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We have found the Wadsley‐Roth class of crystallographic shear structures in chemical systems based on Nb2O5 to undergo lithium insertion reactions at ambient temperature to stoichiometries of 0.4 to 1.4 Li per host metal on reaction with n‐BuLi. For the general case of structures with intersecting shear planes, minimal structural distortion occurs on lithiation even for compounds with the largest ReO3‐normallike block sizes. We report crystal‐chemical data for 14 lithium insertion compounds of this type, and the behavior of selected host compounds mixed with carbon as the positive electrodes in small lithium secondary test cells.

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A new class of electrode materials for high energy density, rechargeable batteries based on topochemical reactions of lithium and transition metal compounds is evolving. The physical and structural properties relevant to the ability of transition metal oxides with framework structures to topochemically incorporate lithium are discussed. Perovskite-related structures are particularly attractive hosts for lithium.

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