La Mantia, Fabio
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La Mantia, Fabio
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La Mantia, Fabio
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Mantia, Fabio La
La Mantia, F.
Mantia, F. La
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GND
18 results
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Item type:Publication, Self-discharge in Li-ion aqueous batteries: A case study on LiMn2O4(Elsevier Science, 2021-03-20); ; ; ; Aqueous rechargeable lithium-ion batteries have attracted great attention as an alternative to traditional battery technologies, being able to overcome the issues caused by flammable and expensive organic electrolytes. In particular, LiMn2O4 has reached very fast second-level charge capability by the synthesis of unconventional morphology and particle sizes, allowing charging rates up to 600 C and 93% retention of the capacity after 10,000 cycles. However, the self-discharge process and aging mechanisms for aqueous batteries have been rarely studied, which contrasts with the extensive bibliography of the same phenomena in LMO cells based on organic electrolytes. In this article, the mechanisms involved in the loss of reversible specific charges were studied by diverse techniques like OCV, EIS, and In-situ Raman. The results revealed a more favorable self-discharge process compared with using organic electrolytes owing to the lower stability of water. The self-discharge process can be divided into three different regions with a sequential lower decay rate of voltage and capacity as well as two different evolutions of the electric parameters. This study opens new questions about the nature, composition, and mechanisms of the self-discharge in aqueous media which will play a critical role in the electrochemical performance of novel aqueous Li-ion batteries.journal articleBand:373102 46 - Some of the metrics are blocked by yourconsent settings
Item type:Publication, Towards the commercialization of rechargeable aqueous zinc ion batteries: The challenge of the zinc electrodeposition at the anodeThe low efficiency of the electrodeposition of metallic zinc from mild-acidic electrolytes in realistic operating conditions currently represents the main challenge hindering the commercialization of aqueous Zn-ion batteries (ZIBs). These devices offer good environmental compatibility, low production costs, and high powder densities, thus are considered as a viable energy storage solution for stationary applications. The electrodeposition of metallic zinc is generally affected by dendrites, spontaneous evolution of gaseous hydrogen, and precipitation of insulating passivation products on the electrode surface. The recent scientific literature has provided many strategies addressing the zinc electrodeposition through the optimization of the electrode, of the aqueous electrolyte, or of the electrode–electrolyte interface. However, industrially relevant requirements such as realistic values of anode usage, current densities, and capacity limits, must be implemented in the future research studies.journal articleBand:3852 77 - Some of the metrics are blocked by yourconsent settings
Item type:Publication, Dynamic Impedance Spectroscopy of Nickel Hexacyanoferrate Thin Films(2019-10-31); ; ; Dynamic multi-frequency analysis (DMFA) is capable of acquiring high-quality frequency response of electrochemical systems under non-stationary conditions in a broad range of frequencies. In this work, we used DMFA to study the kinetics of (de-)intercalation of univalent cations (Na+ and K+) in thin films of nickel hexacyanoferrate (NiHCF) during cyclic voltammetry. For this system, the classic stationary electrochemical impedance spectroscopy fails due to the instability of the oxidized form of NiHCF. We are showing that such spectra can be fitted with a physical model described by a simple two-step intercalation mechanism: an adsorption step followed by an insertion step. The extracted kinetic parameters are depending on the state of charge as well on the nature of the inserted cation.journal articleBand:6Heft:21268 325 - Some of the metrics are blocked by yourconsent settings
Item type:Publication, Modeling of electrochemical oxide film growth – impact of band-to-band tunnelingThe Point Defect Model (PDM) describes the corrosion resistance properties of oxide films based on interfacial reactions and defect transport, which are affected by the electric field inside the oxide film. The PDM assumes a constant electric field strength due to band-to-band tunneling (BTBT) of electrons and the separation of electrons and holes by high electric fields. In this manuscript we present a more complex expansion of the common models to simulate steady state oxide films to test this assumption. The R-PDM was extended by including the transport of electrons and holes and BTBT. It could be shown that BTBT only occurs in very rare cases of narrow band gaps and high electric fields and the impact of electrons and holes does indeed lead to a buffering effect on the electric field, but does not lead to a constant electric field strength. Modeling the transport of electrons and holes on the oxide film allows to specifically estimate their potential impact on the film growth. Especially during modeling of oxide films with narrow band gap and/or electrochemical reactions at the film/solution interface the electrons and holes needs to be included to the model.journal article160 113 - Some of the metrics are blocked by yourconsent settings
Item type:Publication, What is the trigger for the hydrogen evolution reaction? - towards electrocatalysis beyond the Sabatier principle(2020-04-29); ; ; ; The mechanism of the hydrogen evolution reaction, although intensively studied for more than a century, remains a fundamental scientific challenge. Many important questions are still open, making it elusive to establish rational principles for electrocatalyst design. In this work, a comprehensive investigation was conducted to identify which dynamic phenomena at the electrified interface are prerequisite for the formation of molecular hydrogen. In fact, what we observe as an onset of the macroscopic faradaic current originates from dynamic structural changes in the double layer, which are entropic in nature. Based on careful analysis of the activation process, an electrocatalytic descriptor is introduced, evaluated and experimentally confirmed. The catalytic activity descriptor is named as the potential of minimum entropy. The experimentally verified catalytic descriptor reveals significant potential to yield innovative insights for the design of catalytically active materials and interfaces.journal articleHeft:22255 251 - Some of the metrics are blocked by yourconsent settings
Item type:Publication, Extracting the kinetic parameters of the hydrogen evolution reaction at Pt in acidic media by means of dynamic multi-frequency analysis(2019-06-10); ; ; Herein, we use dynamic multi-frequency analysis (DMFA) to investigate the reaction kinetics of a paradigm electro-catalytic reaction, i.e. the hydrogen evolution reaction (HER) at polycrystalline Pt electrodes in acidic media. DMFA allows measuring dynamic impedance spectra under non-steady state conditions, as it is the case to avoid the formation of hydrogen bubbles. The extracted impedance spectra were fitted using electrical equivalent circuits (EECs) based on an analytical model, which took into account a Volmer-Tafel mechanism for hydrogen evolution. We found that the EECs based on this model can serve as suitable electrical analog in order to describe the physico-electrochemical processes that govern the different stages of the HER.journal article225 364 - Some of the metrics are blocked by yourconsent settings
Item type:Publication, Transition state theory in systems of interacting particles(2018-12-19); Chemical equilibrium is fully characterized at thermodynamic level by the free energy: the equilibrium is written in terms of equality of chemical potentials. Rate of chemical reactions can be calculated for ideal solutions by using mass-action equations, with reaction rate constants related to energy barriers through the transition state theory. The two approaches merge in the case of equilibrium and ideal solutions. Here, we discuss how to extend the transition state theory in the case of non-ideal solutions, i.e. of interacting particles, at equilibrium. We find bounds of the exchange reaction rate. However, we show that the value of the exchange reaction rate cannot be calculated from equilibrium thermodynamic parameters (i.e. from the free energy), i.e. it is possible to find different Hamiltonians giving the same free energy but different exchange reaction rate.Report221 121 - Some of the metrics are blocked by yourconsent settings
Item type:Publication, Dynamic Impedance Spectroscopy: Fitting Multivariate Impedance Spectra using B-Spline BasisClassical approaches to modelling dynamic or multivariate impedance spectroscopy data rely on either fitting individual spectra using an iterative procedure or using a joint least-squares analysis combined with partial prior knowledge of the model as a function of parameters which show a dependence on a control variable such as voltage or time. However, these approaches often fail to provide accurate results due to their sensitivity to the initial guess of the model parameters and the lack of an adaptive modelling approach. We address these limitations by introducing an approach that combines the parametric modelling of single spectra and use cubic B-splines to introduce the dependence of such parameters on the control variable. We illustrate our method by analyzing a set of 50 spectra obtained from dynamic impedance studies of electron transfer involving a redox couple in solution. We further demonstrate that the spline-based method is less sensitive to initial guesses, outperforms classical fitting methods in preserving the model parameters’ dependence on the control variable and yields a significantly lower weighted residual mean square value compared to classical approaches.conference paper37 73 - Some of the metrics are blocked by yourconsent settings
Item type:Publication, Lithium recovery from diluted brine by means of electrochemical ion exchange in a flow-through-electrodes cellLithium is becoming an important raw material due to the expansion of the market of lithium-ion batteries, required for electric vehicles and for stationary energy storage. The current method of lithium extraction is slow, inefficient and it has a strong environmental impact. In the last decade a new technology, called “electrochemical ion pumping”, based on the electrochemical selective capture of lithium cations from the brine, followed by the release of the ions into a so-called “recovery solution”, was proposed. In this work, we developed a flow-through-electrodes reactor, with which it was possible to capture lithium from a diluted solution containing 1 mM LiCl and 1 M NaCl, and concentrate it in a recovery solution. After 9 cycles, it was possible to produce 5 mL of 100 mM LiCl solution with 94% purity starting from more than one liter source solution. We have estimated the energy required by the process, finding that the major contribution is given by the hydraulic energy for pumping the electrolyte through the cell. The evaluation shows that the technology is economically feasible and it can enable a sustainable future production of lithium.journal articleBand:47536 86 - Some of the metrics are blocked by yourconsent settings
Item type:Publication, Prussian blue analogues as aqueous Zn-ion batteries electrodes: Current challenges and future perspectivesThe urgency of integrating renewable energy sources in the power grid has pushed the development of aqueous metal-ion batteries because of their low cost, nontoxicity, high safety, and environmentally friendliness. Among the variety of aqueous metal-ion batteries that are currently under development, aqueous Zn-ion batteries (A-ZIBs) have recently gained a great attention because of their high specific energy and high reversibility in aqueous solutions, together with the low cost and high abundancy of the zinc. In this article, the authors intend to present an overview of the Prussian blue analogue materials, which are among the most promising materials for positive electrodes in A-ZIBs because of their easier synthesis route, reversible ion-insertion, high safety, and low toxicity, highlighting their strength points and open challenges.journal articleBand:2136 50