Ultrahigh energy density batteries based on α-LixBN2 (1 ⩽ x ⩽ 3) positive electrode materials are predicted using density functional theory calculations. The utilization of the reversible LiBN2 + 2 Li+ + 2 e− 

$\rightleftharpoons$
⇌ Li3BN2 electrochemical cell reaction leads to a voltage of 3.62 V (vs Li/Li+), theoretical energy densities of 3251 Wh/kg and 5927 Wh/l, with capacities of 899 mAh/g and 1638 mAh/cm3, while the cell volume of α-Li3BN2 shrinks only 2.8% per two-electron transfer on charge. These values are far superior to the best existing or theoretically designed intercalation or conversion-based positive electrode materials. For comparison, the theoretical energy density of a Li–O2/peroxide battery is 3450 Wh/kg (including the weight of O2), that of a Li–S battery is 2600 Wh/kg, that of Li3Cr(BO3)(PO4) (one of the best designer intercalation materials) is 1700 Wh/kg, while already commercialized LiCoO2 allows for 568 Wh/kg. α-Li3BN2 is also known as a good Li-ion conductor with experimentally observed 3 mS/cm ionic conductivity and 78 kJ/mol (≈0.8 eV) activation energy of conduction. The attractive features of α-LixBN2 (1 ⩽ x ⩽ 3) are based on a crystal lattice of 1D conjugated polymers with –Li–N–B–N– repeating units. When some of the Li is deintercalated from α-Li3BN2 the crystal becomes a metallic electron conductor, based on the underlying 1D conjugated π electron system. Thus, α-LixBN2 (1 ⩽ x ⩽ 3) represents a new type of 1D conjugated polymers with significant potential for energy storage and other applications.

Topics
Density functional theory, Energy storage, Thermodynamic functions, Supramolecular chemistry, Crystal lattices, Crystal structure, Electrochemistry, Ionic conductivity, Batteries
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