bluuebunny/crossref_metadata_2025_split huggingface dataset:
(Invited) Transport Limits for Zinc Aqueous Electrolyte Batteries: Investigation over Multiple Length Scales
Authors: Takeuchi Esther S. , Marschilok Amy C. , Takeuchi Kenneth J. 
Published: August 2024

Large scale grid level storage would benefit from low cost environmentally sustainable batteries. A system class under investigation is rechargeable zinc anode batteries utilizing aqueous electrolytes. These systems hold promise due to their potential for safe low-cost scalable energy storage. Consideration of the systems over various length scales is warranted due to the complexity of the possible reactions and pernicious parasitic processes. Further, the diversity and intricacies of these battery systems inherently reduce the probability of optimization experiments alone resulting in marketable products.
Many of the fundamental issues influencing ion and electron transport and electron transfer and how the transport phenomena evolve under flux are not yet fully undefined. More complete understanding demands multiple characterization approaches used in concert, to tie together information gathered at the local or atomic level and the mesoscale with systems level performance from electrochemical impedance spectroscopy (EIS), galvanostatic cycling (GC), and related techniques. This presentation will provide insight into probes of the reaction mechanisms, evolution of zinc interfaces, methods to determine limitations of cathode function at high rate, and impact of the findings on the electrochemical behavior of the batteries.
Green Hydrogen Production Using Manganese – Vanadium Redox Flow Batteries
Authors: Chaurasia Shabdiki B. , Aravamuthan Sundar Rajan , Sullivan Connor S. , Ross Michael B. , Agar Ertan 
Published: August 2024

The redox flow batteries (RFBs) can be tuned to allow mining of surplus energy capacity and supplement green hydrogen economy as a one-stop station [1, 2].With this concept, an RFB can undergo two sequential discharging modes: i) electrochemical discharge of redox active species, and ii) chemical discharge to produce hydrogen gas, when surplus electricity is available, on the surface of electrocatalysts contained in additional external tanks (i.e., dual circuit RFB) [3, 4]. Herein, electrolytes with Mn3+/Mn2+ (RFB catholyte ~ 1.5 V vs. SHE) and V3+/V2+ (RFB anolyte ~ −0.26 V vs. SHE) redox species are flown to spatially separated external catalytic reactors to drive redox mediated water electrolysis. The fully charged V2+ redox mediator in the anolyte provides electrons to achieve hydrogen evolution reaction (HER) and thereby itself gets discharged to V3+ redox state before circulating back to flow battery tanks.
Considering the additional layer of redox-mediated water electrolysis, it is imperative to identify benchmark cycling performance for a robust dual circuit RFB operation. In the first phase of our study, electrochemical behavior of Mn3+/Mn2+ redox couple in the favorable presence of V5+ as an additive was elucidated using ultramicroelectrode voltammograms. Despite significant performance enhancement, capacity fade during galvanostatic cycling could not be fully eliminated owing to Mn3+ disproportionation reaction and manganese crossover. Also, charge/discharge cycling profiles suggest that the inevitable Mn3+ disproportionation affects the true state-of-charge in electrolytes which in turn hinders their potential to generate hydrogen gas. Working towards hydrogen generation, our recent efforts have been to evaluate kinetics for hydrogen evolution reaction (HER) on different carbon substrate – electrocatalyst combinations in acidic V3+/V2+ environment. Overall, this study aims to provide a profound understanding of reliable operating conditions to establish a synergy between Mn3+ disproportionation during the conventional energy storage mode and the total volume of hydrogen gas produced during the secondary mode.

References

Reynard, D. and H. Girault, Combined hydrogen production and electricity storage using a vanadium-manganese redox dual-flow battery. Cell Reports Physical Science, 2021. 2(9): p. 100556.

Amstutz, V., et al., Renewable hydrogen generation from a dual-circuit redox flow battery. Energy & Environmental Science, 2014. 7(7): p. 2350-2358.

Peljo, P., et al., All-vanadium dual circuit redox flow battery for renewable hydrogen generation and desulfurisation. Green Chemistry, 2016. 18(6): p. 1785-1797.

Piwek, J., et al., Vanadium-oxygen cell for positive electrolyte discharge in dual-circuit vanadium redox flow battery. Journal of Power Sources, 2019. 439: p. 227075.
Stable Cycling of Ultrahigh Mass Loaded MnO2 for Low-Cost Sodium-Ion Batteries
Authors: Luo Yunkai , Chandrasekaran Swetha , Hu Bintao , Freyman Megan C. , Lin Dun , Li Yat , Worsley Marcus Andre , Dunn Bruce S. 
Published: August 2024

Achieving cost-effective and sustainable solutions for large-scale energy storage is critical for advancing the global clean energy transition. The intermittent nature of green energy underscores the inadequacy of current large scale energy storage technologies like pumped hydroelectricity which is susceptible to geographic and water resource constraints, making batteries a prime candidate for this role. Although lithium-ion batteries (LIBs) with high energy and power density are a viable solution, the high cost and uneven distribution of lithium reserves limits the widespread application of LIBs for grid energy storage. Considering these developments and the challenges posed by limited lithium reserves, sustainable and low-cost sodium-ion batteries (SIBs) emerge as a promising alternative.
Among the various battery electrode materials, manganese dioxide (MnO2) stands out as a promising choice for large-scale energy storage applications due to its earth abundance, cost-effectiveness and non-toxic nature. Although MnO2 is known as a pseudocapacitive material with superior cycling stability in aqueous electrolytes, its dissolution in non-aqueous electrolytes has restricted its widespread use in long lifetime batteries. In this study, we demonstrate that an ether-based electrolyte solution (1M NaClO4 in diglyme) is able to achieve stable cycling of electrodeposited ε-MnO2 as a cathode for SIBs, reaching a over 75% capacity retention over 1000 cycles. This response surpasses conventional ester-based electrolytes (58% of 1M NaClO4 in EC/PC). A comparative cycling stability study, coupled with electrochemical quartz crystal microbalance characterization, validates the efficacy of the ether-based electrolyte in mitigating MnO2 dissolution. Furthermore, the integration of 3D printed graphene aerogel (3D GA) as a scaffold for electrodeposited MnO2 leads to enhanced electrochemical performance of the MnO2 electrode (3D MnO2/GA), resulting in a high areal capacity of 4.4 mAh cm-2 at a current density of 10 mA cm-2. The 3D MnO2/GA electrode possesses scalable electrochemical performance with mass loadings from 20 mg cm-2 to 80 mg cm-2. Using this electrode, a high mass loaded sodium-ion battery (SIB) device was fabricated by using utilizing 58 mg cm-2 3D MnO2/GA as the cathode and 16 mg cm-2 dip-coated TiO2@Cu foam as the anode. This MnO2 | TiO2 device delivered a notable areal capacity of 6.2 mWh cm-2 and a high areal power density of 70.7 mW cm-2. Moreover, the SIB device demonstrates 85% capacity retention after 500 cycles, underscoring the stable cycling of this high-energy and power-density SIB device.
High Entropy Alloys as Bifunctional Catalysts for Reversable Metal Air Batteries
Authors: Stalcup Matt , Percival Stephen J. 
Published: August 2024

The development of stable non-noble metal bifunctional catalysts for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) are essential for technologies such as reversible metal air batteries. We have shown that synthesis of high entropy alloy nanoparticles formed through a novel synthesis method where metal precursor containing aqueous nanodroplets freely diffusing in an emulsion solution, collide with an electrode surface and the metal precursors are reduced, thus forming a homogeneous particle containing the predetermined metal composition. Afterwards, the particles are annealed at a low temperature causing a phase separation of the metals, forming a metal nanoparticle that is surrounded by a stabilizing metal oxide. We have demonstrated that equimolar Fe, Ni, Co, Cr, and Mn solutions produce bifunctional FeNiCo metal nanoparticles surrounded by CrMnOx that are very active for both OER and ORR. The synthesis technique also affords the flexibility to tailor composition of the nanoparticles and potentially provide access to previously difficult to synthesize compositions and may alter the electrocatalytic reaction pathways and activities.
Sandia National Laboratories is a multimission laboratory managed and operated by National Technology and Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International Inc., for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-NA0003525
Amorphous Cobalt Tin Oxide/Reduced Graphene Oxide Decorated on Graphite Felt as Positive Electrode for Vanadium Redox Flow Battery
Authors: Huang Zih-Jhong , Lin Hsin-Te , Kabtamu Daniel Manaye , Wang Chen-Hao 
Published: August 2024

The Vanadium Redox Flow Battery (VRFB) stands out as one of the most promising large-scale energy storage systems. Nevertheless, the graphite electrode materials commonly used in VRFBs often exhibit drawbacks such as limited electrochemical activity and insufficient conductivity, ultimately resulting in suboptimal performance for the VRFB. In this study, we utilized highly conductive reduced graphene oxide (rGO) as a carrier for cobalt tin oxide (CoSnO3), aiming to enhance their catalytic capability towards vanadium ions. CoSnO3/rGO composite was confirmed using XRD and TEM, revealing nanoboxes morphology and amorphous structure. XPS and EPR analysis showed an increase in oxygen vacancies after composite formation.
In order to further prove the effect of CoSnO3/rGO composite catalyst modified graphite felt, the modified graphite felt electrode was applied to the positive electrodes of VRFB, and the charge and discharge tests at different current densities were carried out. At a current density of 160 mA/cm², the composite demonstrated a voltage efficiency of 74.22%, surpassing the heat treated graphite felt by 2.69%. Noteworthy enhancements in capacitance were also evident at this specific current density. Furthermore, stability testing over 50 cycles revealed no significant degradation, underscoring the superior performance and outstanding durability of the CoSnO3-rGO modified graphite felt throughout charge and discharge cycling. The result of this study highlight the promising potential of CoSnO3-rGO composites as efficient catalysts for vanadium redox flow batteries, providing improvements in electrochemical performance and long-term stability.
(Invited) Fluorinated Linear Carbonate Electrolyte for Lithium-Ion Batteries with Fast-Charging, High Voltage, and Wide Operating Temperatures
Authors: Tan Sha , Yen Dean , Hu Enyuan 
Published: August 2024

Lithium-ion batteries (LIBs) are key solutions to clean energy. Their high energy densities have led to the dominance of LIBs in mobile devices and electric vehicles. However, traditional electrolyte limits their operation at high voltage and extreme environmental temperatures. Here, we designed a new multifunctional electrolyte, in which lithium bis(fluorosulfonyl)imide (LiFSI) is used as salt and fluorinated diethyl carbonate (DFDEC) is used as the major solvent. With this optimized electrolyte, the graphite||LiNi0.8Mn0.1Co0.1O2 (NMC811) full cells are capable of fast-charging and can deliver long-term cycling with a cutoff voltage as high as 4.5V. Specifically, the battery shows the capacity retention of 84.3% after 500 cycles with an average coulombic efficiency (CE) as high as 99.93%. Synchrotron-based characterization suggests the formation of anion derived, LiF-rich interphases on the surfaces of both graphite anode and NMC811 cathode. Thanks to the fast ion transport and stable interphase, the cell in the optimized electrolyte demonstrates stable cycling behavior within a wide operating temperature. At high temperature (60 ºC), the full cell delivers 88.8% of its initial capacity after 130 cycles at a high current density of 1C. At low temperature (-20 ºC), the optimized electrolyte enables a capacity retention of 90.9% after 100 cycles when charging and discharging at 0.2C.
Acknowledgment: The work done at Brookhaven National Laboratory was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technology Office of the U.S. DOE through Applied Battery Research for Transportation (ABRT) program under contract no. DE-SC0012704. The electrodes used in this study were produced at the U.S. Department of Energy’s (DOE) CAMP (Cell Analysis, Modeling and Prototyping) Facility, Argonne National Laboratory. The CAMP Facility is fully supported by the DOE Vehicle Technologies Office (VTO). This research used beamline 7-ID-2 (SST-2) of the National Synchrotron Light Source II, U.S. DOE Office of Science User Facilities, operated for the DOE Office of Science by Brookhaven National Laboratory under contract number DE-SC0012704. SEM measurements for this manuscript were performed at Center for Functional Nanomaterials, a U.S. DOE office of Science User Facility, at Brookhaven National Laboratory under the contract number DE-SC0012704.
Balancing Activity and Stability through Compositional Engineering of ORR Catalysts
Authors: Khalakhan Ivan , Briega Martos Valentin , Xie Xianxian , Cherevko Serhiy , Matolínová Iva 
Published: August 2024

Widespread adoption of advanced energy technologies, such as proton-exchange membrane fuel cells (PEMFCs), relies on the development of efficient and durable electrocatalysts for the oxygen reduction reaction (ORR). Given its unique properties, platinum has been the exclusive option for meeting activity demands, whether in its monometallic form or various bimetallic alloys with other metals1. Nevertheless, the challenge persists with durability due to catalyst degradation under the hostile electrochemical environment of the PEMFC cathode, leading to an irreversible detrimental effect on fuel cell performance. Studies of the degradation mechanisms of ORR catalysts and their underlying principles have highlighted that, among various degradation mechanisms, inhibiting the dissolution of Pt is crucial for suppressing their deterioration2.
Owing to its high oxidation potential, gold has attracted increasing attention as an element that can be utilized to stabilize Pt and Pt-based ORR catalysts3. However, as Au is inactive towards ORR, achieving a balance between catalyst activity and stability requires precise compositional engineering.
Targeting that aim, varying amounts of Au were added to model Pt and PtNi catalysts prepared by magnetron co-sputtering. A systematic study, employing multiple complementary characterization techniques such as Synchrotron Radiation Photoelectron Spectroscopy (SRPES), X-ray Diffraction (XRD), Rotation Disc Electrode (RDE), Scanning Flow Cell coupled to an Inductively Coupled Mass Spectrometer (SFC-ICP-MS), enabled us to gain a comprehensive understanding of the composition–activity–stability relationship to find optimal Pt–Au and PtNi-Au alloying for maintaining high ORR activity and improving catalyst stability4.

References:

(1) Nørskov, J. K.; Rossmeisl, J.; Logadottir, A.; Lindqvist, L.; Kitchin, J. R.; Bligaard, T.; Jónsson, H. Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode. J. Phys. Chem. B
2004, 108 (46), 17886–17892.
(2) Bogar, M.; Yakovlev, Y.; Sandbeck, D. J. S.; Cherevko, S.; Matolínová, I.; Amenitsch, H.; Khalakhan, I. Interplay Among Dealloying, Ostwald Ripening, and Coalescence in PtXNi100–X Bimetallic Alloys under Fuel-Cell-Related Conditions. ACS Catal.
2021, 11 (18), 11360–11370.
(3) Lopes, P. P.; Li, D.; Lv, H.; Wang, C.; Tripkovic, D.; Zhu, Y.; Schimmenti, R.; Daimon, H.; Kang, Y.; Snyder, J.; et al. Eliminating Dissolution of Platinum-Based Electrocatalysts at the Atomic Scale. Nat. Mater.
2020, 19 (11), 1207–1214.
(4) Xie, X.; Briega-Martos, V.; Farris, R.; Dopita, M.; Vorokhta, M.; Skála, T.; Matolínová, I.; Neyman, K. M.; Cherevko, S.; Khalakhan, I. Optimal Pt–Au Alloying for Efficient and Stable Oxygen Reduction Reaction Catalysts. ACS Appl. Mater. Interfaces
2023, 15 (1), 1192–1200.
Simplified Ftacv Model to Quantify the Electrochemically Active Sitedensity in PGM-Free ORR Catalysts
Authors: Friedman Ariel , Elbaz Lior 
Published: August 2024

The development of platinum group metal-free catalysts is considered the most prominent path for reducing the
cost of low-temperature fuel cells (LTFC). Despite the great advancement in the field, its further progress is
currently limited by the ability to understand and mitigate the catalysts’ degradation mechanisms, which up to
recent years was limited by the lack of activity descriptors. Recent work showed that this could be solved using
Fourier-transformed alternating current voltammetry that enables to deconvolute Faradaic currents arising from
the redox reaction of the active sites from the capacitive currents, and by that accurately measure the electrochemically
active site density of these catalysts in situ fuel cells. However, the analysis of the results can be
complex, requiring simulation software for accurate parameter extraction. Herein, a simplified analysis of
Fourier-transformed alternating current voltammetry is presented. This was done by mapping the influence of
various variables, such as resistivity, capacitance, and thermodynamic and kinetic dispersion, on the accuracy of
electrochemically active site density measurements. Under specific, yet realistic, operating conditions, a single
equation with the peak current of the 5th harmonic as the only variable can be used to quantify electrochemically
active site density with high accuracy. This approach was demonstrated using molecular catalysts, iron phthalocyanine,
as a model molecule, and a commercial, heat-treated catalyst.
Redox Stability Analysis of Co-Doped Barium Niobate Thin Films Via Cyclic Voltammetry
Authors: Denoyer Luke H , Ramaiyan Kannan , Benavidez Angelica , Ferlauto Andre Santarosa , Fonseca Fabio Coral , Garzon Fernando H. 
Published: August 2024

The electrochemical oxidative coupling of methane (E-OCM) to higher hydrocarbons, requires anodes that are stable under reducing conditions. We have previously demonstrated high activity with long term stability/durability for the perovskite anode BaMg0.33Nb0.67-xFexO3-δ (BMNF) while performing E-OCM1. Our group has also improved the total conductivity and activity of barium niobate perovskites via exchange of Mg for Ca (from 18 mS/cm-1 to 41 mS/cm-1), while also decreasing the Goldschmidt tolerance factor below 1 for increased cubic perovskite structural stability2. Perovskite metal oxide thin films can be produced with well-defined thicknesses and stoichiometries through pulsed laser deposition (PLD)3. These thin films are utilized in cyclic voltammetry experiments on YSZ substrates to further elucidate the chemical stability and oxygen sub-stoichiometry of high temperature SOFC/SOEC electrodes. Through application of reducing potentials to the electrode of interest, the voltage and current responses can be correlated to effective oxygen activities in which reduction of the electrode may occur. Usage of this technique with calcium and iron doped barium niobate perovskites (BaCa0.33Nb0.67-xFexO3-δ - BCNF) provides insights into the thermochemical stability and iron doping effects under highly reducing environments. The BCNF thin film electrodes were characterized via grazing incidence XRD and XRF for crystal structure and chemical composition. After initial characterization, cyclic voltammetry experiments were performed in a novel cell setup. These BCNF thin films show promise for evaluating stability mechanisms for E-OCM operation while providing details on compositional changes and oxygen loss of BCNF in reducing environments.

References:

(1) Denoyer, L. H.; Benavidez, A.; Garzon, F. H.; Ramaiyan, K. P. Highly Stable Doped Barium Niobate Based Electrocatalysts for Effective Electrochemical Coupling of Methane to Ethylene. Adv. Mater. Interfaces
2022, 9 (27), 2200796.
(2) Ramaiyan, K.; Denoyer, L. H.; Benavidez, A.; Garzon, F. H. Role of Dopants in Fine-Tuning the Electrical and Catalytic Properties of Barium Niobate Perovskites Towards High-Temperature Electrolyzer Application. ECS Trans.
2023, 111 (6), 1139.
(3) Anh, D. T. V.; Olthuis, W.; Bergveld, P. Sensing Properties of Perovskite Oxide La0.5Sr0.5CoO3−δ Obtained by Using Pulsed Laser Deposition. Sens. Actuators B Chem.
2004, 103 (1), 165–168.
(Invited) Insights from the Interplay of the Electrode Structure and the Microenvironment for Electrochemical CO2 Conversion
Authors: Wong Andrew Barnabas 
Published: August 2024

The electrochemical CO2 reduction reaction (CO2RR) represents a critical approach toward the carbon-neutral generation of hydrocarbons. However, despite intense research efforts, the need remains to increase the selectivity and activity of electrocatalysts for CO2RR. Thus, there has been increasing interest in optimizing the microenvironment to boost the activity and selectivity of electrocatalytic sites for CO2 conversion.
This presentation discusses several strategies that are being pursued in my research group to optimize the microenvironment for CO2 conversion based on a detailed understanding of model systems for electrochemical CO2 conversion to C2+ products on Cu. Here, microenvironment-level insights from two model systems will be discussed:

The effect of localization of Ag co-catalysts in Cu nanowire arrays

The impact of the 3D interface on the microenvironment within model Cu nanowire array cathodes to boost C2 product activity

Overall, these insights can aid in the rational design of electrodes for electrochemical CO2 conversion.

Figure 1
(Invited) Enhancing Alkaline Water Electrolyzers: Insights into Activation Protocols, Loading and Ionomer Effects
Authors: Shviro Meital 
Published: August 2024

Alkaline water electrolyzers (AWEs) are playing an increasingly important role in the renewable energy landscape due to their scalability and independence from scarce materials.1,2

This presentation will examine the various elements of AWE performance, emphasizing the critical role of activation protocols, loading dynamics, and ionomer characteristics.
Our investigation examined activation protocols and deciphering insights into the electrochemical initiation processes that are critical to optimizing AWE performance. At the same time, we investigate the nuanced relationship between loading and efficiency seeking the optimal catalyst loading for enhanced hydrogen production while maintaining operational stability. In addition, the influence of ionomers is investigated to understand their role.
By integrating these investigations, our work contributes to a holistic understanding of AWEs and provides practical insights to optimize their performance in renewable energy systems.

References

1 Aili, D.; Kraglund, M. R.; Rajappan, S. C.; Serhiichuk, D.; Xia, Y.; Deimede, V.; Kallitsis, J.; Bae, C.; Jannasch, P.; Henkensmeier, D.; Jensen, J. O. Electrode Separators for the Next-Generation Alkaline Water Electrolyzers. ACS Energy Lett. 2023, 8, 1900– 1910

Karacan C., Lohmann-Richters F. P., Shviro M., Keeley G. P., Müller M., Carmo M., and Stolten D., J. Electrochem. Soc., 2022, 169, 054502