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Progress in Rechargeable Magnesium Battery Technology

Profile image of Elena LeviElena Levi

2007, Advanced Materials

https://doi.org/10.1002/ADMA.200701495
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Abstract

Rechargeable magnesium batteries were first presented about seven years ago. Their components included magnesium metal or a Mg alloy anode, Mg x Mo 6 S 8 (0 < x < 2) Chevrel phase cathodes, and electrolyte solutions that contained an ether solvent and a complex electrolyte, a product of the reaction between a MgBu 2 Lewis base and an AlCl 2 Et Lewis acid (Bu = butyl, Et = ethyl). These systems, while demonstrating impressive cycleability, suffered from several drawbacks: i) The micrometric size Mg 0-2 Mo 6 S 8 Chevrel phase cathode suffers from some kinetic limitation and the phenomenon of partial charge trapping (of Mg ions) at low temperatures. ii) The electrochemical window of the first generation of electrolyte solutions, THF/Mg(AlCl 2 BuEt) 2 was around 2.2 V, which limited the possible use of cathode materials with a higher redox potential (and higher capacity) than Chevrel phases. iii) For practical use, the synthesis of the components of rechargeable Mg batteries needs simplification.

Figures (8)
Figure 1. X-ray powder diffraction patterns of MogSg, MogS7Se, and Mo¢S¢Se2 obtained by the new synthesis at 900°C (1a-c, respectively) and by the regular high-temperature method, up to 1250°C (1d-f, respec- tively).
Figure 1. X-ray powder diffraction patterns of MogSg, MogS7Se, and Mo¢S¢Se2 obtained by the new synthesis at 900°C (1a-c, respectively) and by the regular high-temperature method, up to 1250°C (1d-f, respec- tively).
dering should be reflected by the electrochemical response of the mixed hosts.
dering should be reflected by the electrochemical response of the mixed hosts.
Table 1. Example: Fine structural data obtained by the Rietveld analysis for one of the Chevrel phases prepared by the new synthesis.
Table 1. Example: Fine structural data obtained by the Rietveld analysis for one of the Chevrel phases prepared by the new synthesis.
Figure 3. Anion ordering vs. Se concentration in the mixed Chevrel phases. Circles, this work; squares, based on the structural data of ref. [15]. Table 2. Lattice parameters of the synthetic products and anion ordering.
Figure 3. Anion ordering vs. Se concentration in the mixed Chevrel phases. Circles, this work; squares, based on the structural data of ref. [15]. Table 2. Lattice parameters of the synthetic products and anion ordering.
Figure 4. Comparison of typical steady state cyclic voltammograms of electrodes comprising Mg,Mo¢Ss_,Se, (n = 0, 1, 2) nanoparticles (new synthe sis) and microparticles (regular, high temperature synthesis) as indicated. The scanning rate was 10 uV s'!. The electrolyte solution was 0.25 Mg(AICI,BuEt), in THF, 25°C. a) Comparison among the three types of nanomaterials prepared by the new synthesis (as indicated). b) Comparisor between nano- and micrometer-scale Mg,Mog¢Sg electrodes. c) Comparison between nano- and micrometer-scale Mg,MogS7Se, electrodes. d) Compar ison between nano- and micrometer-scale Mg,MogS¢Se2 electrodes.
Figure 4. Comparison of typical steady state cyclic voltammograms of electrodes comprising Mg,Mo¢Ss_,Se, (n = 0, 1, 2) nanoparticles (new synthe sis) and microparticles (regular, high temperature synthesis) as indicated. The scanning rate was 10 uV s'!. The electrolyte solution was 0.25 Mg(AICI,BuEt), in THF, 25°C. a) Comparison among the three types of nanomaterials prepared by the new synthesis (as indicated). b) Comparisor between nano- and micrometer-scale Mg,Mog¢Sg electrodes. c) Comparison between nano- and micrometer-scale Mg,MogS7Se, electrodes. d) Compar ison between nano- and micrometer-scale Mg,MogS¢Se2 electrodes.
Figure 5. Typical capacity vs. cycle number, capacity vs. rate curves, and voltage profiles of various Mg,Mo¢Sg_,Se,, (y = 0, 1, 2) electrodes during gal- vanostatic discharge-charge cycling at various rates in 0.25 m Mg(AICI,BuEt)2/THF solutions. a) Capacity vs. cycle number curves of electrodes com- prising the nano-materials, 25 °C, C/8 rate. b) Comparison between capacity vs. rate for electrodes Comprising nano Mg,Mo¢Ss_,Se,, materials (indi- cated), 15°C. c) Typical voltage vs. capacity curves of electrodes comprising the nanomaterials, 25 °C, C/8 rate. d) Same as (c), electrodes comprising microparticles.
Figure 5. Typical capacity vs. cycle number, capacity vs. rate curves, and voltage profiles of various Mg,Mo¢Sg_,Se,, (y = 0, 1, 2) electrodes during gal- vanostatic discharge-charge cycling at various rates in 0.25 m Mg(AICI,BuEt)2/THF solutions. a) Capacity vs. cycle number curves of electrodes com- prising the nano-materials, 25 °C, C/8 rate. b) Comparison between capacity vs. rate for electrodes Comprising nano Mg,Mo¢Ss_,Se,, materials (indi- cated), 15°C. c) Typical voltage vs. capacity curves of electrodes comprising the nanomaterials, 25 °C, C/8 rate. d) Same as (c), electrodes comprising microparticles.
Figure 6. Comparison between the voltammetric behavior of THF solutions containing 0.25 m of the reaction product between 1:2 MgBuz and AICI,Et (ethyl-butyl complex, standard solutions) and 0.4 m of the reaction product between 1:2 AICI; and PhMgCl (all phenyl complex solution) as indicated. 25 mV s"', Pt wire working electrode, 25 °C.Right insert: Enlargement of the cyclic voltammograms near 0 V vs. Mg R.E., comparing the over-potential for Mg deposition in the two solutions. Left insert: The charge balance upon typical Mg deposition-dissolution cycles in these solutions (100 % cycling efficiency of Mg deposition).
Figure 6. Comparison between the voltammetric behavior of THF solutions containing 0.25 m of the reaction product between 1:2 MgBuz and AICI,Et (ethyl-butyl complex, standard solutions) and 0.4 m of the reaction product between 1:2 AICI; and PhMgCl (all phenyl complex solution) as indicated. 25 mV s"', Pt wire working electrode, 25 °C.Right insert: Enlargement of the cyclic voltammograms near 0 V vs. Mg R.E., comparing the over-potential for Mg deposition in the two solutions. Left insert: The charge balance upon typical Mg deposition-dissolution cycles in these solutions (100 % cycling efficiency of Mg deposition).

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    magnesium metal is an ideal rechargeable battery anode material because of its high volumetric energy density, high negative reduction potential and natural abundance. Coupling mg with high capacity, low-cost cathode materials such as electrophilic sulphur is only possible with a non-nucleophilic electrolyte. Here we show how the crystallization of the electrochemically active species formed from the reaction between hexamethyldisilazide magnesium chloride and aluminum trichloride enables the synthesis of a non-nucleophilic electrolyte. Furthermore, crystallization was essential in the identification of the electroactive species, [mg 2 (µ-Cl) 3 ·6THF] + , and vital to improvements in the voltage stability and coulombic efficiency of the electrolyte. X-ray photoelectron spectroscopy analysis of the sulphur electrode confirmed that the electrochemical conversion between sulphur and magnesium sulfide can be successfully performed using this electrolyte.

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