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      The Influence of Dimethyl Sulfoxide as Electrolyte Additive on Anodic Dissolution of Alkaline Zinc-Air Flow Battery

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          Abstract

          The present work describes the effects of dimethyl sulfoxide (DMSO) in KOH aqueous electrolyte on the performance of a zinc-air flow battery. Aqueous electrolytes containing 7 M KOH and (0 to 20)% v/v DMSO were studied revealing a critical role of DMSO on the dissolution and deposition of zinc. The anodic zinc dissolution process was studied via cyclic voltammetry, Tafel polarization and electrochemical impedance spectroscopy (EIS). The presence of DMSO showed improved zinc dissolution performance with the highest peak of zinc dissolution being the electrolyte containing 5% v/v DMSO. Tafel analysis demonstrated a significant decrease in polarization resistance and an increase in corrosion rate due to the introduction of DMSO to the electrolyte. This suggests that DMSO has the ability to suspend zinc oxide in the electrolyte, thus preventing passivation of the zinc surface. EIS results revealed that by adding DMSO to the electrolyte, charge transfer resistance increased. This is attributed to the formation of passive layers having arisen from DMSO adsorption, the formation of zincate ions in the vicinity of the zinc surface, and the deposition of discharged products. A difference in Nyquist plots was observed for 20% v/v DMSO/KOH and 0% v/v DMSO/KOH electrolytes implying non-Debye relaxation behavior taking place due to the surface effects. The electrolytes were implemented in a zinc-air flow battery. Maximum power densities of 130 mW/cm 2 (5% v/v DMSO) and 125 mW/cm 2 (20% v/v DMSO) were obtained and were observed to be about 43% and 28% higher than that of the DMSO-free electrolyte. Results indicated that when 20% v/v DMSO was added to KOH solution, there was 67% zinc utilization efficiency (550 mAh/g) which provided 20% improvement in discharge capacity. Further, the battery with 20% v/v DMSO demonstrated excellent cyclability. Overall, DMSO shows great promise for enhancement of zinc dissolution/deposition in zinc-air batteries.

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          Recent Advances in Aqueous Zinc-Ion Batteries

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            Discharge Performance of Zinc-Air Flow Batteries Under the Effects of Sodium Dodecyl Sulfate and Pluronic F-127

            Zinc-air batteries are a promising technology for large-scale electricity storage. However, their practical deployment has been hindered by some issues related to corrosion and passivation of the zinc anode in an alkaline electrolyte. In this work, anionic surfactant sodium dodecyl sulfate (SDS) and nonionic surfactant Pluronic F-127 (P127) are examined their applicability to enhance the battery performances. Pristine zinc granules in 7 M KOH, pristine zinc granules in 0–8 mM SDS/7 M KOH, pristine zinc granules in 0–1000 ppm P127/7 M KOH, and SDS coated zinc granules in 7 M KOH were examined. Cyclic voltammograms, potentiodynamic polarization, and electrochemical impedance spectroscopy confirmed that using 0.2 mM SDS or 100 ppm P127 effectively suppressed the anode corrosion and passivation. Nevertheless, direct coating SDS on the zinc anode showed adverse effects because the thick layer of SDS coating acted as a passivating film and blocked the removal of the anode oxidation product from the zinc surface. Furthermore, the performances of the zinc-air flow batteries were studied. Galvanostatic discharge results indicated that the improvement of discharge capacity and energy density could be sought by the introduction of the surfactants to the KOH electrolyte. The enhancement of specific discharge capacity for 30% and 24% was observed in the electrolyte containing 100 ppm P127 and 0.2 mM SDS, respectively.
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              Ethanol as an electrolyte additive for alkaline zinc-air flow batteries

              Zinc-air flow batteries exhibit high energy density and offer several appealing advantages. However, their low efficiency of zinc utilization resulted from passivation and corrosion of the zinc anodes has limited their broad application. In this work, ethanol, which is considered as an environmentally friendly solvent, is examined as an electrolyte additive to potassium hydroxide (KOH) aqueous electrolyte to improve electrochemical performance of the batteries. Besides, the effects of adding different percentages of ethanol (0–50% v/v) to 8 M KOH aqueous electrolyte were investigated and discussed. Cyclic voltammograms revealed that the presence of 5–10% v/v ethanol is attributed to the enhancement of zinc dissolution and the hindrance of zinc anode passivation. Also, potentiodynamic polarization and electrochemical impedance spectroscopy confirmed that adding 5–10% v/v ethanol could effectively suppress the formation of passivating layers on the active surface of the zinc anodes. Though the addition of ethanol increased solution resistance and hence slightly decreased the discharge potential of the batteries, a significant enhancement of discharge capacity and energy density could be sought. Also, galvanostatic discharge results indicated that the battery using 10% v/v ethanol electrolyte exhibited the highest electrochemical performance with 30% increase in discharge capacity and 16% increase in specific energy over that of KOH electrolyte without ethanol.
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                Author and article information

                Contributors
                soorathep.k@chula.ac.th
                Journal
                Sci Rep
                Sci Rep
                Scientific Reports
                Nature Publishing Group UK (London )
                2045-2322
                18 October 2019
                18 October 2019
                2019
                : 9
                : 14958
                Affiliations
                [1 ]ISNI 0000 0001 0244 7875, GRID grid.7922.e, Department of Chemical Engineering, Faculty of Engineering, , Chulalongkorn University, ; Bangkok, 10330 Thailand
                [2 ]ISNI 0000 0001 2286 8343, GRID grid.461574.5, Department of Process and Environmental Engineering, INSA Toulouse, ; Toulouse, France
                [3 ]ISNI 0000 0001 0244 7875, GRID grid.7922.e, High-performance computing unit (CECC-HCU), Center of Excellence on Catalysis and Catalytic Reaction Engineering (CECC), , Chulalongkorn University, ; Bangkok, 10333 Thailand
                [4 ]ISNI 0000 0001 2173 7691, GRID grid.39158.36, Division of Materials Science and Engineering, Faculty of Engineering, , Hokkaido University, ; Kita 13 Nishi 8, Sapporo, Hokkaido 060-8628 Japan
                Author information
                http://orcid.org/0000-0003-1518-1417
                http://orcid.org/0000-0002-8334-2449
                http://orcid.org/0000-0002-3129-2750
                Article
                51412
                10.1038/s41598-019-51412-5
                6802117
                31628355
                5d277fab-ab13-4bd2-a8ec-14427f064827
                © The Author(s) 2019

                Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.

                History
                : 19 June 2019
                : 1 October 2019
                Funding
                Funded by: FundRef https://doi.org/10.13039/501100002873, Chulalongkorn University (CU);
                Categories
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                © The Author(s) 2019

                Uncategorized
                chemical engineering,batteries
                Uncategorized
                chemical engineering, batteries

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