Tuning electrochemical potential of LiCoO2 with cation substitution: first-principles predictions and electronic origin

Arun Kumar Varanasi, Arghya Bhowmik, Tanmay Sarkar, Umesh V. Waghmare, Mridula Dixit Bharadwaj

Research output: Contribution to journalJournal articleResearchpeer-review


With a goal to improve the performance of LiCoO2 as a cathode material in Li-ion batteries, we simulate substitution of various elements (X = Be,Mg, Al, Ga, Si and Ti) for Co using first-principles density functional theory and predict changes in its electrochemical potential. While the electrochemical potential of LiCoO2 is enhanced with substitution of Be,Mg, Al and Ga for Co, an opposite effect is predicted of Si and Ti substitution. We determine the electronic origin of these changes in electrochemical potential using (a) Bader method of topological analysis of charge density, (b) partial density of electronic states to estimate oxidation states of metal and oxygen, and charge re-distribution upon lithiation. We find that the distribution of electronic charge donated by Li is influenced by the nature of the X–O bond. A larger electron transfer to O (in XO6 octahedron) upon lithiation leads to stronger Li intercalation and thereby higher electrochemical voltage. Our findings provide a platform for a rational design of cathode materials in Li batteries with enhanced voltage.
Original languageEnglish
Pages (from-to)315–321
Publication statusPublished - 2014
Externally publishedYes


  • Lithium-ion battery cathode
  • Density functional theory
  • Bader charge analysis
  • Electrochemical potential

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