First-Principles Theory of Cation and Intercalation Ordering in LixCoO2

Several types of cation- and vacancy-ordering exist the LixCoO2 battery material. The ordering patterns are of interest due to the fact that they can control the voltage in rechargeable Li batteries. We present a first-principles total energy theory which can predict both cation- and vacancy-ordering patterns at both zero and finite temperatures. Also, by calculating the energetics of the Liintercalation reaction, this theory can provide first-principles predictions of battery voltages of LixCoO2/Li cells. Our calculations allow us to search the entire configurational space to predict the lowest-energy ground state structures, search for large voltage cathodes, explore metastable low-energy states, and extend our calculations to finite temperatures, thereby searching fororder-disorder transitions and states of partial disorder.