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Characterization of the Cathodic Thermal Behavior of Molten CaCl2 and Its Hygroscopic Chloride Mixture During Electrolysis

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Title: Characterization of the Cathodic Thermal Behavior of Molten CaCl2 and Its Hygroscopic Chloride Mixture During Electrolysis
Authors: Shibuya, Ryota Browse this author
Natsui, Shungo Browse this author →KAKEN DB
Nogami, Hiroshi Browse this author
Kikuchi, Tatsuya Browse this author →KAKEN DB
Suzuki, Ryosuke O. Browse this author →KAKEN DB
Issue Date: 12-Jun-2020
Publisher: The Electrochemical Society (ECS)
Journal Title: Journal of the electrochemical society
Volume: 167
Issue: 10
Start Page: 102507
Publisher DOI: 10.1149/1945-7111/ab9961
Abstract: A liquid metal electrochemically deposited in CaCl2 or its chloride melts serves as an effective reductant for active metal oxides. Although a very low oxygen concentration can be achieved at a considerably high electrolysis efficiency, the existence of small amount of water impurity in molten chlorides, which is very difficult to detect, causes low electrolysis efficiency. In this study, to clarify the morphological and thermal characteristics of a cathodic electrode in a slightly hygroscopic LiCl-KCl-CaCl2 melt, we simultaneously performed electrochemical measurements and thermal measurements using an ultrafine thermocouple inserted inside a Mo electrode (i.d. 1.57 mm). Concomitantly, changes in the electrode interface were recorded at 500-mu s intervals using a synchronized high-speed digital camera. Despite the small amount of water included in the system, the measured heat absorption was much smaller than thermodynamically predicted, which suggested that the generated hydrogen decreased the purity of the liquid alloy electrodeposited on the cathode surface possibly through hydride formation. By using the synchronized thermal measurement, it was possible to trace the change in the electrodeposition pattern of impurity water quickly and sensitively, which was difficult to determine in only the electrochemical potential-current response.
Rights: © The Electrochemical Society, Inc. 2020. All rights reserved. Except as provided under U.S. copyright law, this work may not be reproduced, resold, distributed, or modified without the express permission of The Electrochemical Society (ECS). The archival version of this work was published in Journal of the electrochemical society, Vol. 167 No. 10.
Type: article (author version)
Appears in Collections:工学院・工学研究院 (Graduate School of Engineering / Faculty of Engineering) > 雑誌発表論文等 (Peer-reviewed Journal Articles, etc)

Submitter: 夏井 俊悟

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