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Donald R. Sadoway. Newhouse, Jocelyn Marie Massachusetts Institute of Technology. Department of Materials Science and Engineering. Massachusetts Institute of Technology. Department of Materials Science and Engineering 2014-09-19T19:36:51Z 2014-09-19T19:36:51Z 2014 2014 http://hdl.handle.net/1721.1/89840 890128566 Thesis: Ph. D., Massachusetts Institute of Technology, Department of Materials Science and Engineering, 2014. This electronic version was submitted by the student author. The certified thesis is available in the Institute Archives and Special Collections. Cataloged from student-submitted PDF version of thesis. Includes bibliographical references (pages 179-188). A one-dimensional, integrative model of the voltage during liquid metal battery operation has been developed to enhance the understanding of performance at the cell level. Two liquid metal batteries were studied: Mg-Sb for initial development of the model and Li-Bi for demonstration of generality. The baseline of the model is the thermodynamic potential, which is the maximum potential upon discharge. Emf measurements were used to confirm the literature values for Mg-Sb liquid alloys and calibrate a two-phase Mg-Sb reference electrode. The charge transfer kinetics at the alloying electrode were studied using the galvanostatic pulse method and a novel working electrode design. The contribution of the charge transfer reaction to the cell operation was found to be negligible for both the Mg-Sb and Li-Bi electrodes (less than 5 mV). Mass transport in the positive electrode was examined and found to depend significantly on the concentration dependence of the interdiffusivity and the volume change with alloying. The interdiffusivities for both Mg-Sb and Li-Bi were measured. A semi-analytical expression was proposed and agreed with the numerical solution determined using the finite difference method. Mass transport in the electrolyte was modeled using a boundary layer diffusion approximation. For the IR drop, the solution resistance was assumed to be constant. The predicted operating voltage for both the Mg-Sb and Li-Bi was consistent with experimental data. by Jocelyn Marie Newhouse. Ph.D. 188 pages eng Massachusetts Institute of Technology M.I.T. theses are protected by copyright. They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission. See provided URL for inquiries about permission. http://dspace.mit.edu/handle/1721.1/7582 Materials Science and Engineering. Modeling the operating voltage of liquid metal battery cells Thesis application/pdf Publication unknown unknown <Publication xmlns="https://www.openaire.eu/cerif-profile/1.1/" id="5a5a1ba1-503c-4a35-ba2d-8d42ad527f82"> <Type xmlns="https://www.openaire.eu/cerif-profile/vocab/COAR_Publication_Types">http://purl.org/coar/resource_type/c_1843</Type> <Language>eng</Language> <Title>Modeling the operating voltage of liquid metal battery cells</Title> <PublishedIn> <Publication> </Publication> </PublishedIn> <PublicationDate>2014</PublicationDate> <Authors> <Author> <DisplayName>Newhouse, Jocelyn Marie</DisplayName> <Affiliation> <OrgUnit> </OrgUnit> </Affiliation> </Author> </Authors> <Editors> </Editors> <Publishers> <Publisher> <DisplayName>Massachusetts Institute of Technology</DisplayName> <OrgUnit /> </Publisher> </Publishers> <License>http://dspace.mit.edu/handle/1721.1/7582</License> <Keyword>Materials Science and Engineering.</Keyword> <Abstract>A one-dimensional, integrative model of the voltage during liquid metal battery operation has been developed to enhance the understanding of performance at the cell level. Two liquid metal batteries were studied: Mg-Sb for initial development of the model and Li-Bi for demonstration of generality. The baseline of the model is the thermodynamic potential, which is the maximum potential upon discharge. Emf measurements were used to confirm the literature values for Mg-Sb liquid alloys and calibrate a two-phase Mg-Sb reference electrode. The charge transfer kinetics at the alloying electrode were studied using the galvanostatic pulse method and a novel working electrode design. The contribution of the charge transfer reaction to the cell operation was found to be negligible for both the Mg-Sb and Li-Bi electrodes (less than 5 mV). Mass transport in the positive electrode was examined and found to depend significantly on the concentration dependence of the interdiffusivity and the volume change with alloying. The interdiffusivities for both Mg-Sb and Li-Bi were measured. A semi-analytical expression was proposed and agreed with the numerical solution determined using the finite difference method. Mass transport in the electrolyte was modeled using a boundary layer diffusion approximation. For the IR drop, the solution resistance was assumed to be constant. The predicted operating voltage for both the Mg-Sb and Li-Bi was consistent with experimental data.</Abstract> <Access xmlns="http://purl.org/coar/access_right" > </Access> </Publication>