A routine for the determination of the microstructure of stacking-faulted nickel cobalt aluminium hydroxide precursors for lithium nickel cobalt aluminium oxide battery materials

The microstructures of six stacking-faulted industrially produced cobalt- and aluminium-bearing nickel layered double hydroxide (LDH) samples that are used as precursors for Li(Ni(1−x−y)Co(x)Al(y))O(2) battery materials were investigated. Shifts from the brucite-type (AγB)□(AγB)□ stacking pattern to the CdCl(2)-type (AγB)□(CβA)□(BαC)□ and the CrOOH-type (BγA)□(AβC)□(CαB)□ stacking order, as well as random intercalation of water molecules and carbonate ions, were found to be the main features of the microstructures. A recursive routine for generating and averaging supercells of stacking-faulted layered substances implemented in the TOPAS software was used to calculate diffraction patterns of the LDH phases as a function of the degree of faulting and to refine them against the measured diffraction data. The microstructures of the precursor materials were described by a model containing three parameters: transition probabilities for generating CdCl(2)-type and CrOOH-type faults and a transition probability for the random intercalation of water/carbonate layers. Automated series of simulations and refinements were performed, in which the transition probabilities were modified incrementally and thus the microstructures optimized by a grid search. All samples were found to exhibit the same fraction of CdCl(2)-type and CrOOH-type stacking faults, which indicates that they have identical Ni, Co and Al contents. Different degrees of interstratification faulting were determined, which could be correlated to different heights of intercalation-water-related mass-loss steps in the thermal analyses.