Modeling and simulation of Constant Phase Element for battery Electrochemical Impedance Spectroscopy

Locorotondc, Edoardo; Pugi, Luca; Berzi, Lorenzo; Pierini, Marco; Scavuzzc, Santo; Ferraris, Alessandro; Airale, Andrea Giancarlo; Carello, Massimiliana

doi:10.1109/rtsi.2019.8895597

Cited by 17 publications

(9 citation statements)

References 13 publications

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“…Although both the baseline and PvFc samples fitted best with a normal capacitance element, the 2xPEO curve, which showed less curvature variability fitted best with a constant phase element (CPE). This implies that at the state before cycling, the capacitance of the 2xPEO sample more closely resembled a capacitor than a battery since a CPE is more representative of an electrical double layer than the more complex combination of charge-transfer reactions we expect to see in our electrochemical system . This could be a consequence of the lower electrical conductivity of 2xPEO as mentioned before since it could be exacerbating the sluggish kinetics of the sulfur reduction reaction with a lack of electron movement.…”

Section: Resultsmentioning

confidence: 69%

“…This implies that at the state before cycling, the capacitance of the 2xPEO sample more closely resembled a capacitor than a battery since a CPE is more representative of an electrical double layer than the more complex combination of chargetransfer reactions we expect to see in our electrochemical system. 23 This could be a consequence of the lower electrical conductivity of 2xPEO as mentioned before since it could be exacerbating the sluggish kinetics of the sulfur reduction reaction with a lack of electron movement. In addition, they all fitted best with the charge-transfer impedance being a Gerischer impedance to account for the effects of diffusion through a porous layer.…”

Section: Electrochemical Performancementioning

confidence: 97%

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Poly(vinylferrocene) as an Ionomer and Sulfur-Confining Additive for Lithium–Sulfur Batteries

Torres,

Bhargav,

Manthiram

2023

ACS Appl. Mater. Interfaces

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Lithium−sulfur (Li−S) batteries are promising owing to their high energy density, environmental benignity, and low cost. Most of the commonly used binders in Li−S battery cathodes are inert and have no significant effect on the challenges of sulfur as a cathode material, such as the polysulfide shuttle effect, low ionic/electronic conductivity, and a sluggish redox reaction. In this work, we demonstrate the use of poly(vinylferrocene) (PvFc) as a binder additive that can effectively increase the ionic conductivity of the cathode and act as a sulfide-confining agent. Electrochemical tests performed with PvFc as part of the binder mixture used to cast the cathodes demonstrate an increase in rate capability and cycle life when compared to the baseline samples. Ionic conductivity measurements and X-ray photoelectron spectroscopy suggest that the π-cation molecular interaction between the cyclopentadienyl rings from ferrocene and Li + behaves like an ion couple with ferrocene acting as a static, covalently bound acceptor of Li + ions that enhances their mobility through the cathode. This coupled with the affinity between the ferrocenyl cations and the Li salt anions, which provides more distribution of counterions for Li + movement and improves accessibility to the cathode S reservoir, make PvFc a promising ionomer for Li−S batteries. In addition, the π-cation bonds between cyclopentadienyl and lithium polysulfides produce a sulfide-confining effect that mitigates capacity fade through polysulfide dissolution. This work demonstrates an expansion in the utility of PvFc as a component in Li-ion batteries, which so far is mostly limited to use as an active material in organometallic batteries.

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Section: Resultsmentioning

confidence: 69%

Section: Electrochemical Performancementioning

confidence: 97%

Poly(vinylferrocene) as an Ionomer and Sulfur-Confining Additive for Lithium–Sulfur Batteries

Torres,

Bhargav,

Manthiram

2023

ACS Appl. Mater. Interfaces

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“…Capacitive contributions were analyzed as constant phase elements (CPE), whose impedance is defined as:

where

is the angular frequency, Q is the admittance for

and n is the depression parameter, with values between −1 and 1. When n = 1, CPE represents a perfect capacitor, and when n = −1, it represents a perfect inductor [ 42 ]. For capacitance modeling, values of n are typically between 0.8 and 1 [ 43 ].…”

Section: Resultsmentioning

confidence: 99%

Full-Self-Powered Humidity Sensor Based on Electrochemical Aluminum–Water Reaction

Bošković

Šljukić

Radović

et al. 2021

Sensors

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A detailed examination of the principle of operation behind the functioning of the full-self-powered humidity sensor is presented. The sensor has been realized as a structure consisting of an interdigitated capacitor with aluminum thin-film digits. In this work, the details of its fabrication and activation are described in detail. The performed XRD, FTIR, SEM, AFM, and EIS analyses, as well as noise measurements, revealed that the dominant process of electricity generation is the electrochemical reaction between the sensor’s aluminum electrodes and the water from humid air in the presence of oxygen, which was the main goal of this work. The response of the sensor to human breath is also presented as a demonstration of its possible practical application.

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“…The reference electrode was a commercial Ag/AgCl design, which was routinely calibrated against a standard Calomel electrode. [37][38][39][40]. Alternatively, it is possible to use a convolution integral [41].…”

Section: Methodsmentioning

confidence: 99%

Apparent disagreement between cyclic voltammetry and electrochemical impedance spectroscopy explained by time-domain simulation of constant phase elements

Gannon

Dunnill

2020

International Journal of Hydrogen Energy

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A selection of electrodes was analysed using cyclic-voltammetry (CV) and electrochemical impedance spectroscopy (EIS), and a large apparent resistance was observed with CV that was absent with EIS. The explanation for this resistance anomaly was traced to the constant phase element (CPE) behaviour which is exhibited by the electrode double-layer capacitance. Computer simulations of the transient-response of an RQ network (where Q represents a CPE) to a voltage ramp revealed bi-exponential behaviour, with two separate time-constants. One is equal to the product of R and Q, but the other is fixed at about 0.3 seconds. This finding is supported by observation, by mathematical derivation, and by a novel mixed-domain five-component equivalent circuit model. In addition, example code is provided as a basis for transient simulations of constant phase elements with arbitrary voltage waveforms. This explanation assists in the correct interpretation of potentially misleading cyclic voltammetry results.

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Modeling and simulation of Constant Phase Element for battery Electrochemical Impedance Spectroscopy

Cited by 17 publications

References 13 publications

Poly(vinylferrocene) as an Ionomer and Sulfur-Confining Additive for Lithium–Sulfur Batteries

Poly(vinylferrocene) as an Ionomer and Sulfur-Confining Additive for Lithium–Sulfur Batteries

Full-Self-Powered Humidity Sensor Based on Electrochemical Aluminum–Water Reaction

Apparent disagreement between cyclic voltammetry and electrochemical impedance spectroscopy explained by time-domain simulation of constant phase elements

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