First-principles investigation of the cooperative Jahn-Teller effect for octahedrally coordinated transition-metal ions

Marianetti, Chris A.; Morgan, Dane; Ceder, Gerbrand

doi:10.1103/physrevb.63.224304

Cited by 106 publications

(96 citation statements)

References 36 publications

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“…However, the relaxations do allow for local distortions associated with the Jahn-Teller effect to occur when defects are introduced, e.g., by a vacancy. The JahnTeller distortions are typically less than 0.3 eV/Jahn-Teller ion (14). Specifically, our calculation results suggest the fully relaxed 2x2x2 LaMnO 3 and LaCoO 3 perovskites are about 0.05 eV/Jahn-Teller ion more stable than the constrained 2x2x2 cubic supercells.…”

Section: Magnetism and Jahn-teller Distortionsmentioning

confidence: 63%

Ab initio Defect Energetics in LaBO₃ Perovskite Solid Oxide Fuel Cell Materials

2009

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Perovskite materials of the form ABO 3 are a promising family of compounds for use in solid oxide fuel cell (SOFC) cathodes. Study of the physics of these compounds under SOFC conditions with ab initio methods is particularly challenging due to high temperatures, exchange of oxygen with O 2 gas, and correlated electron effects. This paper discusses an approach to performing ab initio studies on these materials for SOFC applications and applies the approach to calculate oxygen vacancy formation energies in LaBO 3 (B = Mn, Fe, Co, Ni) compounds.

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Section: Magnetism and Jahn-teller Distortionsmentioning

confidence: 63%

Ab initio Defect Energetics in LaBO₃ Perovskite Solid Oxide Fuel Cell Materials

2009

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“…With GGA a distorted unit cell is found with the short and the long Ni-O bond length being 1.92Å and 2.13Å, respectively, compared to experimental values of 1.91Å and 2.14Å 39 , and a stabilization energy relative to an undistorted cell of only -2meV, within the range of numerical errors, compared to -11 meV in Ref. 39 . With GGA+U no appreciable distortion is observed.…”

Section: Totalmentioning

confidence: 72%

First-principles prediction of redox potentials in transition-metal compounds withLDA+U

et al. 2004

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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 x MPO 4 (M=Mn, Fe Co, Ni), layered Li x MO 2 (x =Co, Ni) and spinel-like Li x M 2 O 4 (M=Mn, Co), can be reproduced accurately.

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“…On the other hand, Mn and Ni-based spinels show the largest volume changes as their reduction occurs by filling one or more eg orbitals. For both Mn 3+ and Ni 3+ this volume increase is compounded by the fact that these ions are Jahn-Teller active which, in its anharmonic form, leads to additional volume increase 62 . The combined small size and high charge of Al 3+ lead to almost zero volume change for several spinels.…”

Section: Resultsmentioning

confidence: 99%

Spinel compounds as multivalent battery cathodes: a systematic evaluation based on ab initio calculations

Liu

Rong

Malik

et al. 2015

Energy Environ. Sci.

482

642

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contributed equally to this work. AbstractBatteries that shuttle multi-valent ions such as Mg 2+ and Ca 2+ ions are promising candidates for achieving higher energy density than available with current Li-ion technology. Finding electrode materials that reversibly store and release these multi-valent cations is considered a major challenge for enabling such multi-valent battery technology. In this paper, we use recent advances in high-throughput firstprinciples calculations to systematically evaluate the performance of compounds with the spinel structure as multivalent intercalation cathode materials, spanning a matrix of five different intercalating ions and seven transition metal redox active cation. We estimate the insertion voltage, capacity, thermodynamic stability of charged and discharged states, as well as the intercalating ion mobility and use these properties to evaluate promising directions. Our calculations indicate that the Mn2O4 spinel phase based on Mg and Ca are feasible cathode materials. In general, we find that multivalent cathodes exhibit lower voltages compared to Li cathodes; 2 the voltages of Ca spinels are ~ 0.2V higher than those of Mg compounds (versus their corresponding metals), and the voltages of Mg compounds are ~1.4 V higher than Zn compounds; consequently, Ca and Mg spinels exhibit the highest energy densities amongst all the multivalent cation species. The activation barrier for the Al 3+ ion migration in the Mn2O4 spinel is very high (~1400 meV for Al 3+ in the dilute limit); thus, the use of an Al based Mn spinel intercalation cathode is unlikely.Amongst the choice of transition metals, Mn-based spinel structures rank highest when balancing all the considered properties. Broader ContextThe high price and limited volumetric capacity of the lithium ion battery (LIB) challenges its application in electric vehicles and portable electronics. Multivalent batteries, such as those utilizing Mg 2+ or Ca 2+ as the working ions, are promising candidates for beyond LIB technology due to the increase in volumetric capacity and reduced cost. In the present work, we use first-principles calculations to systematically evaluate the theoretical performance of the spinel structure host with the general formula AB2O4 across a matrix of chemical compositions spanning A={Al, Y, Mg, Ca, Zn} and B={Ti, V, Cr, Mn, Fe, Co, Ni} for multivalent battery applications. The evaluation incorporates screening on voltage, capacity, thermodynamic structural and thermal stability as well as ion mobility and discusses the results in the context of available host structure sites, preference of the intercalating cation, and the oxidation state of the redox-active cation. Overall, the Mn2O4 spinel phases paired with Mg 2+ or Ca 2+ emerge as the most promising multivalent cathode materials. As the first comprehensive screening of multivalent intercalation compounds across size, valence, and redox-states of the involved cations, our work is intended to

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First-principles investigation of the cooperative Jahn-Teller effect for octahedrally coordinated transition-metal ions

Cited by 106 publications

References 36 publications

Ab initio Defect Energetics in LaBO₃ Perovskite Solid Oxide Fuel Cell Materials

Ab initio Defect Energetics in LaBO₃ Perovskite Solid Oxide Fuel Cell Materials

First-principles prediction of redox potentials in transition-metal compounds withLDA+U

Spinel compounds as multivalent battery cathodes: a systematic evaluation based on ab initio calculations

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First-principles investigation of the cooperative Jahn-Teller effect for octahedrally coordinated transition-metal ions

Cited by 106 publications

References 36 publications

Ab initio Defect Energetics in LaBO3 Perovskite Solid Oxide Fuel Cell Materials

Ab initio Defect Energetics in LaBO3 Perovskite Solid Oxide Fuel Cell Materials

First-principles prediction of redox potentials in transition-metal compounds withLDA+U

Spinel compounds as multivalent battery cathodes: a systematic evaluation based on ab initio calculations

Contact Info

Product

Resources

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Ab initio Defect Energetics in LaBO₃ Perovskite Solid Oxide Fuel Cell Materials

Ab initio Defect Energetics in LaBO₃ Perovskite Solid Oxide Fuel Cell Materials