Challenges of a Rechargeable Magnesium Battery: A Guide to the Viability of this Post Lithium-Ion Battery PDF
Preview Challenges of a Rechargeable Magnesium Battery: A Guide to the Viability of this Post Lithium-Ion Battery
SPRINGER BRIEFS IN ENERGY Claudiu B. Bucur Challenges of a Rechargeable Magnesium Battery A Guide to the Viability of this Post Lithium-Ion Battery Foreword by Thomas D. Gregory SpringerBriefs in Energy SpringerBriefs in Energy presents concise summaries of cutting-edge research and practical applications in all aspects of Energy. Featuring compact volumes of 50 to 125 pages, the series covers a range of content from professional to academic. Typical topics might include: A snapshot of a hot or emerging topic A contextual literature review A timely report of state-of-the art analytical techniques An in-depth case study A presentation of core concepts that students must understand in order to make independent contributions. Briefs allow authors to present their ideas and readers to absorb them with minimal time investment. Briefs will be published as part of Springer’s eBook collection, with millions of users worldwide. In addition, Briefs will be available for individual print and electronic purchase. Briefs are characterized by fast, global electronic dissemination, standard publishing contracts, easy-to-use manuscript preparation and formatting guidelines, and expedited production schedules. We aim for publication 8-12 weeks after acceptance. Both solicited and unsolicited manuscripts are considered for publication in this series. Briefs can also arise from the scale up of a planned chapter. Instead of simply contributing to an edited volume, the author gets an authored book with the space necessary to provide more data, fundamentals and background on the subject, methodology, future outlook, etc. SpringerBriefs in Energy contains a distinct subseries focusing on Energy Analysis and edited by Charles Hall, State University of New York. Books for this subseries will emphasize quantitative accounting of energy use and availability, including the potential and limitations of new technologies in terms of energy returned on energy invested. More information about this series at http://www.springer.com/series/8903 Claudiu B. Bucur Challenges of a Rechargeable Magnesium Battery A Guide to the Viability of this Post Lithium- Ion Battery Foreword by Thomas D. Gregory Claudiu B. Bucur Toyota Research Institute of North America Ann Arbor, MI, USA ISSN 2191-5520 ISSN 2191-5539 (electronic) SpringerBriefs in Energy ISBN 978-3-319-65066-1 ISBN 978-3-319-65067-8 (eBook) DOI 10.1007/978-3-319-65067-8 Library of Congress Control Number: 2017950294 © The Author(s) 2018 This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission or information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar methodology now known or hereafter developed. The use of general descriptive names, registered names, trademarks, service marks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. The publisher, the authors and the editors are safe to assume that the advice and information in this book are believed to be true and accurate at the date of publication. Neither the publisher nor the authors or the editors give a warranty, express or implied, with respect to the material contained herein or for any errors or omissions that may have been made. The publisher remains neutral with regard to jurisdictional claims in published maps and institutional affiliations. Printed on acid-free paper This Springer imprint is published by Springer Nature The registered company is Springer International Publishing AG The registered company address is: Gewerbestrasse 11, 6330 Cham, Switzerland Foreword Since the dawn of mankind, we have attempted to enhance our comfort and produc- tivity by using naturally occurring materials to generate energy. This energy was initially utilized locally, and the subsequent ability to transmit it to remote locations was a far-reaching innovation. Wood and other rudimentary solid fuels were fol- lowed by modern, energy-dense alternatives such as liquid hydrocarbons which could be safely and economically transported over large distances and rapidly loaded into a mobile device such as a portable generator or vehicle. Combustion of these fuels generates thermal energy which was initially used directly and later con- verted to mechanical and electrical energy. On-demand harnessing of electrical energy that led to the rise of the central electric power station which coupled with advances in long-range transmission of electricity had a dramatic impact on society. Unfortunately, it currently limits urban development by the necessity of an electric wire which connects the power station to every end user. In addition, our modern transportation infrastructure relies almost entirely on liquid fuels and internal com- bustion engines which work well but are inefficient, have high maintenance costs, and generate substantial amounts of greenhouse gases. A revolutionary (although rather slowly developing) innovation has been the incorporation of electrochemical energy storage in the form of batteries into our energy infrastructure. For example, early electric vehicles were powered by lead- acid and nickel-iron batteries; later, hybrid electric vehicles used nickel-metal hydride batteries. Nickel-cadmium and nickel-metal hydride battery development also led to practical cordless phones, power tools, and other portable devices. However, the most far-reaching development in the battery space has been the invention and commercialization of lithium-ion batteries which has revolutionized portable electronics and made long-range electric vehicles a reality. With continu- ous improvement over the past 25 years, lithium-ion batteries are rapidly approach- ing practical limits in terms of energy density and cost. In addition, large-scale implementation of this technology may have the outcome of straining resources such as lithium (Li), cobalt (Co), and nickel (Ni). However, cheap and energy-dense magnesium (Mg), when coupled with other abundant low-cost materials such as sulfur, has the potential to produce a v vi Foreword game- changing battery technology which could propel society to the next level of electrification, especially in the vital transportation field. In 1981, I initiated an effort at The Dow Chemical Company aimed at developing a high-energy density rechargeable battery based on Mg. Events such as gasoline shortages were respon- sible for intense interest in electric vehicles, but the rechargeable battery technology of that era was not capable of achieving the then-desired 220 Wh/kg specific energy. My assessment at the time, however, was that portable applications likely repre- sented a more immediate business opportunity and a potential stepping-stone to longer-term EV applications for a high-energy density battery and would help drive the development of new battery applications. The first rechargeable Li metal batter- ies had been introduced commercially shortly before this, but safety and reliability problems prevented widespread adoption, and their presence in the marketplace was short-lived. However, this also represented the first use of electrochemical intercala- tion cathodes in nonaqueous batteries, a development which proved to be a water- shed event in battery technology. As part of my project proposal to Dow management, I drew up a sketch of a proposed Mg battery that included a Mg metal anode and an intercalation cathode with an electrolyte capable of both reversible Mg plating and Mg ion intercalation, although to the best of my knowledge, no one had up to that point demonstrated sufficient reversibility of either of those electrochemical reac- tions. Shortly thereafter, Ronald Hoffman (who had worked on aqueous Ni-Zn bat- tery development at another company) joined our team and began conducting our cathode research. He first used di-n-butyl magnesium in chemical intercalation experiments around 1982 and conducted electrochemical testing of materials that showed promise in these screening experiments using 1 M Mg(ClO)/THF electro- 4 2 lyte. Simultaneously with the cathode development work, building on earlier litera- ture, I developed electrolytes based on ethereal solutions of Grignard reagents that possessed reasonable ionic conductivity and could reversibly plate and dissolve Mg metal at high current efficiency. A key discovery in that effort was that the addition of Lewis acids, particularly AlCl , to the Grignard electrolytes significantly 3 improved their performance. However, the plating cells I was using utilized a large quantity of electrolyte, and it was not obvious whether the Grignard compounds were stable or simply decomposing as electrolysis proceeded as reported in previ- ous literature. Therefore, I needed a cell with a small, well-defined electrolyte vol- ume to test electrolyte stability in a reasonably short experiment. I used a fluoropolymer tubing union from Swagelok Company to make a cell that fulfilled these requirements, and we later added a side port in some cells to allow introduc- tion of a reference electrode. Such experimental cells are now widely known in the literature as “Swagelok cells.” Finding that I could dissolve a Mg anode and plate it at the cathode at ca. 100% current efficiency while passing more equivalents of charge through the cell than were present in the Mg in the electrolyte (and with no appreciable change in cell voltage) indicated that the Grignard electrolytes were not decomposing. As our electrolyte development efforts expanded, Richard Winterton, an organometallic chemist, joined the project and synthesized the Mg organobo- ranes that we used in some of our later work. By 1985, however, it had become apparent to us that we still had a long way to go and our anticipated timing and Foreword vii resource requirements didn’t fit Dow’s time horizon for R&D projects at that point in time, so the project was terminated. Once we had filed all the primary patent applications covering the technology, I gave our first external talk on this effort at the spring 1988 Electrochemical Society meeting in Atlanta, GA, and we followed that with the publication of a full paper [Gregory TD, Hoffman RJ, Winterton RC (1990) Nonaqueous Electrochemistry of Magnesium Applications to Energy Storage. J Electrochem Soc 137:775–780. doi: https://doi.org/10.1149/1.2086553]. Significant advances in Mg battery science and technology have been docu- mented in the literature since our early work at The Dow Chemical Company, the vast majority of it building on the concept of a Mg metal anode and a cathode utiliz- ing reversible Mg ion intercalation with electrolytes containing organometallic Mg compounds and derivatives. In 2000, Prof. Doron Aurbach and his colleagues at Bar-Ilan University reported on the high mobility of Mg2+ ions in Chevrel phase materials and demonstrated a long cycle life rechargeable Mg battery using such materials as cathodes. Professor Gerbrand Ceder at the University of California– Berkeley has brought the power of computational chemistry to bear on this field and has substantially accelerated the search for new cathode materials and increased our understanding of electrolyte chemistry. We have learned that Mg nonaqueous elec- trochemistry is considerably more complex than that of Li and that factors such as ionic mobility and thermodynamic stability of many Mg compounds make discov- ery of intercalation cathodes which exhibit high-voltage vs. Mg and long-term reversibility a difficult endeavor. Conversion cathodes with high specific capacity may represent a viable alternative, even if at the expense of lower cell voltage. The potential societal benefits for success in this field are substantial, and widespread efforts continue at universities, government research labs, and commercial organi- zations. I look forward to seeing continued advancements in this field as new gen- erations of researchers take up this quest. Thomas D. Gregory The Dow Chemical Company (Retired)/Borealis Technology Solutions LLC Midland, MI, USA Preface The industrial revolution (1750–1850) fueled the largest economic growth in the history of the world. It has provided the means for a gigantic leap forward toward the modern world of mechanized manufacturing, motorized transportation, central power stations, big cities, cheap agriculture, clean water, commercial flights, tele- communications, personal computing, space travel, and a longer and better life for all of us. Two main contributions have been the invention of the combustion engine and the long-distance transfer of electricity. Most of our daily life hinges on the development of these two monumental discoveries. However, some have recently proposed that the current rate of innovation is slowing down in part due to more resources being dedicated to discoveries which impact society on a more superficial level. For example, according to recent metrics, most recent startups focus on e-business (Alibaba, Amazon, Twitter, Facebook, Groupon, or Snapchat). According to these critics, these e-companies do not improve the quality of our life in as a grandiose fashion as the first commercial airliner did at the turn of the last century. Therefore, monumental, game-changing inventions are sought after more than ever in today’s incremental world. While many radical new ideas are being pursued (Randell Mill’s SunCell® would be high on that list), the world seems to have entered an electrification race. Gradual improvements in technologies such as elec- trochemical storage and photovoltaics have reached a tipping point which could foster a new era of decentralized power generation and autonomous storage. These alternative methods of energy storage have already started to compete with the 150-year-old model of the central power station. Today, most electricity is generated at a central power plant and is transferred as alternative current via high-voltage cables to power large, congested nearby cities. Advanced commerce and modern lifestyles are enabled by automotive transporta- tion powered by internal combustion engines which are fueled by a network of gasoline stations. However, advances in solar, wind, and battery technology have reached the necessary critical mass to offer an alternative. Electric cars and solar roofs are now a commercial reality. In the near future, economies of scale promise to bring down their cost which will make autonomous power generation and usage an option for anyone interested. With a current energy density of 265 Wh/kg (and ix x Preface possible improvements of up to 20%), the lithium-ion battery has the required life- time to power personal terrestrial vehicles or autonomous or ad hoc power grids. According to Tesla and Volkswagen, the price of 1 kWh of lithium-ion storage will drop to $100 by 2020 which translates into a $10,000–$15,000 cost for the battery pack in any personal car (sedan or SUV). Tesla has the aggressive goal of a one mil- lion mile warranty for its drivetrain which amounts to the complete lifetime of the vehicle. Nonetheless, we dare to look further and desire higher energy densities and lon- ger lifetimes at ever cheaper prices. This quest is the exciting field of post-lithium- ion batteries which may open the door to currently inaccessible markets such as electric commercial flight or commercial terrestrial transportation which require a strenuous, nonstop schedule of operation. These new markets require large improve- ments in energy density (>500 Wh/kg) and cycle life (>10,000 full cycles) or steep cost reductions. Rechargeable magnesium batteries are promising next-generation batteries due to the safety, low cost, and high volumetric energy density of magne- sium. For example, an ultralow-cost contender is the intrinsically safe magnesium- sulfur battery (280 Wh/kg) which may cost less than $10 for 1 kWh of energy. Sony Corporation is reportedly working on this battery and is planning to bring it to market by 2020. Such a post-lithium-ion battery may create entirely new markets and improve the standard of living for all mankind. This brief is written for the battery enthusiast, who may either desire to invest in the field, is curious about a new exciting area of research, or is simply a college student who wants to learn more about future battery tech. A minimal familiarity with concepts of lithium-ion is necessary to grasp concepts related to electrolyte or cathode development. The brief starts off with a short history of battery and how we reached the tipping point of lithium-ion and makes the case for a transition beyond lithium-ion. A rechargeable battery with a magnesium metal anode is then pro- posed, and recent developments in the field of magnesium electrolytes and elec- trodes are discussed and critiqued. Challenges in these key areas are unearthed, analyzed, and explained. In the end, a conclusion summarizes key recent findings and proposes future direction. The author would like to acknowledge Dr. John Muldoon for his support and collaboration in areas including magnesium battery research during his tenure at the Toyota Research Institute of North America. Fight on, John! Ann Arbor, MI, USA Claudiu B. Bucur
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