Redox-Active Organic Molecule As High Performance Cathode Material for Non-Aqueous Rechargeable Magnesium-Ion Batteries
Authors: Pan Baofei , Vaughey John T. , Zhang Zhengcheng , Burrell Anthony K. , Liao Chen 
Published: February 2020

The rapid worldwide energy consumption is necessitating more energy generation from environmentally benign sources like solar, wind, or tide. However, the lack of efficient energy storage devices is the major limitation for the practical harvest of these clean energies. Rechargeable batteries are the promising solution for the efficient energy storage. We have witnessed the great success of secondary lithium-ion batteries (LIBs) in portable electronic devices in the last two decades.  However, the cost and safety barriers make traditional LIBs not desirable to meet the requirements for large power applications, such as the electric or plug-in hybrid vehicles. In contrast, the multivalent ion rechargeable batteries such as Mg1-3 and Ca4
,
5 ion batteries are more promising as larger and safer energy storage devices due to their advantages in safety, cost and capacity. For instance, compared to lithium, magnesium metal is non-toxic, more air resistant and free from the dangerous dendrite formation. The higher natural abundance of magnesium makes it more than 20 times cheaper than lithium in cost. In addition, the divalent characteristic of magnesium ion (Mg2+) enables magnesium to have a nearly doubled volumetric capacity as an anode than the lithium (3832 mA cm-3
vs 2062 mA cm-3). All these merits have brought significant attention on magnesium-ion batteries as the new generation rechargeable energy storage device. Inspired by the pioneer work by Aurbach group for the development of the famous dichloro-complex magnesium electrolyte (2EtAlCl2-MgBu2),6 a lot of efforts have been devoted to the development of high voltage electrolytes for rechargeable magnesium-ion batteries. In contrast to the rapid development of effective magnesium electrolytes capable of reversibly plating/stripping magnesium with wide electrochemical windows, the design of high potential cathode material for magnesium ion batteries is far behind. To date, the Chevrel phase Mo6S8 is still the only cathode material with excellent cycling reversibility and reasonable rate capability in rechargeable magnesium-ion batteries. However, Mo6S8 could only operate at a relatively low voltage in magnesium-ion batteries (< 1.3 V) with a typical below 100 mAh g-1 capacity. Thus, development of high operating voltage cathode material deserves great attention in nowadays. Herein, we would like to present our recent progress on the development of high voltage and high performance rechargeable magnesium-ion batteries using redox active organic molecules as cathode material. As shown in Figure 1(a), when the 0.3M Mg(HMDS)2-4MgCl2 in THF solution was used as the electrolyte,7 excellent reversible redox processes have been observed in the cyclic voltammetry measurement when the redox active organic molecule was used as the cathode material. The redox potential was detected at around 1.7 V (vs Mg/Mg2+), which is much higher than the well-known Chevral phase Mo6S8. The compatibility and reversibility of the organic cathode material with the electrolyte and magnesium metal anode was further demonstrated in the batteries upon cycling. As shown in Figure 1(b), excellent cycling performance has been observed with around 120 mAh g-1 initial specific discharge capacity at the current rate of 0.5C, and still about 102 mAh g-1specific discharge capacity was obtained in 100 cycles (around 84% capacity retention). The results further suggest the great success of using redox active organic molecules as cathode material for secondary multivalent-ion batteries.

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Figure 1