Can Electrochemical Impedance Spectroscopy be Replaced by Direct Current Techniques in Battery Diagnosis?

Electrochemical impedance spectroscopy (EIS), a conventional and alternating-current-(AC)-based technique for impedance measurement, is commonly used in battery diagnosis. However, it requires expensive equipment and demanding operating conditions and is complex and model-dependent in data analysis. Recently, novel direct current (DC) analytics have emerged as an alternative to EIS. They are simple yet powerful, being capable of revealing impedance information that traditionally could only be obtained through EIS and determining Li-ion diffusion coefficient. Besides, a complete EIS spectrum can be predicted based on constant current charging curves in the support of machine learning methods. This work highlights the similarities and discrepancies between DC techniques and EIS in the electrochemical analysis of Liion batteries. Looking ahead, DC techniques may be a promising substitute for EIS in future battery diagnosis, requiring simplified equipment while offering a deep understanding of battery impedance and its underlying electrochemical processes.

Fast formation of anode-free Li-metal batteries by pulsed current.

Anode-free Li-metal batteries offer high energy density but are prone to dendrite formation during charging which can cause catastrophic failures. Ensuring dendrite-free smooth Li deposits during charging is therefore necessary. Suppressing dendrite growth can be achieved by pulsed current charging, especially during the formation cycle that largely determines the corrosion trajectory of a cell. As opposed to the constant-current technique, pulsed current techniques apply intermittently stopped current flows. This work investigates the electroplating of metallic Li onto a Cu foil current collector under constant-current and pulsed current formation protocols. In addition to smoother, less resistive electroplated metallic Li deposits and increased Coulombic efficiency, we show that by employing an optimized pulsed current formation protocol, the formation process is accelerated by a factor of 2 and the Coulombic efficiency was increased by 10% compared to a C/20 protocol. Finally, by employing a simple regression coupled to experimentation, we propose the pseudo-IR-drop to be used for live adjustment of pulsed current protocols i.e., individually approach each cell at all SOC during formation.

Resolving the Dilemma of Fe-N-C Catalysts by the Selective Synthesis of Tetrapyrrolic Active Sites via an Imprinting Strategy.

Combining the abundance and inexpensiveness of their constituent elements with their atomic dispersion, atomically dispersed Fe-N-C catalysts represent the most promising alternative to precious-metal-based materials in proton exchange membrane (PEM) fuel cells. Due to the high temperatures involved in their synthesis and the sensitivity of Fe ions toward carbothermal reduction, current synthetic methods are intrinsically limited in type and amount of the desired, catalytically active Fe-N4 sites, and high active site densities have been out of reach (dilemma of Fe-N-C catalysts). We herein identify a paradigm change in the synthesis of Fe-N-C catalysts arising from the developments of other M-N-C single-atom catalysts. Supported by DFT calculations we propose fundamental principles for the synthesis of M-N-C materials. We further exploit the proposed principles in a novel synthetic strategy to surpass the dilemma of Fe-N-C catalysts. The selective formation of tetrapyrrolic Zn-N4 sites in a tailor-made Zn-N-C material is utilized as an active-site imprint for the preparation of a corresponding Fe-N-C catalyst. By successive low- and high-temperature ion exchange reactions, we obtain a phase-pure Fe-N-C catalyst, with a high loading of atomically dispersed Fe (>3 wt %). Moreover, the catalyst is entirely composed of tetrapyrrolic Fe-N4 sites. The density of tetrapyrrolic Fe-N4 sites is more than six times as high as for previously reported tetrapyrrolic single-site Fe-N-C fuel cell catalysts.

Boosting Rechargeable Batteries R&D by Multiscale Modeling: Myth or Reality?

This review addresses concepts, approaches, tools, and outcomes of multiscale modeling used to design and optimize the current and next generation rechargeable battery cells. Different kinds of multiscale models are discussed and demystified with a particular emphasis on methodological aspects. The outcome is compared both to results of other modeling strategies as well as to the vast pool of experimental data available. Finally, the main challenges remaining and future developments are discussed.

Atomically Resolved Anisotropic Electrochemical Shaping of Nano-electrocatalyst.

Catalytic properties of advanced functional materials are determined by their surface and near-surface atomic structure, composition, morphology, defects, compressive and tensile stresses, etc; also known as a structure-activity relationship. The catalysts structural properties are dynamically changing as they perform via complex phenomenon dependent on the reaction conditions. In turn, not just the structural features but even more importantly, catalytic characteristics of nanoparticles get altered. Definitive conclusions about these phenomena are not possible with imaging of random nanoparticles with unknown atomic structure history. Using a contemporary PtCu-alloy electrocatalyst as a model system, a unique approach allowing unprecedented insight into the morphological dynamics on the atomic-scale caused by the process of dealloying is presented. Observing the detailed structure and morphology of the same nanoparticle at different stages of electrochemical treatment reveals new insights into atomic-scale processes such as size, faceting, strain and porosity development. Furthermore, based on precise atomically resolved microscopy data, Kinetic Monte Carlo (KMC) simulations provide further feedback into the physical parameters governing electrochemically induced structural dynamics. This work introduces a unique approach toward observation and understanding of nanoparticles dynamic changes on the atomic level and paves the way for an understanding of the structure-stability relationship.

Methodology for Investigating Electrochemical Gas Evolution Reactions: Floating Electrode as a Means for Effective Gas Bubble Removal.

The future significance of energy conversion has stimulated intense investigation of various electrocatalytic materials. Hence electrocatalysts have become the subject of electrochemical characterization on a daily basis. In certain cases of interest, when measuring electrochemical reactions beyond the onset potentials, however, appropriateness of existing electroanalytical methods may be questioned and alternative approaches need to be developed. The present study highlights some shortcomings in the electrochemical investigation of gas evolving reactions. The oxygen evolution reaction (OER) is selected as a case example with a specific focus on the electrochemical stability of a nanoparticulate iridium catalyst. When conventional electrochemical methods, such as thin film rotating disc electrodes are employed to study the materials' stability, the intrinsic degradation is masked by oxygen bubbles, which are inherently being formed during the reaction, especially when high current densities are used. In this Letter, we present a solution to this issue, the so-called floating electrode arrangement. Its elegant usage enables fast and reliable electrochemical characterization of oxygen evolution electrocatalysts.

Fluid-enhanced surface diffusion controls intraparticle phase transformations.

Phase transformations driven by compositional change require mass flux across a phase boundary. In some anisotropic solids, however, the phase boundary moves along a non-conductive crystallographic direction. One such material is LiXFePO4, an electrode for lithium-ion batteries. With poor bulk ionic transport along the direction of phase separation, it is unclear how lithium migrates during phase transformations. Here, we show that lithium migrates along the solid/liquid interface without leaving the particle, whereby charge carriers do not cross the double layer. X-ray diffraction and microscopy experiments as well as ab initio molecular dynamics simulations show that organic solvent and water molecules promote this surface ion diffusion, effectively rendering LiXFePO4 a three-dimensional lithium-ion conductor. Phase-field simulations capture the effects of surface diffusion on phase transformation. Lowering surface diffusivity is crucial towards supressing phase separation. This work establishes fluid-enhanced surface diffusion as a key dial for tuning phase transformation in anisotropic solids.

A Double-Passivation Water-Based Galvanic Displacement Method for Reproducible Gram-Scale Production of High-Performance Platinum-Alloy Electrocatalysts.

Preparation of large quantities of high-performance supported Pt-alloy electrocatalysts is crucial for the faster development and implementation of low-temperature proton exchange membrane fuel cells (PEMFCs). One of the prospective nanofabrication synthesis methods is based on the galvanic displacement (GD) reaction. A facile, highly reproducible, gram scale, water-based double passivation GD method is now presented for the synthesis of carbon-supported Pt-M nanoparticles (M=Cu, Ni, Co). It offers great flexibility over the catalyst design, such as the choice of the sacrificial metal (M), variation of the chemical composition of alloy, variation of total metal loading (Pt+M) on carbon support, or even variation of the carbon support itself. The obtained Pt-alloy catalysts are several times more active compared to a Pt reference and exhibits better stability during accelerated degradation tests performed at 60 °C.

Electrochemical Dissolution of Iridium and Iridium Oxide Particles in Acidic Media: Transmission Electron Microscopy, Electrochemical Flow Cell Coupled to Inductively Coupled Plasma Mass Spectrometry, and X-ray Absorption Spectroscopy Study.

Iridium-based particles, regarded as the most promising proton exchange membrane electrolyzer electrocatalysts, were investigated by transmission electron microscopy and by coupling of an electrochemical flow cell (EFC) with online inductively coupled plasma mass spectrometry. Additionally, studies using a thin-film rotating disc electrode, identical location transmission and scanning electron microscopy, as well as X-ray absorption spectroscopy have been performed. Extremely sensitive online time-and potential-resolved electrochemical dissolution profiles revealed that Ir particles dissolve well below oxygen evolution reaction (OER) potentials, presumably induced by Ir surface oxidation and reduction processes, also referred to as transient dissolution. Overall, thermally prepared rutile-type IrO2 particles are substantially more stable and less active in comparison to as-prepared metallic and electrochemically pretreated (E-Ir) analogues. Interestingly, under OER-relevant conditions, E-Ir particles exhibit superior stability and activity owing to the altered corrosion mechanism, where the formation of unstable Ir(>IV) species is hindered. Due to the enhanced and lasting OER performance, electrochemically pre-oxidized E-Ir particles may be considered as the electrocatalyst of choice for an improved low-temperature electrochemical hydrogen production device, namely a proton exchange membrane electrolyzer.

Importance of non-intrinsic platinum dissolution in Pt/C composite fuel cell catalysts.

The dissolution of different platinum-based nanoparticles deposited on a commercial high-surface area carbon (HSAC) support in thin catalyst films is investigated using a highly sensitive electrochemical flow cell (EFC) coupled to an inductively coupled plasma mass spectrometer (ICP-MS). The previously reported particle-size-dependent dissolution of Pt is confirmed on selected industrial samples with a mean Pt particle size ranging from 1 to 4.8 nm. This trend is significantly altered when a catalyst is diluted by the addition of HSAC. This indicates that the intrinsic dissolution properties are masked by local oversaturation phenomena, the so-called confinement effect. Furthermore, by replacing the standard HSAC support with a support having an order of magnitude higher specific surface area (a micro- and mesoporous nitrogen-doped high surface area carbon, HSANDC), Pt dissolution is reduced even further. This is due to the so-called non-intrinsic confinement and entrapment effects of the (large amount of) micropores and small mesopores doped with N atoms. The observed more effective Pt re-deposition is presumably induced by local Pt oversaturation and the presence of nitrogen nucleation sites. Overall, our study demonstrates the high importance and beneficial effects of porosity, loading and N doping of the carbon support on the Pt stability in the catalyst layer.

Effect of ordering of PtCu3 nanoparticle structure on the activity and stability for the oxygen reduction reaction.

In this study the performance enhancement effect of structural ordering for the oxygen reduction reaction (ORR) is systematically studied. Two samples of PtCu3 nanoparticles embedded on a graphitic carbon support are carefully prepared with identical initial composition, particle dispersion and size distribution, yet with different degrees of structural ordering. Thus we can eliminate all coinciding effects and unambiguously relate the improved activity of the ORR and more importantly the enhanced stability to the ordered nanostructure. Interestingly, the electrochemically induced morphological changes are common to both ordered and disordered samples. The observed effect could have a groundbreaking impact on the future directions in the rational design of active and stable platinum alloyed ORR catalysts.

A method for fast estimation of the rate-limiting step in lithium-ion batteries.

Transport of charge in electrodes for lithium-ion batteries is complex. For accurate description one needs to use a multilevel approach which addresses processes on different scales - from the ones occurring inside active nanoparticles to those governing the transport in composite electrodes or in separators of sub-millimeter thickness. Here we attempt an approximation that allows for a fast estimation of the rate-limiting step in given electrochemical cell. Despite thoroughly simplified description of transport, the method gives suprisingly good prediction of polarisation resistance as a function of charge/discharge rate and of the electrode thickness. The method might be helpful for fast evaluation of new materials or new electrode designs in everyday laboratory testing.

Stability of commercial Pt/C low temperature fuel cell catalyst: electrochemical IL-SEM study.

Platinum catalyst stability has been investigated under potentiostatic and potentiodynamic conditions with and without the presence of chloride anions. The combination of rotating disc electrode (RDE) and identical location scanning electron microscopy (IL-SEM) methods reveals that potentiodynamic degradation is much more severe compared to the potentiostatic and that chloride enhances platinum dissolution thus catalyst degradation. IL-SEM method nicely shows the platinum dissolution and redeposition on the top of a catalyst film.

Tuning the photocatalytic activity of nanocrystalline titania by phase composition control and nitrogen doping, using different sources of nitrogen.

Titania nanoparticles were synthesized by employing the hydrothermal method and using TiOSO(4) as a titanium source. By varying pH between 0.5 and 1.0 and adding isopropanol to the hydrothermal reaction mixture, different mixtures of anatase, rutile, and brookite were obtained. The samples were also doped with nitrogen at different N concentrations using, respectively, urea, ammonium nitrate, and tripropylamine as nitrogen sources. The samples were characterized by X-ray powder diffraction, field emission scanning electron microscopy, infrared spectroscopy, UV-Vis diffuse reflectance spectroscopy and according to their specific surface area. Additionally, their photocatalytic activity was measured in a gas-solid reactor system. The results show that low pH favours rutile formation, whereas a higher pH yields mixed phase titania polymorphs. Isopropanol addition also favours rutile formation, and boosted the photocatalytic activity of the resulted particles. Contrary to most data in the literature, rutile turned out to be the more active phase in the present investigation. Nitrogen doping, on the other hand, did not contribute to higher photocatalytic activity, but was rather detrimental to it.

Poly(propylene imine) dendrimer caps on mesoporous silica nanoparticles for redox-responsive release: smaller is better.

To elucidate the importance of the size of capping agents in stimulus-induced release systems from mesoporous silica nanoparticles (MSNs), the effectiveness of poly(propylene imine) dendrimers in controlling the model drug release was studied. MCM-41-type MSNs were synthesized and characterized. Fluorescent compounds (fluorescein disodium salt and carboxyfluorescein) were loaded in the porous structure of the MSNs and entrapped in the silica matrix with the dendrimers of generations I through V by anchoring dendrimers on the MSN surface through disulfide bonds. Stimulus-induced release of the cargo was studied in the presence of dithiothreitol (DTT). Dendrimers of generations I and II were found to be more effective in model drug retention and subsequent release than higher generations. Moreover, MSNs modified with larger amounts of dendrimers lowered the cargo release in the presence of DTT. These findings are of importance for optimizing drug delivery systems based on responsive MSNs as they enable tuning of the amount of the released cargo by choosing the capping agent of appropriate size.

Entering Voltage Hysteresis in Phase-Separating Materials: Revealing the Electrochemical Signature of the Intraparticle Phase-Separated State.

Hysteresis is a general phenomenon regularly observed in various materials. Usually, hysteretic behavior is an intrinsic property that cannot be circumvented in the nonequilibrium operation of the system. Herein, it is shown that, at least with regard to the hysteretic behavior of phase-separating battery materials, it is possible to enter (deeply) the hysteretic loop at finite battery currents. This newly observed electric response of the electrode, which is inherent to phase-separating materials, is related to its microscopic origin arising from a (significant) share of the active material residing in an intraparticle phase-separated state. This intriguing observation is further generalized by revealing that a phase-separating material can feature (significantly) different chemical potentials at the same bulk lithiation level and temperature when exposed to the same finite current and external voltage hysteresis. Therefore, the intraparticle phase-separated state significantly affects the DC and AC characteristics of the battery. The experimental evidence for entering the intraparticle phase-separated state is supported by thermodynamic reasoning and advanced modeling. The current findings will help advance the understanding, control, diagnostics, and monitoring of batteries composed of phase-separating materials while also providing pertinent motivation for the enhancement of battery design and performance.

Mechanistic Study of Fast Performance Decay of PtCu Alloy-based Catalyst Layers for Polymer Electrolyte Fuel Cells through Electrochemical Impedance Spectroscopy.

In the past, platinum-copper catalysts have proven to be highly active for the oxygen reduction reaction (ORR), but transferring the high activities measured in thin-film rotating disk electrodes (TF-RDEs) to high-performing membrane electrode assemblies (MEAs) has proven difficult due to stability issues during operation. High initial performance can be achieved. However, fast performance decay on a timescale of 24 h is induced by repeated voltage load steps with H2/air supplied. This performance decay is accelerated if high relative humidity (>60% RH) is set for a prolonged time and low voltages are applied during polarization. The reasons and possible solutions for this issue have been investigated by means of electrochemical impedance spectroscopy and distribution of relaxation time analysis (EIS-DRT). The affected electrochemical sub-processes have been identified by comparing the PtCu electrocatalyst with commercial Pt/C benchmark materials in homemade catalyst-coated membranes (CCMs). The proton transport resistance (Rpt) increased by a factor of ~2 compared to the benchmark materials. These results provide important insight into the challenges encountered with the de-alloyed PtCu/KB electrocatalyst during cell break-in and operation. This provides a basis for improvements in the catalysts' design and break-in procedures for the highly attractive PtCu/KB catalyst system.

Preparation of Atomically Flat Gold Substrates for AFM Measurements.

Sample preparation is the most important part of a successful measurement with an atomic force microscope (AFM). While various kinds of substrates are used for that purpose, atomically flat gold proved to possess some advantages, namely chemical inertness against oxygen, stability against radicals and suitability for formation of self-assembled monolayers (SAMs) of organic alkanethiols. Fast and simple preparation procedures to achieve quality atomically flat gold substrates are necessary to achieve reproducible results in high resolution imaging. Here we report an improved technique to produce atomically flat gold in a reliable way. We demonstrate its use on the example of high resolution imaging of single walled carbon nanotubes as test molecules.

Improving the HER Activity and Stability of Pt Nanoparticles by Titanium Oxynitride Support.

Water electrolysis powered by renewables is regarded as the feasible route for the production of hydrogen, obtained at the cathode side through electrochemical hydrogen evolution reaction (HER). Herein, we present a rational strategy to improve the overall HER catalytic performance of Pt, which is known as the best monometallic catalyst for this reaction, by supporting it on a conductive titanium oxynitride (TiON x ) dispersed over reduced graphene oxide nanoribbons. Characterization of the Pt/TiON x composite revealed the presence of small Pt particles with diameters between 2 and 3 nm, which are well dispersed over the TiON x support. The Pt/TiON x nanocomposite exhibited improved HER activity and stability with respect to the Pt/C benchmark in an acid electrolyte, which was ascribed to the strong metal-support interaction (SMSI) triggered between the TiON x support and grafted Pt nanoparticles. SMSI between TiON x and Pt was evidenced by X-ray photoelectron spectroscopy (XPS) through a shift of the binding energies of the characteristic Pt 4f photoelectron lines with respect to Pt/C. Density functional theory (DFT) calculations confirmed the strong interaction between Pt nanoparticles and the TiON x support. This strong interaction improves the stability of Pt nanoparticles and weakens the binding of chemisorbed H atoms thereon. Both of these effects may result in enhanced HER activity.

Enhanced Photocatalytic Hydrogen Evolution from Water Splitting on Ta2O5/SrZrO3 Heterostructures Decorated with CuxO/RuO2 Cocatalysts.

Photocatalytic H2 generation by water splitting is a promising alternative for producing renewable fuels. This work synthesized a new type of Ta2O5/SrZrO3 heterostructure with Ru and Cu (RuO2/CuxO/Ta2O5/SrZrO3) using solid-state chemistry methods to achieve a high H2 production of 5164 µmol g-1 h-1 under simulated solar light, 39 times higher than that produced using SrZrO3. The heterostructure performance is compared with other Ta2O5/SrZrO3 heterostructure compositions loaded with RuO2, CuxO, or Pt. CuxO is used to showcase the usage of less costly cocatalysts to produce H2. The photocatalytic activity toward H2 by the RuO2/CuxO/Ta2O5/SrZrO3 heterostructure remains the highest, followed by RuO2/Ta2O5/SrZrO3 > CuxO/Ta2O5/SrZrO3 > Pt/Ta2O5/SrZrO3 > Ta2O5/SrZrO3 > SrZrO3. Band gap tunability and high optical absorbance in the visible region are more prominent for the heterostructures containing cocatalysts (RuO2 or CuxO) and are even higher for the binary catalyst (RuO2/CuxO). The presence of the binary catalyst is observed to impact the charge carrier transport in Ta2O5/SrZrO3, improving the solar to hydrogen conversion efficiency. The results represent a valuable contribution to the design of SrZrO3-based heterostructures for photocatalytic H2 production by solar water splitting.