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Electrolyte roadblocks to a magnesium

rechargeable battery

Article in Energy & Environmental Science · March 2012

DOI: 10.1039/c2ee03029b

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Environmental Science
Cite this: DOI: 10.1039/c2ee03029b
www.rsc.org/ees PERSPECTIVE
Electrolyte roadblocks to a magnesium rechargeable battery†
John Muldoon,*a Claudiu B. Bucur,a Allen G. Oliver,b Tsuyoshi Sugimoto,c Masaki Matsui,a Hee Soo Kim,a
Gary D. Allred,d Jaroslav Zajicekb and Yukinari Kotanie
Received 31st October 2011, Accepted 21st December 2011
DOI: 10.1039/c2ee03029b

Low cost, non-dendritic magnesium metal is an ideal anode for a post lithium ion battery. Currently,
development of magnesium electrolytes governs the rate of progress in this field, because electrolyte
properties determine the class of cathodes utilized. A review of the latest progress in the area of
magnesium battery electrolyte and a perspective on mitigating present challenges is presented herein.
Firstly, density functional theory has been shown to predict the potential window of magnesium
electrolytes on inert electrodes. Secondly, we report initial efforts aimed to overcome the corrosive
property of these magnesium organohaloaluminates towards less noble metals such as stainless steel.
This is a major challenge in developing high voltage magnesium electrolytes essential for batteries
which operate above 3V. We lastly touch on cathode candidates including the insertion and conversion
classes. One conversion cathode we pay particular attention to is electrophilic sulfur which can be
married with magnesium metal anodes by utilizing non-nucleophilic electrolytes obtained by simple
crystallization of in situ generated magnesium organohaloaluminates. Effectively, non-nucleophilic
electrolytes open the door to research on magnesium/sulfur batteries.

1. Introduction
The United States Energy Information Administration (EIA)
reports that the energy consumed globally in 2008 was estimated
at 1.4 PWh and is expected to rise by 40% within the next
25 years.1 Energy input from cosmic radiation drives most
activity on earth and is naturally stored as a variety of carbon
reserves which are non-renewable over the time scale of their
exploitation. EIA worldwide energy statistic for 2008 reports the
a
Toyota Research Institute of North America, 1555 Woodridge Avenue,
Ann Arbor, MI, 48105, USA. E-mail: john.muldoon@tema.toyota.com;
Tel: +734-995-4403
b
University of Notre Dame, Notre Dame, IN, 46556, USA
c
Toyota Motor Corporation, 1 Toyota-cho, Toyota, Aichi, 471-8572, Japan
d
Synthonix, Inc., 2713 Connector Drive, Wake Forest, NC, 2758, USA
e
Toyota Motor Corporation, 1200 Mishuku, Susono, Shizuoka, 410-1193,
Japan
† CCDC reference numbers 852856 and 852857. For crystallographic
data in CIF or other electronic format see DOI: 10.1039/c2ee03029b
proven total reserve of fossil fuels, such as coal and oil, is capable
of generating 12.2 PWh. As a consequence, the inevitable tran-
sition away from fossil fuels as the main global energy source will
require diversification into alternative, green energy sources, such
as direct solar, hydroelectric, thermal, and wind energy capture.
This shift will require the advent of novel, high energy storage
technologies able to compensate the intermittent characteristics
of alternative energy and provide power on demand or on
schedules similar to those provided by current electric grids.2,3 As
a result, Toyota considers global sustainability and minimizing
industrial and automotive pollution a top priority. With this
objective in mind, Toyota introduced the first generation Prius
Hybrid Electric Vehicle (HEV) in Japan in 1997. Since then it has
continued to improve the hybrid system and has applied it to
other vehicles. Currently, Toyota sells 17 hybrid models
including a 3rd generation Prius and has achieved 3.1 million
HEV sales worldwide. This approach has reduced CO2 emissions
by 19 million tons as of March, 2011.4 In addition, Toyota has

Broader context
Recently, lithium ion batteries have been used to power hybrid vehicles and electric vehicles (EV). In order for EVs to be competitive
in driving range and cost to vehicles powered by combustion engines, a dramatic improvement is required in the energy density of
lithium ion batteries. Without a doubt, the Holy Grail in battery research is the development of post lithium ion batteries. This may
require shifting from alloys to pure metal anodes and from insertion to conversion cathodes such as sulfur or air. Magnesium’s
thermodynamic properties make this metal an obvious candidate as an anode. In this perspective we report the recent progress in the
area of magnesium batteries and discuss how the properties of an electrolyte are crucial in determining a viable cathode.

This journal is ª The Royal Society of Chemistry 2012 Energy Environ. Sci.
demonstrated a Plug-in Hybrid EV (PHEV) based on a third
generation Toyota Prius (model ZVW30) outfitted with 5.2 kWh
lithium-ion batteries, with an all-electric range of 23 km. In order
to develop EVs with a range and cost competitive to those of
conventional combustion engines, development of higher energy
batteries will be required; therefore research of post Li ion
technologies is paramount. Post Li ion batteries (PLiB) can be
defined as those batteries with a theoretical energy density higher
than that of a Li ion battery containing a carbon anode and
a lithium cobalt oxide cathode (2000 Whl
1).
Without a doubt, the Holy Grail in battery research is the
development of PLiB which may require shifting from alloys to
pure metal anodes. Li metal anode is a superior candidate
because of high volumetric capacity (2062 mAh cm
3) and very
Dr Muldoon received his B.Sc
(Hons) in chemistry from
Queens University of Belfast.
He completed his Ph.D at
University of Notre Dame under
the direction of Prof. Brown
studying air oxidation of
organics using terminal oxo
complexes of late transition
metals. He worked as research
associate at The Scripps
Research Institute under Prof.
Sharpless (Nobel laureate in
John Muldoon Chemistry 2001) and Prof.
Fokin, developing applications
of click chemistry including in
situ click chemistry to discover HIV protease inhibitors and
acceleration for chemical reactions on water. He is currently
a principal scientist at Toyota Research Institute of North Amer-
ica. His research interests include future energy solutions such as
Li ion batteries, multivalent batteries and fuel cells.
Dr Bucur obtained his Ph.D
from Florida State University
under the direction of Professor
Schlenoff in 2008, studying
polymers at surfaces, poly-
electrolytes and polyelectrolyte
structures. In 2010 he has
completed his post doctoral
studies in novel biomembranes
for corrosion inhibition with the
US Department of Agriculture.
Currently, he is a research
associate for the post lithium ion
Claudiu B: Bucur research group in the Toyota
Research Institute of North
America. His research interests
include new battery chemistry, most notably, the analysis of new
electrolytes using techniques such as electrochemistry and in situ
analysis.
Energy Environ. Sci.
negative reduction potential (
3.04V vs. NHE). Despite recent
renewed enthusiasm towards Li metal anodes, pioneering work
in this area dates back nearly 100 years (1912) and was carried
out by G.N Lewis. Previous attempts at commercializing
a rechargeable battery containing a Li metal anode have been
dissuaded by the inherent instability of Li metal, especially
during charging. Unfortunately, batteries containing Li metal
anodes suffer from thermal runaway, which is characterized by
temperatures quickly rising above the melting point of metallic
Li.5,6 This inherent safety issue can be related to dendrite
formation on the Li metal anode which short-circuits the
battery.7 In an effort to mitigate this intrinsic instability of
batteries containing a Li metal anode, research shifted towards
lithiated graphites and alloy-based anodes containing Si and
Dr Matsui received his M.S. in
Materials Science and Engi-
neering from Kyoto University
in 2001. From 2001–2008 he
worked as an engineer of Toyota
Motor Corporation, developing
various electrolytes for Lithium
Ion Battery. In 2008 he
completed his Ph.D. at Tokyo
Metropolitan University under
the direction of Prof. Kanamura
studying the surface layer
formation process at Cathode-
Masaki Matsui Electrolyte interphase of
Lithium Ion Battery by using in
situ FTIR, XPS, AFM and so
on. Currently he is a Senior Principal Scientist at Toyota Research
Institute of North America in charge of Post Lithium Ion Research
Group. His research interest is Solid-State Chemistry for the
application of electrochemical devices.
Mr. Kotani graduated from
Tokyo University of Agriculture
and Technology in 1992. In the
same year, he joined Toyota
Motor Corporation and worked
as a materials engineer. Since
2004 he engaged in the research
for new hydrogen storage mate-
rials and battery materials for
eco-friendly vehicles such as
FCHV, EV and PHV. In 2008
Toyota established the new
battery research division for
Yukinari Kotani accelerating the post lithium
iron battery research and his
focus was on high energy
batteries such as all-solid, metal-air and multivalent ion batteries
for extending the cruising range of EV’s.
This journal is ª The Royal Society of Chemistry 2012
Sn.3,8–14 Consequently, one of the major challenges in the
commercialization of PLiBs containing a Li metal anode will be
the suppression of dendritic growth; this is not a trivial task.7
In contrast to Li metal, magnesium (Mg) metal anodes are not
plagued by dendritic formation.15,16 Additionally, Mg is safer
than Li when exposed to air, more abundant in the earth crust
(currently 24 times cheaper then Li), and provides a larger
volumetric capacity of 3832 mAh cm
3. On the other hand, Mg
has a reduction potential of
2.356V vs. NHE, which is 700 mV
less negative than Li and has a unique electrochemistry which
prohibits its reversible deposition in aprotic solvents containing
currently commercial ionic salts such as magnesium bis(tri-
fluoromethane sulfonyl)-imide or magnesium perchlorate.
Reduction of these electrolytes results in the formation of an
electronically blocking surface layer which does not conduct
magnesium ions and inhibits deposition.17,18 However, efficient
Mg deposition in ethereal solutions of Grignard reagents dates
back to 1925 and has been regularly reported on ever since.19–28
Furthermore, Mg has also been successfully deposited from
magnesium organohaloaluminates popularized by Aurbach et al.
which have far superior coulombic efficiencies, voltage stabilities
and current densities to solutions of Grignard reagents. These
organohaloaluminates are generated in situ from the reaction
between an organomagnesium compound (Lewis base) and
a Lewis acid.29–34 The voltage stability and coulombic efficiency
of the magnesium organohaloaluminate electrolytes are highly
dependant upon the chemical structure and ratio of both the
Lewis acid and Lewis base.30
The first rechargeable batteries with Mg metal anodes were
demonstrated in 2000. These Mg batteries showed impressive
cycle life (>3500 cycle measured), low capacity fading over pro-
longed cycling, negligible self-discharge and a wide operating
temperature range. These batteries were considered only as
replacements for nickel-cadmium or lead-acid batteries because
the high formula weight and low voltage of Chevrel phase
MgxMo3S4 insertion cathodes lowered their overall energy
density.30,35 NuLi et al. has reported the feasibility of higher
voltage mesoporous magnesium manganese silicate cathodes and
thus improved the overall energy density of rechargeable
batteries containing Mg metal anodes.36,37 Nevertheless,
a fundamental challenge of magnesium intercalation is the
difficulty of two electron transfer during Mg2+ insertion in
inorganic hosts. This is due to a strong polarization of the small,
divalent Mg2+ ion when compared to similarly sized, but
monovalent Li+ ion.38
On the other hand, magnesium batteries will benefit from the
use of conversion cathodes which inherently possess higher
theoretical volumetric capacities than insertion cathodes and do
not rely on intercalation of Mg2+. One such ideal cathode is
electrophilic sulfur, which has a high theoretical volumetric
capacity of 3459 mAh cm
3 and is of great interest when coupled
with a Mg metal anode.2 This coupling can only occur in non-
nucleophilic electrolytes. The theoretical volumetric energy
density of a Mg/S battery exceeds 4500 Whl
1, which is
approximately twice that of a Li ion battery composed of
a graphite anode and a cobalt oxide cathode. A more attractive
cathode is air. Mg/air batteries have a theoretical voltage of
2.93V vs. Mg with a volumetric energy density of
14046 Whl
1.39,40 The high energy density can be explained by
This journal is ª The Royal Society of Chemistry 2012
oxygen being an unlimited cathode and the capacity of the
battery only being limited by the volume of the Mg metal anode.
However, none of the existing magnesium organohaloaluminate
electrolytes are moisture/air stable and therefore are not
compatible with an air cathode.
This critical perspective will overview key historical events
leading to the advent of rechargeable magnesium batteries as well
as report the current state of the art and a brief synopsis of our
recent progress in the area of magnesium electrolytes. It will
incorporate the use of density functional theory (DFT) calcula-
tions in an effort to guide synthetic routes for new electrolytes
with higher voltage stabilities and without the shortcomings of
magnesium organohaloaluminates previously observed,
including their nucleophilicity and their reactivity with elec-
trodes. The electroactive species of these magnesium electrolytes
and the important role of the anion on their performance will
also be presented. In addition, we will briefly discuss some of the
major hurdles which must be overcome in the development of
a metal anode battery coupled with sulfur or an air cathode.
2. Magnesium organohaloaluminate electrolytes:
history and state of the art
It has been a vital task to develop a magnesium battery elec-
trolyte which overcomes the low anionic stability of Grignard
reagents. For example, ethylmagnesium bromide and butyl-
magnesium chloride have a voltage stability of 1.5V vs. Mg,
therefore limiting the choice of available cathodes.41 Initially,
Gregory et al. synthesized an electrolyte (Mg[B(C4H9)4]2) from
the reaction between dibutylmagnesium and the Lewis acid tri-n-
butylborane which showed improved anionic stability over
Grignard reagents, but a lower coulombic efficiency.42 Based on
his work, it was assumed that the character of the Lewis acid
could be the determining factor in improving the voltage stability
and that transmetalation was a key step in the formation of the
electrochemically active product.32,34 Derived from this premise,
Aurbach et al. investigated how different combinations/ratios of
organomagnesium compounds (R2Mg) to Lewis acids affected
the coulombic efficiency and oxidative stability of electrolytes.
Shockingly, he observed no magnesium deposition from tetra-
hydrofuran (THF) solutions of dialkylmagnesium Lewis bases in
combination with a wide variety of Lewis acids (BPh2Cl,
BPhCl2, B[(CH3)2N]3, BEt3, BBr3, BF3, SbCl3, SbCl5, PPh3,
PEt2Cl, AsPh3, FeCl3, and TeF3).30 However, the in situ gener-
ated magnesium organohaloaluminate with a given formula of
Mg(AlCl2BuEt)2 formed from the reaction of one equivalent of
dibutylmagnesium and two equivalents of ethylaluminum chlo-
ride resulted in an electrolyte with an electrochemical stability of
2.4V and 100% coulombic efficiency.34,43 In an attempt to
analyze the structure of this electrolyte, single crystals were
precipitated from a THF solution by addition of hexane.
Surprisingly, the crystal (Mg2(m-Cl)3$6THF)(EtAlCl3) obtained
was not reported electrochemically active when dissolved
in THF.30,32,44
The main limitation of this first generation magnesium orga-
nohaloaluminate electrolyte was the electrochemical instability
attributed to the relatively weak Al–C bond which breaks via b-H
elimination.45 The electrochemical stability window was
improved by substituting alkyl groups on the Lewis acid with
Energy Environ. Sci.
phenyl groups, therefore excluding b-H elimination as a possible
oxidation route. In effect, the in situ generated magnesium
organohaloaluminate called APC formed from the reaction of
one equivalent of AlCl3 with two equivalents of PhMgCl dis-
played a much improved electrochemically stable window of
3.3V vs. Mg on a Pt working electrode. Additionally this elec-
trolyte possesses a specific conductivity of 2  10
3 U
1 cm
1 and
a coulombic efficiency of 100%. NMR and Raman spectroscopy
studies reveal that the solution consists of a mixture of Mg
complexes including MgCl2, MgCl, Mg2Cl3+, Ph2Mg and
PhMgCl all of which are coordinated by THF.34 The overall
nucleophilic nature of this magnesium organohaloaluminate can
be explained by the nucleophilicity of Mg complexes such as
PhMgCl and Ph2Mg present in the electrolyte mixture. Unfor-
tunately, the in situ generated magnesium organohaloaluminates
reported so far, while having high coulombic efficiencies, are
nucleophilic, and air sensitive and therefore preclude their use
with electrophilic cathodes such as sulfur or oxygen. For
example, a 2 : 1 mixture of PhMgCl and AlCl3 in THF has been
shown incompatible with an electrophilic sulfur cathode. Gas
chromatography-mass spectroscopy analysis confirmed that this
electrolyte directly reacts with sulfur to form phenyl disulfide and
biphenyl sulfide.46
Our approach to solving the mismatch between electrohilic Fig. 1 ORTEP plot (25% thermal probability ellipsoids) of (Mg2(m-
sulfur and nucleophilic magnesium organohaloaluminates was to Cl)3$6THF) (HMDSAlCl3) (panel A, hydrogen atoms, solvent of crys-
focus on using non-nucleophilic Hauser bases as electrolytes. As tallization and secondary disorder component removed for clarity,
such, potassium hexamethyldisilazide is a non-nucleophilic base reprinted with permission of Nature Communications ª2011 Macmillan
so the corresponding Hauser base (hexamethyldisilazide Publishers Ltd.) and (Mg2(m-Cl)3$6THF)(Ph2AlCl2) (panel B, 50%
magnesium chloride) (HMDSMgCl) was a good starting point thermal probability ellipsoids, hydrogen atoms omitted for clarity).
for synthesizing a Mg/S battery electrolyte. HMDSMgCl has
been previously reported as capable of undergoing reversible reported by Aurbach et al.31 For example, contradictory to these
magnesium deposition with a similar current density to that of reports, (Mg2(m-Cl)3$6THF)(EtAlCl3) obtained from the reac-
Grignard reagents.41 Following the previous work of Aurbach tion of n-butylmagnesium and ethylaluminum chloride was, in
et al., the current density for the magnesium deposition was fact, electrochemically active.46 Similarly, the electrochemical
increased by a factor of seven upon addition of AlCl3. Unfor- activity of the reaction product between a 2 : 1 ratio of PhMgCl
tunately, the voltage stability did not improve and was equal to and AlCl3 was also confirmed. Crystallization of this in situ
that of HMDSMgCl. In order to examine the product of the generated electrolyte has the general formula (Mg2(m-
reaction between HMDSMgCl and AlCl3, crystals were obtained Cl)3$6THF)(PhnAlCl4-n) (n ¼ 1–4) 2. Its major product was
by slow diffusion of hexane. The crystal (Mg2(m- confirmed by single X-ray diffraction as (Mg2(m-
Cl)3$6THF)(HMDSAlCl3) was identified by single X-ray Cl)3$6THF)(Ph2AlCl2) (Fig. 1B).47
diffraction (Fig. 1A).
The cation consisted of two octahedrally coordinated Mg
centers, bridged by three chlorine atoms. The three remaining
sites on each Mg center are coordinated through the oxygen by
THF solvent. The anion is composed of an Al atom tetrahedrally
coordinated by one HMDS group and three chlorides. This
crystal is electrochemically active and its crystallization
improved both the voltage stability and coulombic efficiency
when compared to the in situ generated electrolyte formed from
the reaction of a 3 : 1 mixture of HMDSMgCl and AlCl3. Bulk
analysis of crystalline electrolyte 1 by NMR and mass spec-
trometry confirms the major product is (Mg2(m-
Cl)3$6THF)(HMDSAlCl3) and the minor product is (Mg2(m-
Cl)3$6THF)(HMDS2AlCl2).46 Electrolyte 1 can be stored up to
Fig. 2 Electrochemical performance of 0.2M electrolyte (Mg2(m-
one year in a glove box without any loss in electrochemical Cl)3$6THF) (HMDSnAlCl4-n) (n ¼ 1,2) after one year of storage under
performance (Fig. 2). Ar by cyclic voltammetry on a Pt working electrode with 0.02 cm2 surface
Electrochemical activity of crystallized electrolyte 1 prompted area, at a scan rate of 25 mV s
1, 21  C with a Mg reference and counter
the investigation of crystallized products obtained from in situ electrode. Inset shows 100% coulombic efficiency for deposition-disso-
generated magnesium organohaloaluminates previously lution of Mg.

Energy Environ. Sci. This journal is ª The Royal Society of Chemistry 2012
 The cation (Mg2(m-Cl)3$6THF)+ is consistently present in all
of the electrochemically active, crystallized magnesium organo-
haloaluminates, which suggests it is the electrochemically active
species generated from the reaction between an organo-
magnesium compound and a Lewis acid (Fig. 3). However, the
equilibrium between the magnesium cations (Mg2(m-
Cl)3$6THF)+ and MgCl2/MgCl+ cannot be discounted and the
assumption that the (Mg2(m-Cl)3$6THF)+ cation is solely
responsible for magnesium deposition cannot be made with
confidence. Scheme 1 shows the proposed steps in the formation
of 1.46 The initial reaction involves the transmetalation of HMDS
group to yield the HMDSAlCl3
anion [Eq. (1)]. One credible
scenario to account for the formation of the cation (Mg2(m-
Cl)3$6THF)+ is MgCl+ rapidly reacting with MgCl2 [Eq. (3)].
MgCl2 is present from the Schlenk equilibrium [Eq. (2)], and its
depletion drives the equilibrium to the right. A proposed
pathway to account for the minor product (Mg2(m-
Cl)3$6THF)(HMDS2AlCl2) involves further reaction of
HMDSMgCl with the HMDSAlCl3
anion [Eq. (5)].
Crystallization results in non-nucleophilic magnesium orga-
nohaloaluminates by removing the nucleophilic components of
the in situ generated electrolyte. For example, crystallization of
the magnesium organohaloaluminate generated from the reac-
tion of a 2 : 1 ratio of PhMgCl and AlCl3 removes the nucleo-
philic PhMgCl and Ph2Mg components which are the reason for
this electrolyte’s reactivity with elemental sulfur. In effect, the
formation of biphenyl sulfide and phenyl disulfide observed in
the in situ generated organomagnesium electrolyte is not detected
in the reaction of crystallized product 2 with elemental sulfur.
Similarly, NMR studies clearly demonstrate that electrolyte 1
has no reactivity with sulfur. No change is observed in the33S
NMR spectrum of elemental sulfur in the presence of these
crystallized electrolytes even after one week.46 In conclusion,
crystallized magnesium organohaloaluminate electrolytes are
non-nucleophilic whereas in situ generated magnesium organo-
haloaluminate electrolytes are nucleophilic and incompatible
with electrophilic cathodes such as sulfur.
All magnesium organohaloaluminate electrolytes synthesized
thus far have the same cation (Mg2(m-Cl)3$6THF)+ therefore
their dissimilar stabilities are governed by their unique anions.
We believed that DFT may aid in the screening of electrolyte
Scheme 1 Proposed steps in the formation of 1.
candidates by modeling their oxidative and reductive stability.48
The oxidative stability of an electrolyte governs the choice of
a cathode. The oxidative stability can be estimated from the
calculated Highest Occupied Molecular Orbital (HOMO) energy
as the oxidation reaction involves removal of an electron from
this orbital. The more negative the HOMO energy the higher the
oxidative stability of the electrolyte. Similarly, the reductive
stability of the electrolyte is extremely important. A low reduc-
tive stability of the anion or the solvent may result in the
formation of an electronically insulating surface layer which does
not conduct magnesium ions. The reductive stability can be
estimated from the Lowest Unoccupied Molecular Orbital
(LUMO) energy, as reduction involves the addition of an elec-
tron to this orbital. In this case, the more positive the LUMO
energy the higher the reductive stability of the electrolyte.
Since electrolytes contain ions, DFT modeling must also take
into account the influence of solvents. Hocking et al., has
examined the effect of a dielectric model (COSMO) on DFT-
calculated structures of organometallic complexes. It was found
that gas-phase DFT calculations do not correctly reproduce
experimental trends unless solvation corrections were included.49
Recently, Aurbach examined the oxidative stability of the
components of the in situ generated magnesium organo-
haloaluminate electrolyte obtained from PhMgCl and AlCl3
through DFT calculations, using the IEFPCM model to include
solvent influences.34 Calculations used to predict the oxidative
stability of electrolyte candidates used anion geometry optimi-
zations performed at the B3LYP/6-311+g-dp level in THF (3 ¼
7.58) solution, via COSMO. Table 1 summarizes the calculated
HOMO and LUMO energy levels for a number of magnesium
electrolytes. However, the structural flexibility of
(HMDS)2AlCl2
makes its geometry difficult to optimize. It is
important to note that when an electrolyte is a mixture of

Table 1 Summary of HOMO and LUMO energy levels for the anion
component of the crystallized electrolytes

Electrolyte Anion HOMO (eV) LUMO (eV)

a

1 (HMDS)2AlCl2 — —
(HMDS)AlCl3

5.670 0.061
2 Ph4Al

5.384 0.182
Ph3AlCl

5.678 0.047
Ph2AlCl2

6.045 0.058
PhAlCl3

6.402
0.062
Fig. 3 Typical cyclic voltammograms of Mg deposition-dissolution in Cl4Al

6.742
1.384
0.2M electrolyte. Blue line depicts (Mg2(m-Cl)3$6THF)(PhnAlCl4-n) (n ¼ 3 Ph4B

4.819
0.536
1–4), green line (Mg2(m-Cl)3$6THF)(EtAlCl3) and red line (Mg2(m- 4 (C6F5)3BPh

5.559
0.422
Cl)3$6THF)(HMDSnAlCl4-n) (n ¼ 1,2). Experiments are conducted on a
The structural flexibility of (HMDS)2AlCl2
makes its geometry
a Pt electrode with 0.02 cm2 surface area, at a scan rate of 25 mV s
1, difficult to optimize.
21  C with a Mg reference and counter electrode.

This journal is ª The Royal Society of Chemistry 2012 Energy Environ. Sci.
components the oxidative stability of the electrolyte is governed
by the species with the most positive HOMO energy. Therefore,
in the case of 2 where the general formula is (Mg2(m-
Cl)3$6THF)(PhnAlCl4-n) (n ¼ 1–4), the oxidative stability is
determined by AlPh4
anion and in the case of 1 it is determined
by the HMDS2AlCl2
anion. Based on this logic, our DFT
calculations predict the electrolyte order of oxidative stability to
be 4 > 2 > 3 > 1.This is based on the assumption that the HOMO
energy level gap between the (HMDS)AlCl3
and
(HMDS)2AlCl2
anions is similar to the energy gap between
PhAlCl3
and Ph2AlCl2
anions.
In order to investigate whether theoretical calculations predict
the experimental results accurately, we synthesized additional
model electrolytes (Mg2(m-Cl)3$6THF)(BPh4) 3 and (Mg2(m-
Cl)3$6THF)[B(C6F5)3Ph] 4. Treatment of triphenylboron with 3
equivalents of PhMgCl yields 3. The structure of 3 was confirmed
by single X-ray diffraction (Fig. 4).50 In an analogous reaction, 4
can be synthesized by simply replacing triphenylboron with
tris(pentafluorophenyl)borane, B(C6F5)3 as the Lewis acid. It is
important to mitigate the reactivity of B(C6F5)3 with THF. Both
electrolytes can be readily crystallized from hexane. Evaluation
of magnesium electrolytes was conducted on a Pt working elec-
trode. Electrolytes 1, 2, 3 and 4 have oxidative stabilities of 3.2V,
3.3V, 2.6V, and 3.7V vs. Mg, respectively (Fig. 5). In order to
understand the true benefits of DFT calculations in evaluating
the properties of electrolytes it is crucial to perform these
calculations on a larger population of synthesized electrolytes.
Based on the small sample size presented, we believe DFT could
be a valuable tool. While the oxidative stability of the electrolytes
can be determined on an inert working electrode, the reactivity of
these electrolytes with components of a coin cell should also be
evaluated.
NuLi et al. has noticed a dependence of the oxidative stability
of Grignard reagents on the type of working electrode.51 Pellion
Technologies similarly reported the oxidative stability of in situ
generated magnesium organohaloaluminate electrolyte depends
on the metal electrode used.52 Furthermore, Aurbach et al. has
also reported that in situ generated APC electrolyte contains the
Grignard reagent PhMgCl so it was plausible to infer that this
Grignard reagent was the culprit for corrosion of metals by the in
situ generated magnesium organohaloaluminate electrolytes
reported in the Pellion patent. As previously stated crystalliza-
tion results in the removal of byproducts and yields a pure
magnesium organohaloaluminate. Therefore, the oxidative
stability of a crystallized electrolyte with various working elec-
trodes was investigated. Fig. 6 shows the oxidative stability of 1
Fig. 4 ORTEP plot (50% thermal probability ellipsoids) of
(Mg2(m-Cl)3$6THF)(BPh4). Hydrogen atoms are omitted for clarity.
Energy Environ. Sci.
Fig. 5 Linear scan voltammograms depicting typical voltage stability of
(Mg2(m-Cl)3$6THF)(HMDSnAlCl4-n) (n ¼ 1,2) (blue), (Mg2(m-
Cl)3$6THF)(PhnAlCl4-n) (n ¼ 1–4) (turquoise), (Mg2(m-
Cl)3$6THF)(BPh4) (red) and (Mg2(m-Cl)3$6THF)[B(C6F5)3Ph] (green)
on a Pt working electrode with a surface area of 0.02 cm2. Scan rate for all
scans is 25 mV s
1; magnesium reference and counter electrodes are used
at a temperature of 21  C.
on several working electrodes. Most notably, the voltage stability
is 2.2V vs. Mg on a stainless steel working electrode. It is worth
noting that 2 behaves similarly to 1 (not plotted). This experi-
ment complements reports by NuLi and Pellion and shows that
even crystallized magnesium organohaloaluminates are corrosive
in nature.
Two electrochemical signals indicative of metal corrosion are
current density hysteresis53,54 during cyclic oxidative stability
tests as well as a decrease in oxidative stability on less noble
working electrodes. Thus, the oxidative stability of 1 differs from
an inert to a less noble working electrode as displayed in Fig. 6.
Faradaic currents at positive potentials due to oxidation of metal
electrodes should not be confused with faradaic currents corre-
sponding to oxidation of electrolyte on inert electrodes. SEM
images of a stainless steel working electrode at potentials above
2.2V vs. Mg confirm corrosion by display of pits (Fig. 7). Pits are
also observed in electrolyte 2 above 2.2V vs. Mg. Therefore,
corrosion of metals by magnesium organohaloaluminate elec-
trolytes limits charging in a coin cell battery configuration to
under 2.2V due to the utilization of less noble metals such as
stainless steel and nickel in the casing and current collector
material.
Fig. 6 Linear scan voltammograms of (Mg2(m-
Cl)3$6THF)(HMDSnAlCl4-n) (n ¼ 1,2) with a scan rate of 25 mV s
1
depicting characteristic voltage stabilities on various working electrodes
(green–stainless steel, black–Ni, blue–Pt, turquoise–Au and red–glassy
carbon) with areas of 0.02 cm2 and a magnesium reference and counter at
a temperature of 21  C.
This journal is ª The Royal Society of Chemistry 2012

Fig. 7 SEM of stainless steel before (A) and after (B) exposure to 0.2M
(Mg2(m-Cl)3$6THF)(HMDSnAlCl4-n) (n ¼ 1,2) at 2.6V vs. Mg for 1 week.
Chronoamperometry is conducted in a two electrode Teflon Swagelok
cell with a Mg reference and glassy carbon current collectors at
a controlled temperature of 21  C.
The synthesis of a new generation of high performance
magnesium electrolytes without the limitation of metal corrosion
is paramount if coin cells are to be operated above 2.2V. A
reasonable cause for the corrosion observed in current magne-
sium organohaloaluminates is the presence of halides in the
cation and anion components of the electrolyte. This effect is
currently under scrutiny. Preliminary results demonstrate that
the anion has a dramatic effect. For example, the magnesium
organoborate electrolyte 3 with a halogen free anion BPh4

exhibits the same oxidative stability (2.6V vs. Mg) on both
stainless steel and Pt electrodes. In addition, cyclic voltammo-
grams of 3 do not exhibit hysteresis on stainless steel (Fig. 8A).
Electrolyte 3 shows a 400 mV improvement over 1 and 2 on
stainless steel. In order to enhance the oxidative stability of 3 we
considered using the fluorinated Lewis acid B(C6F5)3. As previ-
ously noted, the reaction of B(C6F5)3 with PhMgCl results in the
formation of 4 which has an oxidative stability of 3.7V vs. Mg on
Pt. This is denoted by a linear scan voltammogram between OCV
and 4.5V vs. Mg (Fig. 8B). Unfortunately, when the voltage is
Fig. 8 Cyclic voltammograms of (Mg2(m-Cl)3$6THF)(BPh4) (panel A)
and (Mg2(m-Cl)3$6THF)[B(C6F5)3Ph] (panel B) on platinum (green) and
stainless steel (blue) working electrode with an area of 0.02 cm2 at
a temperature of 21  C. Clockwise arrows designate passivation while
counterclockwise arrows denote hysteresis. Scan rate is 25 mV s
1 and the
counter and reference electrodes are both magnesium.
This journal is ª The Royal Society of Chemistry 2012
scanned back to OCV, 4 exhibits hysteresis and establishes
a stability of 2.2V vs. Mg on a stainless steel working electrode.
In the search for a non-reacting electrode material, glassy carbon
has been found inert to magnesium organohaloaluminates and is
ideal for high voltage oxidative stability tests (Pt working elec-
trodes still suffer from a lower level of pitting corrosion at high
positive potentials). Nonetheless, Pt working electrodes are
better suited for coulombic efficiency characterization due to an
apparent limitation of glassy carbon electrodes to intermediate
efficiencies of Mg deposition/dissolution. When properly used, Pt
and glassy carbon electrodes ensure that electrochemical exper-
iments characterize redox events pertaining solely to the
magnesium electrolyte and eliminate reactions between the
electrolyte and electrodes. In conclusion, DFT calculations may
be used to predict the oxidative stability of electrolytes on inert
electrodes but cannot predict their performance on less noble
electrodes due to the unaccounted phenomenon of corrosion.
For example, magnesium electrolyte performance on stainless
steel must be evaluated experimentally. Ongoing efforts to
improve the voltage stability on a stainless steel working elec-
trode will be reported in the future, including investigations on
the effects of the cation.
3. Conversion cathodes for a magnesium battery
The observed corrosion of metals in magnesium electrolytes
currently renders the high voltage insertion cathode strategy
difficult to implement due to desired high operating voltages in
excess of 3.0V vs. Mg in a coin cell configuration due to the
presence of stainless steel components. Presently, magnesium
electrolytes 1,2 and 4 are limited to 2.2V vs. Mg while magnesium
electrolyte 3 extends the operating potential by 400 mV. It is
important to consider that the operating voltage of a magnesium
battery may be around 100 mV lower than the voltage stability of
the electrolyte observed in a three electrode cell. The develop-
ment of noncorrosive high voltage electrolytes for evaluating
high voltage insertion cathodes in a coin cell is crucial. However,
low voltage but high capacity conversion cathodes are currently
the best choice for a magnesium battery. Two attractive
conversion cathodes for PLiB are sulfur and air. The concept of
utilizing sulfur as a positive electrode with a Li metal anode was
introduced in the 1960’s.55 An often disregarded challenge
associated with using a Li metal anode is dendrite formation due
to uneven deposition during charging which may result in
shortage of the battery followed by thermal runway. Therefore,
a Mg/S battery is a potentially interesting candidate for PLiB
because it circumvents this challenge. Unfortunately, the in situ
generated magnesium organohaloaluminate electrolytes repor-
ted so far, while having high coulombic efficiencies are nucleo-
philic and therefore preclude the use of electrophilic sulfur. For
example, the overall nucleophilic nature of the in situ generated
magnesium organohaloaluminate APC can be explained by the
nucleophilicity of Mg complexes such as PhMgCl and Ph2Mg
present in the electrolyte mixture. Crystallization of APC results
in a non-nucleophilic electrolyte 2 by removal of the nucleophilic
components. In effect, the formation of biphenyl sulfide and
phenyl disulfide observed in APC is not detected in the reaction
of crystallized product 2 with elemental sulfur. Similarly, NMR
studies of the reactivity of 1 with sulfur clearly demonstrate that
Energy Environ. Sci.
the electrolyte is indeed non-nucleophilic. In fact all crystallized
magnesium organohaloaluminates and magnesium organo-
borates are non-nucleophilic and therefore chemically compat-
ible with electrophilic sulfur.
When a coin cell is charged above the experimentally deter-
mined corrosion onset potential, it is possible to confuse corro-
sion with recharging of the battery. In effect, use of battery cells
accommodating carbon cloth or carbon paper as current
collectors is suggested for magnesium batteries due to their
inertness towards magnesium electrolytes. Therefore, it is crucial
to confirm the desired charge/discharge chemistry at the cathode
through chemical analysis such as X-ray diffraction or X-ray
photoelectron spectroscopy (XPS). One of the most direct
methods of confirming this chemistry in a Mg/S battery is XPS
because it can determine the change in the oxidation state of the
sulfur cathode. Fig. 9 compares high-resolution (HRES) S 2p
spectra obtained from sulfur cathodes (as-prepared, after a first
discharge, and after a complete discharge/charge cycle), to
standard samples of S and magnesium sulfide (MgS) powder.
After discharging, the majority of the sulfur (S 2p3/2 ¼ 164.0 eV)
is reduced to magnesium sulfide (MgS, 2p3/2 ¼ 160.9 eV) and
magnesium polysulfides ((MgSx, 1 < x < 8, S 2p3/2 ¼ 162.0–
163.0 eV). Upon charging, the majority of the MgS is oxidized to
S via polysulfide intermediates therefore the desired chemistry is
observed.46
While there are numerous scientific and technical challenges
which must be overcome, the major obstacle in the development
of a Mg/S battery is capacity fade on repeating charge/discharge
cycles which require dramatic improvements in the sulfur
cathode. It is thus important to mitigate the solubility of sulfur
and polysulfide anions in the electrolyte. Furthermore, during
cycling, polysulfide anions can migrate to the magnesium anode
where they are reduced to magnesium sulfide, causing capacity
loss. Notable progress in diminishing capacity fade of a Li/S
battery has been widely reported and discussed this year in
comprehensive reviews to which the reader is referred to for
details.5,56,57 One of the most promising approaches was recently
reported by Nazar et al. where a dramatic improvement by the
use of a nanostructured, polymer modified, mesoporous carbon-
sulfur composites was displayed.58 Entrapment of the sulfur in
a carbon cage in combination with a polymer coating substan-
tially retards the polysulfide diffusion therefore improving life
time. Recently, Tarascon et al. have demonstrated improvements
in life time using mesoporous metal organic frameworks (MOF)
as a host material for sulfur impregnation.59 Progress in Mg/S
battery research can dramatically benefit from the advancements
in Li/S battery. As a next step to reduce the Mg/S battery
capacity fade we are investigating both the combination of the
nano modified mesoporous carbon and MOF sulfur composites
with new electrolytes. Unfortunately, battery solvents most Fig. 9 XPS analysis of sulfur cathode. (a) Discharge and charge of a Mg/
commonly used to mitigate this problem in Li/S batteries, such as S coin cell at 50 and 25 mA, respectively. XPS spectra were taken from
carbonates, are reduced on Mg metal and form a passivating, coin cells at various stages of cycling. (b) HRES S 2p spectra of the
cathode as-prepared (I), after first discharge (II) and after first charge
electronically blocking, solid electrolyte interface which prevents
(III) are compared with standard samples of S powder (top) and MgS
Mg deposition.60 Therefore, we are considering other ether
powder (bottom). Note that the S 2p peaks contain both a 2p3/2 and 2p1/2
containing solvents including diglyme,44 ionic liquids29,61 and spin–orbit splitting state. The 2p3/2 states, located at lower binding
block copolymer gel electrolytes62–64 as a replacement for THF energies, were used for chemical state identification and are emphasized
with hopes of mitigating the solubility of polysulfides in THF. with filled symbols. This figure is reprinted with permission of Nature
The first step in this process is confirming the compatibility of Communications ª2011 Macmillan Publishers Ltd.
these new electrolytes with the Mg anode in order to verify that

Energy Environ. Sci. This journal is ª The Royal Society of Chemistry 2012
reversible magnesium deposition/dissolution is allowed to occur.
The marrying of carbon-sulfur composites with magnesium
electrolytes is actively being investigated. In principle, a conver-
sion cathode even more exciting than sulfur is air. Notable
progress in the development of a Li/air battery has been widely
reported and discussed in recent comprehensive reviews.5,57,65,66
Similar to the challenges of Li/air, the discovery of an electro-
lcatalyst67 used to reduce the overpotential for the discharge–
charge cycles and an air stable non-volatile electrolyte are
necessary for a Mg/air battery.
4. Conclusion
One of the great successes in recent years has been the develop-
ment and commercialization of lithium ion batteries for portable
electronics, power tools, and electric vehicles. Without a doubt,
the Holy Grail in battery research is the development of high
energy post lithium ion batteries. This may require shifting from
alloys to pure metal anodes and from insertion to conversion
cathodes such as sulfur or air. Magnesium’s thermodynamic
properties make this metal an obvious candidate as an anode.
The major advantage of magnesium metal is the lack of dendrite
formation during charging while its major disadvantage is a more
positive reduction potential than lithium metal. As highlighted in
this perspective the main challenge of developing a high energy
rechargeable magnesium battery is rooted in material discovery.
The investigation of magnesium batteries presents rich oppor-
tunities for research and collaboration between chemists and
electrochemists. This fundamental research will enable identi-
fying and overcoming hurdles in developing magnesium
batteries. Future emphasis in this field should fall on the devel-
opment of novel electrolytes because their properties govern the
choice of cathodes. Furthermore, magnesium batteries necessi-
tate progress in both conversion and insertion cathodes. While
major progress has already been made the road is still long and
many rewards are waiting for those willing to travel it.
Acknowledgements
I am grateful for the support and guidance of Kazuaki Sato in the
area of DFT calculations. Also, I would like to thank Dr Paul
Fanson and Takashi Kuzuya for useful comments about the
manuscript. I hope my perspective will be a meaningful addition
to the extensive body of work of Professor Aurbach, the father of
magnesium batteries, to whom I dedicate this paper.
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Energy Environ. Sci. This journal is ª The Royal Society of Chemistry 2012