In a spinel framework like LMNO, Li + migration occurs from a T d site to another T d site via an empty O h (gate) site. There are two different gate sites (4a and 12d) in P 4 3 32 LMNO and thus two distinct migration paths for Li + (see Figure ). Li diffusivity calculations have been used to explain the rate capabilities of LMNO. Most theoretical studies have considered the diffusion of Li + via the vacancy mechanism, which involves hopping of a single Li + from one site to another (V - Li hopping in the opposite direction). Our calculated Li + migration barriers via the vacancy mechanism (Figure ) are similar to previous studies. The activation energies for Li + to migrate through 4a (path 1) and 12d (path 2) gate sites are 0.34 eV and 0.30 eV, respectively. This is consistent with our findings that Li interstitials preferentially sit on the 12d sites. Finally, we show that the Li + interstitialcy migration makes the Li-Frenkel pair (Li + i -V - Li )