Magnesium battery

Magnesium batteries are batteries with magnesium as

the active element at the anode of an electrochemical
cell. Both non-rechargeable primary cell and rechargeable secondary cell chemistries have been investigated.
Magnesium primary cell batteries have been commercialised and have found use as reserve and general use
batteries.

itary from 1968 until c.1984 when it was replaced by a

lithium thionyl chloride battery.[7][8]
A magnesium-air fuel cell has theoretical operating voltages of 3.1V and energy densities of 6.8 kWh/kg.
General Electric produced a magnesium air fuel cell operating in neutral NaCl solution as early as the 1960s.
The magnesium air battery is a primary cell, but has the
potential to be 'refuelable' by replacement of the anode
and electrolyte. Magnesium air batteries have been commercialised and nd use as land based backup systems
as well as undersea power sources, using seawater as the
electrolyte.[9]

Magnesium secondary cell batteries are an active research

topic, specically as an alternative to lithium ion based
battery chemistries. A solid magnesium anode allows
a higher volumetric energy density than lithium, carrying two electrons per ion, display a volumetric capacity of 3833 mAh cm3 vs. 2036 mAh cm3 for Li
metal,[1] although its specic energy is under half that of
lithium (18.8 MJ/kg vs. 42.3 MJ/kg).[note 1][note 2] In comparison to metallic lithium anodes, magnesium anodes
have not exhibited dendrite formation during charging,[2]
which may allow magnesium metal to be used without
an intercalation compound at the anode;[note 3] eliminating the intercalation layer raises the theoretical maximum
relative volumetric energy density to around 5 times that
of a lithium ion cell.[4] Magnesium batteries may have a
cost advantage over lithium due to the abundance of magnesium on earth.[2]

2 Secondary cells
As of 2015 the barriers to producing a commercially useful magnesium battery were the lack of practical electrolytes and cathode materials for magnesium ions.[2]

2.1 Electrolyte

In 2015 an electrolyte based on monocarborane

Insertion type anodes ('magnesium ion') have also been CB11 H12 - displayed > 99 % coulombic eciency, high
anodic stability (3.8 V vs. Mg); and was non-corrosive.
researched.
produced the rst halogen-free, simple-type Mg salt
Potential uses of Mg-based batteries were recognised
that is compatible with Mg metal and is oxidatively
as early as the 1990s, and the rst rechargeable cell
stable.[1][10][11]
was reported in 2000, based on Chevrel-type Mo6 S8
cathode with a magnesium organohaloaluminate/THF
electrolyte.[4] However, the halide electrolytes were 2.2 Passivation
highly corrosive to other battery components.

A key drawback to using a metallic magnesium anode is the tendency to form a passivating (non conducting) layer when recharging, blocking further charging (unlike lithium);[12] The passivating layers were
thought to originate from decomposition of the electrolyte during magnesium ion reduction. Common
counter ions such as perchlorate and tetrauoroborate
were found to contribute to passivation, as were some
common polar aprotic solvents such as carbonates
and nitriles.[13] Grignard based ethereal electrolytes
have been shown not to passivate;[14] Magnesium
organoborates also showed electroplating without passivation. The compound Mg(BPh2 Bu2 )2 was used
in the rst demonstrated rechargeable magnesium battery, although its usefulness was limited by electrochemical oxidation.[15] Other electrolytes researched include mixed grignard/aluminium trichloride compounds,

Primary cells

Primary magnesium cells have been developed since the

early 20th century. Cathode materials include silver chloride, copper(I) chloride, palladium(II) chloride, copper(I)
iodide, copper(I) thiocyanate, manganese dioxide and air
(oxygen).[5] For example, a water-activated silver chloride/magnesium reserve battery became commercially
available by 1943.[6]
The magnesium dry battery type BA-4386 was fully commercialised, with costs per unit approaching that of zinc
batteries - in comparison to equivalent zinc-carbon cells
the batteries had greater capacity by volume, and longer
shelf life. The BA-4386 was widely used by the US mil1

borohydrides, phenolates, alkoxides, mixed magnesium

chloride/aluminium chloride systems in THF, amido
based complexes (e.g. based on hexamethyldisilazane),
carborane salts, a Mg(BH4 )(NH2 ) solid state electrolyte, and gel polymers containing Mg(AlCl2 EtBu)2 in
tetraglyme/PVDF.[16] For solvent based systems, ethers
have been generally used in research (2014).[17]

2.3

Insertion electrodes

Insertion electrodes, based on reversible insertion of

magnesium metal into metal alloy anodes (such as
Bismuth/Antinomy or Tin) have been shown to be able to
prevent anode surface passivation, but suered from anode destruction due to volumetric changes on insertion,
as well as slow kinetics.[18]
Another basic drawback compared to lithium is magnesiums higher charge (+2) in solution, which can increase viscosity and reduce mobility in the electrolyte.[19]
In solution a number of species may exist depending
on counter ions/complexing agents - these often include singly charged species (e.g. MgCl+ in the presence of chloride) - though dimers are often formed (e.g.
Mg2 Cl3 + ).[20] The movement of the magnesium ion into
cathode host lattices is also (as of 2014) problematically
slow.[21]

2.4

REFERENCES

cathode materials.[26]
In 2014 a rechargeable magnesium battery was reported
utilising a ion exchanged, olivine type MgFeSiO4 cathode
with a bis(triuoromethylsulfonyl)imide/triglyme electrolyte - the cell showed a capacity of 300mAh/g with
a voltage of 2.4V.[27] MgMnSiO4 has also been investigated as a potential Mg2+ insertion cathode.[28]

3 Notes
[1] Li: Standard Electrode Potential 3.04 ; cationic charge
+1 ; Faraday constant 96485.33289 C/mol ; Energy per
mole 293315.411986 J/mol ; Atomic mass 6.94 g/mol ;
Energy density (mass) 42264.4685858 J/g ; density 0.534
g/cm3 ; energy density (volumetric) 22569.2262248
J/cm3
[2] Mg: Standard Electrode Potential 2.372 ; cationic
charge +2 ; Faraday constant 96485.33289 C/mol ;
Energy per mole 457726.41923 J/mol ; Atomic mass
24.305 g/mol ; Energy density (mass) 18832.6031364
J/g ; density 1.738 g/cm3 ; energy density (volumetric)
32731.0642511 J/cm3
[3] The requirement to intercalate the 'metallic' lithium
greatly reduces the energy density of a lithium-ion battery
compared to a metallic lithium battery ie 372 mAh/g vs
3862 mAh/g (or 837 mAh/cm3 vs. 2061 mAh/cm3) for
lithium/graphite (as LiC6 ) vs. Li metal.[3]

Cathode

Potential cathodes include those used in magnesium primary batteries. New cathode materials investigated include zirconium disulde, cobalt(II,III) oxide, tungsten
selenide, vanadium pentoxide and vanadate compounds.
Cobalt based spinels showed inferior kinetics to insertion compared to their behaviour with lithium.[5] In 2000
the chevrel phase form of Mo6 S8 displayed good suitability, enduring 2000 cycles at 100% discharge with a
15% loss; drawbacks were poor low temperature performance (reduced Mg mobility, compensated by substituting Selenium), as well as a low voltage, c. 1.2V, and
low energy density (110mAh/g). A molybdenum disulde cathode showed improved voltage and energy density, 1.8V and 170mAh/g. Transition metal sules are
considered promising candidates for magnesium ion battery cathodes.[22] A hybrid magnesium cell using a mixed
magnesium/sodium electrolyte with sodium insertion into
a nanocrystalline iron(II) disulde cathode was reported
in 2015.[23]
Manganese dioxide based cathodes have shown good
properties, but deteriorated on cycling.[24] Modied manganese based spinels (post spinels) are an active topic of
research (2014) for magnesium ion insertion cathodes.[25]
As of 2014 secondary magnesium battery research had
not progressed as far as producing a commercialisable
battery, with specic challenges being the electrolytes and

4 References
[1] Media, BioAge. Green Car Congress: Toyota Research
team reports signicant advance in electrolytes for highenergy Mg batteries. www.greencarcongress.com. Retrieved 2016-05-10.
[2] Mohtadi & Mizuno 2014, p. 1292, col.2.
[3] Mohtadi & Mizuno 2014, p.1292, col.1.
[4] Orikasa et al 2014, Introduction.
[5] Mohtadi & Mizuno 2014, 3.
[6] Blake, Ivan C. (August 1952), Silver ChlorideMagnesium Reserve Battery (PDF), JOURNAL OF THE
ELECTROCHEMICAL SOCIETY
[7] Crompton, Thomas Roy (2000), Battery Reference Book,
39
[8] ARMY'S PROCUREMENT OF BATTERIES: Magnesium
vs. Lithium, US Government Accountability Oce, 26
Sep 1985
[9] Zhang, Tianran; Tao, Zhanliang; Chen, Jun (Mar
2014), Magnesium-air batteries: From principle to
application, Materials Horizons 1 (2): 196206,
doi:10.1039/c3mh00059a

4.1

Sources

[10] Tutusaus, Oscar; Mohtadi, Rana; Arthur, Timothy S.;

Mizuno, Fuminori; Nelson, Emily G.; Sevryugina, Yulia
V. (2015-06-26). An Ecient Halogen-Free Electrolyte
for Use in Rechargeable Magnesium Batteries. Angewandte Chemie International Edition 54 (27): 79007904.
doi:10.1002/anie.201412202. ISSN 1521-3773.
[11] Carter, Tyler J.; Mohtadi, Rana; Arthur, Timothy S.;
Mizuno, Fuminori; Zhang, Ruigang; Shirai, Soichi;
Kampf, Je W. (2014-03-17). Boron Clusters as
Highly Stable Magnesium-Battery Electrolytes. Angewandte Chemie International Edition 53 (12): 31733177.
doi:10.1002/anie.201310317. ISSN 1521-3773. PMC
4298798. PMID 24519845.
[12] Bucur, Claudiu B.; Gregory, Thomas; Oliver, Allen G.;
Muldoon, John (2015), Confession of a Magnesium
Battery, J. Phys. Chem. Lett. 6 (18): 35783591,
doi:10.1021/acs.jpclett.5b01219
[13] Mohtadi & Mizuno 2014, 1.1.
[14] Mohtadi & Mizuno 2014, 2; Fig.1, p. 1293.
[15] Mohtadi & Mizuno 2014, 2.
[16] Mohtadi & Mizuno 2014, Table 1, p. 1298.
[17] Mohtadi & Mizuno 2014, 2.1.
[18] Mohtadi & Mizuno 2014, 1.2.
[19] Van Noorden, Richard (5 Mar 2014), The rechargeable
revolution: A better battery, www.nature.com
[20] Mohtadi & Mizuno 2014, 2.1.5.
[21] Mizuno, Fuminori; Singh, Nikhilendra; Arthur, Timothy
S.; Fanson, Paul T.; Ramanathan, Mayandi; Benmayza,
Aadil; Prakash, Jai; Liu, Yi-Sheng; Glans, Per-Anders;
Guo, Jinghua (11 November 2014), Understanding and
overcoming the challenges posed by electrode/electrolyte
interfaces in rechargeable magnesium batteries, Front.
Energy Res., doi:10.3389/fenrg.2014.00046
[22] Mohtadi & Mizuno 2014, 3.3.
[23] Walter, Marc; Kravchyk, Kostiantyn V.; Ibez,
Maria; Kovalenko, Maksym V. (2015), Ecient
and Inexpensive SodiumMagnesium Hybrid Battery, Chem.
Mater.
27 (21):
74527458,
doi:10.1021/acs.chemmater.5b03531
[24] Mohtadi & Mizuno 2014, 3.4.
[25] Example sources:
Ling, Chen; Mizuno, Fuminori (2013), Phase Stability of Post-spinel Compound AMn2O4 (A = Li,
Na, or Mg) and Its Application as a Rechargeable
Battery Cathode, Chem. Mater. 25 (15): 3062
3071, doi:10.1021/cm401250c
Kim, Chunjoong; Phillips, Patrick J.; Key, Baris;
Yi, Tanghong; Nordlund, Dennis; Yu, YoungSang; Bayliss, Ryan D.; Han, Sang-Don; He,
Meinan; Zhang, Zhengcheng; Burrell, Anthony
K.; Klie, Robert F.; Cabana, Jordi (10 June

2015), Direct Observation of Reversible Magnesium Ion Intercalation into a Spinel Oxide
Host, Advanced Materials 27 (22): 33773384,
doi:10.1002/adma.201500083
[26] Mohtadi & Mizuno 2014, Conclusion, p.1309.
[27] Orikasa et al 2014.
[28] NuLi, Yanna; Yang, Jun; Wang, Jiulin; Li, Yun
(2009), Electrochemical Intercalation of Mg2+ in
Magnesium Manganese Silicate and Its Application as
High-Energy Rechargeable Magnesium Battery Cathode, J. Phys. Chem. C 113 (28): 1259412597,
doi:10.1021/jp903188b

4.1 Sources
Mohtadi, Rana; Mizuno, Fuminori (2014),
Magnesium batteries: Current state of the art,
issues and future perspectives, Beilstein J. Nanotechnol. 5: 12911311, doi:10.3762/bjnano.5.143
Orikasa, Yuki; Masese, Titus; Koyama, Yukinori;
Mori, Takuya; Hattori, Masashi; Yamamoto, Kentaro; Okado, Tetsuya; Huang, Zhen-Dong; Minato, Taketoshi; Tassel, Cdric; Kim, Jungeun;
Kobayashi, Yoji; Abe, Takeshi; Kageyama, Hiroshi;
Uchimoto, Yoshiharu (2014), High energy density rechargeable magnesium battery using earthabundant and non-toxic elements, Scientic Reports
4 (5622), doi:10.1038/srep05622

5 External links

6 TEXT AND IMAGE SOURCES, CONTRIBUTORS, AND LICENSES

Text and image sources, contributors, and licenses

6.1

Text

Magnesium battery Source: https://en.wikipedia.org/wiki/Magnesium_battery?oldid=732203937 Contributors: Edcolins, Bgwhite,

Edgar181, Lfstevens, JohannSnow, Xiiophen, Calvin0628 and Anonymous: 2

6.2

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6.3

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