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Rapid mapping of electrochemical processes in energy-conversion devices
Electrochemical impedance spectroscopy (EIS) is ubiquitously applied to identify physicochemical processes governing the performance of energy-conversion devices. However, deconvolution and interpretation of impedance phenomena are limited by measurement throughput and a dearth of scalable analysis methods. Here, we demonstrate an approach to quickly collect and coherently analyze large volumes of electrochemical data. In this study, we accelerate impedance characterization by combining rapid measurements in time and frequency domains, which are interpretably transformed using the distribution of relaxation times (DRT) and a new distribution of phasances (DOP) model. This method provides excellent agreement with EIS and decreases measurement time by an order of magnitude. High-throughput spectra are then distilled into detailed electrochemical maps. This approach is applied to a Li-ion battery and a protonic ceramic electrochemical cell as practical case studies, demonstrating how mapping can richly characterize physicochemical relationships that are difficult to decipher with conventional measurement and analysis methods.
ARJUNA: An Electrochemical Interface Mapping Probe for Solid-State Batteries
Solid-state batteries (SSBs) are promising candidates for next-generation energy storage, although their performance can be compromised by interfacial heterogeneity within the electrolyte. Furthermore, ensuring the quality of large form-factors electrolyte film is crucial for establishing a robust manufacturing platform for solid-state batteries. Herein, we report on the use of ARJUNA, an electrochemical interface mapping system, to characterize heterogeneities at solid electrolyte interfaces and to serve as a quality control system for SSB manufacturing. In addition to spatial mapping, the proposed system can also probe the interface behavior as a function of pressure and temperature. We present the operating principle, design, instrumentation, and evaluation of the system alongside a typical hybrid solid electrolyte produced using two common manufacturing processes. This report showcases the capability of ARJUNA to probe the heterogeneity and quality of processed solid electrolyte films.
Electrochemical Structure of the Plasma–Liquid Interface
Nonthermal atmospheric pressure plasma in contact with a liquid yields a variety of energetic photons, ions, and electrons, which can be transported into the plasma–liquid interface (PLI). Similar to the electrochemical interface formed between a solid electrode and electrolyte in conventional electrochemical systems, the charge-transfer process across the PLI is able to promote reduction–oxidation (redox) reactions. However, in the case of free plasma jets in contact with liquids, the absence of solid electrodes obscures the spatial locations of the electrochemical half-reactions. Herein, we present a spatial electrochemical measurement technique used to characterize an aqueous solution in contact with an atmospheric pressure plasma jet. The technique is based on measuring the potential difference between two identical Ag/AgCl electrochemical electrodes positioned at different locations within the solution. More specifically, electrochemical maps were made by measuring the potential of one electrochemical electrode positioned at different locations near the PLI with respect to the other electrochemical electrode positioned far away from the PLI in the bulk solution. Regions in the map with negative and positive potential differences between these electrochemical electrodes were used to identify the electrodeless cathode and anode, respectively. Here, visualization of the spatial distribution of molecular colorimetric redox indicators by multispectral imaging revealed that reduction was occurring near the plasma jet centerline while oxidation was occurring further away in solution, which constitutes an independent confirmation of the electrochemical maps.
Nonequilibrium Electrochemical Phase Maps: Beyond Butler–Volmer Kinetics
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Quantitative local state of charge mapping by operando electrochemical fluorescence microscopy in porous electrodes
We introduce operando quantitative electrochemical fluorescence state of charge mapping (QEFSM), a non-invasive technique to study operating electrochemical systems along with a new design of optically transparent microfluidic redox flow cells compatible with the most demanding optical requirements. QEFSM allows quantitative mappings of the concentration of a particular oxidation state of a redox-active species within a porous electrode during its operation. In this study, we used confocal microscopy to map the fluorescence signal of the reduced form of 2,7-anthraquinone disulfonate (AQDS) in a set of multistep-chronoamperometry experiments. Calibrating these images and incorporating an analytical model of quinhydrone heterodimer formation with no free parameters, and accounting for the emission of each species involved, we determined the local molecular concentration and the state of charge (SOC) fields within a commercial porous electrode during operation. With this method, electrochemical conversion and species advection, reaction and diffusion can be monitored at heretofore unprecedented transverse and axial resolution (1 μm and 25 μm, respectively) at frame rates of 0.5 Hz, opening new routes to understanding local electrochemical processes in porous electrodes. Here, we observed pore-scale SOC inhomogeneities appearing when the fraction of electroactive species converted in a single pass through the electrode becomes large.
Visualizing Charge Transport and Nanoscale Electrochemistry by Hyperspectral Kelvin Probe Force Microscopy
Charge-transport and electrochemical processes are heavily influenced by the local microstructure. Kelvin probe force microscopy (KPFM) is a widely used technique to map electrochemical potentials at the nanometer scale; however, it offers little information on local charge dynamics. In this study, we implement a hyperspectral KPFM approach for spatially mapping bias-dependent charge dynamics in timescales ranging from the sub-millisecond to the second regime. As a proof of principle, we investigate the role mobile surface charges play in a three-unit-cell LaAlO 3 /SrTiO 3 oxide heterostructure. We explore machine learning approaches to assist with visualization, pattern recognition, and interpretation of the information-rich data sets. Linear unmixing methods reveal hidden bias-dependent interfacial processes, most likely water splitting, which are essentially unnoticed by functional fitting of the dynamic response alone. Hyperspectral KPFM will be beneficial for investigating nanoscale charge transport and local reactivity in systems involving a possible combination of electronic, ionic, and electrochemical phenomena.
Ion Depletion Microenvironments Mapped at Active Electrochemical Interfaces with Operando Freezing Cryo-Electron Microscopy
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Electrochemical Reactions – Fundamentals Mapped from the Atomic to the Macroscopic Scale
Electrochemistry more important than ever Electrocatalysis great prospects Enhanced selective vs thermocatalysis More benign conditions New chemical processes needed for, e.g., sustainability Demand for tailor-made catalysts Atomic scale modeling useful guide Surge to develop methods that can capture realistic systems
Simultaneous mapping of nanoscale dielectric, electrochemical, and ferroelectric surface properties of van der Waals layered ferroelectric via advanced SPM
Ferroelectric surfaces involve a complex interplay between polarization and dielectric properties, internal and external surface charge screening, and ionic and electrochemical effects. There is currently no good way to simultaneously capture all the required information at appropriate length scales. To this end, we present an advanced scanning probe microscopy approach for simultaneously mapping surface potential, dielectric, and piezoelectric properties on the nanoscale. For quantitatively mapping electromechancial properties, we utilize interferometric displacement sensing piezoresponse force microscopy, which measures the effective piezoelectric coefficient free of background artifacts such as the cantilever body electrostatics. The dielectric and surface electrochemical properties are captured during G-mode electrostatic force microscopy/Kelvin probe force microscopy operated in the lift mode. We show the capabilities of this approach on the chemically phase separated composite sample consisting of a van der Waals layered ferroelectric CuInP 2 S 6 phase and a non-polar In 4/3 P 2 S 6 phase. Finally, we demonstrate domain structure evolution during thermally stimulated phase transition.
Mapping phase instability to electrochemical degradation in SrTi 1− x Fe x O 3− δ under solid oxide cell fuel-electrode conditions
Herein, we clearly link structural phase stability and electrochemical performance in SrTi 1− x Fe x O 3− δ fuel electrodes as a function of p O 2 (1.3 × 10 −18 , 1.3 × 10 −20 , 1.3 × 10 −21 atm respectively).
Instrument for spatially resolved, temperature-dependent electrochemical impedance spectroscopy of thin films under locally controlled atmosphere
We demonstrate an instrument for spatially resolved measurements (mapping) of electrochemical impedance under various temperatures and gas environments. Automated measurements are controlled by a custom LabVIEW program, which manages probe motion, sample motion, temperature ramps, and potentiostat functions. Sample and probe positioning is provided by stepper motors. Dry or hydrated atmospheres (air or nitrogen) are available. The configurable heater reaches temperatures up to 500 °C, although the temperature at the sample surface is moderated by the gas flow rate. The local gas environment is controlled by directing flow toward the sample via a glass enclosure that surrounds the gold wire probe. Software and hardware selection and design are discussed. Reproducibility and accuracy are quantified on a Ba(Zr,Y)O 3-δ proton-conducting electrolyte thin film synthesized by pulsed laser deposition. The mapping feature of the instrument is demonstrated on a compositionally graded array of electrocatalytically active Ba(Co,Fe,Zr,Y)O 3-δ thin film microelectrodes. The resulting data indicate that this method proficiently maps property trends in these materials, thus demonstrating the reliability and usefulness of this method for investigating electrochemically active thin films.
Lewis Acids and Electron-Withdrawing Ligands Accelerate CO Coordination to Dinuclear Cu I Compounds
A series of dinuclear molecular copper complexes were prepared and used to model the binding and Lewis acid stabilization of CO in heterogeneous copper CO 2 reduction electrocatalysts. Experimental studies (including measurement of rate and equilibrium constants) and electronic structure calculations suggest that the key kinetic barrier for CO binding may be a σ-interaction between CuI and the incoming CO ligand. The rate of CO coordination can be increased upon the addition of Lewis acids or electron-withdrawing substituents on the ligand backbone. Conversely, K eq for CO coordination can be increased by adding electron density to the metal centers of the compound, consistent with stronger π-backbonding. Lastly, the electrochemically measured kinetic results were mapped onto an electrochemical zone diagram to illustrate how these system changes enabled access to each zone.
Parametric analysis of anodic degradation mechanisms for fast charging lithium batteries with graphite anode
In this work, we report the impact of the temperature-driven synergistically-coupled anodic degradation mechanisms on the electrochemical performance of lithium batteries with graphite anode over multiple cycles. Temperature dependence of electrochemical reactions and damage mechanisms, such as solid electrolyte interface (SEI) growth, lithium plating/stripping, dead lithium storage/dissolution, and film cracking are incorporated into the degradation model. Results of a parametric analysis are presented, evaluating the effects of charging rates (1–6 C), operating temperatures (-15 – 45°C) and electrode design parameters, on the relative performance fade in the lithium-ion battery. Thermo-electrochemical process maps are developed to provide insights into the relationship between electrode performance and failure mechanisms. The simulation results predict a severe capacity loss due to lithium plating at low temperatures, which is further aggravated at high charging rates. A common strategy for mitigating lithium plating, through charging at high temperatures, also results in rapid capacity loss due to accelerated SEI formation. Simulation results are used to identify the combination of operating conditions and electrode design parameters that improve the electrochemical performance of the battery. These results demonstrate an opportunity to design safe and high-performance lithium-ion batteries, guided by anodic degradation models.
Twisto-Electrochemical Activity Volcanoes in Trilayer Graphene
In this work, we develop a twist-dependent electrochemical activity map, combining a low-energy continuum electronic structure model with modified Marcus–Hush–Chidsey kinetics in trilayer graphene. We identify a counterintuitive rate enhancement region spanning the magic angle curve and incommensurate twists in the system geometry. We find a broad activity peak with a ruthenium hexamine redox couple in regions corresponding to both magic angles and incommensurate angles, a result qualitatively distinct from the twisted bilayer case. Flat bands and incommensurability offer new avenues for reaction rate enhancements in electrochemical transformations.
Systematic mapping on the evaluation of electrochemical CO2 conversion to fuels/chemicals/value-added products and way forward for breakthroughs in electrocatalysis
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pH Regulates Ion Dynamics in Carboxylated Mixed Conductors
Coupled ionic and electronic transport underpins processes as diverse as electrochemical energy conversion, biological signaling, and soft adaptive electronics. Yet, how chemical environments such as pH modulate this coupling at the molecular scale remains poorly understood. Here, we show that the protonation state of carboxylated polythiophenes provides precise chemical control over ion dynamics, doping efficiency, solvent uptake, and mechanical response. Using a suite of multimodal operando techniques, supported by simulations, we reveal that pH dictates the balance of cation/anion uptake during electrochemical doping. Mapping across pH uncovers a quasi-nonswelling regime (≈pH 3–3.5) where charge compensation proceeds with minimal volumetric change yet pronounced stiffening. These findings establish molecular acidity as a general strategy to program ionic preference and mechanical stability, offering design principles for pH-responsive mixed conductors and soft electronic materials that couple ionic, electronic, and mechanical functionality.
Gradient Architecture Design in Scalable Porous Battery Electrodes
Because it has been demonstrated to be effective toward faster ion diffusion inside the pore space, low-tortuosity porous architecture has become the focus in thick electrode designs, and other possibilities are rarely investigated. Here, to advance current understanding in the structure-affected electrochemistry and to broaden horizons for thick electrode designs, we present a gradient electrode design, where porous channels are vertically aligned with smaller openings on one end and larger openings on the other. With its 3D morphology carefully visualized by Raman mapping, the electrochemical properties between opposite orientations of the gradient electrodes are compared, and faster energy storage kinetics is found in larger openings and more concentrated active material near the separator. As further verified by simulation, this study on gradient electrode design deepens the knowledge of structure-related electrochemistry and brings perspectives in high-energy battery electrode designs.