bluuebunny/crossref_metadata_2025_split huggingface dataset:
Effect of Applied Stress on the Interfacial Kinetics, Ionic Conductivity, and Other Phenomena in Thin-Film Solid-State Batteries
Authors: Bhargava Bhuvsmita , Theodoru Stefan , Crofton Lane , Kozen Alexander C , Warecki Zoey , Stewart David Murdock , Song Yueming , Rubloff Gary , Albertus Paul 
Published: February 2024

Controlled stress is critical to both fabrication and operation of solid-state batteries to ensure pristine, low-impedance interfaces. The effects of externally applied stresses on overall cell performance and degradation due to altered thermodynamics, interfacial kinetics, and bulk transport of the active species have been studied in several prior works. In addition to the applied stack pressure which can vary up to 100s MPa, internal and localized stresses up to a few ~1 GPa can be generated from volume changes during charge and discharge. Electrode volume changes can result in cracking and delamination, causing loss of conductive pathways and active electrode-electrolyte area, and electrolyte fracture in the case of dendrite growth. The extent of these stress-electrochemistry couplings depends on the material and geometry of interfaces that affects the local stress distribution. To decouple some of these stress-potential, stress-kinetics, and stress-transport coupling phenomena, we use a nanoindenter platform to apply controlled uniaxial compressive forces to a thin-film electrochemical devices and batteries1. Interfaces in a thin-film sample can be uniform and planar over large areas, helping us study the effect of stress on the interfacial electrochemistry more directly and with greater quantitative accuracy. In this work we present our observations and analysis on the direct electrochemical-mechanical coupling in thin-film TiO2 and V2O5 metal oxide thin films as the working electrode with the single-ion Li+ conductor solid electrolyte LiPON. Preliminary results show that external uniaxial compressive load affects the electrochemistry observed through cyclic voltammetry and electrochemical impedance spectroscopy (EIS) measurements on thin-film batteries with TiO2 and V2O5 electrodes.
References:
(1) Song, Y.; Bhargava, B.; Stewart, D. M.; Talin, A. A.; Rubloff, G. W.; Albertus, P. Electrochemical-Mechanical Coupling Measurements. Joule
2023, S2542435123001137. https://doi.org/10.1016/j.joule.2023.03.001.
(Invited) Computing the Newns-Anderson Chemisorption Function from First Principles
Authors: Oberhofer Harald 
Published: February 2024

In analysing the interactions of adsorbates with extended surfaces, theory, and to a large degree also experiments, tend to rely on adsorption models such as the famous Newns-Anderson model. There, the interaction of adsorbate and substrate is represented by the interaction of the adsorbate's one-electron frontier orbitals with the delocalised Bloch states of the substrate. Together with its simplified cousin, the d-band model, such adsorption models yielded significant insight into the chemistry of extended surfaces.
The Newns-Anderson Model gives rise to a so-called chemisorption function, a density of states weighted by the electronic coupling between adsorbate and substrate states, measuring the line broadening of an adsorbate frontier state upon adsorption. In my contribution, I will describe our efforts to compute the chemisorption function from first principles, employing a diabatization scheme to estimate electronic couplings between states. Recognizing the periodic nature of the substrate and the finite extent of computational supercells, we extend the original chemisorption function by a Brillouin zone integration to account for the (generally localized) adsorbate states' coupling to different substrate states at different points in reciprocal space. Including this integration, the chemisorption function not only converges well with both lateral simulation cell size and slab depth, but also compares well with experiments. We test our approach against highly accurate experimental measurements of ultrafast charge transfer of a probe Ar atom on various metal surfaces and find that the chemisorption function reproduces both absolute transfer rates and rate asymmetries due to spin on magnetic surfaces. Next to its predictiveness, though, the Newns Anderson chemisorption function allows us to investigate the charge transfer mechanism in terms of e.g. contributions of states with different angular momentum character, showing the importance of phase cancellation effects in interpreting charge transfer at surfaces.
How Relevant Are SEI Studies from Half Cell Samples to Understand Aging Mechanisms in Potassium Batteries? An in-Depth Photoelectron Spectroscopy Study
Authors: Panasenko Iurii , Wildersinn Leonie , Jeschull Fabian 
Published: February 2024

Owing to a shared common technological basis, monovalent K-ion battery (KIB) systems follow in the footsteps of Li-ion batteries (LIBs) with the aim to develop a broader portfolio of available battery technologies and to put them on a more sustainable material basis. For example, both cations intercalate into a graphite host structure, which can be used in combination with carbonate-based electrolytes as negative electrode. Especially in half cells, the degradation of graphite electrodes in KIBs is significantly accelerated in comparison to LIBs. Previous surface studies demonstrated that the formation of a durable and protective solid electrolyte interphase (SEI), that is paramount for long cycle life in alkali-ion batteries, is a major bottleneck for KIBs because of less benign SEI properties[1][2].
Recently reported crosstalk phenomena in half cell configurations due to the highly reactive potassium counter electrode make the analysis of surface layers a particular challenge [2][3]. In this presentation, a detailed characterization of the SEI formation on graphite was performed in both half and full cell configurations by in-house and synchrotron-based photoelectron spectroscopy (PES) in order to demonstrate fundamental differences in surface layer composition under the influence of a reactive counter electrode. While it is generally acknowledged that PES results show differences in SEI composition and thickness between both configurations, our results clearly demonstrate that in case of KIBs the changes become severe. This challenges interpretations of SEI layer properties made in half cells, as they are distinctly different from those in full cells. More importantly, this also affects interpretations on the major electrolyte degradation pathways in these systems. Using PES depth profiling and complementing results with gas chromatography, as well as DFT calculations, delivers new insights on the irreversible processes in KIBs.

Reference
s
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[1] Naylor, et al., ACS Appl. Mater. Interfaces. 11 (2019) 45636–45645.
[2] Allgayer et al., ACS Appl. Energy Mater. 5 (2022) 1136–1148.
[3] Hosaka et al., ACS Energy Lett. 6 (2021) 3643–3649.
Novel Approaches for Improving Solubility of Pyridinium Anolytes in Non-Aqueous Redox Flow Batteries
Authors: Hickey David P. , Samaroo Sharmila , Hegensbach Charley , Guarr Thomas F. 
Published: February 2024

Organic redox flow batteries (ORFBs) offer significant promise as a means of efficient grid-scale energy storage to compliment the intermittent power supply of renewable energy sources such as solar and wind power. ORFBs efficiently store energy in the form of redox-active organic molecules (ROMs) by passing them over two polarized electrodes to generate an oxidized (catholyte) and a reduced (anolyte) species, which are held in separate tanks until energy is needed. Structural diversity of anolytes and catholytes for ORFBs has expanded dramatically over the past decade as researchers have raced to discover or design ROMs suitable for use in grid-scale energy storage devices; however, a lack of correlations between ROM structure and a desired chemical or physical property has led to a “guess and check” approach that can overlook possibly transformative electrolyte structures. Recent work has demonstrated the ability to employ multivariate regression analysis to correlate computationally derived structural descriptors of ROMs to their corresponding stability. Based on this, we considered the possibility of employing a similar approach to identify quantitative structure-property relationships (QSPRs) for critical physical properties of ORFB electrolytes, such as solubility.
Electrolyte solubility is an essential design characteristic in ORFBs as it directly impacts the corresponding battery’s energy storage capacity. Nevertheless, the fundamental question, “What makes an electrolyte soluble?” (especially in organic solvents) still lacks a concise answer despite decades of progress. As part of a collaboration with the Guarr group at the Michigan State University Bioeconomy Institute, our group has identified a novel class of pyridinium anolytes with exceptionally low redox potentials and highly persistent charged states. We will discuss our group’s recent progress to combine experimental and computational techniques to develop QSPR models to accurately predict solubility of pyridinium anolytes. The resulting models have provided new insights into the role that self-interaction between anolyte species in solution plays in dictating their corresponding solubility. Using these models, we have successfully expanded the solubility range for a class of pyridinium derivatives by >200% in acetonitrile.
Investigation of Interfacial Behavior of Ni-Rich NCM Cathode Particles in Sulfide-Based Solid-State Electrolyte
Authors: Mukhan Orynbassar , Yun Ji-Su , Kim Sung-soo 
Published: February 2024

All-solid-state batteries (ASSBs) are currently investigated as a future battery technology with conventional layered cathode materials because they can offer benefits in the gravimetric and volumetric energy densities compared to flammable liquid electrolyte lithium-ion batteries with graphite intercalation anode. The solid electrolyte is believed to suppress dendritic growth and low Coulombic efficiency on the lithium metal anode side, which are the key issues for the use of a lithium metal electrode in conventional batteries with liquid electrolyte. Moreover, layered transition metal oxides such as LiNixCoyMnzO2 (NCM, 0 < x, y, z < 1) are one of the most promising positive electrode active material candidates being developed to increase the energy density. In particular, recent studies have shown a tendency to decrease the cobalt content and increase the nickel content to increase energy density and price competitiveness, so high-nickel NCM can be the optimal material suitable for this purpose. However, the remaining interfacial challenges of the cathode / solid electrolyte interface still need to be solved.
Herein, we investigated the kinetics such as charge transfer resistance at the interface between high nickel (Ni0.94) NCM particles and argyrodite (Li6PS5Cl) solid electrolytes using the microcavity electrode with the negative and positive pulsed current measurement technique and compared with liquid electrolytes using the same manner measurement technique. The cavity-electrode system is adopted to analyze the electrochemical properties of active particles and electrolytes confined in the cavity to exclude the effects of surrounding interfaces, barriers, and side reactions caused by battery components around the electrodes and the impact of loading and current collectors of the composite electrode. Therefore, understanding the electrode-electrolyte interface between cathode active particles and solid electrolytes is crucial for theoretical studies on the interfacial phenomenon in solid electrolyte batteries.
(Invited) Confocal Raman Microscopy in the Study of Ion Insertion Processes and Material Dimensional Change
Authors: Korzeniewski Carol , Xu Jiahe 
Published: February 2024

Confocal Raman microscopy is being applied to quantify chemical composition at electrode-solution interfaces and within electrode-supported films under electrochemical potential control. Experimental strategies (i.e., cell designs and data acquisition and processing techniques) that are enabling sensitive in-situ spectral measurements will be discussed with focus on redox transformations at electrode-solution interfaces and within electrode-supported polymer membranes and thin films. Emphasis will be on the ability to investigate ion insertion/de-insertion processes and measure material dimensional (e.g., swelling/de-swelling) changes as the applied potential is varied (in-situ).
The microscope system being utilized employs a high numerical aperture oil immersion objective to achieve (i) diffraction-limited focusing and probe volume characteristics and (ii) high efficiency in collecting Raman scattered radiation from molecules of interest. With the objective mounted to an inverted microscope frame, the electrochemical cell is positioned above the objective on the microscope stage. A glass microscope coverslip attached to the bottom of the electrochemical cell serves as the optical window. One electrochemical cell platform has been constructed around an optically transparent indium tin oxide (ITO) coated coverslip that serves as both the cell working electrode and optical window. The objective brings excitation radiation through the coverslip and to a focus a few micrometers above the ITO surface. Species diffusing into the confocal probe volume region are detected and quantified based on their Raman spectral band frequencies and intensities. A second electrochemical cell platform has a thin layer design and enables use of conventional disk working electrodes. The performance of this cell together with a spectral difference technique that allows detection of transformations within redox polymers supported on carbon electrodes will be discussed.
The platform is being applied to detect swelling/de-swelling in electrode-supported redox polymers in response to changes in material redox state. Molecular composition (i.e., the mix of polymer framework, solvent and mobile ions) within the confocal probe volume is measured quantitatively from Raman spectra. Tracking the frequency and intensity of spectral bands as electrode potential is varied enables voltage-induced swelling and de-swelling to be correlated to changes in the composition of specific types of mobile species (solvent and ions). Similar application of the strategy to investigate material dimensional change with variation in atmospheric composition will be highlighted.
Transient Short Circuit-Based Degradation of Lithium and Sodium Anode-Free Batteries
Authors: Menkin Svetlana , Fritzke Jana Beatrice , Larner Rebecca , Grey Clare P. 
Published: February 2024

The demand for an extended range of electric vehicles has created a renaissance of interest in replacing the common lithium-ion with a higher energy-density metal anode (e.g., Li or Na). However, alkali metal cells suffer from capacity fading and potential safety issues. The uneven metal electrodeposition often results in dendrite formation and potentially hazardous situations such as cell short-circuiting and thermal runaway.
Though lithium plating has been studied widely, a better understanding of the short-circuiting mechanisms and metal battery failure is required. Moreover, a considerable performance gap exists between symmetric metal cells and realistic metal batteries.
"Soft shorts" are small localised electrical connections between two electrodes that allow the co-existence of direct electron transfer and interfacial reaction. Although soft shorts were identified as a major safety issue in the early nineties, their detection and prevention were not widely studied. Therefore, a fundamental understanding of passivated metals' plating and a reliable testing method for soft short circuits is critical for realising metal batteries, such as Li-Air, Li-S, and anode-free batteries.
Here we compared short circuit formation mechanisms and degradation in symmetric cells and anode-free lithium and sodium batteries using coupled galvanostatic impedance spectroscopy (GEIS) and in-situ nuclear magnetic resonance spectroscopy (NMR) for the first time.
The coupling of in-situ NMR and EIS allows the observation of metal batteries' electrochemical and chemical dynamics and degradation in real time without affecting the cells' operation.
We demonstrated that lithium and sodium short circuit formation mechanisms fundamentally differ and strongly depend on electrolyte composition and SEI stability. This new understanding of the metal plating mechanism is crucial to develop the next generation of rechargeable batteries with high energy density, prolonged cycling life and improved sustainability.
Electrochemical Scanning Probe Microscopy Evaluation of Li-Ion Battery Cathode Degradation through in Situ Oxygen Evolution Measurement and Interfacial Property Characterization
Authors: Mishra Abhiroop , Rodriguez Lopez Joaquin 
Published: February 2024

Degradation processes involving oxygen evolution significantly limit the performance, reversibility, and capacity of high energy density Li-ion battery (LiB) cathodes. In addition, oxygen evolution processes create hazardous conditions for LiB operation. Despite the importance of these processes, characterization of evolved O2 with sufficient spatial and temporal versatility is hampered by the complex setups required to perform electrochemical mass spectrometry, the gold standard for evaluating this process. Recently, we introduced a scanning electrochemical microscopy (SECM) approach that enables in-situ, real-time (i.e., few ms temporal resolution), chemically selective detection of O2.[1] Measurements were accomplished by positioning an SECM probe (i.e., an Au ultramicroelectrode) near operating cathode surfaces for detecting O2 via the oxygen reduction reaction (ORR). The superior signal-to-noise of this method enabled the observation of two peaks corresponding to a steady-state evolution at high voltage and a transient O2 evolution at low voltage on materials such as lithium cobalt oxide (LCO) and NMC electrodes.
Here, we expand the capabilities of our technique by incorporating correlated measurements aimed at understanding how oxygen evolution profiles are related to surface electrochemical and mechanical properties. Specifically, we will focus on the use of feedback-mode SECM and the use of reactive mediators to evaluate the changes in the rates of electron transfer measured on materials undergoing O2 and after structural degradation. Furthermore, the use of electrochemical AFM allows us to measure the mechanical properties of these interfaces, in an attempt to tie the structural changes and the evolution of oxidizing species with the formation of cathode-electrolyte interfaces. Altogether, these multimodal SECM and AFM methods elucidate the manifold chemical, structural, and performance changes underpinning LiB cathode operation.
[1] Mishra, A.; Sarbapalli, D.; Hossain, M.S.; Gossage, Z.T.; Li, Z.; Urban, A.; Rodríguez-López, J. Highly Sensitive Detection and Mapping of Incipient and Steady-State Oxygen Evolution from Operating Li-Ion Battery Cathodes via Scanning Electrochemical Microscopy. J. Electrochem. Soc., 2022, 169, 086501.

Figure 1
Electrochemical Characterization of Artificial Solid Electrolyte Interphase Developed on Graphite Via ALD
Authors: Schlaier Jonas , Fedorov Roman , Huang Shixian , Ein-Eli Yair , Schneider Michael , Heubner Christian , Michaelis Alexander 
Published: February 2024

During formation of Li-ion batteries, a ‘natural’ solid electrolyte interphase (SEI) is formed at the anode side by decomposition products of the electrolyte. The properties of the SEI are extremely decisive for the overall battery properties, such as rate capability and cycling stability. However, the SEI formation consumes Li, leading to so called ‘formation losses’ that can make up to 15% of the theoretical energy density of the battery. Several approaches have been presented to overcome formation losses while preserving excellent overall battery properties. Particularly, electrochemical prelithiation and the application of artificial SEIs prior cell assembly are considered to effectively reduced formation losses while improving the interfacial charge transfer properties and increasing cycling stability.
Herein, the authors present an innovative approach of applying a multifunctional artificial SEI on anode material powders via consecutive atomic layer deposition (ALD) cycles. As a model system, graphite powder has been chosen to be modified and characterized.
The resulting electrodes show substantially improved electrochemical performance in half cells and full cells, regarding initial capacity loss, CE and cycling stability. Furthermore, model electrodes consisting of a single layer of graphite particles were manufactured, which exclude the effects of a typical composite electrode and therefore reveal the intrinsic properties of the active material. Using this approach, the interfacial kinetics and the rate capability are investigated comparatively between pristine and ALD coated electrodes, revealing the impact of the artificial SEI on the materials level.
Analysis of the Impact of Operating Conditions on Performance of H2 Gas – Aqueous Manganese Redox Flow Batteries
Authors: Farrow Catherine , Mezzavilla Stefano , Pandya Dillon , Ranta Emilia , Fernihough Oliver , Liddington Ben , Kavei Ashkan , von Werne Tim 
Published: February 2024

In recent years the need to move to renewable energy sources as a means of combating climate change has become increasingly clear. Long duration energy storage (LDES) is essential for the incorporation of renewable energy generation into grid-scale energy systems. Redox Flow Batteries (RFB) offer a promising solution due to scalability, safety, and cost. The hybrid H2 gas – aqueous Mn RFB has been identified as a candidate1.
Recognising the absence of an established protocol for measurement of RFB system performance, this study uses charge- discharge polarisations to explore the sensitivity of the H2/Mn performance to changes in temperature. When designing a RFB for commercial usage it is important to balance improved performance with the necessary stability that is required for any potential LDES system. In this work we use a developed stress test to demonstrate the impact of temperature on the systems stability.
Varying temperature showed improvement of 2.8 mV/ oC in charging overpotentials of and 5.7 mV/ oC in discharging overpotential. However, this must be weighed against the impact on the stability of the cell. These findings serve as inputs for the development of the control system essential for the successful operation of the H2/Mn RFB system.

1Rubio-Garcia, J. et al. Hydrogen / manganese hybrid redox flow battery. J. Phys. Energy (2018)
1015006.