bluuebunny/crossref_metadata_2025_split huggingface dataset:
Operando Tracking of Ionic and Electronic Percolation in Electrodes for Energy Storage Application Using AC-in Plane Impedance
Authors: Maurel Victor , Taberna Pierre-Louis , Simon Patrice 
Published: July 2022

Achieving efficient electronic and ionic electrode percolation is one of the most important parameters to improve batteries and supercapacitors power performance. Various electrical and electrochemical techniques (Cyclic voltammetry, Electrochemical Impedance Spectroscopy, EQCM, SECM, in-situ XRD, etc) can be used to assess the electronic and ionic transport properties in these electrodes. However, there are only few studies and techniques on tracking the change in resistance of an electrode during electrochemical polarization [1, 2, 3], which plays a key-role on its electrochemical performance.
In this study, we propose a new method to achieve operando resistance measurement under alternative current (AC), that we’ll call in-plane impedance measurement, under bias potential. In these experiments, the electrodes are deposited onto an insulating substrate so that, differently from conventional electrochemical impedance spectroscopy experiments, here the electrode in-plane conductivity is measured. Moreover, this method allows for distinguishing the ionic part of the in-plane electrode impedance from the electronic part that appears at high and low frequencies, respectively.
In this work, in-plane electronic and ionic transport properties of porous carbon (YP50F) and MXene (Ti3C2) electrode are studied while being fully charged or. During polarization, both the ionic and electronic percolation change with the applied potential for both electrode, that could be associated with electrode volume and conductivity change under potential and/or because of some doping caused by ionic specific electrosorption. This operando in-plane impedance measurement method furthers the fundamental understanding of ionic and electronic transport properties and may turn out to be effective tool to improve the electrochemical performances of capacitive, pseudocapacitive, or battery-like electrodes.

References:

[1] R.I. Tucceri. A review about the surface resistance technique in electrochemistry. Surface Science Reports 56 85-157 (2004).
[2] E. Pollak et al. The Dependence of the Electronic Conductivity of Carbon Molecular Sieve Electrodes on Their Charging States. J. Phys. Chem. B. 110 7443-7448 (2006).
[3] Yu. M. Vol’fkovich, et al. Surface Conductivity Measurements for Porous Carbon Electrodes. Russian Journal of Electrochemistry. 49 (6) 594-598 (2013).

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Design Considerations for Practical Li-S Battery Components for Electric Aviation
Authors: Dornbusch Donald , Viggiano Rocco P. , Wu James , Lin Yi , Connell John , Lvovich Vadim 
Published: July 2022

The development of high-energy, high-safety, and high-power batteries beyond electric automobile requirements is vital for future electric aviation applications. The transition to non-volatile solid-state electrolytes (SSE) promises many advantages over traditional flammable liquid electrolytes and may also be an enabling technology for next generation chemistries. However, significant manufacturing challenges must be overcome before the adoption of such technology. This study focuses on advancement of previous electrolyte development to produce sulfide-polymer composites with densified thicknesses between 20-30 microns using a tape-casting technique with an elastomer binder [1]. Parameters such as binder type, binder loading, and filler loading are modified to determine their impact on electrochemical performance and mechanical stability. The composites were determined to retain reasonable ionic conductivity with improved flexibility and scalability critical for practical manufacturing of such cells. Films were produced 10-15 times thinner than comparable bulk powder electrolytes and within the range of commercial polyolefin separators (25 micron) used in commercial liquid containing lithium-ion cells. Composite conductivities were maintained above 0.2mS/cm, which holds promise for future electric aviation applications. Processing techniques are investigated to further improve electrochemical performance.
[1] Donald A. Dornbusch, Rocco P. Viggiano, John W. Connell, Yi Lin, Vadim F. Lvovich. Practical considerations in designing solid state Li-S cells for electric aviation, Electrochimica Acta, 2021, 139406, ISSN 0013-4686, https://doi.org/10.1016/j.electacta.2021.139406.
Topology Optimization of Flow Fields for Porous Electrodes
Authors: Lin Tiras Y , Baker Sarah , Duoss Eric B , Beck Victor A 
Published: July 2022

Power-efficient energy storage is important for the successful integration of renewables into the electrical grid, and one promising storage device is the redox flow battery. In this presentation, we discuss the design of the flow field component of a redox flow battery using topology optimization. The flow field is a flow manifold that distributes and guides fluid with reactant both into and out of the reactive porous electrode. The popular two-dimensional interdigitated flow field, where a series of interlocking flow channels force fluid into the electrode, is a design that is commonly used in the lab, and we perform our optimization to improve upon this design. Specifically, we aim to minimize the electrical and flow pressure power losses, and we find that different operating conditions, i.e., flow rate and current density, lead to different optimal designs. We observe fully three-dimensional features in our optimized designs, where primary flow channels appear along with smaller branching channels that guide fluid to the electrode. This provides evidence that three-dimensional structures can provide improvement over conventional two-dimensional designs. While high power efficiency can certainly be attained using a traditional interdigitated flow field, the dimensions of the fluid channels and solid lands need to be carefully chosen for the desired operating conditions. In this presentation, we show that our method can computationally guide this design process.
This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344. LLNL release number: LLNL-ABS-830167.
Physics-Based Use Case Analysis: Route Planning and Dynamic Load Prediction for Battery-Electric Buses
Authors: Eggleton Erica , Schwartz Daniel T. 
Published: July 2022

The electrification of transportation and goods delivery networks, including ground, marine, and air, is becoming a reality around the world. These networks are logistically complex, and with this transition there is an added knowledge gap in the understanding of the energy storage system, such as lithium-ion battery packs. In Seattle, the local transit agency King County Metro is a national leader in transitioning to a fully electrified bus fleet and is the case study for this work. As transit agencies, such as King County Metro, adopt electrified vehicles, there are many new parameters that must be considered in route planning, fleet maintenance, and charging logistics. The literature shows that a longitudinal vehicle dynamics model can be used to estimate energy and load requirements along a route [1,2]. This work utilizes these known vehicle models, vehicle specifications, and battery information in a software tool. Software inputs include geographical information system (GIS) data, ridership data, and vehicle acceleration profiles. Model results allow the user to rank routes using metrics designed to consider route efficiency, vehicle performance, and known battery degradation events, such as regenerative braking and high-power discharge. This work also introduces how the battery state of charge, overpotential, current window, and deviations from equilibrium influence the route rankings. These results provide both systems-level and module-level insights beyond conventional vehicle and logistics models, allowing the user to make decisions that are predictive rather than reactive and can improve the lifetime of the batteries on-board.
[1] Gallet, M., Massier, T. & Hamacher, T. Estimation of the energy demand of electric buses
based on real-world data for large-scale public transport networks. Appl. Energy 230,
344–356 (2018).
[2] Asamer, J., Graser, A., Heilmann, B. & Ruthmair, M. Sensitivity analysis for energy
demand estimation of electric vehicles. Transp. Res. Part D Transp. Environ. 46, 182–199
(2016).
Computational Design of Porous Electrode Architecture for Electrochemical Flow Reactors and Redox Flow Batteries
Authors: Beck Victor A , Lin Tiras Y 
Published: July 2022

Porous electrodes are utilized across electrochemical technologies including flow reactors and redox flow batteries. Controlling mass transport, conduction, and surface reaction in the electrodes is central to attaining peak device performance. Traditional methods often rely on manipulating the macroscopic electrode dimensions, device-level architecture, and flow distribution (e.g. via flow fields). However, beyond using traditional materials like felts or papers, engineering the internal electrode structure itself has recently emerged as a new design degree-of-freedom. These architected, porous electrodes are enabled by advanced and additive manufacturing techniques and are a promising route to provide greater control over the local transport and reactive environment, further improving device performance. New design tools will be necessary to fully exploit this expanded design space. Here we present a collection of computational design methodologies to automatically generate architected electrode design across scales. Resolved optimization techniques are used to determine optimal electrode architectures at the pore scale. Using homogenization, these techniques are then extended to scale-up the designs beyond typical benchtop dimensions. Using vanadium as a model chemistry, we demonstrate that the computationally designed electrodes yield improved performance across cost-functions and focus particularly on energy efficiency. Further, we analyze the resultant designs to highlight the structural features leading to improved performance.
This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.
LLNL-ABS-830166
(Digital Presentation) A Zero-Dimensional Physics-Based Model for Lithium Carbon Monofluoride (Li/CFx) Batteries
Authors: Parke Caitlin D. , Harris Kailot , Albertus Paul 
Published: July 2022

Lithium carbon monofluoride primary batteries have a high energy density (2180 Wh/kg of active materials based on the typical discharge potential) and low self-discharge. They have traditionally been used in medical devices like pacemakers with low rates of several years [1]. The high energy density of Li/CFx batteries also make them attractive for higher rate uses like aerospace or military applications; however, rate capability and heat generation can pose a significant challenge at higher rates. The theoretical potential of a CFx battery is around 4.5 V, but practical cells operate at 3 V or lower. The ~1.5 V overpotential is attributed to the strength of the C-F bonds, which results in slow kinetics and significant heat generation, especially when considering high rate (e.g., >C/10) and energy dense cell designs. Other challenges include the deposition of insulating lithium fluoride and large volume changes in each electrode [2].
Our work focuses on a high-energy density primary battery with a CFx cathode and lithium anode, designed for high rates with intermittent pulse power requirements. Physics-based modeling is an important tool that can clarify underlying mechanisms and help guide design to satisfy multiple constraints. To understand the challenges posed by this chemistry at higher rates, we have developed a zero-dimensional (0D) physics-based model that captures some of the complex phenomena within the CFx cathode. Included in the model are kinetics described by a concentration-dependent expression, changing porosity and electrochemical active area, and Nernstian thermodynamics. The model may also include a treatment of methods that increase the capabilities beyond the typical limits for the CFx chemistry. The implications of various conditions will be explored, such as the effect of the porosity and loading. The model results will be compared to experimental data from coin cells.
Acknowledgments
The authors would like to thank the Intelligence Advanced Research Projects Agency for funding this work.
References

Zhang, K. J. Takeuchi, E. S. Takeuchi, and A. C. Marschilok, Phys. Chem. Chem. Phys., 17, 22504 (2015).

S. Zhang, D. Foster, J. Wolfenstine, and J. Read, J. Power Sources, 187, 233 (2009).
Lorentz-Force-Mediated Zn Electrodeposition and Br- Ion Convection for Improved Performance in Aqueous Zn-Br2 Static Batteries
Authors: Sheelam Anjaiah , Glasco Dalton Lee , Bell Jeffrey Gordon 
Published: July 2022

Redox flow batteries are one of the prominent electrochemical energy storage devices with large-scale storage and high energy density.1 The highly reversible Zn/Zn2+ (-0.76 V vs. RHE) and Br-/Br2 (1.08 V vs. RHE) redox couple have been employed in Zn-Br2 flow batteries (1.84 V vs. RHE). However, the dendritic growth of Zn electrodeposits during the repetitive discharge process triggers an internal short-circuit between the anode and the cathode.1 Besides this, cross-diffusion of the highly soluble Br- (Br3
-) ion causes a severe self-discharge of the system and reduced cycle life.2 Additives and ion-selective membranes have been employed to mitigate these challenges for improved cycle life and coulombic efficiency in Zn-Br2 batteries.3 Here, we fabricate an aqueous Zn-Br2 static battery with internally contained and moderate magnetic fields, (~ 30, 40, 50 and 60 mT) at the anode and cathode by incorporating 1 mm thick Nd permanent magnets. A solid complex of tetrapropylammonium tribromide was supported on activated carbon and employed as the positive electrode. Introducing a magnetic field can generate the Lorentz force (acting on Br- and Zn2+ ions), and create a controllable magnetohydrodynamic mass transport during the charge-discharge processes. Among the various magnetic fields, ~50 mT resulted in the highest coulombic efficiency (99 % for 100 cycles) and suppressed Zn dendritic growth. To rationalize the effect of magnetic fields on the efficiency and cycle life, Raman analysis, X-ray diffraction, scanning electron microscopy, electrochemical impedance spectroscopy, and cyclic voltammetry (for the calculation of diffusion coefficient of Br- ion) are performed on the positive and negative electrodes of Zn-Br2 battery.

References:

(1) Z. Yuan, X. Liu, W. Xu, Y. Duan, H. Zhang, X. Li, Nat. Commun., 9
, 3731 (2018).
(2) L. Gao, Z. Li, Y. Zou, S. Yin, P. Peng, Y. Shao, X. Liang, iScience,
23, 101348 (2020).
(3) E. Sánchez-Díez, E. Ventosa, M. Guarnieri, A. Trovò, C. Flox, R. Marcilla, F. Soavi, P. Mazur, E. Aranzabe, R. Ferret, J
. Power Sources,
481, 228804 (2021).
(Invited, Digital Presentation) Aggregation Switchable Fullerene-Peptides Conjugates
Authors: Ma Yue , Yamakoshi Yoko 
Published: July 2022

Intensive research has been applied on chemical functionalization of fullerenes over the past decades, aiming at utilizing their broad availabilities in chemical biology field. Chemical moieties was induced to improve their water solubility and thus enhance their properties or interaction with biomolecules. In our previous study, we reported the synthesis of fullerene-PEG conjugates and demonstrated their ability for photoinduced DNA damage and ROS generation under visible light irradiation.
In this work, we report a water-soluble fullerene derivative by constructing a fullerene-peptide conjugates. The aggregation behavior as well as bio properties has been systematically studied for this series of fullerene-peptide conjugates (Figure 1a). By altering the attached peptides, fullerenes could exist as monomer or micelle in aqueous phase (Figure 1b).

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(Invited) On-Surface Synthesis of Acene Polymers
Authors: Santos Jose , Jelínek Pavel , Ecija David , Martin Nazario 
Published: July 2022

The design and study of π-conjugated polymers has received great attention along the last decades. The relevant optical and electronic properties stemming from their delocalised π-electrons allow for a number of applications in the emerging field of organic electronics. However, the inherent limited solubility of planar π-conjugated systems hinders their development, forcing chemists to introduce ancillary solubilising side-chains. On the other hand, ultrahigh-vacuum on-surface synthesis has become a powerful discipline that enables designing with atomistic precision a new plethora of molecular compounds, polymers, and nanomaterials that otherwise are unachievable by conventional organic chemistry.
Herein we present a novel on-surface chemical transformation that allows obtaining π-conjugated acene polymers from simple aromatic molecules carrying =CBr2 functionalities. The deposition of such precursors on an Au(111) surface gives rise to close-packed assemblies. Thermal annealing promotes the debromination of the species that thereafter homocouple and give rise to long anthracene wires linked by acetylene bridges, featuring a bandgap of 1.5 eV (see figure below).
When larger acenes or periacenes are used (i.e. pentacene, bisanthene, peripentacene) the resulting polymers undergo dramatic structural and electronic changes. Non-contact-AFM evince that the benzoid subunits evolve from aromatic (anthracene) to quinoid (pentacene, bisanthene...), while the alkyne linkers turn into cumulenic. The STM images allow witnessing the HOMO-LUMO levels crossing from anthracene to pentacene. This swap destabilises the aromatic structure and enables a biradical-quinoid one, that permit almost vanishing bandgaps below 0.35 eV. These findings can also be rationalised by topological band gap theory: DFT, tight binding and GW calculations predict that polymers these quasi-metallic polymers exhibit a topologically non-trivial electronic structure. Our results herald novel pathways to engineer π-conjugated polymers on solid surfaces, addressing the relevant family of acenes and, thus, contributing to develop the field of on-surface chemistry and to steer the design of modern low bandgap polymers.

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(Invited) Toward the Isolation of Giant C120-C200 Fullertubes
Authors: Noble Cora A. , Koenig Ryan M , Ashcroft Chloe A. , Franklin Hannah M. , Bourret Emmanuel , Stevenson Steven 
Published: July 2022

The newly reported purification and isolation of pristine and unfunctionalized C90 and C100 fullertubes has generated excitement due to their unique “hybrid” structure of ½-fullerene endcaps, but with a single wall nanotubular belt and mid-section. Unique features of these fullertubes include a (1) defined molecular weight, (2) reproducible structure, (3) pristine tubular belt region, and (4) natural solubility into organic solvents without functionalization or polymer wrapping. Hence, the surface of the fullertube belt region would inherently be smooth and free from surface coatings, derivatization, or oxidation. These features provide a unique molecular architecture for investigating the true nature of electronic and photophysical properties of the fullertube's tubular belt.
In this presentation, we will discuss our lab’s recent progress toward the isolation of segmentally longer fullertubes of higher aspect ratios as we seek to move from C120 fullertubes to C150 fullertubes and beyond.

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(Invited) Synthesis and Optical Properties of Rod-Shaped Graphene Nanoparticles
Authors: Medina Lopez Daniel , Liu Thomas , Elias Christine , Rondin Loïc , Lauret Js , Campidelli Stephane 
Published: July 2022

The scientific community has given much interest to graphene in recent years because of its good mechanical, thermal and electrical properties. Nonetheless, applications in optics and optoelectronics can be limited due to the absence of a bandgap. In order to engineer a bandgap, we can reduce the size of graphene into graphene quantum dots (GQDs). GQDs synthesis is primarily described via top-down methods (lithography, hydrothermal and electrochemical approaches).[1] Though effective, these methods do not allow accurate control of the size, shape and edges of the GQDs. On the other hand, bottom-up graphene materials have developed exponentially for the last decade with the synthesis of highly controlled graphene nanoribbon structures and moderately soluble graphene quantum dots.[2,3] Our group demonstrated that bottom-up GQDs could act as single-photon emitters exhibiting high brightness and stability.[4]
In order to investigate the structure-property relationship, we designed a series of rod-shaped graphene nanoparticles that differ only by their length, keeping the same morphology, symmetry and edge states (see figure). These nanoparticles are fully soluble, which facilitate their purification and individualization in solution and give rise to well-defined absorption spectra. Here we report on the synthesis of these GQDs, and we will present results on advanced characterization of their optical properties.[5]
[1] Yang, J.-S., Martinez, D. A. & Chiang, W.-H. Synthesis, Characterization and Applications of Graphene Quantum Dots in Recent Trends in Nanomaterials: Synthesis and Properties, Khan, Z. H., Springer Singapore, (2017).
[2] Narita, A., Wang, X.-Y., Feng, X. & Müllen, K. New advances in nanographene chemistry. Chem. Soc. Rev.
44, 6616–6643 (2015).
[3] Wang, X.-Y., Yao, X. & Müllen, K. Polycyclic aromatic hydrocarbons in the graphene era. Sci. China Chem.
62, 1099–1144 (2019)
[4] Zhao, S. et al. Single photon emission from graphene quantum dots at room temperature. Nat. Commun.
9, 3470 (2018).
[5] D. Medina-Lopez et al., submitted

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Flexible, Freestanding, Bio-Compatible Electrodes for Integrated Supercapacitor
Authors: Ghodbane Myriam , Ashraf Juveiriah M. , Karam Zainab , Busa Chiara 
Published: July 2022

On the route to sustainable technology and chemistries for bio-compatible energy storage devices, water-based formulations represent a promising alternative to the solvent now in use. Several polymer-based options, including poly(2-hydroxyethyl methacrylate) (poly[HEMA]) and silicon hydrogels show excellent biocompatibility, good mechanical properties and durability.
Alongside, in supercapacitors and batteries, carbon nanotubes (CNTs) and carbon nanostructures (CNSs) are a versatile alternative to the consolidated graphitic electrode. CNTs are well-known to provide excellent mechanical properties together with electrical conductivity and large surface area.
In this work, we introduce a novel concept for integrating freestanding CNTs-based energy storage system within hydrogels, preventing direct exchange with the environment. A systematic approach in regards with the electrochemical performances (CV, GCD, EIS) and the mechanical properties identifies favourable geometries for full systems, among several solutions.