bluuebunny/crossref_metadata_2025_split huggingface dataset:
Paper-Derived Carbon Electrodes, a Versatile Option to Develop Electrochemical Sensors
Authors: Elashkar Nourhan Esmat , Ayres Lucas B , Vidal Ezequiel , Arroyo Netz , Garcia Carlos D 
Published: September 2023

Carbon-based materials are particularly well-suited for electroanalytical applications due to their distinct properties, such as high chemical stability, large electroactive areas, wide electrochemical potential window in aqueous solutions, low electrical resistance, rich surface chemistry, and activity towards a variety of redox reactions. While carbon electrodes can be produced via thermal decomposition of gaseous hydrocarbons followed by their surface-induced recombination, this method is not cost-effective and suffers from both low efficiency (~20%) and limited selectivity towards graphitic forms. Alternatively, carbon electrodes can be developed via pyrolytic treatment of non-volatile substrates. This approach yields carbon materials that are rich in graphitic phases and provides researchers a much richer selection of starting materials and source-to-product efficiencies ~70%. Our team has applied this approach to develop several optically transparent carbon electrodes and has described a method for fabricating carbon electrodes by pyrolysis of paper, using a tube furnace and under a mild reducing atmosphere. The resulting electrodes not only feature the properties of traditional carbon materials but also preserve the 3D structure of the starting material, are mildly hydrophobic, and offer a wide electrochemical window and can be patterned using laser engraving. Moreover, the process also enables the incorporation of metallic nanoparticles within the structure of the material (by pyrolyzing paper pre-soaked in a solution containing the selected cation), significantly improving the conductivity of the material. Thus, this presentation will provide a brief summary of the reactions leading to the fabrication of these substrates as well as discuss the most recent applications towards their use as sensors in microfluidic devices.
Special emphasis will be placed on the use of these electrodes for the detection of S. aureus, application that required the modification of the material with a thin layer of sputtered gold (that minimizes lateral resistivity and significantly improves the electron transfer process) and with chitosan (used as a binder to offer flexibility). This biosensor was controlled using a custom-built potentiostat (via a wireless connection), which was used to detect the presence of the bacteria via the oxidation of the ferrocyanide (produced by the bacteria’s respiration cycle) in the presence of mannitol.
More information about the group can be found in our web site scienceweb.clemson.edu/uacl/
Mechanistic Study of Lithium Electrodeposition Using Dynamic Electrochemical Impedance Spectroscopy
Authors: Sacci Robert L , Sahore Ritu , Westover Andrew S 
Published: September 2023

Lithium metal batteries have increased energy density over standard graphite-based Li-ion anodes. However, Li metal anodes have difficulty forming stable passivation layer (called solid electrolyte interphase, SEI) leading to poor use of Li inventory. That is, LI metals require larger cathode loading, which reduces the energy density gain. A holistic approach to Li anode incorporation includes electrolyte design, mechanism understanding, and battery engineering. A factor that has not been fully appreciated is the nature of the Lithium metal itself, namely its SEI before incorporation into the battery device may affect the subsequent SEI formation. Here, we present a mechanistic study on lithium SEI formation on various lithium sources, as well as the Li cycling.
We utilized dynamic impedance spectroscopy (dEIS) to probe the formation and evolution of the SEI during Li cycling of various Li sources. dEIS superimposes a multisine waveform atop the dc stimulus signal. After applying a sliding window FFT protocol that takes the complex ratio of the measured potential and current signals time-resolved complex impedance can be obtained. We will discuss the differences between the Li cycling profiles using Lipon (a glassy solid electrolyte) and a liquid electrolyte. We will relate the differences in cycling performance, particularly the SEI evolution to the surface chemistry of the as-received Li metal source.
The US Department of Energy's Energy Efficiency and Renewable Energy Vehicles Technologies Office provided funding for this work under the US-German Cooperation on Energy Storage: Lithium-Solid-Electrolyte Interfaces program.
Stable Organic Radical for Enhancing Metal-Monolayer-Semiconductor Junctions Performance
Authors: Fabre Bruno , De Sousa Jesus Alejandro , Pfattner Raphael , Rovira Concepcio , Mas-Torrent Marta , Crivillers Nuria 
Published: September 2023

Among the large amount of families of molecules investigated in molecular junctions (MJs), stable free organic radicals have gained an increasing attention over the last years.1 Thanks to their open-shell electronic configuration, these molecules are paramagnetic, redox and optically active, which make them appealing species for a variety of applications.2 Chlorinated trityl radicals, and in particular the perchlorotriphenylmethyl radicals have shown to be highly stable as active molecular units in MJs.3 Such functional molecules have been recently covalently bound to photoactive, hydrogen-terminated silicon surfaces and the so modified surfaces have been demonstrated to function as light-triggered capacitance switches with good stability.4

Herein, the charge transport of these systems, employing the open- and closed-shell molecules (Rad-PTM and αH-PTM, Figure 1a), is investigated as solid-state Metal/monolayer/Semiconductor (MmS) junctions using an eutectic Gallium-Indium liquid metal as the top electrode. A characteristic diode behavior is observed which is tuned by the electronic characteristics of the organic molecule. Our results clearly indicate that the presence of the SOMO-SUMO molecular orbitals impacts on the device performance. The junction incorporating the radical shows an almost two orders of magnitude higher rectification ratio (R = 104.04) in comparison with the non-radical one (R = 102.30) at ± 1 V bias. Interestingly, the high stability of the fabricated MmS permits to interrogate the system under irradiation, evidencing that at the wavelength where the photon energy is close to the band gap of the radical, there is a clear enhancement of the photoresponse.5

(1) Ratera, I.; Vidal-Gancedo, J.; Maspoch, D.; Bromley, S. T.; Crivillers, N.; Mas-Torrent, M. J. Mater. Chem. C
2021, 9, 10610–10623.
(2) Mas-Torrent, M.; Crivillers, N.; Mugnaini, V.; Ratera, I.; Rovira, C.; Veciana, J. J. Mater. Chem.
2009, 19, 1691–1695.
(3) Bejarano, F.; Olavarria-Contreras, I. J.; Droghetti, A.; Rungger, I.; Rudnev, A.; Gutiérrez, D.; Mas-Torrent, M.; Veciana, J.; Van Der Zant, H. S. J.; Rovira, C.; et al. J. Am. Chem. Soc.
2018, 140, 1691–1696.
(4) De Sousa, J. A.; Bejarano, F.; Gutiérrez, D.; Leroux, Y. R.; Nowik-Boltyk, E. M.; Junghoefer, T.; Giangrisostomi, E.; Ovsyannikov, R.; Casu, M. B.; Veciana, J.; et al. Chem. Sci.
2020, 11, 516–524.
(5) De Sousa, J. A.; Pfattner, R.; Gutiérrez, D.; Bromley, S. T.; Veciana, J.; Rovira, C.; Mas-Torrent, M.; Fabre, B.; Crivillers, N. ACS Appl. Mater. Interf., submitted.

Figure 1
Electrochemical Colloquium and Beyond: Opportunities for Online Education in Electrochemistry
Authors: Akbashev Andrew 
Published: September 2023

Electrochemistry represents an exceptionally multifaceted and hard-to-teach subject. First, it requires knowledge of very distinct fields, including chemical thermodynamics, surface science, quantum mechanics, solid state ionics, catalysis, photovoltaics, cellular biology, and others. As a result, no electrochemistry curriculum can cover all the material needed for comprehensive understanding of the subject, meaning that the course is often shaped by the teacher’s personal preferences and agenda (e.g., fundamental electrochemistry, energy storage, corrosion, bioelectrochemistry, etc.). Second, the very core of electrochemistry – electrical double layer – is heavily debated within the professional community and does not have a satisfactory and consensual description suitable for textbooks and teaching. Unlike the kinetics of molecular reactions in solutions or at gas-solid interfaces, the kinetics of electrochemical reactions with the double layer region, even in simplest cases, is almost impossible to predict from first principles. All this causes confusion among both students and teachers – how should we teach when the key concept cannot be described adequately? Third, the field of electrochemistry is evolving, older concepts are reconsidered, and the new ones are introduced. This makes it difficult for students to relate course material to what is going on in real research. Finally, electrochemistry is vital for industry, which makes it particularly tempting for teachers to introduce a substantial “engineering” component into the curriculum and turn it into “applied electrochemistry course” (covering energy storage and conversion, corrosion, electroplating, etc.). While being well-intended, this leads to oversimplification of electrochemistry and offers a general (and often confusing) overview of the field.
In my talk, I will discuss the difficulties of teaching electrochemistry courses and how online platforms can offer possible solutions. Specifically, I will draw on my experience with the Electrochemical Online Colloquium, which aims to make fundamental science and essential knowledge freely accessible to the public. My argument is that a holistic understanding of electrochemistry cannot be achieved if one ignores knowledge gained in neighboring fields. At the same time, discussion of open questions and critical assessment of concepts by experts helps a student understand what is truly well-established in the field and what is not. I will also discuss future opportunities for online education in electrochemistry and how we can improve the quality of research in this field.
(Keynote) Electrochemical Proton-Coupled Electron Transfer Theory
Authors: Hammes-Schiffer Sharon 
Published: September 2023

Proton-coupled electron transfer (PCET) plays a vital role in a wide range of electrochemical processes. This talk will describe theoretical and computational methods that have been developed to study electrochemical PCET and a variety of applications to molecular and heterogeneous electrocatalysis. My group has formulated a general PCET theory that includes the quantum mechanical effects of the electrons and transferring protons, as well as the motions of the donor-acceptor modes and solvent or protein environment. This PCET theory enables the calculation of rate constants and kinetic isotope effects for comparison to experiment. Our extension of this theory to electrochemical PCET incorporates the electronic structure of the electrode and the interfacial electric fields arising from the electrical double layer. Theoretical formulations for both homogeneous and heterogeneous electrochemical PCET provide analytical expressions for the rate constants and current densities as functions of applied potential. This theory has been applied to proton discharge on metal electrodes, as well as PCET at metal oxides and graphite-conjugated catalysts. These applications highlight the importance of using a theory that quantizes the transferring proton and includes the effects of hydrogen tunneling and excited electron-proton vibronic states. The insights from these theoretical studies are useful for the design of electrocatalytic systems to control the movement and coupling of electrons and protons for energy conversion processes.
References

Venkataraman, A. V. Soudackov, and S. Hammes-Schiffer, Theoretical formulation of nonadiabatic electrochemical proton-coupled electron transfer at metal-solution interfaces, J. Phys. Chem. C
112, 12386-12397 (2008).

K. Goldsmith, Y. C. Lam, A V. Soudackov, and S. Hammes-Schiffer, Proton discharge on a gold electrode from triethylammonium in acetonitrile: Theoretical modeling of potential-dependent kinetic isotope effects, J. Am. Chem. Soc.
141, 1084-1090 (2019).

C. Lam, A. V. Soudackov, and S. Hammes-Schiffer, Kinetics of proton discharge on metal electrodes: Effects of vibrational nonadiabaticity and solvent dynamics, J. Phys. Chem. Lett.
10, 5312-5217 (2019).

E. Warburton, P. Hutchison, M. N. Jackson, M. L. Pegis, Y. Surendranath, and S. Hammes-Schiffer, “Interfacial field-driven proton-coupled electron transfer at graphite-conjugated organic acids,” J. Am. Chem. Soc.
142, 20855-20864 (2020).

E. Warburton, A. V. Soudackov, and S. Hammes-Schiffer, Theoretical modeling of electrochemical proton-coupled electron transfer, Chem. Rev.
122, 10599-10650 (2022).
Mechanistic Insights into Ion Transport in Polymerized Ionic Liquids
Authors: Zhu Zhenghao , Popov Ivan , Sokolov Alexei P. , Paddison Stephen J. 
Published: September 2023

Polymerized ionic liquids (polyILs) continue to be of great interest as electrolytes in energy conversion and storage devices. However, challenges in enhancing the ionic conductivity to ~10-3 S/cm still hinder the application of these materials. Therefore, it is urgent to improve the conductivity in these electrolytes, which strongly relies on advances in molecular-level understanding of ion transport mechanisms governing charge transport. To this end, ionic correlations and the mechanisms of ion transport in the polyILs and their corresponding ILs have been systematically studied by altering the molecular chemistry of the cation and the anion using classical molecular dynamics simulations.
We first hypothesized that immobilization of one of the ions in the polymer may lead to a significant increase in negative correlations in the dynamics of the mobile ions. To verify this hypothesis, we used a polymethylmethacrylate (PMMA) based backbone with attached imidazolium cations and mobile anions, including TFSI−, PF6
−, BF4
−, and Br−. The increase in temperature enhances both intrachain and interchain ion hopping while reducing the rattling of mobile ions. The analysis of ionic correlations in both ILs and polyILs systems at various temperatures revealed that the inverse Heaven ratio was not temperature dependent in either of the systems. We further investigated the effect of side-chain flexibility of polyILs on ionic correlations by changing the side-chain length. The higher flexibility enhances local mobility of the imidazolium cations, leading to an increasing number of associating cations from more polymer chains to the anions. Another key factor in tuning ionic correlations in concentrated ionic systems is electrostatic interactions, whose role was investigated by changing the dielectric constant of the simulated systems. We believe these molecular-level insights will advance the rational design of novel polyILs for electrochemical applications.
(Invited) Numerical Simulation of Ohmic Impedance
Authors: Orazem Mark E. 
Published: September 2023

Impedance spectroscopy measurements are often confounded by high-frequency phenomena associated with frequency-dependent ohmic resistance. Newman introduced the concept of frequency dispersion to account for the effect of the disk electrode geometry on the impedance response [1]. The phenomenon described by Newman in terms of frequency-dependent capacitance and ohmic resistance may be considered as an ohmic impedance, a transfer function associated with the resistance of the electrolyte to passage of current under the influence of geometry-induced (and frequency-dependent) non-uniform current and potential distributions [2].
Two kinds of models are described in the presentation. Finite-element models account for the influence of geometry on the impedance response for a disk electrode. These models demonstrate the ohmic impedance. The second model is an interpretation model used to extract properties from impedance data. For most cases, data are truncated to avoid being confounded by ohmic impedance. On rare instances, the ohmic impedance may be extracted by regression to data.
Gharbi et al. [3] suggested that the ohmic impedance follows the form of the Havriliak-Negami equation. The Havriliak-Negami equation was found to provide a good fit to the ohmic impedance calculated for different electrode geometries, including interdigitated electrodes [4] as well as disk electrodes [3].
The ohmic impedance was obtained by Levenberg-Marquardt regression of a process model that accounted for the ohmic impedance [5]. The experiments were performed using ferri/ferrocyanide redox species (10 mM each) in a 0.5 M KCl solution. The working electrode consisted of a 5-mm-diameter Au disk rotating at 800 rpm. A Pt gauze (4 cm2) was used as the counterelectrode, a saturated Ag/AgCl electrode was used as a reference electrode, and the temperature of double-walled electrochemical cell was held at 25 ±0.1°C.
The process model was expressed in terms of an ohmic impedance and an expression that accounted for the influence of a local constant-phase element on the faradaic reaction and the convective diffusion impedance, expressed in terms of a series expansion following the work of Tribollet and Newman [6]. Regressions were weighted by the experimentally determined error structure of the data, and the resulting parameters characteristic of the ohmic impedance were in excellent agreement with numerical simulations.
References

J. S. Newman, J. Electrochem. Soc., 117 (1970), 198.

V. Huang, V. Vivier, M. E. Orazem, N. Pébère, and B. Tribollet, J. Electrochem. Soc., 154 (2007), C81-C88.

O. Gharbi, A. Dizon, M. E. Orazem, M. T.T. Tran, B. Tribollet, and V. Vivier, Electrochim. Acta, 320 (2019), 134609.

A. Dizon and M. E. Orazem, Electrochim. Acta, 337 (2019), 135000.

W. Watson and M. E. Orazem, EIS: Measurement Model Program, ECSArXiv, 2020, https://ecsarxiv.org/kze9x/.

B. Tribollet and J. S. Newman, J. Electrochem. Soc., 130 (1983), 2016.
Degradation and Multi-Time-Scale State Estimation of Li-Ion Batteries in Satellites
Authors: Bolay Linda , Hosono Eiji , Sone Yoshitsugu , Latz Arnulf , Horstmann Birger 
Published: September 2023

In-orbit satellite REIMEI, developed by the Japan Aerospace Exploration Agency (JAXA), has been relying on off-the-shelf Li-ion batteries since its launch in 2005 [1]. The performance and durability of Li-ion batteries is impacted by various degradation mechanisms, one of which is the growth of the solid-electrolyte interphase (SEI). Long-term SEI growth is the greatest contributor to capacity fade in lithium-ion batteries.
In this contribution, we will address several aspects of the modeling and simulation of the batteries of satellite REIMEI. We simulate long-term degradation under the generic LEO satellite cycling conditions in a P2D framework. The simulations are validated with experiments and in-flight data provided by JAXA [1]. Our group has developed models for long-term SEI growth [2,3]. To show the inhomogeneous growth of the SEI in 3D, we perform microstructure-resolved simulations [4].
These studies are the foundation for analyzing the states of the batteries, which cannot be measured in operando. To estimate the state of charge and state of health, we make use of filter techniques and the in-flight data of the satellite batteries. Kalman filters are particularly suitable for the noisy data. Since the states change on different timescales, a multi-time-scale algorithm is applied, where two filters are combined. With this approach, we aim to reliably predict the lifetime of satellite batteries in orbit.

References

[1] M. Uno, et al., J. Power Sources, 196(20) (2011) 8755–8763.
[2] F. Single, et al., ChemSusChem, 11(12) (2018) 1950–1955.
[3] L. von Kolzenberg, et al., ChemSusChem, 13(15) (2020) 3901–3910.
[4] L. Bolay, et al., J. Power Sources Advances, 14 (2022) 100083.
Predicting Oxygen Release and Surface Reconstructions in Li-Ion Battery Cathodes Via Automated Construction of Computational Surface Phase Diagrams and Machine Learning
Authors: Li Xinhao , Lam Wing-Chi Ashley , Yeu In Won , Mishra Abhiroop , Rodriguez Lopez Joaquin , Urban Alexander 
Published: September 2023

Although LiNiO2 (LNO) is chemically very similar to LiCoO2 (LCO), LNO and related Co-free Ni-rich cathodes suffer from continuing surface degradation via oxygen gas release during electrochemical cycling that leads to the formation of surface phases with high impedance. While the surface degradation of LNO and related cathode compositions have been characterized experimentally on a phenomenological level, an understanding of the surface reconstructions that form on the atomic scale and the intrinsic surface instability of LNO compared with other related cathode compositions is still lacking.
To shed light on surface reactivity, we developed a thermodynamic methodology for the prediction of voltage and temperature-dependent surface electrode reconstructions [1] and a computational framework to automate the time-consuming enumeration of surface reconstructions, the construction of symmetric surface-slab models, and the analysis of surface phase diagrams [2]. By applying first-principles atomistic modeling, we determined the self-reduction mechanism of LNO and compared the stable surface reconstructions with those of LCO. To further assess the surface stability of more complicated NMC/NCA cathodes with the help of our own generated LNO and LCO databases, we developed a supervised machine learning (ML) model to train on geometrical and electronic fingerprints from surface and bulk models, respectively. Our results provide insight into the initial stages of surface degradation in Ni-rich cathodes and lay the foundation for the computational design of stable cathode materials against oxygen release.

Li, X.; Wang, Q.; Guo, H.; Artrith, N.; Urban, A. ACS Appl. Energy Mater. 2022, 5 (5), 5730–5741.

Li, X.; Qu, J.; Yeu, I.; Li, Z.; Rodríguez-López, J.; Urban, A., in preparation, 2023
Materials Graph Networks Assisting the Discovery of New Solid-State Electrolyte Materials
Authors: Duangdangchote Salatan , Voznyy Oleksandr 
Published: September 2023

Finding novel solid-state electrolyte materials with specific desired properties is one of the main challenges of first principles-based modelling due to its high computational cost. Recently, machine learning (ML) has been used exclusively in the materials discovery field due to its remarkable capabilities to process large amounts of data and extract useful information insights. The implementation of ML into atomic-scale materials modeling can accelerated materials sampling with first principles accuracy, this should provide a short workflow and highly reduce the computational cost.
In this work, we facilitate the ML model that can effectively screen for targeted properties from the entire chemical database possibility, including those materials that have never been examined. Currently, we are developing a materials graph networks framework for representing periodic crystal systems with the capability to learn atomistic chemical insights, especially for the discovery of new solid-state electrolyte materials.
In this talk, we will discuss the basic theory and our recent work towards the development of ML model that can extensively discover and explore materials. We will highlight the computational-guided evolution approaches and screening high-performance Li conductor materials. Finally, we will end on discussing the future of ML-assisted materials discovery to the future of all-solid-state lithium batteries.