Magnesium batteries: research and applications

350 Pages·2020·29.48 MB·English

by  Fichtner, Maximilian

Magnesium Batteries
Research and Applications
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Energy and Environment Series
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23: Magnesium Batteries: Research and Applications
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Magnesium Batteries
Research and Applications
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6 Preface
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oi: Magnesium is one of the few elements on Earth that offers real long-
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or reserves of Mg minerals are widespread and easy accessible and these
c.
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s.r reserves should last approximately 430 000 years (seawater not included),
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u if the consumption remains constant. Another reason is that magnesium
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s:// is recyclable and virtually non- toxic. Rather, it is an essential element in
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o mals and humans. In batteries, the Mg ion can transport and store two
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01 charges per ion and, thus, offers the potential for higher storage capacities,
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er which is complemented by the fact that a Mg metal anode can work safely
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m in a cell with a liquid electrolyte. In contrast, Li ions are stored in graphite
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ept in the anode of current Li ion batteries, for safety reasons – and are thereby
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on 1 A good, working and rechargeable Mg battery would not only be technical
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e progress, which could potentially improve the performance of battery- driven
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bli applications, it would also be a relief, because it opens up the possibility for
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difficult to achieve with current Li ion technology due to the limitation of
certain raw materials and the expensive recycling process for lithium.
The work on Mg batteries started with some scattered publications a few
decades ago. The feasibility was demonstrated in principle but it became
clear that the classical concepts for electrolytes and electrodes cannot just
be transferred or applied to Mg battery technology and more questions were
raised than answered. Then, the field moved more in the focus of battery
research in the 2000s, after a breakthrough had been achieved with the

Energy and Environment Series No. 23
Magnesium Batteries: Research and Applications
Edited by Maximilian Fichtner
© The Royal Society of Chemistry 2020
Published by the Royal Society of Chemistry, www.rsc.org
v
View Online
vi Preface
development of a new and effective electrolyte. However, there were still no
more than 10 to 15 publications per year. This changed considerably in the
2010s when the number of publications steadily increased so that at the end
of the decade, between 120 and 150 publications per year had been made on
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00 various topics of Mg batteries.
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7 Mg batteries.
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oi: on solid- state magnesium ion conductors by C. Battaglia et al. Theoretical
g | d modelling of multivalent ions in inorganic hosts is critical for an under-
or standing of the dynamics and storage process of Mg in materials and will be
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s.rs introduced by G. Gautam and P. Canepa. The anode side seems simple and
ub straightforward because pure Mg metal has been claimed to be suitable as
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s:// an anode material. However, the chapter by E.M. Sheridan et al. shows that
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on Complementing work is presented by M. Matsui in a chapter where the elec-
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3 materials and related mechanisms are introduced by H.D. Yoo and S.H. Oh.
n 1 B. Ingram will further expand upon this discussion with a contribution on
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ed high voltage cathodes, which includes a techno- economical evaluation based
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blis on a methodology developed in their laboratory. The part on cathode mate-
Pu rials will be complemented by an overview on organic electrodes by J. Bitenc
and R. Dominko and a further contribution from Z. Zhao- Karger, who gives
an overview of the properties and status of Mg sulfur batteries.
An unusual but interesting concept is the dual- ion battery, which relies
on the combination of the Mg ion plus a second ion, both reversibly
stored in different electrodes. The concept, first results and interesting
effects of the co- intercalation of cations and anions will be presented by
H. Li et al. As aqueous (primary) Mg batteries are still one of the most
widespread applications, D. Hoeche will present an overview on the sta-
tus of this technology.
Finally, although the development of Mg batteries is still at an early stage
and the performance of Mg batteries is not yet competitive, data already
available from laboratory cells has been collected by C. Tomasini Montene-
gro et al. The data was evaluated for the first life- cycle analysis of Mg batteries
and gives clear indications for further directions in the development of Mg
battery cells.
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Preface vii
At this point, I would like to cordially thank all of the authors and co-
authors for their commitment and dedication and their contributions to all
of the relevant topics of Mg battery technology, making “Magnesium Batter-
ies – Research and Applications” a comprehensive reflection of the state- of-
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07- Maximilian Fichtner
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16 Helmholtz- Institute Ulm (HIU), Helmholtzstr. 11, Ulm, 89081, Germany
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oi: Chapter 1 Motivation for a Magnesium Battery 1
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Acknowledgement 14
References 14
Chapter 2 Non- aqueous Electrolytes for Mg Batteries 17
R. Mohtadi and O. Tutusaus
2.1 Introduction 17
2.2 Halide- ion Containing Electrolytes 18
2.2.1 Carbon- based Anions 19
2.2.2 Nitrogen- based Anions 20

Energy and Environment Series No. 23
Magnesium Batteries: Research and Applications
Edited by Maximilian Fichtner
© The Royal Society of Chemistry 2020
Published by the Royal Society of Chemistry, www.rsc.org
ix
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x Contents
2.2.3 Oxygen- based Anions 21
2.2.4 Halides as Anions 27
2.2.5 Weakly Coordinating Anions 32
2.3 Chloride- free Magnesium Electrolytes 33
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g | d S. Payandeh, A. Remhof and C. Battaglia
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ub 3.2 Phosphate- based Solid- state Magnesium-
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on 3.2.2 Other Oxygen Containing Solid- state
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1 Magnesium- ion Conductors 69
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n 1 3.5 Solid- state Magnesium- ion Conductors Based
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Pu References 75
Chapter 4 Theoretical Modelling of Multivalent Ions in
Inorganic Hosts 79
Gopalakrishnan Sai Gautam and Pieremanuele Canepa
4.1 Introduction 79
4.1.1 Thermodynamics of Multivalent
Electrodes 80
4.1.2 Kinetics of Ionic Diffusion in Materials 91
4.1.3 Density Functional Theory as a Tool
to Assess Thermodynamic and Kinetic
Properties 96
4.1.4 Application of First- principles Methods to
Multivalent Ion Intercalation Hosts 98
4.2 Conclusions 109
Acknowledgement 110
References 110
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Contents xi
Chapter 5 Anode Materials for Rechargeable Mg Batteries 114
K. Jayasayee, R. Berthelot, K. C. Lethesh and E. M. Sheridan
5.1 Introduction 114
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g | d 5.3 Alloying- type Negative Electrode Materials 127
or 5.3.1 Electrochemical Behavior of Single
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ub 5.3.2 Electrochemical Behavior of Bimetallic
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on Alloys 134
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n 1 M. Matsui
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blis 6.1 Introduction 142
Pu 6.2 Overview of the Electrolyte Solutions 143
6.3 Deposition Mechanism 150
6.4 Surface Morphologies of Electrodeposited
Magnesium Metal 151
6.5 Passivation Layer and Possible SEI Layer 157
6.6 Intermetallic Anodes 160
6.7 Summary 163
References 164
Chapter 7 Insertion Electrodes for Magnesium Batteries:
Intercalation and Conversion 167
H. D. Yoo and S. H. Oh
7.1 Introduction 167
7.2 Materials for Intercalation 169
7.2.1 Layered Sulfides and Selenides 169
7.2.2 Layered Oxides 171
7.2.3 Graphite 173