Layered-oxide $\mathrm{LiNi_xMn_yCo_{1-x-y}O_2}$ (NMC) positive electrodes with high Nickel content, deliver high voltages and energy densities. However, a high nickel content, e.g., $x$ = 0.8 (NMC 811), can lead to high surface reactivity, which can trigger thermal runaway and gas generation. While claimed safer, all-solid-state batteries still suffer from high interfacial resistance. Here, we investigate niobate and tantalate coating materials, which can mitigate the interfacial reactivities in Li-ion and all-solid-state batteries. First-principles calculations reveal the multiphasic nature of Li-Nb-O and Li-Ta-O coatings, containing mixtures of $\mathrm{LiNbO_3}$ and $\mathrm{Li_3NbO_4}$, or of $\mathrm{LiTaO_3}$ and $\mathrm{Li_3TaO_4}$. The concurrence of several phases in Li-Nb-O or Li-Ta-O modulates the type of stable native defects in these coatings. Li-Nb-O and Li-Ta-O coating materials can form favorably lithium vacancies $\mathrm{Vac^{'}_{Li}}$ and antisite defects $\mathrm{Nb^{\bullet \bullet \bullet \bullet}_{Li}}$ ($\mathrm{Ta^{\bullet \bullet \bullet \bullet}_{Li}}$) combined into charge-neutral defect complexes. Even in defective crystalline $\mathrm{LiNbO_3}$ (or $\mathrm{LiTaO_3}$), we reveal poor Li-ion conduction properties. In contrast, $\mathrm{Li_3NbO_4}$ and $\mathrm{Li_3TaO_4}$ that are introduced by high-temperature calcinations can provide adequate Li-ion transport in these coatings. Our in-depth investigation of the structure-property relationships in the important Li-Nb-O and Li-Ta-O coating materials helps to develop more suitable calcination protocols to maximize the functional properties of these niobates and tantalates.