Origin of storage capacity enhancement by replacing univalent ion with multivalent ion for energy storage

Publication Type:
Journal Article
Citation:
Electrochimica Acta, 2018, 282 pp. 30 - 37
Issue Date:
2018-08-20
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© 2018 Elsevier Ltd The storage capacity or capacitance of a material could be enhanced significantly by replacing univalent ion with multivalent ion in the energy storage field. However, the mechanism of the enhancement is unknown. Here, we dedicate to understand the origin of the enhancement on the storage capacity of multivalent ions over univalent ions. The experimental results show that the specific capacitance and charge-discharge rate of α-MnO 2 are doubled by using Ca 2+ cation to replace Na + cation in the electrolyte as the energy storage medium. The First-principles calculations are used for a further understanding for the enhancement on the capacity, charge rate and the insertion mechanism. The given number of cations (two Na + or Ca 2+ ions) can be preferably stabled in one α-MnO 2 unit cell to decrease the irreversible tetragonal-orthorhombic deformation caused by John-Teller effect. Because the insertion of Ca 2+ triggers double electron transfer than Na + , the capacity and charge-discharge rate of α-MnO 2 using Ca 2+ cation as storage medium are doubled. The result pave a path to understand the enhancement on the storage capacity by replacing the univalent ions (such as Li + , Na + , K + , etc.) with multivalent ions (such as Ca 2+ , Mg 2+ , Zn 2+ , Al 3+ , etc.).
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