bluuebunny/crossref_metadata_2025_split huggingface dataset:
Physics Based Temperature Dependent EIS Simulation on 18650 NMC/Graphite Cell
Authors: Civan Fazlı Eren , Katırcı Gökberk , Ülgüt Burak 
Published: September 2023

Electrochemical Impedance Spectroscopy (EIS) is a non-destructive method that provides crucial insights regarding the battery processes. EIS is mainly done by applying a small amplitude AC with a 10 mHz to 1 MHz frequency range. One can determine the electrolyte's ohmic resistance, the Solid Electrolyte Interface (SEI) capacitance, electron transfer rate and the diffusion mechanisms at separate frequency regions from each other.
One disadvantage of EIS is the ambiguity of the analyses of the data. The equivalent circuit models used are not unique, and the correspondence between the various elements in the equivalent circuits to electrochemical phenomena are suspect. A new approach on EIS analysis is sought after in order to improve the interpretation. For example, distribution of relaxation times (DRT) was proposed by Zhang et al. in 2015 .
Using physics-based models in order to model EIS has been published by Murbach and Schwartz in 2018. In their work, they created a physics-based simulation which uses a pseudo two-dimensional battery model. Their main aim was to present a new approach to EIS data analysis by using a physics-based model rather than equivalent circuit models. They created a data set with 38.800 separate spectra and match the experimental data by using least squares matching approach with the previously computed data. Though this work improved the understanding, multiple calculated data sets matched the experiments with similar errors.
Ultimately, in order to achieve an EIS analysis method that is directly related to the fundamental parameters regarding the electrochemistry, degeneracies have to be removed via temperature dependence and the non-linearities as extra dependent variables. This way, the ambiguities and the suspicious parameter assigning can be fixed.
We will be reporting on T-dependent linear and nonlinear simulations on 18650 NMC/Graphite battery. All the simulations were done on Python by using a physics-based model PyBaMM (Sulzer, Valentin, et al. "Python battery mathematical modelling (PyBaMM)." Journal of Open Research Software 9.1 (2021).). Impedance data was obtained via simulating voltage as a function of current within 100 µHz to 10 kHz frequency range. Temperature range was set to -25°C to 65°C with 10°C increments. The linear and non-linear impedance is analyzed as a function of temperature. Our results will be compared with experimental temperature dependent linear/nonlinear spectra in order to obtain proper fundamental parameters
(Invited) Highly Stable, Crosslinked Polymer Membranes for Non-Aqueous Flow Batteries
Authors: Crivellaro Giovanni , Vezzu Keti , Pagot Gioele , Sgarbossa Paolo , Di Noto Vito 
Published: September 2023

Long-term energy storage is a crucial stepping stone for the introduction of renewable sources in the energy mix due to their intermittent nature. Non-aqueous Flow Batteries (NFBs) are expected to operate at higher potential differences in comparison to conventional aqueous systems, thus yielding an improved power density. However, among the several issues of NFBs, it is pivotal to develop ion-conducting separators stable in organic solvents.
Here we present a new family of ionomers which proved promising as candidates to implement this crucial function. The ionomers are founded on the strong ionic interactions between the functionalities of a polyamide-based material (P) and a perfluorosulfonic acid macromolecule (N). The latter interactions establish crosslinks between the two starting macromolecules. Consequently, the polymeric structure of the final ionomer is reorganized, improving the mechanical properties and curtailing the swelling upon immersion in organic solvents.
The membranes obtained from two of the proposed ionomers, labelled “P-N0.77” and “P-N0.89”, show a swelling < 7% after 1000 hours of immersion both in acetonitrile (ACN) and in a 1:1 vol./vol. mixture of ethylene carbonate and propylene carbonate (EC:PC). Upon exchanging the membranes with tetraethylammonium (TEA+) cations, a common benchmark mobile specie for NFBs, it is shown that: (i) P-N0.77 exhibits a conductivity of 0.4∙10-3 S∙cm-1 and 0.9∙10-3 S∙cm-1 at 25°C in 0.1 M TEA+ in ACN and 0.1 M TEA+ in EC:PC, respectively; and (ii) P-N0.89 shows a conductivity of 1.5∙10-3 S∙cm-1 and 0.5∙10-3 S∙cm-1 in the same conditions.
These results suggest that the proposed materials are suitable for application in NFBs, opening the door to the long-term operation of these devices.
Impedance Analysis of Semiconductor Electrodes Biased in the Accumulation Regime for Fuels Evolution
Authors: Spitler Mark 
Published: September 2023

This work explores the theory and experimental use of impedance analyses of semiconductor electrodes in the accumulation regime of semiconductor electrodes under bias. It contrasts with the established practice of measuring capacitance of the semiconductor-electrolyte biased in the depletion region to obtain semiconductor doping densities and flatband potentials (Ufb). The goal is to establish Ufb and the solution Helmholtz capacitance for an electrode in the working bias region where research is done on semiconductor electrodes for CO2 reduction and H2 evolution.
The technique of measuring the capacitance of semiconductor electrodes when polarized in the depletion region was introduced by DeWald1 and is based upon the work of Garrett and Brattain2 where mathematical expressions were derived for the electric field of a semiconductor space charge region. A significant assumption in that work was that a Boltzmann expression could be used to determine the population of the majority charge carriers in the bands created through ionization of dopant. Research in this area is extensive and has been summarized.3

However, for degenerate semiconductors or for bias potentials of the semiconductor where the fermi level at the electrode surface equals the energy of the band edges, a full fermi function must be employed to describe population statistics in the solid. This is the condition commonly found in systems for fuels production at semiconductor electrodes. The solid state physics theory for this situation is known4 and describes the electric field in a semiconductor space charge region. However, it was put aside during the development of impedance evaluations in semiconductor electrochemistry because its mathematical complexity was too tedious to evaluate at that time. Only limits and simplifications were explored.5

With modern computational software, this theory has become straightforward to calculate and it becomes possible to apply it to experimental systems in a description of behavior over the entire range of doping and polarization. The nature of this full theoretical description will be discussed and illustrated through experimental measurements of Si and InP semiconductor electrodes.
References:

DeWald, J.F., J. Phys. Chem. Sol., 14, 1960, 155-161.

Garrett, C.G.B. and Brattain, W.H., Phys. Rev., 99, 1955, 376-387.

Memming, R., Semiconductor Electrochemistry, Second Edition, Wiley-VCH,, Weinheim, Germany, 2015.

Seiwatz, R. and Green, M., J. Appl. Phys., 29, 1958, 1034-1040.

Many, A., Goldstein, Y., and Grover, N.B., Semiconductor Surfaces, North-Holland Publishing, New York, 1971.
Exploring Various Catalysts for Nitrogen Reduction to Ammonia
Authors: Dheer Lakshay , Thapa Ranjit , Waghmare Umesh Vasudeo , Bajdich Michal 
Published: September 2023

Electrochemical nitrogen reduction reaction (eNRR), one of the most studied problems in catalysis, has the potential to replace the century-old Haber-Bosch process for ammonia synthesis. However, a low-cost, highly selective and efficient catalyst for eNRR is yet to be discovered. Metal based catalysts have been at the heart of numerous studies for eNRR, however there has been a shift towards metal-free catalysts due to their environmentally benign nature and low cost. In this study, we analyze 2D boron-based electrocatalysts for nitrogen reduction and explore the effect of carbon substitution on their activity. Using first-principles calculations, we demonstrate that pristine and carbon (C) substituted 𝛼 borophene catalyze eNRR at exceptionally low limiting potentials of -0.33 V and -0.25 V, respectively. These 𝛼 borophene based catalysts also show high selectivity towards eNRR over the competing hydrogen evolution reaction (HER). Our results show that C-substituted 𝛼 borophene exhibits outstanding catalytic activity towards eNRR via the distal pathway with a small activation barrier of 0.56 eV, almost half the value reported for Ru (0001). Finally, we identify two novel descriptors, adsorption energy of *NNH and charge transfer to *N2, which can be used in high-throughput screening of catalysts for eNRR. These findings demonstrate the strong potential of metal-free borophene based catalysts for efficient electrochemical reduction of N2, enabling low-cost and sustainable NH3 synthesis.
We revisit the nitrogenase FeM cofactor (M=Fe/Mo/V) based catalysts for eNRR to decipher the key mechanism at play. Further, catalysts based on transition metal nitrides (TMNs) and transition metal dichalcogenides (TMDCs) are also being explored for the study and compared with the state-of-the-art materials available. The dominance of one NRR mechanism like the Mars Van Krevelen (MvK) mechanism on TMNs over others like the dissociative NRR is also examined. These findings will provide a more comprehensive and elaborate view of the ammonia synthesis for N2 reduction reaction space.
Facet-Dependent Selectivity of Rutile IrO2 for Oxygen and Chlorine Evolution Reactions
Authors: Vitale-Sullivan Molly E. , Carvalho Quinn Quinn , Stoerzinger Kelsey A 
Published: September 2023

Water electrolysis is a promising route for sustainable production of hydrogen as an energy storage medium and valuable precursor for industrial chemical syntheses such as ammonia and methanol. Direct electrolysis of seawater circumvents costly desalination and purification steps to reduce the price of renewable hydrogen to achieve cost parity with carbon-intensive steam reforming. However, the significant concentration of chloride salts in seawater poses a challenge to selectivity of seawater electrolysis. In aqueous chloride electrolytes, the chlorine evolution reaction (CER) is kinetically favored over the oxygen evolution reaction (OER). Rutile-type iridium dioxide (IrO2) is a state-of-the-art electrocatalyst for water electrolysis but is also a benchmark chlorine evolution electrocatalyst in the industrial chlor-alkali process. Understanding OER/CER selectivity is needed to make seawater electrolysis a viable energy conversion technology in the future.
In this work, we seek to understand the relationship between crystallographic facet and competitive reaction pathway between OER and CER on epitaxial, rutile IrO2 thin films. We investigate facet-dependent OER and CER activity on a series of single-crystalline IrO2 thin films using a rotating disk electrode geometry. The OER/CER selectivity, reaction rate order, and reaction intermediate electroadsorption affinities are explored to add fundamental insight into the reactivity of rutile IrO2 surface. To gain further insight into OER intermediate adsorption affinities, we paired electrochemical measurements with surface-sensitive ambient pressure x-ray photoelectron spectroscopy (AP-XPS). Moving forward, our facet-dependent study of OER/CER selectivity of rutile IrO2 can be used to design selective seawater electrocatalysts for cost-effective and sustainable hydrogen production.
Experimental Determination of the Intrinsic Oxygen Reduction Kinetics on Polycrystalline Platinum and the Role of the Adsorbed Oxygen
Authors: Brandes Benedikt Axel , Buchauer Fabian Luca , Hjelm Johan 
Published: September 2023

The Oxygen Reduction Reaction (ORR) is a fundamental reaction in electrochemical devices such as fuel cells and sensors. The ORR only occurs on few catalytically active surfaces, mainly platinum and its alloys and understanding its mechanism is critically important to develop new catalysts and applications. In contrast to the related Hydrogen evolution/oxidation reaction, the intrinsic ORR activity is rarely determined due to simultaneous formation of Pt-O species. Therefore, the ORR activity is measured at a benchmark potential making its susceptible to the measurement characteristics, such as "activation", scan rate, and scan direction.
We found that by using a specially designed experimental procedure one can separate the effect of Pt-O on the ORR kinetics without extensive modelling or fitting. As a results an exemplary Pt-O corrected Tafel plot on polycrystalline platinum is displayed in figure 1.
In this presentation we will discuss the underlying method, its application on a range of different ORR environments, the nature of the Pt-O species, and the implications for ORR mechanism itself.

Figure 1
(Invited) Using Single Nanoparticle Electrochemistry to Better Understand the Oxygen Evolution Reaction at Cobalt Oxide Nanocatalysts
Authors: Tschulik Kristina , Amin Hatem M.A. , Hosseini Pouya , Corva Manuel , Liu Zhibin 
Published: September 2023

Transition metal oxides are highly promising catalysts for alkaline water splitting thanks to their relatively high abundancy and high catalytic activity. Due to their limited electrical conductivity they are often used as nanoparticles and their catalytic performance is assessed based on experiments at composite electrodes. Besides the nanocatalyst of interest, these electrodes contain catalytically inactive binders and conductive additives. This makes it highly challenging – if not impossible – to distinguish influences of catalyst properties from matrix effects. For example, observed effects of particle morphology on electrocatalytic activity may simply originate from different wetting/blocking of catalyst active sites by the used additives or by different iR drop across the composite film, instead of signifying different charge transfer kinetics [1]. To overcome this limitation, we use single nanoparticle electrochemistry and study electrocatalysis at individual catalyst nanoparticles [2]. Employing this approach, we are able to clearly reveal that Co3O4 nanocubes are more active for the oxygen evolution reaction (OER) than spheres. Moreover, we can link our experimental data to theory data obtained from DTU+U calculations, thanks to the comparably small size of the electrochemical system [3]. For OER catalysis at single Co3O4 nanocubes in KOH(aq), we demonstrate and rationalize the effect of support materials on catalyst activity that had been debated previously [4].

References

[1] N. Blanc, C. Rurainsky, K. Tschulik, J. Electroanal. Chem. 872(2020)114345
[2] A. El Arrassi, Z. Liu, M. V. Evers, N. Blanc, G. Bendt, S. Saddeler, D. Tetzlaff, D. Pohl, C. Damm, S. Schulz, K. Tschulik, J. Am. Chem. Soc. 141 (2019) 9197
[3] Z. Liu, H. M.A. Amin, Y. Peng, M. Corva, R. Pentcheva, K. Tschulik, Adv. Funct. Mater., (2022) accepted.
[4] Z. Liu, M. Corva, H.M.A. Amin, N. Blanc, J. Linnemann, K. Tschulik, Int. J. Mol. Sci. 22 (2021)13137.
Figure 1: Single nanoparticle electrochemistry shows higher OER activity for cobalt oxide cubes than spheres [3].

Figure 1
Testbed for Simulating Pulsewaveform for Development of Wearable Piezoresistive Pressure Sensors
Authors: Jafarizadeh Borzooye , Chowdhury Azmal Huda , Pala Nezih , Wang Chunlei 
Published: September 2023

Due to their non-invasive method of continuous monitoring of weak human physiological data, flexible and skin-mountable wearable health monitoring devices have attracted a lot of attention in recent years. According to their mode of operation, ultra-sensitive pressure sensors can generally be divided into piezoresistive, capacitive, triboelectric, and piezoelectric sensors. Particularly, piezoresistive sensors have received a lot of attention due to its rapid response, wide detection range, straightforward structure, and comparatively easy signal measuring system. Although previous attempts to obtain the complete pulse waveform of the human heartbeat were successful, their signal capture required the use of unwearable measuring equipment. In order to resolve this shortcoming of the current supposedly wearable systems, we outline three requirements for a sensor to be wearable (i.e. could be paired with a simple and compact signal acquisition device). The first of these is the sensitivity; through a complete literature review we determine the lower limit of sensitivity that if obtained, the sensor can acquire the pulsewaveform from the body peripheries such as wrist or ankle. Second is the response time of the sensor. The piezoresistive sensor must have a shorter response time than the period of fastest heartbeat. And lastly is the cyclability; the durability tests of the sensor must show ample stability and consistency in the signal output after operation for months.
To verify that the sensors pass the requirements above, we have custom-built a testbed capable of measuring these three characteristics. The testbed specifically makes use of a secondary pressure sensor to confirm the sensitivity. Secondly, by using an encoder instead of merely relying on a sensor's rise or fall time, it is capable to more accurately determine the response time of the sensor. Furthermore, because the testbed is motorized, it is streamlined to mimic operation over an extended cycles.
Finally, in this study we fabricated an exemplary piezoresistive pressure sensor using environmentally friendly materials and tested it in the testbed and then mounted it on the wrist of a human subject and acquired the pulsewaveform with a simple and wearable signal acquisition device to confirm the capability as a wearable pulsewave monitoring device. The details of this study will be presented in the meeting.
In Operando Measurement of the Lithium-Ion Concentration in the Battery Electrolyte to Study Degradation Modes
Authors: Wahl Markus Solberg , Lamb Jacob , Boles Steven T , Burheim Odne Stokke 
Published: September 2023

In operando measurements of the lithium-ion concentration inside a lithium-ion battery (LiB) using a fiber-optic sensor are demonstrated. The concentration changes in the electrolyte are correlated to the incremental capacity response of the battery during charge and discharge. The goal is to study battery degradation based on the dynamic and state-of-charge dependent concentration of lithium ions in the electrolyte.
Batteries lose capacity over time, both due to charging/discharging and to shelf ageing (calendar ageing). Extending the lifetime of a battery directly reduces its environmental footprint. This ageing is caused either by i) unwanted chemical reactions, reducing the number of available lithium-ions or increasing the impedance, or ii) by physical changes that reduces the available lithium storage capacity of the electrodes. Both mechanisms affect the spatial distribution of lithium ions.
Ageing has traditionally been studied through monitoring the operational performance (e.g., coulombic capacity, internal resistance), or through post-mortem investigations. Other advanced methods, such as thermal neutron imaging or X-ray tomography has also been used to estimate the internal composition of the battery through image analysis [1,2]. This study presents live concentration measurements using an optical fiber placed between the electrodes. The intrinsic properties of optical fibers (e.g., small, chemically inert, electrically insulating) make them ideal for internal sensing in the chemically harsh interior of a battery.
The fiber is placed in the electrolyte between the electrodes, see Fig. 1a. Because the reflected intensity depends on the concentration of lithium ions (Fig. 1b), we are able to demonstrate and analyze how the concentration changes during cycling (Fig. 1c). Both single-cycle and long-term effects are investigated. Information about how the lithium concentration changes during cycling is valuable both as an input parameter in battery modelling, and to increase the understanding of battery ageing. For the latter, the lithium-concentration during cycling of batteries is evaluated in correlation with an incremental capacity analysis.

Siegel, J.B.; Lin, X.; Stefanopoulou, A.G.; Hussey, D.S.; Jacobson, D.L.; Gorsich, D. Neutron Imaging of Lithium Concentration in LFP Pouch Cell Battery. J. Electrochem. Soc.
2011, 158, A523, doi:10.1149/1.3566341.

Senyshyn, A.; Mühlbauer, M.J.; Dolotko, O.; Hofmann, M.; Ehrenberg, H. Homogeneity of lithium distribution in cylinder-type Li-ion batteries. Sci. Rep.
2015, 5, 1–9, doi:10.1038/srep18380.

Figure 1
Digital Communication through Solids Using Magnetostriction
Authors: Faltas Mina , Pillars Jamin R. , Elkady Ihab 
Published: September 2023

Digital communication through solid materials such as metals, ceramics, organic solids, or semiconductors has many applications. Only communication through metals has been attempted via ultrasonic waves. However, its performance is significantly hindered by echo interference. A way to enable communication through these solids is by the exploitation of magnetostriction. Magnetostriction is a property where a magnetic material changes its shape during the process of magnetization, essentially converting magnetic energy into kinetic energy. The kinetic energy produced by the magnetic material can then be taken through the solid media through which communication is intended to occur. The kinetic signal on the other side of the solid media could be converted to whatever type of energy is suitable for the application.
This energy transduction channel, using magnetic energy and kinetic energy, can optimally be achieved through a soft magnetic material with high magnetostriction. A nickel-iron-cobalt based alloy was used to develop a material with a saturation magnetostriction over 200ppm, that can be electrodeposited out of an acidic aqueous chemistry. Initial high intrinsic stress in the deposited alloy was controlled with additives and altering the complexing, enabling consistent deposits of over a millimeter in thickness.
The electrodeposited material’s performance is characterized and correlated to material properties such as alloy composition, microstructure, grain size, coercivity, magnetic saturation, Young’s Modulus, etc. The characterization methods used to analyze the magnetostrictive material and the effect of modulating plating parameters to control material properties will be presented. Additionally, the effect of annealing the material in an inert environment at varying temperatures and dwell times will be examined.

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International Inc., for the U.S. Department of Energy’s National Nuclear Security Administration
under contract DE-NA0003525.

This paper describes objective technical results and analysis. Any subjective views or opinions
that might be expressed in the paper do not necessarily represent the views of the U.S.
Department of Energy or the United States Government.
SNL is managed and operated by NTESS under DOE NNSA contract DE-NA0003525