The morphologies of crystalline lithium peroxide (Li2O2) discharge products in Li-O2 batteries have been shown to exhibit a dependency on subtle variations within the battery cell-operating environment including exposure to ambient air, moisture, or additives. As a result, imaging battery discharge products in real time under carefully controlled environmental conditions is a challenging obstacle for complete mechanistic understanding of Li2O2 growth and deposition during discharge in metal-air batteries. Here, we report the design of a completely enclosed cell for high-resolution in situ AFM imaging of Li-O2 battery discharge products. The air-and moisture-free electrochemical cell environment enabled the observation of different product morphologies during AFM imaging when LiTFSI in oxygen-saturated tetraethylene glycol dimethyl ether (tetraglyme) solvent was employed. This in situ AFM cell development brings complimentary information to various proposed mechanisms for lithium oxygen reaction.
Molecular adhesion promoters are a central component of modern coating systems for the corrosion protection of structural materials. They are interface active and form ultrathin corrosion inhibiting and adhesion-promoting layers. Here we utilize thiol-based self-assembled monolayers (SAMs) as model system for demonstrating a comprehensive combinatorial approach to understand molecular level corrosion protection mechanisms under anodic polarization. Specifically, we compare hydrophilic 11-Mercapto-1-undecanol and hydrophobic 1-Undecanethiol SAMs and their gold-dissolution inhibiting properties.…
Strontium cobaltite (SrCoOx) is known as a material showing fast topotactic electrochemical Redox reaction so-called oxygen sponge. Although atomic scale phenomenon of the oxidation of SrCoO2.5 into SrCoO3 is known, the macroscopic phenomenon has not been clarified yet thus far. Here, we visualize the electrochemical oxidation of SrCoOx macroscopically. SrCoOx epitaxial films with various oxidation states were prepared by the electrochemical oxidation of SrCoO2.5 film into SrCoO3-d film. Steep decrease of both resistivity and the absolute value of thermopower of electrochemically oxidized SrCo…
A dedicated in situ heating setup in a scanning electron microscope (SEM) followed by an ex situ atomic force microscopy (AFM) and electron backscatter diffraction (EBSD) is used to characterize the nucleation and early growth stages of Fe-Al intermetallics (IMs) at 596 °C. A location tracking is used to interpret further characterization. Ex situ AFM observations reveal a slight shrinkage and out of plane protrusion of the IM at the onset of IM nucleation followed by directional growth. The formed interfacial IM compounds were identified by ex situ EBSD. It is now clearly demonstrated that th…
Understanding elemental corrosion currents and visualizing corroding topographies provide a detailed insight into corrosion mechanisms at the nano-scale. Here, we develop a strategy to understand the elemental composition, corrosion resistivity and local stability of passive materials. Specifically, we utilize a pulse voltammetry approach in a novel electrochemical AFM cell and complement this data by real-time dissolution currents based on spectro-electrochemical online analysis in an ICP-MS flow cell. We study the oxide properties and their protective behaviour, when formed under different a…
Atomic force microscopy-based nanoindentation (AFM-NI) enables characterization of the basic mechanical properties of wood pulp fibers in conditions representative of the state inside a paper sheet. Determination of the mechanical properties under different loads is critical for the success of increasingly advanced computational models to understand, predict and improve the behavior of paper and paperboard. Here, AFM-NI was used to indent fibers transverse to and along the longitudinal axis of the fiber. Indentation moduli and hardness were obtained for relative humidity from 25 % to 75 %. The…
As a typical immiscible binary system, copper (Cu) and lithium (Li) show no alloying and chemical intermixing under normal circumstances. A notable example that takes advantages of the immiscibility between Cu and Li is the widespread utilization of Cu foils as the anodic current collector in Li-ion batteries. Here we show that the nanoscale size effect can play a subtle yet critical role in mediating the chemical activity of Cu and therefore its miscibility with Li, such that the electrochemical alloying and solid-state amorphization will occur in such an immiscible system when decreasing Cu …
Herein, we report a improved method for the physical grafting of 1-nitropyrene (Pyr-NO2) onto highly graphitized carbon onion. This is achieved through a lowering of the onset potential of the pyrene polymerization via in situ reduction of the NO2 group. The additional redox activity pertaining to the reduced NO2 enables exceeding the faradaic capacity which is associated with the p-doping of the grafted pyrene backbone, as observed for pyrene, 1-aminopyrene, and unreduced Pyr- NO2. Theoretical calculations demonstrate the charge transfer and binding enthalpy capabilities of Pyr-NO2, which are…
Macroscopic ensembles of nanocarbons, such as fibres of carbon nanotubes (CNT), are characterised by a complex hierarchical structure combining coherent crystalline regions with a large porosity arising from imperfect packing of the large rigid building blocks. Such structure is at the centre of a wide range of charge storage and transfer processes when CNT fibres are used as electrodes and/or current collectors. This work introduces a method based on wide and small-angle X-ray scattering (WAXS/SAXS) to obtain structural descriptors of CNT fibres and which enables in situ characterisation duri…
Electrochemical water splitting is an environmentally friendly technology to store renewable energy in the form of chemical fuels. Among the earth-abundant first-row transition metal-based catalysts, mixed Ni-Fe oxides have shown promising performance for effective and low-cost catalysis of the oxygen evolution reaction (OER) in alkaline media, but the synergistic roles of Fe and Ni cations in the OER mechanism remain unclear. In this work, we report how addition of Ni changes the reactivity of a model iron oxide catalyst, based on Ni deposited on and incorporated in a magnetite Fe3O4 (001) si…
To visualize the topography of thin oxide films during growth, thereby enabling to study its growth behavior quasi real-time, we have designed and integrated an atomic force microscope (AFM) in a pulsed laser deposition (PLD) vacuum setup. The AFM scanner and PLD target are integrated in a single support frame, combined with a fast sample transfer method, such that in-situ microscopy can be utilized after subsequent deposition pulses. The in-situ microscope can be operated from room temperature (RT) up to 700$^\circ$C and at (process) pressures ranging from the vacuum base pressure of 10$^{-6}…
The assembly of aligned carbon nanotubes (CNT) into fibers (CNTF) is a convenient approach to exploit and apply the unique physico-chemical properties of CNTs in many fields. CNT functionalization has been extensively used for their implementation into composites and devices. However, CNTF functionalization is still in its infancy, due to the challenges associated with preservation of CNTF morphology. Here, we report a thorough study of the gas-phase functionalization of CNTF fabrics using ozone that was generated in situ from a UV-source. By contrast with liquid-based oxidation methods, this …
Clean hydrogen production through efficient and cost-effective electrochemical water splitting is highly promising to meeting future global energy demands. The design of Earth-abundant materials with both high activity for hydrogen evolution reaction (HER) and electrochemical stability in both acidic and alkaline environments summarize the outcomes needed for practical applications. Here, we report a non-noble 3d metal Cl-chemical doping of liquid phase exfoliated single/few-layer flakes of MoSe2 for creating MoSe2 nanoflakes/3d metal oxide-hydr(oxy)oxide hybrid HER-catalysts. We propose that …
Two-dimensional transition metal-dichalcogenides are emerging as efficient and cost-effective electrocatalysts for hydrogen evolution reaction (HER). However, only the edge sites of their trigonal prismatic phase show HER-electrocatalytic properties, while the basal plane, which is absent of defective/unsaturated sites, is inactive. Here, we tackle the key challenge that is increasing the number of electrocatalytic sites by designing and engineering heterostructures composed of single-/few-layer MoSe2 flakes and carbon nanomaterials (graphene or single-wall carbon nanotubes (SWNTs)) produced b…
Non-equilibrium electrochemistry raises new challenges for atomistic simulation: we need to perform molecular dynamics for the nuclear degrees of freedom with an explicit description of the electrons, which in turn must be free to enter and leave the computational cell. Here we present a limiting form for electron open boundaries that applies when the magnitude of the electric current is determined by the drift and diffusion of ions in solution, and which is sufficiently computationally efficient to be used with molecular dynamics. We demonstrate its capabilities by way of tight binding simula…
Atomic force microscopy (AFM) is a well-known tool for studying surface roughness and to collect depth information about features on the top atomic layer of samples. By combining secondary ion mass spectroscopy (SIMS) with focused ion beam (FIB) milling in a scanning electron microscope (SEM), chemical information of sputtered structures can be visualized and located with high lateral and depth resolution. In this paper, a high vacuum (HV) compatible AFM has been installed in a TESCAN FIB-SEM instrument that was equipped with a time-of-flight secondary ion mass spectroscopy (ToF-SIMS) detector…
The CO_{2} electro-reduction reaction (CORR) is a promising avenue to convert greenhouse gases into high-value fuels and chemicals, in addition to being an attractive method for storing intermittent renewable energy. Although polycrystalline Cu surfaces have long known to be unique in their capabilities of catalyzing the conversion of CO_{2} to higher-order C1 and C2 fuels, such as hydrocarbons (CH_{4}, C_{2}H_{4} etc.) and alcohols (CH_{3}OH, C_{2}H_{5}OH), product selectivity remains a challenge. In this study, we select three metal catalysts (Pt, Au, Cu) and apply in situ surface enhanced i…
A new experimental approach for in-situ Raman spectroscopy of the electrode | solid electrolyte interfaces in controlled atmospheres, based on the use of optically transparent single-crystal membranes of stabilized cubic zirconia, has been proposed and validated. This technique makes it possible to directly access the electrochemical reaction zone in SOFCs by passing the laser beam through single-crystal electrolyte onto the interface, in combination with simultaneous electrochemical measurements. The case study centered on the analysis of NiO reduction in standard cermet anodes under open-cir…
Herein, in-situ reduction of bismuth and graphene oxide was performed by a solvothermal method under a nitrogen atmosphere, and the resulting Bi on RGO nanocomposites were used as an anode material for Mg-ion batteries. The nanocomposite of 60% Bi:40% RGO is a beneficial anode material, delivering a discharge capacity as high as 413 and 372 mAh per g at the specific current of 39 mA per g in the 1st and 50th cycles, respectively. In addition, it shows high-rate capability with the discharge capacities of 381, 372, 354, 295, and 238 mAh per g at the specific currents of 53, 100, 200, 500, and 7…
Electrochemistry exploits local current heterogeneities at various scales ranging from the micrometer to the nanometer. The last decade has witnessed unprecedented progress in the development of a wide range of electroanalytical techniques allowing to reveal and quantify such heterogeneity through multiscale and multifonctionnal operando probing of electrochemical processes. However most of these advanced electrochemical imaging techniques, employing scanning probes, suffer from either low imaging throughput or limited imaging size. In parallel, optical microscopies, which can image a wide fie…
Spinel lithium manganese oxide (LixMn2O4) is used as an active material in battery cathodes. It is a relatively inexpensive and environmentally friendly material, but suffers from capacity fade during use. The capacity losses are generally attributed to the formation of the tetragonal phase (x > 1) due to overpotentials at the surfaces of the micron-sized particles that are used in commercial electrodes. In this study, we investigate the mechanisms of tetragonal phase formation by performing electrochemical lithiation (discharging) in-situ in the transmission electron microscope (TEM) utilizin…
To meet growing energy demands, degradation mechanisms of energy storage devices must be better understood. As a non-destructive tool, X-ray Computed Tomography (CT) has been increasingly used by the battery community to perform $\textit{in-situ}$ experiments that can investigate dynamic phenomena. However, few have used X-ray CT to study representative battery systems over long cycle lifetimes (>100 cycles). Here, we report the $\textit{in-situ}$ CT study of Zn-Ag batteries and demonstrate the effects of current collector parasitic gassing over long-term storage and cycling. We design perform…
Methanol occupies a central role in chemical synthesis and is considered an ideal candidate for cleaner fuel storage and transportation. It can be catalyzed from water and volatile organic compounds such as carbon dioxide, thereby offering an attractive solution for reducing carbon emissions. However molecular-level experimental observations of the catalytic process are scarce, and most existing catalysts tend to rely on empirically optimized, expensive and complex nano- composite materials. This lack of molecular-level insights has precluded the development of simpler, more cost-effective alt…
In search of the potential cathode materials for sodium-ion batteries and to understand the diffusion kinetics, we report the detailed analysis of electrochemical investigation of honeycomb structured Na$_{2}$Ni$_{2}$TeO$_{6}$ material using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), galvanostatic charge-discharge (GCD) and galvanostatic intermittent titration technique (GITT). We found the discharge capacities of 82 and 77 mAhg$^{-1}$ at 0.05~C and 0.1~C current rates, respectively, and the mid-working potential of $\approx$3.9~V at 1~C and high capacity retention …
Development of materials for electrochemical energy conversion requires a deep understanding of the factors governing chemical and physical rates at submicron length scales. Many workers have sought to develop chemically sensitive in situ or operando imaging techniques targeting these length scales. However, current methods focus on steady-state or stepwise response. To probe electrode processes both spatially and temporally, we have developed a frequency-resolved implementation of X-ray absorption imaging (FR-XAS) that can measure local electrochemical response in operando during a global sin…
