Rechargeable-battery chemistry based on lithium oxide growth through nitrate anion redox

Next-generation lithium-battery cathodes often involve the growth of lithium-rich phases, which enable specific capacities that are 2−3 times higher than insertion cathode materials, such as lithium cobalt oxide. Here, we investigated battery chemistry previously deemed irreversible in which lithium oxide, a lithium-rich phase, grows through the reduction of the nitrate anion in a lithium nitrate-based molten salt at 150 °C. Using a suite of independent characterization techniques, we demonstrated that a Ni nanoparticle catalyst enables the reversible growth and dissolution of micrometre-sized lithium oxide crystals through the effective catalysis of nitrate reduction and nitrite oxidation, which results in high cathode areal capacities (~12 mAh cm–2). These results enable a rechargeable battery system that has a full-cell theoretical specific energy of 1,579 Wh kg–1, in which a molten nitrate salt serves as both an active material and the electrolyte. Phase-forming conversion chemistry, like that observed in Li–S and Li–O2 batteries, shows great promise, but these systems suffer some drawbacks, such as practically low cathode areal capacities and electrolyte decomposition. Now, high-energy conversion battery chemistry—based on nitrate/nitrite redox where one of the products is soluble—has been enabled by using nanoparticulate Ni/NiO electrocatalysts.