In situ electrochemical cells were assembled with an amorphous germanium (a-Ge) film as working electrode and sodium foil as reference and counter electrode. The stresses generated in a-Ge electrodes due to electrochemical reaction with sodium were measured in real-time during the galvanostatic cycling. A specially designed patterned a-Ge electrode was cycled against sodium and the corresponding volume changes were measured using an AFM; it was observed that sodiation/desodiation of a-Ge results in more than 300% volume change, consistent with literature. The potential and stress response showed that the a-Ge film undergoes irreversible changes during the first sodiation process, but the subsequent desodiation/sodiation cycles are reversible. The stress response of the film reached steady-state after the initial sodiation and is qualitatively similar to the response of Ge during lithiation, i.e., initial linear elastic response followed by extensive plastic deformation of the film to accommodate large volume changes. However, despite being bigger ion, sodiation of Ge generated lower stress levels compared to lithiation. Consequently, the mechanical dissipation losses associated with plastic deformation are lower during sodiation process than it is for lithiation.
The overpotential, dissociation rate, electrode potential distributions and current density are suggested in this study to analyze the Nickel Vanadium Redox Flow Battery (NVRFB). Due to its large capacity and ecofriendly properties, NVRFB may be a viable option in the present state of energy constraint and environmental pollution. Due to their low cost and high energy density, nickel-based flow batteries have gained popularity. This study demonstrates that the Ni2+/Ni+ and V5+/V4+ ions have a higher rate of dissociation at the membrane and a lower rate at the inlet, where the electrolyte flow …
Operando spectro-ptychography reveals dynamical charge-storage and degradation pathways in redox-active electrodes
Stanford University（斯坦福大学）；Lawrence Berkeley National Laboratory（劳伦斯伯克利国家实验室）；University of California, Los Angeles（加州大学洛杉矶分校）；SLAC National Accelerator Laboratory（SLAC国家加速器实验室）；University of California, Berkeley（加州大学伯克利分校）
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…
Direct Evidence of Metal-Ligand Redox in Li-ion Battery Positive Electrodes
WMG, University of Warwick（华威大学WMG学院）；The Faraday Institution（法拉第研究所）；School of Science and Engineering, University of Dundee（邓迪大学科学与工程学院）；School of Metallurgy and Materials, University of Birmingham（伯明翰大学冶金与材料学院）；University College Dublin（都柏林大学学院）；Max Planck Institute for Solid State Research（马克斯·普朗克固体研究所）
A simulation model and design of Titanium Manganese Redox Flow Battery (TMRFB) is proposed to study the distribution of dissociation rate, overpotential, current density, and electrode potential. TMRFB is one of the most promising new energy storages because of its high capacity and eco-friendly characteristics in the current condition of energy scarcity and environmental pollution. Moreover, Mn-based flow batteries are gaining popularity due to their inexpensive cost and high energy density in lieu of all vanadium redox flow batteries which are expensive. This research shows that the surface …
Three Cu(II/I)-phenanthroline and Cu(II/I)-bipyridine redox mediators are studied on various electrodes and in variety of electrolyte solutions using cyclic voltammetry and impedance spectroscopy on symmetrical dummy cells.
We present results of an approach to incorporate redox-active manganese oxide into the 3-dimensional porous structure of carbon xerogels under self-limiting electroless conditions. By varying the structure of the carbon backbone, we found that deposition of manganese oxide preferably takes place on the external surface area of the carbon xerogels. From our detailed analysis we conclude that 3-dimensional carbon xerogels with particle and pore sizes ranging from 10 to 20 nm and low manganese oxide precursor concentration combined with long deposition times are beneficial for fast operating pseu…
Two recent experimental (Li, J.~\emphj{et al}, \emph{Proc.\ Natl.\ Acad.\ Sci.\ U.~S.~A.} {\bf 2014}, 111, 1282-1287) and theoretical studies (Bâldea, I, \emph{Phys.\ Chem.\ Chem.\ Phys.}\ {\bf 2014}, 16, 25942-25949) have addressed the problem of tuning molecular charge and vibrational properties of single molecules embedded in nanojunctions. These are molecular characteristics escaping so far to an efficient experimental control in broad ranges. Here, we present a general argument demonstrating why, out of various experimental platforms possible, those wherein active molecules are asymmetric…
Realizing reversible reduction-oxidation (Redox) reactions of lattice oxygen in batteries is a promising way to improve the energy and power density. However, conventional oxygen absorption spectroscopy fails to distinguish the critical oxygen chemistry in oxide-based battery electrodes. Therefore, high-efficiency full-range mapping of resonant inelastic X-ray scattering (mRIXS) has been developed as a reliable probe of oxygen redox reactions. Here, based on mRIXS results collected from a series of Li1.17Ni0.21Co0.08Mn0.54O2 electrodes at different electrochemical states and its comparison wit…
To pursuit high electrochemical performance of supercapacitors based on Faradaic charge-transfer with redox reaction or absorption/desorption effect, the intercalation efficiency of electrolyte ions into electrode materials is a crucial prerequisite to surpass the pure surface capacity with extra bulk contribution. Here we report layered barium transition metal fluorides, BaMF4 (M = Mn, Co, Ni) to be a series of new electrode materials applied in standard three-electrode configuration. Benefiting from the efficient immersing of electrolyte ions, these materials own prominent specific capacitan…
We demonstrate the reversible in situ photoreduction of molecular junctions of phosphomolybdate [PMo12O40]3- monolayer self-assembled on flat gold electrodes, connected by the tip of a conductive atomic force microscope. The conductance of the one electron reduced [PMo12O40]4- molecular junction is increased by ca. 10, this open-shell state is stable in the junction in air at room temperature. The analysis of a large current-voltage dataset by unsupervised machine learning and clustering algorithms reveals that the electron transport in the pristine phosphomolybdate junctions leads to symmetri…
Insights on the volume variation of LiCoxMn2-xO4 electrode upon cycling: a correlative operando XRD and XAS study
Sorbonne Université, CNRS, Physicochimie des Electrolytes et Nanosystèmes interfaciaux (PHENIX)（索邦大学，法国国家科学研究中心，电解质与界面纳米系统物理化学）；Sorbonne Université, CNRS, Laboratoire de Chimie de la Matière Condensée de Paris (LCMCP)（索邦大学，法国国家科学研究中心，巴黎凝聚态物质化学实验室）；Réseau sur le Stockage Electrochimique de l’Energie (RS2E), FR CNRS 3459（电化学储能研究网络（RS2E），FR CNRS 3459）
University of California Santa Barbara（加州大学圣塔芭芭拉分校）；University of Southern California（南加州大学）；University of California Los Angeles（加州大学洛杉矶分校）；Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory（斯坦福同步辐射光源，SLAC国家加速器实验室）
Electrodeposited Co and Ni Hexacyanoferrates: Insights into Structure and Morphology
Faculty of Physical Engineering/Computer Sciences, University of Applied Sciences Zwickau（茨维考应用科学大学物理工程/计算机科学学院）；Leibniz Institute for Solid State and Materials Research Dresden（德累斯顿 Leibniz 固体与材料研究所）；Institute of Solid State and Materials Physics, TU Dresden（德累斯顿工业大学固体与材料物理研究所）
A general technique to investigate charge storage characteristics of conducting polymer films has been developed. A redox reaction is conducted on a polymer film on a rotating disk electrode under potentiostatic condition so that the rate of charging of the film equals the rate of removal of the charge by the reaction. In an experiment on polyaniline film deposited on platinum substrate, using Fe2+/Fe3+ in HCl as the redox system, the voltammogram shows five distinct linear segments (bands) with discontinuity in the slope at specific transition potentials. These bands are the same as those ind…
Batteries are pivotal components in overcoming some of today's greatest technological challenges. Yet to date there is no self-consistent atomistic description of a complete battery. We take first steps toward modeling of a battery as a whole microscopically. Our focus lies on phenomena occurring at the electrode-electrolyte interface which are not easily studied with other methods. We use the redox split-charge equilibration (redoxSQE) method that assigns a discrete ionization state to each atom. Along with exchanging partial charges across bonds, atoms can swap integer charges. With redoxSQE…
This report presents some of the key laboratory electrochemical battery testing methods that are used in fuel cell research. Methods such as voltammetry, chronoamperometry, chronopotentiometry, and electrochemical impedance spectroscopy are of major importance. All the electrochemical corrosion tests are performed through a tri-electrode polarization cell setup containing a reference electrode, a counter electrode, and the working electrode (metal sample of interest) in an electrolyte solution. All three electrodes are connected to a potentiostat. Corrosion of metal occurs through an oxidation…
Pseudocapacitors are energy-storage devices characterized by fast and reversible redox reactions that enable them to store large amounts of electrical energy at high rates. We simulate the response of pseudocapacitive electrodes under realistic conditions to identify the microscopic factors that determine their performance, focusing on ruthenia (RuO2) as a prototypical electrode material. Electronic-structure methods are used together with a self-consistent continuum solvation (SCCS) model to build a complete dataset of free energies as the surface of the charged electrode is gradually covered…
The surface area of electrodeposited thin films of Ni, Co, and NiCo was evaluated using electrochemical double-layer capacitance, electrochemical area measurements using the [Ru(NH$_3$)$_6$]$^{3+}$/[Ru(NH$_3$)$_6$]$^{2+}$ redox couple, and topographic atomic force microscopy (AFM) imaging. These three methods were compared to each other for each composition separately and for the entire set of samples regardless of composition. Double-layer capacitance measurements were found to be positively correlated to the roughness factors determined by AFM topography. Electrochemical area measurements we…
In Li-ion batteries the electrochemical potential drives the redox reactions occurring at the interface between electrolyte and storage material, typically active particles for porous electrodes, allowing Li ions intercalation/extraction from electrodes. The limiting factor of the process is not solely related to the electrochemical affinity, but also to structural features as the morphology of the electrodes. In this note, the relevance of the electrodes architecture is investigated numerically, in terms of the electro-chemo-mechanical response of a battery cell with homogeneous electrodes an…
The reversibility and cyclability of anionic redox in battery electrodes hold the key to its practical employments. Here, through mapping of resonant inelastic X-ray scattering (mRIXS), we have independently quantified the evolving redox states of both cations and anions in Na2/3Mg1/3Mn2/3O2. The bulk-Mn redox emerges from initial discharge and is quantified by inverse-partial fluorescence yield (iPFY) from Mn-L mRIXS. Bulk and surface Mn activities likely lead to the voltage fade. O-K super-partial fluorescence yield (sPFY) analysis of mRIXS shows 79% lattice oxygen-redox reversibility during…
Real-time stress evolution in a graphite-based lithium-ion battery negative-electrode during electrolyte wetting and electrochemical cycling is measured through wafer-curvature method. Upon electrolyte addition, the composite electrode rapidly develops compressive stress of the order of 1-2 MPa due to binder swelling; upon continued exposure, the stress continues to evolve towards an apparent plateau. During electrochemical intercalation at a slow rate, the compressive stress increases with the electrode's state-of-charge, reaching a maximum value of 10 - 12 MPa. There appears to be an approxi…
Enhanced EV market penetration requires durability of the battery with high energy throughput. For long-term cycle stability of silicon-graphite anode capable of high energy density, the reversible redox reactions are crucial. Here, we unveil intriguing electrochemical phenomena such as crosstalk of lithium ion ($Li^{+}$) between silicon and graphite, $Li^{+}$ accumulation in silicon, and capacity depression of graphite under high pressure, which engender the irreversible redox reactions. Active material properties, i.e. the size of silicon and the hardness of graphite, silicon-graphite anode,…
Several SrTiO3 (STO) thin films without electrodes processed by pulsed laser deposition, of thicknesses down to 40 nm, were studied using infrared transmission and reflection spectroscopy. The complex dielectric responses of polar phonon modes, particularly ferroelectric soft mode, in the films were determined quantitatively. The compressed epitaxial STO films on (100) La0.18Sr0.82Al0.59-Ta0.41O3 substrates (strain 0.9%) show strongly stiffened phonon responses, whereas the soft mode in polycrystalline film on (0001) sapphire substrate shows a strong broadening due to grain boundaries and/or o…
When redox active molecules are covalently tethered to the surface of the n-doped silicon, light induces their oxidation by the semiconductor. To visualize this charge separation we have followed the formation and decay of the surface photovoltage by an auxiliary transparent electrode, which serves as a capacitive probe that picks up the transient surface photovoltage. This method has been used in electronics and biophysics but is novel for the surface redox chemistry. The probe provides both the direction of the charge transfer and the resolution of the dynamics. Its application is independen…
Using Density functional theory (DFT) in conjunction with a solvation model we have investigated the phenomenon of eletrode-electrolyte interaction at the electrode surface and its consequences on the electrochemical properties like the charge storage and total capacitance of doped and substituted oxygen functionalised Ti$_{3}$C$_{2}$ supercapcitor electrode. We have studied nitrogen doped, nitrogen substituted and molybdenum substituted Mxenes in acidic electrolyte H$_{2}$SO$_{4}$ solution. By considering nitrogen doping at different sites, we found that the greatest capacitance is obtained f…
We performed self-consistent modelling of electrotransport and electromechanical response of solid electrolyte thin films allowing for steric effects of mobile charged defects (ions, protons or vacancies), electron degeneration and Vegard stresses. We establish correlations between the features of the space-charge dynamics, current-voltage and bending-voltage curves in the wide frequency range of applied electric voltage. The pronounced ferroelectric-like hysteresis of bending-voltage loops and current maxima on double hysteresis current-voltage loops appear for the electron-open electrodes. T…
The use of graphene-based electrodes is burgeoning in a wide range of applications, including solar cells, light emitting diodes, touch screens, field-effect transistors, photodetectors, sensors and energy storage systems. The success of such electrodes strongly depends on the implementation of effective production and processing methods for graphene. In this work, we take advantage of two different graphene production methods to design an advanced, conductive oxide- and platinum-free, graphene-based counter electrode for dye-sensitized solar cells (DSSCs). In particular, we exploit the combin…
Composite cathode coatings made of a high energy density layered oxide (Li1.2Ni0.15Mn0.55Co0.1O2, theoretical capacity ~377 mAh/g), polyvinylidene fluoride (PVdF) binder, and electron-conduction additives, were bonded to an elastic substrate. An electrochemical cell, built by pairing the cathode with a capacity-matched graphite anode, was electrochemically cycled and the real-time average stress evolution in the cathode coating was measured using a substrate-curvature technique. Features in the stress evolution profile showed correlations with phase changes in the oxide, thus yielding data com…
Developing efficient anode materials with low electrode voltage, high specific capacity and superior rate capability is urgently required on the road to commercially viable sodium-ion batteries (SIBs). Aiming at finding a new SIB anode material, we investigate the electrochemical properties of NaxTiO2 compounds with unprecedented penta-oxygen-coordinated trigonal bipyramid (TB) structures by using the first-principles calculations. Identifying the four different TB phases, we perform the optimization of their crystal structures and calculate their energetics such as sodium binding energy, form…
We investigated the reversible resistive switching of poly(3,4-ethylenedioxythiophene):polystyrenesulfonate (PEDOT:PSS) thin films sandwiched between Al electrodes. The J-V sweep curve showed a hysteretic behavior which depends on the polarity of the applied voltage bias. From the analysis of I-V curves, it was revealed that the charge transport through the junction was governed by the bulk space-charge-limited conduction (SCLC) model. Using transmission electron microscopy (TEM) analysis, it was confirmed that the initial high resistance state of PEDOT:PSS films is related with the segregatio…
Manganese oxides have received much attention over the years among the wide range of electrocatalysts for the oxygen evolution reaction (OER) due to their low toxicity, high abundance and rich redox chemistry. While many previous studies focused on the activity of these materials, a better understanding of the material transformations relating to activation or degradation is highly desirable, both from a scientific perspective and for applications. We electrodeposited Na-containing MnOx without long-range order from an alkaline solution to investigate these aspects by cyclic voltammetry, scann…
In this manuscript the theory and phenomena associated with the Little Effect are introduced as the spin induced orbital dynamics of confined fermions under strong magnetic and thermal environments. This Little Effect is considered in details for the electron transfer reactions associated with redox processes of Cu-Ag alloy within deionized water and for the orbital dynamics during the iron catalyzed covalent bond rearrangements associated with amorphous carbon conversion to diamond. Furthermore, prolong extreme conditions of 74,000 amps, 403 V, strong Lorentz compression, and thermal stresses…
Conjugated polymers can be reversibly doped by electrochemical means. This doping introduces new sub-bandgap optical absorption bands in the polymer while decreasing the bandgap absorption. To study this behavior, we have prepared an electrochemical cell allowing measurements of the optical properties of the polymer. The cell consists of a thin polymer film deposited on gold-coated Mylar behind which is another polymer that serves as a counterelectrode. An infrared transparent window protects the upper polymer from ambient air. By adding a gel electrolyte and making electrical connections to t…
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…
