Potassium-ion batteries have emerged as an alternative to lithium-ion batteries as energy storage systems. In particular, KMnO has attracted considerable attention as a cathode material because of its high theoretical capacity and low cost. In this study, partial substitution of Mn in P3-type KMnO with divalent Ni is performed, resulting in a first discharge capacity of approximately 121 mAh (g-oxide) with 82% retention for 100 cycles. Operando synchrotron X-ray diffraction analysis reveals the occurrence of phase transition from P3 to O3 on charge and O3-P3-P'3 transition on discharge at the first cycle, where P'3 is a new distorted form of the P3 phase, accompanied by reversible Mn and Ni redox pairs, as evidenced by X-ray absorption spectroscopy. The reduced variation in the lattice parameters during de/potassiation for P3-K[NiMn]O relative to P3-KMnO is suggested as a possible reason for the enhanced electrochemical performance of K[NiMn]O. These results open the possibility of using inexpensive and high-capacity Mn-based cathode active materials for potassium-ion batteries.
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http://dx.doi.org/10.1021/acsami.9b06915 | DOI Listing |
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