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

Research output: Contribution to journalJournal article – Annual report year: 2014Researchpeer-review

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  • Author: Varanasi, Arun Kumar

    Center for Study of Science, Technology and Policy, India

  • Author: Bhowmik, Arghya

    Center for Study of Science, Technology and Policy

  • Author: Sarkar, Tanmay

    Center for Study of Science, Technology and Policy, India

  • Author: Waghmare, Umesh V.

    Jawaharlal Nehru Centre for Advanced Scientific Research, India

  • Author: Bharadwaj, Mridula Dixit

    Center for Study of Science, Technology and Policy, India

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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
JournalIonics
Pages (from-to)315–321
ISSN0947-7047
DOIs
Publication statusPublished - 2014
Externally publishedYes
CitationsWeb of Science® Times Cited: No match on DOI

    Research areas

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

ID: 110936405