Towards more accurate First Principles prediction of redox potentials in transition-metal compounds with LDA+U

First-principles calculations within the local density approximation (LDA) or generalized gradient approximation (GGA), though very successful, are known to underestimate redox potentials, such as those at which lithium intercalates in transition metal compounds. We argue that this inaccuracy is related to the lack of cancellation of electron self-interaction errors in LDA/GGA and can be improved by using the DFT+U method with a self-consistent evaluation of the U parameter. We show that, using this approach, the experimental lithium intercalation voltages of a number of transition metal compounds, including the olivine Li xMPO4 (M = Mn, Fe Co, Ni), layered LixMO2 (x = Co, Ni) and spinel-like LixM2O4 (M = Mn, Co), can be reproduced accurately.

[1]  G. Ouvrard,et al.  A DFT study of lithium battery materials: application to the β-VOXO4 systems (X=P, As, S) , 2003 .

[2]  N. A. W. Holzwarth,et al.  Electronic structure of FePO 4 , LiFePO 4 , and related materials , 2003 .

[3]  Christian Masquelier,et al.  Magnetic Structures of the Triphylite LiFePO4 and of Its Delithiated Form FePO4 , 2003 .

[4]  Gerbrand Ceder,et al.  A Combined Computational/Experimental Study on LiNi1/3Co1/3Mn1/3O2 , 2003 .

[5]  J. Barker,et al.  Experimental and computational study of the structure and electrochemical properties of monoclinic LixM2(PO4)3 compounds , 2003 .

[6]  G. Ouvrard,et al.  First-Principle Study of the Intercalation Process in the LixV2O5 System , 2003 .

[7]  Ab initio calculation of the voltage profile for LiC6 , 2003 .

[8]  R. Benedek,et al.  Effect of Co on the magnetism and phase stability of lithiated manganese oxides , 2003 .

[9]  Y. Koyama,et al.  Electronic structures and electrode potentials of layered lithium insertion electrodes by the first principles calculation , 2003 .

[10]  Gerbrand Ceder,et al.  Experimental and Computational Study of the Structure and Electrochemical Properties of LixM2(PO4)3 Compounds with the Monoclinic and Rhombohedral Structure , 2002 .

[11]  L. Monconduit,et al.  The LixVPn4 Ternary Phases (Pn = P, As): Rigid Networks for Lithium Intercalation/Deintercalation , 2002 .

[12]  Anton Van der Ven,et al.  First-principles calculations of lithium ordering and phase stability on Li x NiO 2 , 2002 .

[13]  Guohua Li,et al.  LiMnPO4 as the Cathode for Lithium Batteries , 2002 .

[14]  J. Yamaki,et al.  Cathode properties of phospho-olivine LiMPO4 for lithium secondary batteries , 2001 .

[15]  Gerbrand Ceder,et al.  Layered-to-Spinel Phase Transition in Li x MnO2 , 2001 .

[16]  G. Ceder,et al.  First-principles investigation of the cooperative Jahn-Teller effect for octahedrally coordinated transition-metal ions , 2001 .

[17]  F. García-Alvarado,et al.  Influence of the structure on the electrochemical performance of lithium transition metal phosphates as cathodic materials in rechargeable lithium batteries : A new high-pressure form of LiMPO4 (M = Fe and Ni) , 2001 .

[18]  Sai-Cheong Chung,et al.  Optimized LiFePO4 for Lithium Battery Cathodes , 2001 .

[19]  G. Prado,et al.  Lithium batteries: a new tool in solid state chemistry , 1999 .

[20]  Gerbrand Ceder,et al.  Structural stability of lithium manganese oxides , 1999 .

[21]  G. Kresse,et al.  From ultrasoft pseudopotentials to the projector augmented-wave method , 1999 .

[22]  K. Amine,et al.  OLIVINE LICOPO4 AS 4.8 V ELECTRODE MATERIAL FOR LITHIUM BATTERIES , 1999 .

[23]  Anton Van der Ven,et al.  Lithium Diffusion in Layered Li x CoO2 , 1999 .

[24]  J. Dahn,et al.  Ab initio calculation of the lithium-tin voltage profile , 1998 .

[25]  Christopher M Wolverton,et al.  Prediction of Li Intercalation and Battery Voltages in Layered vs. Cubic Li[sub x]CoO[sub 2] , 1998 .

[26]  Gerbrand Ceder,et al.  First‐Principles Evidence for Stage Ordering in Li x CoO2 , 1998 .

[27]  C. Humphreys,et al.  Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study , 1998 .

[28]  Gerbrand Ceder,et al.  Ab initio study of lithium intercalation in metal oxides and metal dichalcogenides , 1997 .

[29]  K. S. Nanjundaswamy,et al.  Phospho‐olivines as Positive‐Electrode Materials for Rechargeable Lithium Batteries , 1997 .

[30]  E. Ethridge,et al.  Reformulation of the LDA+U method for a local orbital basis , 1996, cond-mat/9611225.

[31]  Kresse,et al.  Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. , 1996, Physical review. B, Condensed matter.

[32]  G. Kresse,et al.  Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set , 1996 .

[33]  J. Zaanen,et al.  Density-functional theory and strong interactions: Orbital ordering in Mott-Hubbard insulators. , 1995, Physical review. B, Condensed matter.

[34]  Michael M. Thackeray,et al.  Structural Considerations of Layered and Spinel Lithiated Oxides for Lithium Ion Batteries , 1995 .

[35]  C. Delmas,et al.  Non-cooperative Jahn-Teller effect in LiNiO2: An EXAFS study , 1995 .

[36]  W. R. McKinnon,et al.  Insertion electrodes I: Atomic and electronic structure of the hosts and their insertion compounds , 1994 .

[37]  Tsutomu Ohzuku,et al.  Why transition metal (di)oxides are the most attractive materials for batteries , 1994 .

[38]  Kieffer Mechanical degradation and viscous dissipation in B2O3. , 1994, Physical review. B, Condensed matter.

[39]  G. Sawatzky,et al.  Density-functional theory and NiO photoemission spectra. , 1993, Physical review. B, Condensed matter.

[40]  V. Anisimov,et al.  Band theory and Mott insulators: Hubbard U instead of Stoner I. , 1991, Physical review. B, Condensed matter.

[41]  G. Brachtel,et al.  Zur Kenntnis der Oxomanganate(III):, Über LiMnO2 und β‐NaMnO2 [1] , 1975 .

[42]  R. E. Newnham,et al.  Antiferromagnetism in LiFePO4 , 1967 .

[43]  R. Newnham,et al.  Magnetic properties of LiCoPO4 and LiNiPO4 , 1966 .

[44]  Nathan Wiser,et al.  Dielectric Constant with Local Field Effects Included , 1963 .

[45]  Stephen L. Adler,et al.  Quantum theory of the dielectric constant in real solids. , 1962 .