Although bimetallic oxides have been shown to be beneficial
as
electrode materials in battery systems over their monometallic oxide
counterparts, the implementation of metal molybdates with dual-redox
centers has not been widely studied in aqueous rechargeable Zn-ion
batteries. Manganese molybdate (MnMoO4) was synthesized
via facile cosolvent coprecipitation and implemented as a cathode
material for the first time in this system using 3 M ZnSO4 and 3 M ZnCl2 electrolytes to investigate the impact
of the anion. In the two electrolytes, both manganese and molybdate
metal centers were determined to be redox active using Mn and Mo K-edge operando X-ray absorption spectroscopies
(XAS), with the corresponding voltage plateaus at 1.4 and 0.5 V, respectively.
The difference in anions resulted in a preference regarding the active
redox center, with the sulfate based preferring Mo redox and chloride
based preferring Mn redox. Additionally, the redox reactions also
differ in rate dependency, with Mn and Mo redox reactions preferring
slow and fast current rates, respectively. In both systems, Mn redox
was seen to be the more stable mechanism over prolonged cycling. The
preference was related to the dissolution of the MnMoO4 material by applying Pearson’s hard–soft acid–base
theory and considering the solubilities of the respective salts.