(40f) Regenerable Cu-Intercalated MnO2 Layered Cathode for Highly Cyclable Energy Dense Aqueous-Based Batteries

Regenerable
Cu-intercalated MnO₂ layered cathode for highly cyclable energy
dense aqueous-based batteries

Batteries
are important storage devices that can enable renewable energy integration into
the grid. However, they need to meet certain requirements like safety, low
cost, high cycle life and high energy densities for use in grid applications.
Manganese dioxide (MnO₂)/Zinc (Zn) alkaline batteries have all the
aforementioned desired attributes including very high volumetric energy
densities of >400Wh/L (1) because of the high gravimetric capacities of its
electroactive materials – 617mAh/g for MnO₂ and 820mAh/g for Zn
based on 2 electron reactions. However, their use has been restricted to
primary applications like common household appliances because rechargeability
has been an issue due to the fundamental nature of MnO₂ and Zn (2).
The cathode, MnO₂, has been known to undergo lattice expansion and
crystal structure breakdown beyond a certain depth-of-discharge (DOD).  Prior
work has concentrated on limiting the DOD of MnO₂ (5-10% of
617mAh/g) to make the battery rechargeable (3); however, this has resulted in
low energy densities. Accessing the 2^nd electron capacity (617mAh/g)
of MnO₂ reversibly has been the holy grail of MnO₂/Zn
batteries to obtain very high energy dense batteries for use as low cost safe
aqueous batteries in grid and electric vehicle applications (4).

In this
presentation, we report the breakthrough of reversibly accessing the 2^nd
electron capacity of MnO₂ by using its layered polymorph called
birnessite mixed with bismuth oxide (Bi-birnessite) and intercalating the
layers with Cu ions (5). Bi-birnessite undergoes conversion reactions in
alkaline electrolyte and ultimately forms electro-inactive hausmannite (Mn₃O₄)
because of its poor charge transfer characteristics. Intercalating the layers
of Bi-birnessite with Cu ions is shown to improve its charge transfer
characteristics dramatically and regenerate its layered structure reversibly
for thousands of cycles. We also present a case of Cu-intercalated
Bi-birnessite’s applicability in practical batteries by cycling the material at
high areal capacities (10-29mAh/cm²) for thousands of cycles at
C-rates that are of interest in the battery community. Finally, a
Cu-intercalated Bi-birnessite/Zn battery is shown to reversibly cycle at 140
Wh/L for over 90 cycles.

Figure 1. (a) Volumetric
energy density of a Cu-intercalated Bi-birnessite/Zn cell. Inset shows the
first 5 cycles of the cell. (b) Energy density comparison of different energy
storage systems. (c) Specific capacity (mAh/g) vs cycle number for the
Cu-intercalated Bi-birnessite against a sintered Ni counter electrode. Insets
show specific cycle discharge curves for different wt.% loadings of MnO₂.

References:

1] Gallaway, J. W.;
Hertzberg, B. J.; Zhong, Z.; Croft, M.; Turney, D. E.; Yadav, G. G.; Steingart,
D. A; Erdonmez; C. K.; Banerjee, S. “Operando identification of the point of
[Mn₂]O₄ spinel formation during γ-MnO2 discharge
within batteries” Journal of Power Sources 321, 135-142 (2016).

2] Wei, X.; Desai, D.;
Yadav, G. G.; Turney, D. E.; Couzis, A.; Banerjee, S. “Impact of anode
substrates on electrodeposited zinc over cycling in zinc-anode rechargeable
alkaline batteries”. Electrochimica Acta 212, 603-613 (2016)

3] Ingale, N. D.;
Gallaway, J. W.; Nyce, M.; Couzis, A.; Banerjee, S., “Rechargeability and
economic aspects of alkaline zinc­manganese dioxide cells for electrical
storage and load leveling,” Journal of Power Sources 276, 7­18
(2015)

4] Dzieciuch, M. A.; Gupta, N.; Wroblowa, H. S. “Rechargeable cells with
modified MnO₂ cathodes.” J. Electrochem. Soc. 135, 2415–2418 (1988)

5] Yadav, G. G.; Gallaway, J. W.; Turney, D. E.; Nyce,
M.; Huang, J.; Wei, X.; Banerjee, S. “Regenerable Cu-intercalated MnO₂
layered cathode for highly cyclable energy dense batteries” Nat. Commun. 8,
14424 (2017).