bluuebunny/crossref_metadata_2025_split huggingface dataset:
Single-Flow Batteries Leveraging Multiphase Electrolytes
Authors: Suss Matthew , Rewatkar Prakash , Asarthen Mohamed , Gloukhovski Robert , Kuperman Sofi , Gat Amir 
Published: September 2023

The share of electricity generated from renewable sources is growing rapidly, and thus grid-scale battery storage is becoming more prevalent. Aqueous redox flow batteries have the potential to provide safe and scalable energy storage, but the high cost of storage, particularly the membrane and balance of plant costs, has inhibited commercialization. The recently developed single-flow battery leveraging a multiphase electrolyte promises a low-cost system [1], as it is membraneless and uses only one tank and flow loop, but suffers from low Coulombic efficiency [1]. To unlock the potential of such a system, the interplay between interphase mass transport, multiphase flow phenomena, and battery performance must be unraveled. Here, we will compare our previously developed theoretical battery model derived from a boundary layer analysis [2,3] to results from a dedicated experimental program [4]. This led to several key findings, including that our battery operates in a regime characterized by a high Stanton number, and that our analytical solutions led to excellent predictions in various operational regimes when using the interphase mass transport coefficient as a single-valued fitting parameter [4]. In other regimes, such as at low electrolyte velocity, results indicate that gravity acting on the denser polybromide phase played a significant role, and progress towards incorporating gravitational effects into models will be discussed [4].

Figure 1: Schematic of a discharging single-flow battery leveraging a multiphase flow electrolyte. The flow consists of a continuous, bromine-poor aqueous phase and dispersed, bromine-rich polybromide phase. Bromine in the polybromide phase is largely electrochemically inactive, thus such an electrolyte enables membraneless operation by limiting the crossover of bromine to the zinc anode.

References:

[1] Amit, L., Naar, D., Gloukhovski, R., la O', G.J. and Suss, M.E., 2021. “A Single-Flow Battery with Multiphase Flow”. ChemSusChem, 14(4), pp.1068-1073.
[2] Ronen, R., Gat, A.D., Bazant, M.Z. and Suss, M.E., 2021. “Single-flow multiphase flow batteries: Theory”. Electrochimica Acta, 389, p.138554.
[3] Kuperman, S., Ronen, R., Matia, Y., Zigelman, A., Suss, M.E. and Gat, A.D., 2022. “Modelling the fluid mechanics in single-flow batteries with an adjacent channel for improved reactant transport”. Flow, 2, E11.
[4] Ronen, R., Gloukhovski, R. and Suss, M.E., 2022. “Single-flow multiphase flow batteries: Experiments”. Journal of Power Sources, 540, p.231567.

Figure 1
Improved Formulation and Optimization of Sodium Polysulfide/Bromine Electrolytes for Redox Flow Battery
Authors: Khan Safyan Akram , Mansha Muhammad , Ali Shahid , Ahmad Aziz , Khan Majad , Tahir Muhammad Nawaz , Qamar Mohammad 
Published: September 2023

Sodium polysulfide/bromine RFBs are one the most promising electrolyte couples for scale-up technology. Sodium polysulfide/bromine RFB utilizes aqueous sodium polysulfide and sodium bromide solution as anolyte and catholyte, respectively, separated by a sodium ion exchange membrane.
Polysulfide electrolyte of different concentrations ranging from S:Na ratio of 0.5 that is without the addition of elemental sulfur, up to saturation limit having S:Na ratio of 2.4 with the addition of elemental sulfur are prepared.
Studies of electrolyte composition have been essential to establishing the optimum conditions for practical use. These involve various parameters such as sulfide concentration, the ratio of dissolved sulfur to sulfide, speciation, pH, and the effect of temperature on battery stability and lifetime. Different experimental methodologies were used to investigate the speciation in these concentrated solutions. A titration method was developed to find the concentration of HS- and OH- species in any sodium sulfide and polysulfide solution. Sulfide and polysulfide chemistry is presented in more detail by comparing the UV-ATR spectra. It was found that polysulfide electrolyte shows very complex system containing species such as HS-, OH-, H+ and Sn
2- where n = 2-5 and sulphur oxoanions.
Furthermore, we have established that controlled speciation of polysulfide solution can substantially impact on the electrochemistry in these electrolytes. Controlling the pH, concentrations of HS- and OH- ions in polysulfide electrolytes is extremely important to overcome many challenges of the polysulfide/bromine RFB system.
Therefore, we have developed an improved polysulfide electrolytes with high charge densities but more soluble species in the presence of excessive HS- species. Charging and discharging data on our improved and well optimized polysulfide electrolyte will be presented.
Scale-up of Interdigitated Design from Small Cell to Large Cell for Aqueous Redox Flow Batteries
Authors: Zeng Chao , Kim Soowhan , Fu Yucheng , Chen Yunxiang , Bao Jie , Xu Zhijie 
Published: September 2023

Redox flow batteries present attributes for large-scale energy storage. Interdigitated flow configuration is a promising structure due to its higher power density and lower pressure loss. The screening for new electrolyte is usually first tested on small cell (<10 cm2) due to its easy operation and less electrolyte consumption. To test the electrolyte functionality in practical application condition, large-scale (i.e., 780 cm2) testing is required conventionally in laboratory or industry. The twice testing is due to the fact that the testing results in small cell are different from that for large-scale interdigitated cell. In order to reduce the testing cycles and quickly estimate the application of new electrolytes, scale-up of interdigitated design from small cell to large cell is investigated in this work.
Numerical simulation on different scales of interdigitated cells (10cm2, 78cm2, 130cm2, 780cm2) is conducted to assess the polarization. The local velocity distribution and redox-active species concentration are extracted to show their dominance on the cell performance. It is shown that with similar velocity and concentration distribution, cell with different scales present similar limiting current density and power density, regardless of active area. It implies that the results in small cells can be directly scaled up for large cells without further testing. It provides an avenue for quick estimation of new electrolyte in application condition.
Experimental testing is conducted on vanadium redox flow battery for different scale of interdigitated cell. The experimental results will demonstrate this scale-up from small-scale to middle-scale interdigitated cell.
Role of Acetonitrile Additive in Enhanced Performances of Aqueous Zn Anodes
Authors: Ilic Stefan , Counihan Michael , Lavan Sydney Nicole , Connell Justin G. , Tepavcevic Sanja 
Published: September 2023

Zinc-ion batteries have been proposed as promising candidates to address ever-growing demands for energy storage and limited resources available for the currently used lithium-battery systems. Despite their promise, the apparent advantages of aqueous zinc-ion batteries (low cost and high energy density) are still overshadowed by uncontrolled water interactions at the zinc metal-electrolyte interface, such as the hydrogen evolution reaction and electrode corrosion. A number of different strategies – e.g., water-in-salt, addition of chelating agents and/or co-solvents – have been proposed to overcome the aforementioned interfacial problems. Among them, the addition of acetonitrile to aqueous ZnSO4-based electrolytes has shown great promise, with reports of improved Coulombic efficiencies and increased cycle life. However, the actual role of this additive remains unclear. In this work, we determine the mechanistic principles behind the participation of acetonitrile in enhancing the performance of aqueous Zn batteries. For this purpose, we utilized a combination of X-ray absorption and Raman spectroscopies, cyclic voltammetry, and galvanostatic coin cell cycling. Our results indicate that the addition of acetonitrile perturbs the interfacial solvation structure, rather than the bulk. Specifically, acetonitrile does not penetrate the first solvation shell of the Zn2+ ion, but does modify interfacial solvation behavior, likely by physisorption to the electrode surface. The Coulombic efficiency of half cells was found to depend on electrode material, employed current density and capacity, and only moderately on acetonitrile concentration. Overall, this works points strongly to the need for systematic evaluation of battery performance in co-solvent systems, and provides a new framework for future efforts to optimize ion transport and performance in zinc-ion batteries.
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The submitted manuscript has been created by UChicago Argonne, LLC, Operator of Argonne National Laboratory (“Argonne”). Argonne, a U.S. Department of Energy Office of Science laboratory, is operated under Contract No. DE-AC02-06CH11357. The U.S. Government retains for itself, and others acting on its behalf, a paid-up nonexclusive, irrevocable worldwide license in said article to reproduce, prepare derivative works, distribute copies to the public, and perform publicly and display publicly, by or on behalf of the Government. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan. http://energy.gov/downloads/doe-public-access-plan
(Invited) Submillimeter Bundled Microtubular Flow Battery Cells with Ultrahigh Volumetric Power Density
Authors: Liu Nian 
Published: September 2023

Flow batteries are a promising energy storage solution. However, the footprint and capital cost need further reduction for flow batteries to be commercially viable. The flow cell, where electron exchange takes place, is a central component of flow batteries. Improving the volumetric power density of the flow cell (W/Lcell) can reduce the size and cost of flow batteries. While significant progress has been made on flow battery redox, electrode, and membrane materials to improve energy density and durability, conventional flow batteries based on the planar cell configuration exhibit a large cell size with multiple bulky accessories such as flow distributors, resulting in low volumetric power density. In this talk, I will introduce a submillimeter bundled microtubular (SBMT) flow battery cell configuration that significantly improves volumetric power density by reducing the membrane-to-membrane distance by almost 100 times and eliminating the bulky flow distributors completely. Using zinc–iodide chemistry as a demonstration, our SBMT cell shows peak charge and discharge power densities of 1,322 W/Lcell and 306.1 W/Lcell, respectively, compared with average charge and discharge power densities of <60 W/Lcell and 45 W/Lcell, respectively, of conventional planar flow battery cells. The battery cycled for more than 220 h corresponding to >2,500 cycles at off-peak conditions. Furthermore, the SBMT cell is compatible with zinc–bromide, quinone–bromide, and all-vanadium chemistries. The SBMT flow cell represents a device-level innovation to enhance the volumetric power of flow batteries and potentially reduce the size and cost of the cells and the entire flow battery.
(also see our publication: https://doi.org/10.1073/pnas.2213528120)
(Digital Presentation) Sizing and Economic Assessment of an Electrochemical Rebalancing Process for Vanadium Flow Batteries
Authors: Poli Nicola , Trovo Andrea , Guarnieri Massimo 
Published: September 2023

In all-vanadium flow batteries, electrolyte oxidation from atmospheric oxygen and/or hydrogen evolution due to operations at extreme states of charge may occur. After events like these, an electrolyte imbalance affecting the battery capacity appears that cannot be recovered by a simple mixing operation and a more complex rebalancing process must be undertaken. Among the different rebalancing processes which have been proposed in the literature, this work consider the electrochemical method that uses a specific electrolysis reactor to reduce V(V) in the positive electrolyte to the level of V(II) in the negative electrolyte, so as to equate the states of charge in the two tanks. In order to adjust the balancing mechanism to the system, the rated power of the reactor performing this process should be optimized to the VFB rated energy, imbalance level (namely, the process periodicity) and the rebalancing process duration. In turn, the rated power defines the size and thus the cost of the reactor, namely area and number of cells, given their current density and internal area specific resistance. This work presents a model that assembles these parameters and their interplay, allowing to investigate how the process and the reactor can be optimized. Such model also provides an economical evaluation of the investment and operational expenditures of the rebalancing process, thus providing design criteria for the minimization of these cost figures. For the sake of example, numerical calculations are performed referring to a 500-kWh VFB, that is a quite common rating for VFBs, and they indicate that a cost reduction of almost 70% is achieved if 10-hour processes are run four times per year instead of once a year. At this rebalancing frequency, the 500 kWh VFB needs a 9-kW reactor costing around €15.000.

References

[1] E. Rodby, T.J. Carney, Y.A. Gandomi, J.L. Barton, R.M. Darling, F.R. Brushett, Assessing the levelized cost of vanadium redox flow batteries with capacity fade and rebalancing, J. Power Sources 460 (2020), 2227958.
[2] Rudolph, U. Schröder, I.M. Bayanov, On-line controlled state of charge rebalancing in vanadium redox flow battery, J. Electroanal. Chem. 703 (2013) 29-37.
[3] Li, L. Liu, Y. Zhao, J. Xi, Z. Wu, X. Qiu, The indefinite cycle life via a method of mixing and online electrolysis for vanadium redox flow batteries, J. Power Sources 438 (2019) 226990.
[4] Poli, M. Schaffer, A. Trovò, J. Noack, M. Guarnieri, P. Fischer, Novel electrolyte rebalancing method for vanadium redox flow batteries, Chem. Eng. J. 405 (2021), 126583.
[5] Noack, N. Roznyatovsakaya, K. Pinkwart, J. Tübke, Vanadium proton exchange membrane water electrolyser, J. Power Sources 340 (2017) 144-151.

Figure 1
Atomically Dispersed Transition Metal-Nitrogen-Carbon Electrocatalysts: Design, Synthesis, Characterization, Reactivity and Durability
Authors: Atanassov Plamen , Murphy Eamonn , Ly Alvin , Delafontaine Laurent , Wang Hanson , Khedekar Kaustubh , Huang Ying , Liu Yuanchao , Matanovic Ivana , Zenyuk Iryna 
Published: September 2023

Platinum group metal-free (PGM-free) catalysts have been targeted as possible Earth Abundant Elements solution to many electrochemical energy conversion technologies. Special attention has been given to PGM-free electrocatalysis with atomically dispersed (AD) transition metal moieties decorated over nitrogen-doped carbonaceous materials (a.k.a. M-N-C catalysts). Major applications for M-N-Cs are in cathode catalysts for oxygen reduction reaction (ORR). 1 These materials are employed across the pH-range: in proton exchange membrane fuel cells (PEMFC), biological (microbial) fuel cells (MFC) and alkaline, including anion/hydroxyl exchange membrane fuel cells (AFC, AEMFC/HEMFC). We have successfully introduced M-N-C catalysts synthesized by sacrificial support method (SSM) as a hard template approach based on high temperature pyrolysis.2 In most cases a secondary pyrolysis is being performed to promote AD display of the transition metal.3

This talk will address structure-to-property correlations for M-N-C catalysts in ORR based on electrochemical activity obtained in rotating ring-disk electrodes (RRDE) with those spectroscopic and microscopic observations and density functional theory (DFT) calculations of oxygen binding on AD transition metal. We will discuss the role of the AD transition metal, participation of the surface N-groups as co-catalysts/alternative active sites and the possible role of surface oxides as co-catalysts or hydrophilic/hydrophobic properties descriptor. M-N-C catalysts performance in single membrane electrode assembly (MEA) fuel cells will also be discussed in the context of its surface chemistry and materials structure/morphology. We will focus on local hydrophobicity of SSM-based M-N-C electrocatalystsand its impact on the MEA performance.
A broad spectrum of AD transition metal decorated MNCs have been synthesized and evaluated for catalytic activity in ORR (and other processes). The use of such materials as “active supports” for highly dispersed platinum or platinum alloy nanoparticles will be discussed. New developments in synthesis protocols enabling “green chemistry” scalable solutions will be discussed.
References:

T. Asset and P. Atanassov, Joule, 2020, 4, 33.

Y. Huang, Y. Chen, M. Xu, T. Asset, P. Tieu, A. Gili, D.S. Kulkarni, V. de Andrade, F. De Carlo, H.S. Barnard, A. Doran, D. Parkinson, X. Pan, P. Atanassov, and I.V. Zenyuk, Materials Today, 47 (2021) 53-68

Y. Chen, Y. Huang, M. Xu, T. Asset, X. Yan, K. Artyushkova, M. Kodali, E. Murphy, A. Ly, X. Pan, I.V. Zenyuk, and P. Atanassov, Materials Today, 53 (2022) 58-70
Species Crossover in Electrochemical CO2 Reduction
Authors: Lou Kun , Hu Leiming , Wrubel Jacob A , Neyerlin K.C. 
Published: September 2023

Catalyst studies have improved the overall CO2R (electrochemical CO2 reduction) faraday efficiency (FE)1, however, the experimental FE can be deteriorated by product crossover through the membrane in a practical electrochemical CO2R cell. The CO2R product molecules generated at the cathode are subject to oxidation at the anode if they permeate through the membrane, thus decreasing the practical CO2R product collection. The product loss at the anode also poses a challenge for quantification and study of the crossover behavior2–4. In this work, we will present experimental designs that effectively overcome the oxidation at the anode to reveal the CO2R product crossover.
The CO2R product crossover can be driven by electromigration and the concentration gradient across the membrane. Although the electromigration plays a significant role based on the current density of CO2R operation, the later can be varied by membrane design parameters. The membrane thickness and non-ionic reinforcement layers can effectively change the permeability of various CO2R product species. The CO2R product crossover measurements of commercially available anion exchange membranes will be presented.
From a fundamental perspective, CO2R product crossover is a reflection of membrane selectivity. We also extend the component study to the cell level where parameters like electrolyte concentration/conductivity and electrolyte/CO2 flow rate also affect the crossover. The species other than products in CO2R can have impact on both catalyst performance and crossover. We will discuss the crossover behavior in our standard CO2R setup5,6. Overall, we aim to address the CO2R product crossover by bridging the fundamental study of a component and CO2R integration efforts at NREL.

Ge, L. et al. Electrochemical CO2 reduction in membrane-electrode assemblies. Chem
8, 663–692 (2022).

McCallum, C. et al. Reducing the crossover of carbonate and liquid products during carbon dioxide electroreduction. Cell Rep. Phys. Sci.
2, 100522 (2021).

Wang, N. et al. Suppressing the liquid product crossover in electrochemical CO2 reduction. SmartMat
2, 12–16 (2021).

Zhang, J., Luo, W. & Züttel, A. Crossover of liquid products from electrochemical CO2 reduction through gas diffusion electrode and anion exchange membrane. J. Catal.
385, 140–145 (2020).

Chen, Y. et al. A Robust, Scalable Platform for the Electrochemical Conversion of CO2 to Formate: Identifying Pathways to Higher Energy Efficiencies. ACS Energy Lett.
5, 1825–1833 (2020).

Chen, Y. et al. The effect of catholyte and catalyst layer binders on CO2 electroreduction selectivity. Chem Catal.
2, 400–421 (2022).
Elucidating the Mechanisms of Oxygen Depolarized Cathode Catalyst Degradation
Authors: Yang Kevin , Kodali Mounika , Smeltz Andrew , Mukerjee Sanjeev 
Published: September 2023

Fe-N-C has shown to be a viable low-cost, PGM-free catalyst to replace RhS/C for oxygen-depolarized cathode applications. Though it possesses high intrinsic ORR activity and relatively good immunity towards chloride ion poisoning, further studies must be conducted to explore the degradation pathways of Fe-N-C in a wide pH range to realize its capabilities in concentrated hydrochloric acid and Chlor-alkali electrolysis1.
Moreover, Fe-N-C has been shown to maintain performance after being in operation for more than one hour with three uncontrolled shutdowns, nearly matching RhS/C at a current density of 0.5 A/cm2 with a cell potential of 1.38 V1. Thus, we will perform long-term durability tests under Raman and X-ray absorption spectroscopy (XAS). Furthermore, a single electrochemical flow cell will be designed for both spectrochemical methods to characterize the interaction between the catalyst and the formation of products during the uncontrolled shutdown. Specifically, Raman spectroscopy will be utilized to detect changes in the catalyst structure if any Fe-N4 bonds are broken or changed due to chloride anions upon shutdown. XAS-Fe edge will be employed to elucidate the formation of Fe-Cl bonds due to crossover anions during operation and when the cell is removed from the power supply. By determining the degradation pathways or lack of, we can truly assess the viability of Fe-N-C as a replacement for RhS/C in hydrochloric acid and Chlor-alkali electrolysis. These techniques provide a platform to reduce experimental uncertainty and gain further insight into the degradation of both catalyst and membrane-electrode assembly performance.

References

[1] Jingkun Li, Qingying Jia, Shraboni Ghoshal, Wentao Liang, and Sanjeev Mukerjee Langmuir
2017
33 (37), 9246-9253