The Role of Electronic Properties in the Electrochemical Behavior of Intercalation Compounds From a First Principles Vantage Point

  • A. Van der Ven
  • G. Ceder

Lithium transition metal oxides are remarkable intercalation compounds, exhibiting an array of intriguing electronic and phase transformation phenomena. Their ability to undergo large variations in lithium concentration, often without suffering irreversible changes, makes these materials ideal electrodes for rechargeable lithium batteries. Lithium transition metal oxides consist of a metal oxide host with a crystal structure in which lithium ions occupy a relatively open network of interstitial sites. While some lithium transition metal oxides can serve as an anode in rechargeable lithium batteries, most are more suited for the role of cathode as they typically exhibit a high voltage with respect to a metallic lithium anode, the ideal theoretical reference electrode. In a rechargeable lithium battery, lithium ions are shuttled between an anode and a cathode, whereby lithium ions are removed from and inserted into the electrodes. During deintercalation of a lithium transition metal oxide, vacancies are created on the lithium sites of the host. During intercalation, these sites are refilled by lithium. Removal and insertion of lithium ions can lead to several phenomena that can significantly affect the electrochemical properties of the compound. For one, variations in lithium concentration alter the electronic properties of the transition metal oxide host. The valence electron of each lithium ion is generally donated to the host where it can either shift the valence state of the transition metal ion and/or alter the nature of the bonds between the transition metal and the oxygen ions. Simultaneously, lithium removal from the host may structurally destabilize the metal oxide structure or may lead to order-disorder phase transitions between lithium and vacancies once a critical vacancy concentration is reached. These phenomena often affect the voltage characteristic or the lattice parameters of the compound in important ways.

Within the last decade, much attention has been devoted to understanding the properties of Li x Co02, LixNi02, Li x Mn02, Li x Mn204 1 and Li x FeP04 2, currently among the most important candidate cathode materials for rechargeable lithium batteries. Other compounds receiving attention are typically doped variants of the Co, Ni and Mn compounds. While many lithium transition metal oxides have similar crystal structures, either a layered form or one derived from the spinel structure (Li x FeP04 has the olivine crystal structure), they are often characterized by very different electrochemical properties owing to the unique electronic structure of each transition metal. Li x Co02, for example undergoes a concentration driven metal-insulator phase transformation whereby the electrons over much of the lithium concentration range (x>0.75) are delocalized and exhibit metallic properties.3 In contrast, the Li x Mn204 compound in important lithium concentration regions is characterized by more localized electrons with large magnetic moments leading to phenomena such as charge ordering and Jahn-Teller distortions.4–6 Often, phenomena such as these can be rationalized with crude crystal-field and molecular orbital models. More subtle properties such as the relative stability of similar crystal structures, stable ordered lithium-vacancy arrangements and charge-ordered and magnetic-ordered electronic states are more difficult to predict or rationalize with intuition based on simple electronic structure models. It is here that first-principles numerical-schemes for solving the Schrödinger equation of solids are proving invaluable. The record of the last decade of first principles studies of lithium transition metal oxides has demonstrated that these methods are an important new tool in predicting and understanding the properties of these materials.7–40


Lithium Concentration Intercalation Compound Rechargeable Lithium Batterie Lithium Anode Similar Crystal Structure 
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© Springer Science+Business Media, LLC 2003, First softcover printing 2009

Authors and Affiliations

  • A. Van der Ven
    • 1
  • G. Ceder
    • 1
  1. 1.Department of Materials Science and EngineeringMassachusetts Institute of TechnologyCambridgeU.S.A.

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