Thermal stabilities of delithiated olivine MPO4 (M=Fe, Mn) cathodes investigated using first principles calculations

Ong, Shyue Ping; Jain, Anubhav; Hautier, Geoffroy; Kang, Byoungwoo; Ceder, Gerbrand

doi:10.1016/j.elecom.2010.01.010

Cited by 235 publications

(247 citation statements)

References 28 publications

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“…Tavorite We have found that the calculated oxygen chemical potential at which O 2 is released is a good proxy for the safety of a cathode material at high temperatures. 43,44 To evaluate the safety of the materials considered in this paper, we have calculated the oxygen chemical potentials of each material in the fully delithiated state. The materials that pass the thermodynamic stability screen, are not predicted to release oxygen at room temperature, and are predicted to insert lithium at more than 1V relative to lithium metal are shown in Figure 2.…”

Section: Resultsmentioning

confidence: 99%

Evaluation of Tavorite-Structured Cathode Materials for Lithium-Ion Batteries Using High-Throughput Computing

et al. 2011

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ABSTRACT. Cathode materials with structure similar to the mineral tavorite have shown promise for use in lithium-ion batteries, but this class of materials is relatively unexplored. We use high-throughput density-functional-theory calculations to evaluate tavorite-structured oxyphosphates, fluorophosphates, oxysulfates, and fluorosulfates for use as cathode materials in lithium-ion batteries. For each material we consider the insertion of both one and two lithium ions per redox-active metal, calculating average voltages and stability relative to a database of nearly 100,000 previously-calculated compounds. To evaluate lithium mobility, we calculate the activation energies for lithium diffusion through the known tavorite cathode materials LiVO(PO 4 ), LiV(PO 4 )F, and LiFe(SO 4 )F. Our calculations indicate that tavorite-structured materials are capable of very high rates of one-dimensional lithium diffusion, and several tavorite-structured materials may be capable of reversibly inserting two lithium ions per redoxactive metal.

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Section: Resultsmentioning

confidence: 99%

Evaluation of Tavorite-Structured Cathode Materials for Lithium-Ion Batteries Using High-Throughput Computing

et al. 2011

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“…Hence, moving to a Na-ion battery chemistry may provide the opportunity to obtain lower voltages with such compounds. However, these high-Li-voltage compounds are typically highly thermally unstable in the charged state, [87][88][89][90] and the charged Na analogues are expected to be similarly unstable.…”

Section: Implications For Materials Designmentioning

confidence: 99%

Voltage, stability and diffusion barrier differences between sodium-ion and lithium-ion intercalation materials

Ong

Chevrier

Hautier

et al. 2011

Energy Environ. Sci.

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To evaluate the potential of Na-ion batteries, we contrast in this work the difference between Na-ion and Li-ion based intercalation chemistries in terms of three key battery properties -voltage, phase stability and diffusion barriers. The compounds investigated comprise the layered AMO 2 and AMS 2 structures, the olivine and maricite AMPO 4 structures, and the NA-SICON A 3 V 2 (PO 4 ) 3 structures. The calculated Na voltages for the compounds investigated are 0.18-0.57 V lower than that of the corresponding Li voltages, in agreement with previous experimental data. We believe the observed lower voltages for Na compounds are predominantly a cathodic effect related to the much smaller energy gain from inserting Na into the host structure compared to inserting Li. We also found a relatively strong dependence of battery properties with structural features. In general, the difference between the Na and Li voltage of the same compound, ∆V Na-Li , is less negative for the maricite structures preferred by Na, and * To whom correspondence should be addressed 1 more negative for the olivine structures preferred by Li. The layered compounds have the most negative ∆V Na-Li . In terms of phase stability, we found that open structures, such as the layered and NASICON structures that are better able to accommodate the larger Na + ion generally have both Na and Li versions of the same compound. For the close-packed AMPO 4 structures, our results show that Na generally prefers the maricite structure, while Li prefers the olivine structure, in agreement with previous experimental work. We also found surprising evidence that the barriers for Na + migration can potentially be lower than that for Li + migration in the layered structures. Overall, our findings indicate that Na-ion systems can be competitive with Li-ion systems.

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“…In order to check the phase stability of CaFeAs 2 , we build the convex-hull for all known binary and ternary compounds formed by these elements. The convex-hull construction evaluates the stability of a given compound against any linear combination of possible compounds effectively [55][56][57][58][59]. Hence, it is possible to determine whether a given compound is stable or prefers to decompose to other compounds (within the accuracy of DFT and the approximations to the exchange correlation functional).…”

Section: Thermodynamic Stability and Convex Hull Constructionmentioning

confidence: 99%

Phase stability and large in-plane resistivity anisotropy in the 112-type iron-based superconductor Ca1−xLaxFeAs2

2017

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The recently discovered high-Tc superconductor Ca1−xLaxFeAs2 is a unique compound not only because of its low symmetry crystal structure, but also because of its electronic structure which hosts Dirac-like metallic bands resulting from (spacer) zig-zag As chains. We present a comprehensive first principles theoretical study of the electronic and crystal structures of Ca1−xLaxFeAs2. After discussing the connection between the crystal structure of the 112 family, which Ca1−xLaxFeAs2 is a member of, with the other known structures of Fe pnictide superconductors, we check the thermodynamic phase stability of CaFeAs2, and similar hyphothetical compounds SrFeAs2 and BaFeAs2 which, we find, are slightly higher in energy. We calculate the optical conductivity of Ca1−xLaxFeAs2 using the DFT + DMFT method, and predict a large in-plane resistivity anisotropy in the normal phase, which does not originate from electronic nematicity, but is enhanced by the electronic correlations. In particular, we predict a 0.34 eV peak in the yy component of the optical conductivity of the 30% La doped compound, which correponds to coherent interband transitions within a fast-dispersing band arising from the zig-zag As-chains which are unique to this compound. We also study the Landau free energy for Ca1−xLaxFeAs2 including the order parameter relevant for the nematic transition and find that the free energy does not have any extra terms that could induce ferro-orbital order. This explains why the presence of As chains does not broaden the nematic transition in Ca1−xLaxFeAs2.

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Thermal stabilities of delithiated olivine MPO4 (M=Fe, Mn) cathodes investigated using first principles calculations

Cited by 235 publications

References 28 publications

Evaluation of Tavorite-Structured Cathode Materials for Lithium-Ion Batteries Using High-Throughput Computing

Evaluation of Tavorite-Structured Cathode Materials for Lithium-Ion Batteries Using High-Throughput Computing

Voltage, stability and diffusion barrier differences between sodium-ion and lithium-ion intercalation materials

Phase stability and large in-plane resistivity anisotropy in the 112-type iron-based superconductor Ca1−xLaxFeAs2

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