected to both a periodic triangular voltage waveform and a random voltage excitation. The results are conclusive and very promising for adopting the proposed procedure to estimate the power and energy performance of supercapacitors in response to real-world charging and discharging signals.

physics.app-ph↗

arXiv2022

Further Experimental Evidence of the Dead Matter Has Memory Conjecture in Capacitive Devices

This study provides new sets of experimental results supporting Westerlund's conjecture that Dead Matter Has Memory. Memory effects in the dynamic response of electric double-layer capacitors (EDLCs) that integrate its prior history of stimulation and state have been experimentally observed and reported in a few recent studies. The different excitation signals used to quantify such effects in these studies aimed at charging a device to the same voltage value and the exact same accumulated charge level but in different manners. Having reached the same unique voltage-charge point, it was observed that different yet repeatable discharge patterns occur, proving the existence of memory. The aim of this work is to provide further experimental evidence of the inherent memory effect in EDLCs in response to time-varying stationary input excitations with different statistical properties. In particular, different sets of charging voltage waveforms composed of fixed dc values with superimposed uniformly-distributed random fluctuations of different amplitudes were created and used to charge the same EDLC device to a unique voltage-charge point. The duration of these signals was the same but with different values of variance around the mean value. We observed different time-charge responses depending on the extent of the noise level in these charging waveforms. This is interpreted and discussed in the context of inherent memory using fractional-order voltage-charge equations of non-ideal capacitors.

physics.app-ph↗

arXiv2022

A superstatistics approach to the modelling of memristor current-voltage responses

Memristors are expected to form a major cornerstone in the upcoming renaissance of analog computing, owing to their very small spatial footprint and low power consumption. Due to the nature of their structure and operation, the response of a memristor is intrinsically tied to local variabilities in the device. This characteristic is amplified by currently employed semiconductor fabrication processes, which introduce spatial inhomogeneities into the structural fabric that makes up the layers of memristors. In this work, we propose a novel q-deformed current-voltage model for memristors based on the superstatistics framework, which allows the description of system-level responses while taking local variabilities into account. Applied on a Ag-Cu based synaptic memory cell, we demonstrate that our model has a 4-14% lower error than currently used models. Additionally, we show how the resulting q-parameter can be used to make statements about the internal makeup of the memristor, giving insights to spatial inhomogeneities and quality control.

cond-mat.mes-hall↗

arXiv2022

Non-Debye impedance and relaxation models for dissipative electrochemical capacitors

Electrochemical capacitors are a class of energy devices in which complex mechanisms of accumulation and dissipation of electric energy take place when connected to a charging or discharging power system. Reliably modeling their frequency-domain and time-domain behaviors is crucial for their proper design and integration in engineering applications, knowing that electrochemical capacitors in general exhibit anomalous tendency that cannot be adequately captured with traditional integer-order-based models. In this study we first review some of the widely used fractional-oder models for the description of impedance and relaxation functions of dissipative resistive-capacitive system, namely the Cole-Cole, Davidson-Cole, and Havriliak-Negami models. We then propose and derive new q-deformed models based on modified evolution equations for the charge or voltage when the device is discharged into a parallel resistive load. We verify our results on anomalous spectral impedance response and time-domain relaxation data for voltage and charge obtained from a commercial supercapacitor.

physics.app-ph↗

arXiv2022

Time-Domain and Frequency-Domain Mappings of Voltage-to-Charge and Charge-to-Voltage in Capacitive Devices

In this work, we aim to show that there are generally four possible mapping functions that can be used to map the time-domain or frequency-domain representations of an applied voltage input to the resulting time-domain or frequency-domain electrical charge output; i.e. when the capacitive device is voltage-charged. Alternatively, there are four more possible combinations when the device is current-charged. The dual relationship between each pair of functions for the case of voltage or charge input are provided in terms of single or double Fourier transforms. All eight system functions coincide with each other if and only if a constant time- and frequency-independent capacitance is considered.

physics.app-ph↗

arXiv2022

Modified Poisson-Nernst-Planck theory for low-to-mid frequency immittance of electric double-layer capacitors

Understanding the system-level spectral immittance response of capacitive energy storage devices with analytically tractable physics-based models is not only important for the progress of the technology, but also allows to develop new physical insights more easily. Here, we report a modified Poisson--Nernst--Planck (PNP) system describing charge concentration and electric potential as a model of electro-kinetics for electrodes showing mixed resistive-capacitive behavior. This is done by (i) incorporating time shifts between the current fluxes and both concentration gradients of charged species and the electric field, and (ii) introducing time fractional derivatives in the continuity equation. The aim is to characterize the deviation of immittance from that of ideal capacitors both at close-to-dc frequencies where the impedance angle for example is larger than -90 deg., and also at mid-range frequencies where the system veers progressively toward resistive behavior. This latter tendency is important to model in order to identify the extend of the capacitive bandwidth of the device from the rest. Solution and simulation results to the one-dimensional modified PNP system for symmetric electrolyte/blocking electrode configuration are presented and discussed.

physics.app-ph↗