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Entering voltage hysteresis in phase-separating materials : revealing the electrochemical signature of the intraparticle phase-separated state
Tomaž Katrašnik, Jože Moškon, Klemen Zelič, Igor Mele, Francisco Ruiz-Zepeda, Miran Gaberšček, 2023, izvirni znanstveni članek

Povzetek: Hysteresis is a general phenomenon regularly observed in various materials. Usually, hysteretic behavior is an intrinsic property that cannot be circumvented in the non-equilibrium operation of the system. Herein, we show that, at least with regard to the hysteretic behavior of phase-separating battery materials, it is possible to enter (deeply) the hysteretic loop at finite battery currents. This newly observed electric response of the electrode, which is inherent to phase-separating materials, is, for the first time, related to its microscopic origin arising from a (significant) share of the active material residing in an intraparticle phase-separated state. This intriguing observation was further generalized by revealing that a phase-separating material can feature (significantly) different chemical potentials at the same bulk lithiation level and temperature when exposed to the same finite current and external voltage hysteresis. Therefore, the intraparticle phase-separated state significantly affected the DC and AC characteristics of the battery. The experimental evidence for entering the intraparticle phase-separated state is supported by thermodynamic reasoning and advanced modeling. The current findings will help advance the understanding, control, diagnostics, and monitoring of batteries composed of phase-separating materials while also providing pertinent motivation for the enhancement of battery design and performance.
Ključne besede: battery, phase-separating materials, Lithium iron phosphate, voltage hysteresis, intraparticle phase-separated
Objavljeno v DiRROS: 06.09.2023; Ogledov: 495; Prenosov: 230
.pdf Celotno besedilo (5,07 MB)
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Electrochemical cycling behaviour and shape changes of Zn electrodes in mildly acidic aqueous electrolytes containing quaternary ammonium salts
Benedetto Bozzini, Marco Boniardi, Tommaso Caielli, Andrea Casaroli, Elisa Emanuele, Lucia Mancini, Nicola Sodini, Jacopo Strada, 2023, izvirni znanstveni članek

Povzetek: Secondary Zn–based batteries are a valid alternative to Li for stationary storage, but commercial devices are not yet available, chiefly owing to anode shape-change and passivation issues. Mildly acidic aqueous solutions are actively studied, since they seem to limit unstable growth of Zn, with respect to the alkaline ones, customary for primary batteries. Additives can further improve the performance of mildly acidic electrolytes. In this work we focus on the impact of a series of quaternary ammonium salts (TBAB, CTAB, DMDTDAB, BDMPAC, BPPEI, PDADMAC), selected to represent a comprehensive range of molecular functionalities. Electrochemical measurements (cyclic voltammetry, chronopotentiometry and galvanostatic-cycling in split-cells), combined with 2D and 3D imaging techniques (SEM, stereomicroscopy and in situ tomography) were adopted for the assessment Zn behaviour. This multi-technique approach pinpointed TBAB as the single most effective additive for low-current density operation, while at high current densities the additive-free electrolyte allows better cycling performance, coherently with similar results for alkaline electrolytes.
Ključne besede: battery, electrolyte, electrochemical measurements, quaternary Ammomium salt, X-ray computed microtomography, mobility
Objavljeno v DiRROS: 06.07.2023; Ogledov: 506; Prenosov: 237
.pdf Celotno besedilo (2,52 MB)
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