Structural Synthon Approach to the Study of Stacking Faults in the Layered Double Hydroxides of Lithium and Aluminum

A single layer of the Li‐Al layered double hydroxide (LDH) can be considered to be a structural synthon that can be stacked in a number of ways to give rise to the polytypes of the Li‐Al LDH family. The topotactic imbibition of lithium into gibbsite and bayerite precursors gives rise to crystalline 2H and 1M₁ polytypes respectively. In contrast the sample formed through a gel to crystallite route is found to be a 1M₁ polytype with stacking disorders whose local symmetry corresponds to the 1M₂ polytype. On heating, a solid‐solid 1M₁→1H polytype transformation is observed.