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Magnesium Sulfur Batteries

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Demands in energy storage require a significant improvement in the energy density of battery systems. Therefore innovative systems with a substantially higher specific energy and improved cycle life have to be developed. The combination of Magnesium and Sulfur in a galvanic element addresses several advantages, such as natural abundance, operational safety and a high volumetric capacity. However the research so far was hindered because a stable electrolyte for Mg-S-Batteries was missing [1]. Muldoon et. al. developed a stable and reversibly working non-nucleophilic electrolyte based on a recrystallized Mg2+ salt complex [Mg(µ-Cl)3(THF)6][HMDSAlCl3] (HMDS=hexamethyldisilazid) [2]. This crystalline electrolyte salt though could only be obtained in THF, revealing a disadvantageous overcharging and fast capacity fading [2]. A break-through in Mg/S battery performance was obtained by Fichtner et. al. They at first synthesized a one-step routine between [(HMDS)2Mg]=magnesium bis(hexamethyldisilazid) and AlCl3in different ethers, enhancing solvent choice and possibility of neglecting aforementioned disadvantages [3]. Furthermore a magnesium-anode enhances safety of Mg-S-battery, due to the missing tendency of dendrite formation [4]. Safety as well as capacity and scalability of fabrication of a battery are important factors to assess market opportunities of these secondary cells. Therefore we are focusing on a cell design that is "easy-to-fabricate" with a realistic material loading. Based on the multiannual experience in the development of lithium-sulfur batteries, we extend our activities to the field of magnesium sulfur-battery-development. In a first attempt S-C-cathodes with Sulfur content of 50 wt.% and 70 wt.% were evaluated with a 1.2 M Mg2+-salt electrolyte dissolved in a mixture of 2:1 by volume of bis(2-methoxyethyl)ether and an ionic liquid. The influence of the cathode composition was minimal at this early stage of development. Both types of batteries showed a similar discharge capacity of 600 mAh/g(Sulfur) in the first cycle. Furthermore different approaches for a working Mg-graphite-composite-anode are presented. Such composite-anodes were prepared via die-pressing and could only be obtained in specific composition. The obtained charge-discharge profiles showed remarkably well defined plateaus, which have not been obtained elsewhere, jet (see Figure 1). The preparation routine of the composite-anode was found to have the highest impact on the obtained performance. References [1] R. Mohtadi and F. Mizuno, “Magnesium batteries: Current state of the art, issues and future perspectives.,” Beilstein J. Nanotechnol., vol. 5, pp. 1291–311, Jan. 2014. [2] J. Muldoon, H. S. Kim, T. S. Arthur, G. D. Allred, J. Zajicek, J. G. Newman, A. E. Rodnyansky, A. G. Oliver, and W. C. Boggess, “Structure and compatibility of a magnesium electrolyte with a sulphur cathode.,” Nat. Commun., vol. 2, p. 427, Jan. 2011. [3] J. M. F. Z., Zhao-Karger, X. Zhao, D. Wang, T. Diemant, R. Behm, “Performance Improvement of Magnesium Sulfur Batteries with Modified Non-Nucleophilic Electrolytes,” Adv. Energy Mater., vol. 5, no. 3, p. 1401155, 2015. [4] T. D. Gregory, R. J. Hoffman, and R. C. Winterton, “Nonaqueous Electrochemistry of Magnesium Applications to Energy Storage,” J. Electrochem. Soc., vol. 137, no. 3, p. 775, 1990.
Title: Magnesium Sulfur Batteries
Description:
Demands in energy storage require a significant improvement in the energy density of battery systems.
Therefore innovative systems with a substantially higher specific energy and improved cycle life have to be developed.
The combination of Magnesium and Sulfur in a galvanic element addresses several advantages, such as natural abundance, operational safety and a high volumetric capacity.
However the research so far was hindered because a stable electrolyte for Mg-S-Batteries was missing [1].
Muldoon et.
 al.
developed a stable and reversibly working non-nucleophilic electrolyte based on a recrystallized Mg2+ salt complex [Mg(µ-Cl)3(THF)6][HMDSAlCl3] (HMDS=hexamethyldisilazid) [2].
This crystalline electrolyte salt though could only be obtained in THF, revealing a disadvantageous overcharging and fast capacity fading [2].
A break-through in Mg/S battery performance was obtained by Fichtner et.
al.
They at first synthesized a one-step routine between [(HMDS)2Mg]=magnesium bis(hexamethyldisilazid) and AlCl3in different ethers, enhancing solvent choice and possibility of neglecting aforementioned disadvantages [3].
Furthermore a magnesium-anode enhances safety of Mg-S-battery, due to the missing tendency of dendrite formation [4].
Safety as well as capacity and scalability of fabrication of a battery are important factors to assess market opportunities of these secondary cells.
Therefore we are focusing on a cell design that is "easy-to-fabricate" with a realistic material loading.
Based on the multiannual experience in the development of lithium-sulfur batteries, we extend our activities to the field of magnesium sulfur-battery-development.
In a first attempt S-C-cathodes with Sulfur content of 50 wt.
% and 70 wt.
% were evaluated with a 1.
2 M Mg2+-salt electrolyte dissolved in a mixture of 2:1 by volume of bis(2-methoxyethyl)ether and an ionic liquid.
The influence of the cathode composition was minimal at this early stage of development.
Both types of batteries showed a similar discharge capacity of 600 mAh/g(Sulfur) in the first cycle.
Furthermore different approaches for a working Mg-graphite-composite-anode are presented.
Such composite-anodes were prepared via die-pressing and could only be obtained in specific composition.
The obtained charge-discharge profiles showed remarkably well defined plateaus, which have not been obtained elsewhere, jet (see Figure 1).
The preparation routine of the composite-anode was found to have the highest impact on the obtained performance.
References [1] R.
Mohtadi and F.
Mizuno, “Magnesium batteries: Current state of the art, issues and future perspectives.
,” Beilstein J.
Nanotechnol.
, vol.
5, pp.
1291–311, Jan.
2014.
[2] J.
Muldoon, H.
S.
Kim, T.
S.
Arthur, G.
D.
Allred, J.
Zajicek, J.
G.
Newman, A.
E.
Rodnyansky, A.
G.
Oliver, and W.
C.
Boggess, “Structure and compatibility of a magnesium electrolyte with a sulphur cathode.
,” Nat.
Commun.
, vol.
2, p.
427, Jan.
2011.
[3] J.
M.
F.
Z.
, Zhao-Karger, X.
Zhao, D.
Wang, T.
Diemant, R.
Behm, “Performance Improvement of Magnesium Sulfur Batteries with Modified Non-Nucleophilic Electrolytes,” Adv.
Energy Mater.
, vol.
5, no.
3, p.
1401155, 2015.
[4] T.
D.
Gregory, R.
J.
Hoffman, and R.
C.
Winterton, “Nonaqueous Electrochemistry of Magnesium Applications to Energy Storage,” J.
Electrochem.
Soc.
, vol.
137, no.
3, p.
775, 1990.

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