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ZnNi x Mn x Co 2–2 x O 4 Spinel as a High‐Voltage and High‐Capacity Cathode Material for Nonaqueous Zn‐Ion Batteries
Author(s) -
Pan Chengsi,
Zhang Ruixian,
Nuzzo Ralph G.,
Gewirth Andrew A.
Publication year - 2018
Publication title -
advanced energy materials
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 10.08
H-Index - 220
eISSN - 1614-6840
pISSN - 1614-6832
DOI - 10.1002/aenm.201800589
Subject(s) - spinel , cathode , materials science , intercalation (chemistry) , anode , electrolyte , battery (electricity) , ion , metal , inorganic chemistry , electrode , chemistry , metallurgy , thermodynamics , physics , power (physics) , organic chemistry
Nonaqueous Zn‐ion batteries are regarded as one alternative for Li‐ion batteries. Such batteries not only afford attractive attributes of cost, but also embody the advantages of the high‐specific capacities of Zn anodes, as well as the wide potential window of nonaqueous electrolytes. To fully exploit these advantages, improved cathode materials are highly desired. In this manuscript, a new series of spinels, ZnNi x Mn x Co 2–2 x O 4 , are reported as cathode materials for nonaqueous Zn‐ion batteries. Full cells constructed using this new spinel ( x = 1/2) as a cathode paired with a metal anode showed capacities over 200 cycles of 174 mAh g −1 and an open circuit potential of 2.05 V. The battery exhibits an energy density of 305 Wh kg −1 , which is the highest energy density yet reported for a Zn‐intercalation cathode. The data show that the Zn 2+ ions reversibly intercalate into the spinel structure during the charge/discharge processes, a compositional transformation directly correlated with a multiply reversible conversion between Co 4+ /Co 3+ , Ni 4+ /Ni 3+ /Ni 2+ , and Mn 4+ /Mn 3+ oxidation states within the lattice. The data suggest that Mn, Ni cosubstitution for Co in ZnCo 2 O 4 is an efficient method to facilitate Zn‐deintercalation and enhance discharge capacity, which may provide some guidelines for designing more attractive multivalent cathodes materials.