Rechargeable Intermetallic Calcium-Lithium-O2 Batteries.

The growing demand for rechargeable batteries with high energy density has triggered research on batteries based on polyvalent cations such as Ca2+ , Mg2+ , Al3+ , and Y3+ . Ca is, in particular, a promising anode material as an alternative to Li because of its mechanical strength (ρ=1.55 g cm-3 ), safety in terms of thermal runaway (m.p.=839 °C), earth-abundance (world production of 150 million tons of gypsum in 2012), high specific charge capacity (1.340 mAh g-1 or 2.077 mAh cm-3 ), and standard reduction potential (-2.87 V vs. normal hydrogen electrode, NHE) comparable to that of Li. As with Mg, the practical application of Ca in rechargeable batteries with organic liquid electrolytes has been hindered by the passivation layer resulting from undesirable reactions between metallic Ca and electrolytes, which precludes the possibility of reversible plating of any metal cations on Ca electrodes. Here, a battery system based on intermetallic CaLi2 anodes was developed. Li was used as a host for Ca through the formation of an intermetallic compound, which simultaneously enabled 1) the assembly of a rechargeable battery system with Ca anodes and liquid organic electrolytes and 2) coupling these with an earth-abundant, high-energy-density air cathode without special passivation agents. This strategy is simple and broadly applicable to the other polyvalent cations listed above, opening a new avenue to further engineer the electrode materials required for practical, efficient electrochemical energy-storage systems.