Beyond the specific compound investigated here, the methodology provides a broadly applicable strategy for designing metastable layered oxides with tailored structural features. The insights gained from neutron diffraction on sodium-vacancy distribution and cation disordering may inform the development of other alkali-ion battery systems, enabling electrodes with improved rate capability, durability, and energy density. This work therefore illustrates the central role of advanced neutron techniques in guiding next-generation energy storage materials.