In this paper we study the numerical approximation of Turing patterns corresponding to steady state solutions of a PDE system of reaction-diffusion equations modeling an electrodeposition process. We apply the Method of Lines (MOL) and describe the semi-discretization by high order finite differences in space given by the Extended Central Difference Formulas (ECDFs) that approximate Neumann boundary conditions (BCs) with the same accuracy. We introduce a test equation to describe the interplay between the diffusion and the reaction time scales. We present a stability analysis of a selection of time-integrators (IMEX 2-SBDF method, Crank-Nicolson (CN), Alternating Direction Implicit (ADI) method) for the test equation as well as for the Schnakenberg model, prototype of nonlinear reaction-diffusion systems with Turing patterns. Eventually, we apply the ADI-ECDF schemes to solve the electrodeposition model until the stationary patterns (spots & worms and only spots) are reached. We validate the model by comparison with experiments on Cu film growth by electrodeposition.

Four stainless steels and alloys (17-4 PH, X4CrNiMo 16-5-1, F6NM and UNS N09935) were evaluated in relation to their application in the oil and gas industry. These materials were tested in solutions exhibiting a range of chloride concentrations, pH values and temperatures of interest for the oil and gas producing environments. The pitting sensitivity was investigated by means of potentiodynamic polarisation measurements, based on the ASTM G61 standard, in conjunction with a morphological study performed by scanning electron and optical microscopy. The resistance to stress corrosion cracking (SCC) was evaluated in compliance with the ASTM G123 standard. Erosion–corrosion was assessed by exposing the materials under electrochemical control to a flux of erodent glass microspheres in a rotating disc electrode device. A ranking of the materials resistance was derived, based on appropriate parameters, devised to effectively and synthetically represent the complex sets of environments of interest for the relevant application. Our results showed, as expected, that UNS N09935 displays the best performance with respect to pitting resistance and susceptibility to SCC as well as a very good resistance to erosion–corrosion. Among the other investigated materials, 17-4 PH showed higher resistance to pitting, X4CrNiMo 16-5-1 and F6NM longer time to SCC failure while 17-4 PH and X4CrNiMo 16-5-1 exhibited superior ability to withstand erosion–corrosion damaging.

A detailed description of the preparation and management of reliable and safe corrosion laboratory experiments requiring the presence of hydrogen sulphide (H2S) is reported in this work. The adopted method is based on a modified Kipp’s apparatus allowing to produce on demand just the amount of H2S required for electrolyte saturation. Two benchmark corrosion cases were studied: electrochemical corrosion, monitored by means of potentiodynamic measurements, and sulphide stress corrosion cracking tests, both in H2S-saturated acidic aqueous chloride solutions. The sensitivity to H2S corrosion of a few classical materials of interest in the oil and gas sector, corrosion-resistant alloys, was then examined, proving as the presence of H2S leads to a denobling effect, increases the passive current density and influences significantly the time of cracking in the sulphide stress corrosion cracking tests.

This paper reports on the quantitative assessment of the oxygen reduction reaction (ORR) electrocatalytic activity of electrodeposited Mn/polypyrrole (PPy) nanocomposites for alkaline aqueous solutions, based on the Rotating Disk Electrode (RDE) method and accompanied by structural characterizations relevant to the establishment of structure-function relationships. The characterization of Mn/PPy films is addressed to the following: (i) morphology, as assessed by Field-Emission Scanning Electron Microscopy (FE-SEM) and Atomic Force Microscope (AFM); (ii) local electrical conductivity, as measured by Scanning Probe Microscopy (SPM); and (iii) molecular structure, accessed by Raman Spectroscopy; these data provide the background against which the electrocatalytic activity can be rationalised. For comparison, the properties of Mn/PPy are gauged against those of graphite, PPy, and polycrystalline-Pt (poly-Pt). Due to the literature lack of accepted protocols for precise catalytic activity measurement at poly-Pt electrode in alkaline solution using the RDE methodology, we have also worked on the obtainment of an intralaboratory benchmark by evidencing some of the time-consuming parameters which drastically affect the reliability and repeatability of the measurement.

The cathodic behavior of a model solid oxide electrolysis cell (SOEC) has been studied by means of near-ambient pressure (NAP) X-ray Photoelectron Spectroscopy (XPS) and Near Edge X-ray Absorption Fine Structure Spectroscopy (NEXAFS), aiming at shedding light on the specific role of the metallic component in a class of cermets used as electrodes. The focus is on the surface chemistry and catalytic role of Cu, the increasingly popular metallic component in electrodes used in CO2 electrolysis and CO2/H2O co-electrolysis. The NAP-XPS and NEXAFS results, obtained in situ and operando conditions and under electrochemical control, have provided important insights about the evolution of the chemical composition of the Cu surface. We have found that in dry CO2 ambient carbon deposits are scavenged at low cathodic potential by the oxidising action of nascent O, while at high cathodic polarisations C grows due to activation of CO reduction. Instead, in CO2/H2O mixtures, surface deposit of C is steady over the whole investigated potential range. The presence of adsorbed CO has also been detected during electrolysis of CO2/H2O mixtures, while no CO is found in pure CO2 ambient.

This paper reports an in situ study of the anodic behavior of a model solid oxide electrolysis cell (SOEC) by means of near-ambient pressure X-ray Photoelectron Spectroscopy (XPS) combined with near edge X-ray absorption fine structure (NEXAFS) measurements. The focus is on the anodic surface chemistry of MnOx, a model anodic material already considered in cognate SOFC-related studies, during electrochemical operation in CO2, CO2/H2O and H2O ambients. The XPS and NEXAFS results we obtained, complemented by electrochemical measurements and SEM characterisation, reveal the chemical evolution of Mn under electrochemical control. MnO is the stable chemical form at open-circuit potential (OCP), while Mn3O4 forms under anodic polarisation in all the investigated gas ambients. Carbon deposits are present on the Mn electrode at OCP, but they are readily oxidised under anodic conditions. Prolonged operation of the MnOx anode leads to pitting of the Mn films, damaging of the triple-phase boundary region and also to formation of discontinuities in the Mn patch. This is accompanied by chemical transformations of the electrolyte and formation of ZrC without impact on the surface chemistry of the Mn-based anode.

In this paper we report an SFG/DFG investigation of the adsorption of CN¯ –used as a probe molecule to study the electrochemical double-layer structure – at a polycrystalline Au electrode in 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl) amide ([BMP][TFSA]) room-temperature ionic liquid (RTIL). The adsorption of CN¯ yielded single SFG and DFG bands in the range from ca. 2125 to 2135 cm-1, exhibiting a Stark tuning of ca. 3 cm-1 V-1. Vibrational resonances – corresponding to modes of the RTIL coadsorbed with CN¯, were found in the range from ca. 1200 to 1500 cm-1. The study of the double-layer structure was complemented by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) measurements, from which the differential double-layer capacity (CDL) was estimated.

A tapered-end flow Zn–air fuel cell (ZAFC), mechanically refuelable with Zn microspheres, was employed to study the effect of aging of KOH electrolyte on the Zn anode. A complete description of the architecture of the adopted cell is reported. The electrochemical characterization of the ZAFC was performed by long-term current discharge tests in galvanostatic mode. An insightful investigation on the particulate Zn anode consisting of spheres of diameter 0.4 mm was performed by means of X-ray diffraction (XRD), scanning electron microscope (SEM), and Raman spectroscopy in order to characterize the crystallographic structure, surface morphology, and chemical nature of residual metal and solid corrosion products. Electrochemical impedance spectroscopy (EIS) allowed to obtain information on the charge-transfer mechanism of zinc anode reaction and on the thickness, compactness, and blocking features of the passive film as a function of the aging of the electrolyte. The results of our analysis revealed the formation of a passive layer of zinc consisting of a white and porous film of ZnO precipitate (type I) and a light-gray to black compact film (type II). The failure of the particulate anode was chiefly caused by the increase in zincate concentration in the electrolyte, but it was enhanced by the nonuniform spatial current distribution due to the instability of the passive film at high pH.

Low energy X-ray fluorescence (XRF) and soft X-ray absorption (XAS) microspectroscopies at high space-resolution are employed for the investigation of the coelectrodeposition of composites consisting of a polypyrrole(PPy)-matrix and Mn-based ternary dispersoids, that have been proposed as promising electrocatalysts for oxygen-reduction electrodes. Specifically, we studied Mn–Co–Cu/PP, Mn–Co–Mg/PPy and Mn–Ni–Mg/PPy co-electrodeposits. The Mn–Co–Cu system features the best ORR electrocatalytic activity in terms of electron transfer number, onset potential, half-wave potential and current density. XRF maps and micro-XAS spectra yield compositional and chemical state distributions, contributing unique molecular-level information on the pulse-plating processes. Mn, Ni, Co and Mg exhibit a bimodal distribution consisting of mesoscopic aggregates of micrometric globuli, separated by polymer-rich ridges. Within this common qualitative scenario, the individual systems exhibit quantitatively different chemical distribution patterns, resulting from specific electrokinetic and electrosorption properties of the single components. The electrodeposits consist of Mn3+,4+-oxide particles, accompanied by combinations of Co0/Co2+, Ni0/Ni2+ and Cu0,+/Cu2+ resulting from the alternance of cathodic and anodic pulses. The formation of highly electroactive Mn3+,4+ in the as-fabricated material is a specific feature of the ternary systems, deriving from synergistic stabilisation brought about by two types of bivalent dopants as well as by galvanic contact to elemental metal; this result represents a considerable improvement in material quality with respect to previously studied Mn/PPy and Mn-based/PPy binaries.

Owing to their unique combination of wear resistance and toughness, cemented carbides are developing relevance in a systematically increasing number of applications, many of which involve notably corrosive environments. Petrochemical offshore extraction is one of the most appealing prospective fields of use of cemented carbides for critical general-purpose components (e.g. pumps and valves), as well as specialised devices, such as drilling mud circulation systems, as they undergo extremely severe erosion-corrosion related to the handling of tetraphasic flows comprising condensed and gas-phase hydrocarbons in addition to sand or other solid components of slurries. Moreover, oilfields of current interest bear high concentrations of strongly corrosive impurities. The present study is aimed at contributing to the knowledge of the corrosion and corrosion inhibition processes of a range of alloyed Co- and Ni-based cemented carbide grades in solutions containing cyanide (CN¯) and thiocyanate (SCN¯) - typical corrosive contaminants found in crude oil - and 2-mercaptobenzothiazole (MBT), a prospective corrosion inhibitor in the petrochemical field. To this aim, we employed: (i) linear sweep voltammetry (LSV) to assess the cathodic and anodic activity of the hardmetal grades; (ii) in situ Sum- Frequency Generation (SFG) spectroscopy as a sensitive probe of the potential-dependent interfacial chemistry and corrosion behaviour in terms of both adsorption and interaction of adsorbates with the electronic structure of the substrate; (iii) ex situ spectro-ellipsometry to characterise the films formed on the different grades in the investigated environments.We have found that: (i) the grade with Co‐Ru binder exhibits a generally better corrosion resistance in all investigated ambients; (ii) Ni affords protective action provided the oxidising power is below a given threshold and CN¯ is absent, and (iii) MBT improves the pseudopassivation of all the investigated cemented carbides. Typical potential-dependent SFG spectral scenarios have been pinpointed for the different electrode/electrolyte combinations, accurately matching the electrochemical behaviour assessed by LSV and the optical properties of the corroded surfaces investigated by spectro-ellipsometry. This multi-method study offers a comprehensive and insightful understanding of the corrosion of cemented carbides in contact with additive-containing solutions.

The present paper is focused on the corrosion of austenitic (AISI304) and a Duplex (2205) stainless steel grades in H2O/KOH 50% at 120°C. Linear sweep voltammetry and electrochemical impedance spectrometry measurements were carried out with an AMEL modified potentiostat equipped with a digital FRA in an home-made cell for high-temperature work with gas control. The impedance spectra have been fitted with a novel numerical model. The experiments were complemented by metallographic (in-plane and cross-sectional SEM micrography), structural (X-ray diffractometry) and compositional (EDX line-profiles) characterization of the materials attacked under electrochemically controlled conditions. Electrochemical measurements have shown that AISI304 exhibits a passivating behaviour, with a secondary peak in the passive range and eventual transpassivity. Duplex electrochemical behaviour is characterized by a mixed kinetic control. AISI304 was found to fail by intergranular corrosion and to be covered in passive conditions by acicular compounds and in transpassive conditions by a compact layer of corrosion products. Duplex samples, instead, exhibits a more uniform surface morphology and a compact layer of corrosion products both in passive and in transpassive conditions.

The present paper focuses on the corrosion of austenitic (AISI304) and a duplex (2205) stainless steel grades in molten KOH/NaOH 50 w/o eutectic at 250°C. Experimental activities have been performed consisting in electrochemical measurements (linear sweep voltammetry and electrochemical impedance spectrometry) complemented by metallographic (in-plane and cross-sectional SEM micrography), structural (X-ray diffractometry) and compositional (EDX line-profiles) characterization of the materials attacked under electrochemically controlled conditions. Electrochemical measurements have shown that AISI304 exhibits a passivating behaviour, characterised by two passivation peaks and a transpassive threshold, while Duplex, does not yield a clear indication of passivation. AISI304 was found to fail by intergranular corrosion and to be covered in both passive and transpassive conditions, by an incoherent scale, containing electrolyte species. Duplex samples, instead tends to fail by homogeneous attack and exhibit a range of scale structures, depending on the applied potential.

In this paper we study the corrosion of AISI 304 austenitic stainless steel PEMFC bipolar plates in aqueous and room-temperature ionic-liquid electrolytes. The anodic potential thresholds and dynamics have been investigated by electrochemical (potentiodynamic and potentiostatic) and in situ spectroelectrochemical methods (visible electroreflectance and VIS-UV spectroellipsometry). We measured the values of damage potentials and we followed the time evolution of corrosion current and reflectivity above and below the pitting potential, obtaining an accurate characterisation of the surface conditions under oxidative attack. The ability of AISI 304 to repassivate in Cl --containing aqueous solution as well as the amount of residual surface damage have been assessed quantitatively by following electrode reflectivity under applied potential. Outstanding inertness of AISI 304 in [BMP][TFSA] was proved. The results of this work show that low-cost AISI 304 is a promising interconnect material for both Nafion- and RTIL-based PEMFCs.

Fabrication and testing of fuel-cells based on nanofilm electrodes and interconnects is a hot technological challenge for three key reasons: (i) miniaturisation and integration into electronic devices as well as implementation of on-chip logics, (ii) testing of the performance of nano-materials on their real scale and (iii) use of cuttingedge material characterisation techniques. The principal interest of a nanotechnological approach to material problems in electrochemical energetics is particularly related to long-term durability issues of critically degradable components. Among the degradation modes, mechanical failure by cracking of the functional thin films is being recognised as a crucial one, impairing the implementation of laboratory systems into real-life devices. In this paper we report on corrosion-induced local thinning and correlated cracking of electrode components in a RTIL-based Proton Exchange Membrane Fuel Cell with Pt micro-particles as catalyst, Au feeder electrodes and Fe interconnects. In situ imaging of the multi-material system in electrochemical environment, based on X-ray scanning and optical microscopies, has disclosed the formation of complex cracking patterns, including spiral cracks. A simple mechanical explanation of the peculiar cracking pattern is proposed.

We analyze the effects of cross-diffusion on pattern formation in a PDE reaction-diffusion system introduced in Bozzini et al. 2013 to describe metal growth in an electrodeposition process. For this morphochemical model - which refers to the physico-chemical problem of coupling of growth morphology and surface chemistry - we have found that negative cross-diffusion in the morphological elements as well as positive cross-diffusion in the sur- face chemistry produce larger Turing parameter spaces and favor a tendency to stripeness that is not found in the case without cross-diffusion. The impact of cross-diffusion on pat- tern selection has been also discussed by the means of a stripeness index. Our theoretical findings are validated by an extensive gallery of numerical simulations that allow to better clarify the role of cross-diffusion both on Turing parameter spaces and on pattern selec- tion. Experimental evidence of cross-diffusion in electrodeposition as well as a physico- chemical discussion of the expected impact of cross diffusion-controlled pattern formation in alloy electrodeposition processes complete the study.

In a previous paper, we demonstrated the possibility of growing high-capacitance hybrid materials consisting of nanoporous gold (NPG)-supported MnO2 nanowires (NW) for supercapacitors, by electrochemical etching of electrodeposited single-phase Au-Mn alloys. The present paper concentrates on the electrodeposition of Au-Mn alloys from urea/choline-chloride ionic liquid solutions: the precursors of the high-capacitance hybrid material. The electrodeposition process, giving rise to alloys with 4-26% Mn content, was followed by space-resolved soft X-ray fluorescence (XRF) and absorption (XAS) microspectroscopy, complemented with electrochemical (cyclic voltammetry), structural (X-ray diffraction) and morphological (scanning electron microscopy) characterisations. The purposely developed electrochemical cells, exhibiting a specifically designed current density distribution, have allowed the quasi-in situ mapping of the local morphology-composition changes at the electrodes. Supersaturated Au-Mn solid solutions were obtained in the whole investigated compositional range under mass transport control of Mn. Variations in the Mn oxidation state were evidenced comparing low- and high-Mn content regions. It was found that, notwithstanding the heterogeneity of the current density, the morphologically compact high-Mn regions of the particular alloys with 20-26% Mn show a notable compositional homogeneity, rendering this material ideally suited for the fabrication of the target hybrid.

In two previous papers (C. Mele, M. Catalano, A. Taurino, B. Bozzini. Electrochim. Acta 87 (2013) 918; B. Bozzini, A. Gianoncelli, C. Mele, M. Kiskinova. Electrochim. Acta 114 (2013) 889), we have: (i) fabricated high-capacitance materials consisting of nanoporous gold (NPG)-supported MnO2 nanowires (NW), by electrochemical etching of single-phase Au-Mn alloys electrodeposited from a deep eutectic solvent (DES) electrolyte and (ii) investigated some aspects of the precursor Au-Mn alloy electrodeposition process by following it in situ with space-resolved soft X-ray fluorescence (XRF) and absorption (XAS) microspectroscopies: this study has allowed to single-out the peculiarities of elemental and chemical-state distribution that contribute to the nanostructure fabrication. The present paper completes the electrodeposition study by investigating the potential-dependent interfacial composition of the growing Au-Mn alloys by complementary in situ linear (Raman) and non-linear (Sum-Frequency Generation - SFG) vibrational spectroscopies. The results regarding alloy electrodeposition are compared to those obtained with a pure Au bath. In situ spectroscopy during electrodeposition reveals that both choline cation and urea are present at the growing metal/DES interface, coadsorbed with CN resulting from the decomposition of the Au complex. Electrostatic adsorption controls the surface coverage scenario at the Au/DES interface, while Mn favours the relative surface coverage with urea. Moreover, the interaction of urea with the metal film is modified by the addition of Mn, switching from solid-like to liquid-like at the Mn-alloying potential threshold. Also the CN adsorption scenario is sensitive to surface alloying: the Mn-containing interface shows two adsorption sites with lower degree of metal-adsorbate charge transfer. Finally, the degree of surface enhancement correlates well on the one hand with the applied potential and the interfacial chemistry, and on the other hand with the crystallite morphology induced by alloying Au with Mn. The correlation among the spectroelectrochemical scenario, the potential-dependent alloy composition and the crystallite shape expressed by this investigation fits within the framework set by recent modelling of dynamic electrodeposition morphochemistry and opens up novel opportunities for improving the control over the functional properties of net-shape electrodeposited materials

In this paper we report on the electrochemical reconstruction of a Tarentum hemiobolus Ag coin, severely corroded in marine environment. As assessed by conventional analytical tools, most of the initially metallic Ag coin had been converted to AgCl by exposure to the aggressive coastal burial conditions. X-ray computed microtomography proved that only small portions of the artefact had preserved their metallic nature. Since the engraving was preserved partly in the corrosion product bulk and partly in the metallic rests, electrodeposition of Ag from the AgCl layer, under controlled conditions ensuring shape preservation, resulted in the reconstruction of the coin surface with full recovery of the original engraving. Such optimal electrodeposition conditions were identified by a combination of electrochemical and quasi-in situ X-ray microtomography experiments, carried out with artificially corrored engraved Ag wires. Microtomography of the reconstructed coin confirmed the compaction of the external Ag layer and disclosed that the central core of the coin still contains unconverted AgCl. The presence of such a mineralised core does not however impact the numismatic use of the coin and the safeguard of the original engraving.

In this study an electrochemical approach is proposed for the fabrication of nanoporous gold (NPG)- supported manganese oxide nanowires. This method consists in: (i) electrodepositing an Au–Mn alloy, (ii) selectively corroding Mn under electrochemical control, forming simultaneously the NPG support and the functional Mn-oxide decorating the nanopores. The electrodeposition process is carried out from a bath based on eutectic urea/choline chloride ionic liquid. The electrochemical dealloying/oxidation step is performed in an aqueous solution. The oxidation process, performed by cyclic voltammetry (CV) in aqueous solution, has been monitored in situ by visible reflectivity measurements. The crystal structure and the morphology of the electrodeposited Au–Mn alloy have been examined by XRD and SEM, respectively. The 3D morphology of the nanostructure has been characterised by FIB/FEG-SEM. The specific capacity of NPG-supported nanostructured Mn-oxide has been measured by CV and found to be notably better than that of unsupported electrodeposited Mn-oxide nanowires.

Electrodeposition and ageing under oxygen reduction reaction (ORR) of Mn-X/PPy (X=Co, Mg, Ni; PPy=polypyrrole) and Mn-Ag/G (G=graphene) composite electrocatalysts have been studied by quasi-in-situ soft X-ray absorption and fluorescence microspectroscopy. The fabricated materials exhibit micro-grained morphologies in which Mn is present mainly as Mn2+, accompanied by combinations of Co0/Co2+ and Ni0/Ni2+. Ageing leads to the formation of progressively larger mesoscopic aggregates. Initial ageing yields more active Mn3+ and Mn4+, in agreement with an improved ORR behaviour. Prolonged ageing causes the loss of Mn3+ and Mn4+ from the surface, in correlation with a degradation of the ORR response. In the investigated ageing period, Mn-Mg/PPy exhibits the best durability, with about half of the catalyst grains still showing the presence of Mn3+/Mn4+, while the others consist mainly of Mn2+. In Mn-Ni/PPy, the Ni2+ content tends to increase with ageing whereas Co3+ forms in the Mn-Co/PPy composites.

Electrodeposition of manganese/polypyrrole (Mn/PPy) nanocomposites has been recently shown to be a technologically relevant synthesis method for the fabrication of Oxygen Reduction Reaction (ORR) electrocatalysts. In this study we have grown such composites with a potentiostatic anodic/cathodic pulse-plating procedure and characterised them by a multi-technique approach, combining a suite of in situ and ex situ spectroscopic methods with electrochemical measurements. We have thus achieved a sound degree of molecular-level understanding of the hybrid co-electrodeposition process consisting of electropolymerisation of polypyrrole with incorporation of Mn. By in situ Raman spectroscopy we followed the formation of MnOx and the polymer by monitoring the build-up and development of the relevant vibrational bands. The compositional and chemical-state distribution of the as-deposited material has been investigated ex situ by soft X-ray fluorescence (XRF) mapping and micro-absorption spectroscopy (micro-XAS). XRF shows that the spatial distribution of Mn is consistent in a rather wide range of current densities (c.d.s), while micro-XAS reveals a mixture of Mn valencies, with higher oxidation states prevailing at higher c.d.s. Pyrolysis of electrodeposits, desirable for obtaining more durable and active catalysts, has been followed in situ by photoelectron microspectroscopy, allowing to assess the evolution of: (i) the electrodeposit morphology, resulting in a uniform distribution of nanoparticles; (ii) the chemical state of manganese, changing from a mixture of valences to a final state consisting of Mn(III) and Mn(IV) oxides and (iii) the bonding nature of nitrogen, from initially N-pyrrolic to a combination of pyridinic and Mn–N/graphitic.

In this research we have fabricated and tested Au/Dy2O3 composites for applications as Solid Oxide Fuel Cell (SOFC) electrocatalysts. The material was obtained by a process involving electrodeposition of a Au-Dy alloy from a urea/choline chloride ionic liquid electrolyte, followed by selective oxidation of Dy to Dy2O3 in air at high temperature. The electrochemical kinetics of the electrodeposition bath were studied by cyclic voltammetry, whence optimal electrodeposition conditions were identified. The heat-treated material was characterised from the morphological (scanning electron microscopy), compositional (X-ray fluorescence spectroscopy) and structural (X-ray diffractometry) points of view. The electrocatalytic activity towards H2 oxidation and O2 reduction was tested at 650 °C by electrochemical impedance spectrometry. Our composite electrodes exhibit an anodic activity that compares favourably with the only literature result available at the time of this writing for Dy2O3 and an even better cathodic performance.

In this paper we describe the one-pot fabrication of hydroxyapatite (HA)-heparin composites by electrodeposition onto Ti substrates and their characterisation in terms of structure, morphology, heparin content and bioactivity. HA coatings are well known and widely applied osteointegration enhancers, but post-implant healing rate in dental applications is still suboptimal: e.g. coagulation control plays a key role and the incorporation of an anticoagulant is considered a highly desirable option. In this study, we have developed an improved, simple and robust growth procedure for single-phase, pure HA-heparin films of thickness 1/3 l m. HA-heparin, forming nanowires, has the ideal morphology for bone mineralisation. Staining assays revealed homogeneous incorporation of sizable amounts of heparin in the composite films. The bioactivities of the HA and HA-heparin coatings on Ti were compared by HeLa cell proliferation/viability tests and found to be enhanced by the presence of the anticoagulant.

Electrodeposition of graphene-supported Co for ORR electrocatalysts from an acetonitrile solution has been studied by a multi-technique approach, combining a suite of spectroscopic methods with electrochemical measurements, allowing a molecular-level understanding of potentiostatic and pulsed-potential plating processes from the organic solvent onto a freestanding graphene film. The formation of the graphene film by the light-scribe approach has been monitored by Raman spectroscopy; the electrodeposition process has been clarified by cyclic voltammetry and the compositional and chemical-state distribution of Co have been investigated ex situ by soft X-ray absorption spectroscopy and fluorescence mapping, showing that both spatial distribution and valence state are homogeneous and independent of the local current density. The deposit consists in micrometric aggregates of Co/CoO nanoparticles with diameter ca. 30 nm (pulsed) and 200 nm (potentiostatic deposition). Potentiostatic deposition allows to obtain better ORR electrocatalytic perfomance in terms of nnumber of transferred electrons, onset/ half-wave potential and current density.

In this paper the electrodeposition of DLC films on carbon steel from aqueous acetic acid solutions and their structural and mechanical characterization are reported. The process is performed at room temperature at relatively low cell voltages (from 28 to 220 V) with entirely environmentally friendly chemicals. Qualitative and quantitative evaluation of C hybridisation type have been performed by Raman spectroscopy. Microhardness and adhesion of the supported electrodeposited films have been measured by micro-indentation and scratch-testing. Notably, ductile failure was found to correspondence to a wide range of film growth conditions. The corrosion resistance of DLC-coated steel has been assessed by electrochemical impedance spectrometry in a neutral chloride solution. Optimal electrodeposition conditions were identified for the formation of high-quality DLC films ca. 270 nm thick with a high content of diamondcoordinated carbon and an ideal combination of hardness and adhesion; films formed under these conditions also confer some degree of corrosion protection to the steel substrate.

Synchrotron-based soft-X-ray imaging and microspectroscopy with sub-micrometer spatial resolution are used to investigate the electrodeposition of Mn-Cu-ZnO, a prospective active material for supercapacitors. This study is focused on the correlation of the local current density and the spatial distribution of the composition and chemical-state in electrodeposits grown potentiostatically at -0.7V (vs a saturated calomel electrode), as well as the optimal potential for the achievement of high specific capacitance and cycling stability. The morphology, elemental distribution, and the local chemical state of both the electrode deposits and the grown dendrite structures are followed by using X-ray imaging, X-ray fluorescence mapping, and X-ray absorption microspectroscopy. For transmission soft-X-ray measurements, a thin-layer Hull-type microcell is developed and fabricated by using electron-beam lithography. The information obtained for the spatial distribution of the deposit is complemented by using electrochemical measurements and numerical simulations.

Understanding the lateral variations in the elemental and chemical state of constituents induced by electrochemical reactions at nanoscales is crucial for the advancement of electrochemical materials science. This requires in situ studies to provide observables that contribute to both modeling beyond the phenomenological level and exactly transducing the functionally relevant quantities. A range of X-ray coherent diffraction imaging (CDI) approaches have recently been proposed for imaging beyond the diffraction limit with potentially dramatic improvements in time resolution with chemical sensitivity. In this paper, we report a selection of ptychography results obtained in situ during the electrodeposition of a metal–polymer nanocomposite. Our selection includes dynamic imaging during electrochemically driven growth complemented with absorption and phase spectroscopy with high lateral resolution. We demonstrate the onset of morphological instability feature formation and correlate the chemical state of Mn with the local growth rate controlled by the current density distribution resulting from morphological evolution.

Ni-cerium oxide coatings were electrodeposited from particle-free aqueous baths containing NiCl2.6H2O and CeCl3.7H2O. The mechanism of deposition was studied systematically by a combination of voltammetric, in situ spectoelectrochemical (visible reflectivity VRS, surface Raman spectroscopy SRS), ex situ spectroscopic (spectroscopic ellipsometry SE) methods, as well as by SEM imaging; yielding details on the steps of the composite formation process. Time- and potential-dependent ERS data were interpreted on the basis of an optical model, accounting for the formation of metal and ceramic phases and corresponding relative distribution and morphology. In the ERS curves measured with the pure Ni and Ce-containing solutions, the value of reflectivity drops sharply when the potential is lower than ca. -0.9 V. The ERS curves measured in the Ce-containing solutions exhibit a second drop when the potential is lower than ca. -1.1V while, instead, for pure Ni solution an increase in reflectivity is observed. According to the proposed optical model, the drop found in the reflectivity transient can be explained with the nucleation of Ni on the Cu substrate, while the second one measured with Ce-containing solutions is due to secondary nucleation of Ni. The results showed that the deposition processes of Ni and Ni-cerium oxide can be divided into 2 and 4 stages respectively. (i) In the case on Ni: nucleation and 3D growth, accompanied by roughening; (ii) as far as Ni-cerium oxide is concerned: nucleation, formation of cerium oxide, secondary nucleation and 3D growth and roughening.

Cobalt/polypyrrole ORR electrocatalysts has been electrochemically synthesized by a potentiostatic anodic/cathodic pulse-plating procedure. The deposition electrochemistry has been studied by cyclic voltammetry and in-situ Micro Raman Spectroscopy complemented with scanning X-ray microscopy and micro-spot X-ray absorption spectroscopy (mu-XAS). Linear sweep voltammetry (LSV) under oxygen reduction has been used to assess the electrocatalytic effect of as-electrodeposited Co/PPy. The obtained results have provided new information about the concomitant electropolymerisation and metal incorporation processes occurring under different pulsed co-electrodeposition conditions, important for optimising the electrosynthesis procedure. The colocation of O and Co, evidenced by the O and Co XRF maps indicates that the Co in the formed composite is in oxidized state and for composites formed at low currents using shorter Co pulses coexistence of both CoO and Co3O4 is evidenced by the Co L-3 XAS spectra. Bimodal Co distribution as micro-grains on a background of nano-grains and co-nulcleation of PPy and Co is evidenced by correlation of Co and N XRF maps.

Electrical energy storage based on Zn-air concepts is experiencing increasing interest for applications ranging from consumer electronics to automotive and grid storage, owing to their high energy density, intrinsic safety, environmental friendliness and low cost. Their implementation is nevertheless daunted by veral materials-science riddles, affecting the actually available power density and durability. In this scenario, in operando dynamic physico-chemical information at lengthscales between mesoscopic and nanometric is highly desirable for knowledge-based advancements. This overview summarises recent contributions of in situ and quasi-in situ X-ray methods - absorption and fluorescence microspectroscopies, microtomography - to studies of cathodes, anodes and model cells.

This paper reports the first in-situ synchrotron-based scanning photoelectron microscopy study of an operating YSZ-supported single-chamber SOFCwith Au–MnO2 composite cathode and NiO anode, fedwith 10−5 mbar 1:1 mixture of CH4 fuel and O2 at 650 °C.We employed a YSZ-supported cell with Au–MnO2 composite cathode and NiO anode. The chemical imaging and micro-XPS results were complemented with simultaneous electrochemical measurements, open circuit potential, potentiostatic and impedance spectrometry. The cell was operated under two conditions: (i) with fully oxidized electrodes and (ii) after in-situ reductive activation of the anode. The current delivered by the cell after in-situ reduction was about one order of magnitude higher. The chemical states of Ni and Mn were affected by the in-situ reduction process but they were not modified by the fuel-cell operation. Notwithstanding the absence of chemical state transformations of the electrode materials during the prolonged fuel-cell operation, cell aging brings about morphological change, accompanied by a decrease of the extracted current.

This paper reports a pioneering application of soft X-ray imaging and spectromicroscopy to a hot material stability issue in fuel-cell (FC) technology: the corrosion of metallic bipolar plates in ionic-liquid-based nano polymer electrolyte membrane (PEM) FCs. Using the potential of the X-ray scanning microscopy for in situ characterisation of complex multi-material systems in electrochemical environments with sub-micrometer lateral resolution, we study the electrochemical behaviour of Fe electrodes in contact with the room-temperature ionic liquid (RTIL)1-butyl-1-methyl-pyrrolidinium bis (trifluoromethylsulfonyl) amide ([BMP][TFSA]) in a nano fuel-cell fabricated by lithography. Thanks to the properties of this RTIL, an open electrochemical cell could be used in vacuum (10-6 mbar). The possibility of imaging electrochemically induced morphological features in conjunction with local spectroscopic analysis, yields details of the space distribution and chemical correlations of the corrosion products.

This paper reports on spiral pattern formation in In–Co electrodeposition. We propose an approach to the understanding of this process based on: (i) compositional and chemicalstate distribution analysis by high-resolution photoelectron microspectroscopy and (ii) a mathematical model able to capture the morphological features highlighted in the experiments. Microspectroscopy—complemented by electrochemical, structural and morphological characterisations—combined with mathematical modelling, analytical and numerical investigations, converge in pointing out the key role played by intermetallic electrodeposition in spiral formation.

This research addresses the problem of localised corrosion of stainless steel PEMFC bipolar plates. The susceptibility to pitting and crevice corrosion of austenitic AISI 304 stainless steel has been investigated both by post-mortem microscopic analysis of the end-plates of a laboratory single-cell and by studies of electrochemically corroded stainless steels, in the presence of specially-designed crevice-formers simulating the operating conditions of a PEMFC. This work is based on optical and scanning-electron microscopies as well as potentiostatic and potentiodynamic measurements. The crevice-formers we considered were: Teflon, graphite and AISI 304. The samples, coupled to the crevice-formers have been tested in aqueous solutions containing Cl−, SO4 2− and F−. From the E–log i plot, the values of corrosion, pitting, crevice and protection potential have been obtained and perfect and imperfect passivity conditions have been identified.

Contamination of fuel-cell membranes with metal ions, resulting from the use of ferrous alloys, leads to corrosion and ultimately failure of the device. By using a combination of X-ray spectroscopy techniques, the corrosion processes of Ni and Fe electrodes in contact with a hydrated Nafion film are investigated. The results show diffusion of corrosion products within the film only in the case of the Fe electrodes, whereas Ni electrodes appear corrosion resistant.

Replacement of hydrogen with hydrocarbon fuels in solid-oxide fuel cells (SOFCs) is an appealing alternative for reducing the implementation costs of SOFCs technology, but the electrode stability and susceptibility to carbon deposition still remain important issues to be solved. The present in situ photoelectron microscopy study of a prototype hydrocarbon-fuelled SOFC, operated at 650 °C in C2H4 + H2O gas mixture and voltages in the range 0−3 V, provides insights into morphologychemistry changes of the Ni electrodes and Cr interconnects with decisive impact on the electrochemical activity and durability. The results reveal the combination of thermal and electromigration of Ni across the electrode−electrolyte interface that can cause sensible material losses and structural changes responsible for the deterioration of device performance. The C 1s spectra evidence deposition of C and formation of carbides on the Ni electrodes and Cr interconnects at 650 °C as result of C2H4 dissociation, the process being promoted applying cathodic potential and reversed by switching to anodic potential. Following the attenuation of the C signal under anodic potential, the effect of the stability of different carbides on the reaction rate was observed.

This study dealswith themorphological and chemical-state changes caused by the degradation of nanocomposite electrocatalysts – fabricated by pulsed potentiostatic co-electrodeposition and subsequently pyrolysed – under oxygen reduction reaction (ORR) conditions in aqueous alkaline solution. Variations in shape, dimensions and chemical state of theMn-centres were followed by quasi-in situ synchrotron-based scanning photoelectron microscopy with submicron lateral resolution, combined with ex situ Raman measurements, in correspondence of different cyclovoltammetric ageing stages. The decline of the electrocatalytic performance is accompanied by size variations of theMnOx particles that are initially ~30nmin diameter, then shrink to ~10nmand subsequently grow to ~45 nmafter prolonged ORR. Concerning chemical state, the pristine Mn0,II nanoparticles are converted to MnIII,IV oxy-hydroxides as a result of a dissolution/redeposition process favoured by the oxygen environment.

This paper offers an overview of morphogenetic processes going on in metal electrodeposition processes and provides a systematisation of the morphology classes identified experimentally in terms of an electrokinetic theory accounting for charge-transfer and masstransport rates. In addition, it provides a review of the modelling work by the authors, based on a reaction-diffusion system coupling morphology with surface chemistry of the growing metal and briefly describes the experimental validation of the model.

In this paper a reaction-diffusion system modelling metal growth processes is considered, to investigate - within the electrodeposition context- the formation of morphological patterns in a finite two-dimensional spatial domain. Nonlinear dynamics of the system is studied from both the analytical and numerical points of view. Phase-space analysis is provided and initiation of spatial patterns induced by diffusion is shown to occur in a suitable region of the parameter space. Investigations aimed at establishing the role of some relevant chemical parameters on stability and selection of solutions are also provided. By the numerical approximation of the equations, simulations are presented which turn out to be in good agreement with experiments for the electrodeposition of Au-Cu and Au-Cu-Cd alloys.

This paper describes the numerical modelling of a key material-stability issue within the realm of Molten Carbonate Fuel Cells (MCFC). Differential models have been developed for the 2D and 3D distributions of current density as well as peroxide and carbon dioxide concentrations. By suitable variations of the integration domain - based on the agglomerate concept - one can describe the morphological and attending electrocatalytic evolution of porous NiO electrodes. On the basis of electrochemical data recorded during the operation of a laboratory MCFC, we have shown that this model is able to rationalise the evolution of cathode conditions leading to both improvements of electrocatalytic performance - such as lithiation - and degradation - such as agglomeration

The stability of pyrolyzedMn–Co/polypyrrole (PPy) nanocomposites towards theOxygen Reduction Reaction (ORR) in alkaline solution,was studiedwith a close-knit group of complementarymicroscopic and space-resolved spectroscopic approaches: Atomic Force Microscopy (AFM), Scanning and High-Resolution Transmission Electron Microscopy (SEM, HRTEM) and identical-location Scanning PhotoElectron Microscopy (SPEM). Tracking quasi-in situ the morphochemical evolution of the Mn–Co/PPy catalyst upon electrochemical aging under ORR conditions by this multi-technique approach, has allowed to clarify the key physico-chemical processes underlying the dramatic impact of Co additions to stability improvement.

In this paper we consider a parameter identification problem (PIP) for data oscillating in time, that can be described in terms of the dynamics of some ordinary differential equation (ODE) model, resulting in an optimization problem constrained by the ODEs. In problems with this type of data structure, simple application of the direct method of control theory (discretize-thenoptimize) yields a least-squares cost function exhibiting multiple ‘low’ minima. Since in this situation any optimization algorithm is liable to fail in the approximation of a good solution, here we propose a Fourier regularization approach that is able to identify an iso-frequency manifold S of codimensionone in the parameter space Rm, such that for all parameters in S the ODE solutions have the same frequency of the assigned data. Further to the identification of S, we propose to minimize on this manifold the least squares, the phase (or time lag) and infinity norm errors between data and simulations. Hence, the Fourier-PIP can be regarded as a new constrained optimization problem, where the iso-frequency sub-manifold represents a further constraint. First we describe our approach for simulated oscillatory data obtained with the two-parameter Schnakenberg model, in the Hopf regime. Finally, we apply Fourier-PIP regularization to follow original experimental data with the morphochemical model for electrodeposition (Lacitignola et al 2015 Eur. J. Appl. Math. 26 143–73) in the case of two and three parameters .

In this paper we present an extension of a mathematical model for the morphological evolution of metal electrodeposits – recently developed by some of the authors – accounting for mass-transport of electroactive species from the bulk of the bath to the cathode surface. The implementation of mass-transport effects is specially necessary for the quantitative rationalisation of electrodeposition processes from ionic liquids, since these electrolytes exhibit a viscosity that is notably higher than that of cognate aqueous solutions and consequently mass-transport control is active at all practically relevant plating rates. In this work we show that, if mass-transport is coupled to cathodic adsorption of ionic liquid species and surface diffusion of adatoms, it can lead to electrodeposit smoothing. This seemingly paradoxical theoretical result has been validated by a series of Mn electrodeposition experiments from aqueous baths and eutectic ionic liquids. The latter solutions have been shown to be able to form remarkably smoother coatings than the former ones. Mn electroplates have been proposed for Cd replacement and their corrosion protection performance seems comparable, but so far the required surface finish quality has not been achieved with aqueous electrolytes. Ionic liquids thus seem to provide a viable approach to aeronautic-grade Mn electroplating.

This paper reports on the electrodeposition of Mn-Cu-ZnO for hybrid supercapacitors. This material exhibits a dual structure consisting of Mn-rich highly active, but poorly electronically conducting, grains, which are locked by a Cu-rich highly conductive network that also possesses some degree of charge-storage capacity. This work focuses on morphological, compositional, and chemical-state distributions with submicrometer lateral resolution. This information, which is crucial because doping distribution controls supercapacitor performance, has been obtained by combining electrochemical and in situ Raman measurements with synchrotron-based X-ray fluorescence and absorption microspectroscopy. Using a microfabricated thin-layer three-electrode microcell, we followed the morphochemical changes at different electrodeposition stages and found that pulse-plating allows the growth of Mn-and Cu-doped ZnO as self-organized structures with a consistent spatially stable composition distribution.

This paper proposes a novel mathematical model for the formation of spatio-temporal patterns in electrodeposition. At variance with classical modelling approaches that are based on systems of reaction–diffusion equations just for chemical species, this model accounts for the coupling between surface morphology and surface composition as a means of understanding the formation of morphological patterns found in electroplating. The innovative version of the model described in this work contains an original, flexible and physically straightforward electrochemical source term, able to account for charge transfer and mass transport: adsorbate-induced effects on kinetic parameters are naturally incorporated in the adopted formalism. The relevant nonlinear dynamics is investigated from both the analytical and numerical points of view. Mathematical modelling work is accompanied by an extensive, critical review of the literature on spatio-temporal pattern formation in alloy electrodeposition: published morphologies have been used as abenchmark for the validation of our model. Moreover, original experimental data are presented—and simulated with our model—on the formation of broken spiral patterns in Ni– P–W–Bi electrodeposition.

A corrosion and electrodeposition study of a Zn electrode in 5.3 M KOH, used as a model system for the anode of a secondary Zn–air battery, was performed by means of electrochemical and spectroelectrochemical techniques. The formation of a zinc oxide passive film and its cathodic removal were monitored by electroreflectance spectroscopy, spectroellipsometry and optical second harmonic generation. A dynamic optical model of the growth pathway, morphology and failure modes of the interfacial Zn oxide films was proposed to rationalise the electrokinetics of the secondary battery anode. Some experiments were performed in the absence and in the presence of polyethylene glycol. In situ spectroscopy confirmed and placed on a molecular basis the well-known formation of more compact and uniform electrodeposits crucial for secondary batteries. Keywords Zn–air batteri

In view of improved durability, the study of electrocatalyst supports for PEMFCs alternative to carbon is raising notable research interest. In this paper we investigated the oxidation of ethanol onWC-supported electrodeposited Pt, in pristine and aged conditions by: (i) electrochemical measurements, (ii) in situ spectroscopy (FTIR and sum-frequency generation spectroscopy (SFG)) carried out during the electrooxidation of ethanol and (iii) ex situ synchrotron-based space-resolved photoelectron spectroscopy (SPEM). The complementarity of FTIR and SFG allows an insightful understanding of the electrochemical interface as a function of applied potential and catalyst ageing. In situ FTIR and SFG revealed adsorbed acetate and ethanol, in addition to linearly and bridge-bonded CO and solution-phase CO2. The Stark tuning of CO indicates that it is less strongly bonded to aged electrodes. Quantitative analysis of potential-dependent FTIR and SFG spectra reveals that the population of adsorption sites for CO, acetate and ethanol changes with ageing and correlates with loss of catalytic activity. Changes in catalyst morphology as well as Pt and WC chemical state have been pinpointed by SPEM: electrodeposited Pt nanoparticles tend to agglomerate and the distribution of oxidised and reduced forms of Pt and W correlates with the attack of the catalyst support.

In this paper we consider an analytical and numerical study of a reaction-diffusion system for describing the formation of transition front waves in some electrodeposition (ECD) experiments. Towards this aim, a model accounting for the coupling between morphology and composition of one chemical species adsorbed at the surface of the growing cathode is addressed. Through a phasespace analysis we prove the existence of travelling waves, moving with specific wave speed. The numerical approximation of the PDE system is performed by the Method of Lines (MOL) based on high order space semi-discretization by means of the Extended Central Difference Formulae (D2ECDF) introduced in [1]. First of all, to show the advantage of the proposed schemes, we solve the well-known Fisher scalar equation, focusing on the accurate approximation of the wave profile and of its speed. Hence, we provide numerical simulations for the electrochemical reaction-diffusion system and we show that the results obtained are qualitatively in good agreement with experiments for the electrodeposition of Au–Cu alloys.

The present paper deals with the pattern formation properties of a specific morpho- electrochemical reaction-diffusion model on a sphere. The physico-chemical background to this study is the morphological control of material electrodeposited onto spherical parti- cles. The particular experimental case of interest refers to the optimization of novel metal- air flow batteries and addresses the electrodeposition of zinc onto inert spherical supports. Morphological control in this step of the high-energy battery operation is crucial to the energetic efficiency of the recharge process and to the durability of the whole energy- storage device. To rationalise this technological challenge within a mathematical modeling perspective, we consider the reaction-diffusion system for metal electrodeposition intro- duced in [Bozzini et al., J. Solid State Electr.17, 467–479 (2013)] and extend its study to spherical domains. Conditions are derived for the occurrence of the Turing instability phe- nomenon and the steady patterns emerging at the onset of Turing instability are investi- gated. The reaction-diffusion system on spherical domains is solved numerically by means of the Lumped Surface Finite Element Method (LSFEM) in space combined with the IMEX Euler method in time. The effect on pattern formation of variations in the domain size is investigated both qualitatively, by means of systematic numerical simulations, and quan- titatively by introducing suitable indicators that allow to assign each pattern to a given morphological class. An experimental validation of the obtained results is finally presented for the case of zinc electrodeposition from alkaline zincate solutions onto copper spheres.

Out of the staters collection of the National Archaeological Museum of Taranto, during the full examination of about one hundred coins minted by the Greek colony of Taras between the V century BC and the III century BC, our attention has been devoted to a lead coin, which has been regarded for many years as a genuine silver coin. This artifact, entry number 13 in the inventory list for the Parabita hoard, has been studied with the combined use of surface and micro-analytical techniques (SEM, EDX, PIXE, XRD). The joint use of different analytical techniques allowed us to obtain information about the morphology, the structure and the chemical composition of the analysed coin, that revealed a lead core coated with a bi-layer of copper and silver.

We focus on the morphochemical reaction–diffusion model introduced in Bozzini et al. (2013) and carry out a nonlinear bifurcation analysis with the aim to characterize the shape and the amplitude of the patterns arising as the result of Turing instability of the physically relevant equilibrium. We perform a weakly nonlinear multiple scales analysis, and derive the normal form equations governing the amplitude of the patterns. These amplitude equations allow us to construct relevant solutions of the model equations and reveal the presence of multiple branches of stable solutions arising as the result of subcritical bifurcations. Hysteretic type phenomena are highlighted also through numerical simulations. We show the occurrence of spatial pattern propagation and derive the Ginzburg–Landau equation describing the envelope of the traveling wavefront.

In this paper we focus on the following map identification problem (MIP): given a morphochemical reaction–diffusion (RD) PDE system modeling an electrodepostion process, we look for a time t*, belonging to the transient dynamics and a set of parameters p, such that the PDE solution, for the morphology h(x, y, t^*; p) and for the chemistry theta(x, y, t^*; p) approximates a given experimental map M*. Towards this aim, we introduce a numerical algorithm using singular value decomposition (SVD) and Frobenius norm to give a measure of error distance between experimental maps for h and θ and simulated solutions of the RD-PDE system on a fixed time integration interval. The technique proposed allows quantitative use of microspectroscopy images, such as XRF maps. Specifically, in this work we have modelled the morphology and manganese distributions of nanostructured components of innovative batteries and we have followed their changes resulting from ageing under operating conditions. The availability of quantitative information on space-time evolution of active materials in terms of model parameters will allow dramatic improvements in knowledge-based optimization of battery fabrication and operation.