Cation and vacancy ordering in<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" display="inline"><mml:mrow><mml:msub><mml:mrow><mml:mi mathvariant="normal">Li</mml:mi></mml:mrow><mml:mrow><mml:mi>x</mml:mi></mml:mrow></mml:msub></mml:mrow><mml:mrow><mml:msub><mml:mrow><mml:mi mathvariant="normal">CoO</mml:mi></mml:mrow><mml:mrow><mml:mn>2</mml:mn></mml:mrow></mml:msub></mml:mrow></mml:math>

Wolverton, Christopher; Zunger, Alex

doi:10.1103/physrevb.57.2242

Cited by 137 publications

(61 citation statements)

References 36 publications

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“…At high levels of oxidation, rehybridization shifts occur in the transition-metal ligand bond in order to diminish the effect of changing the valence on the transition metal site. Such shifts have been previously observed with computational methods in LiCoO 2 [1,34] and NaCoO 2 [35], and experimentally in LiCoO 2 [36].…”

Section: Resultssupporting

confidence: 76%

The Li intercalation potential of LiMPO4 and LiMSiO4 olivines with M=Fe, Mn, Co, Ni

Zhou

Cococcioni

Kang

et al. 2004

Electrochemistry Communications

418

315

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The Li intercalation potential of LiMPO 4 and LiMSiO 4 compounds with M = Fe, Mn, Co, and Ni is computed with the GGA+U method. It is found that this approach is considerably more accurate than standard LDA or GGA methods. The calculated potentials for LiFePO 4 , LiMnPO 4 and LiCoOPO 4 agree to within 0.1 V with experimental results. The LiNiPO 4 potential is predicted to be above 5 V. The potentials of the silicate materials are all found to be rather high, but LiFeSiO 4 and LiCoSiO 4 have negligible volume change upon Li extraction.Keywords: Battery cathode; Density functional theory; LDA+U; Olivine; Redox potential Introduction First principles computations have shown to be relevant for predicting many of the properties of Li-insertion materials used as electrodes in rechargeable Li batteries [1][2][3][4][5][6][7][8][9]. One of the critical properties for a Li intercalation material is the potential at which Li can be removed and inserted. While a high potential increases the energy density of the material, if this potential is too high, Li can not be practically removed, and side reactions such as electrolyte breakdown, can occur in the cell. A low potential can also lead to moisture sensitivity of the electrode material. Hence, knowledge of the thermodynamic potential is one crucial aspect when determining whether new materials can be used as cathode materials in rechargeable lithium batteries. In this communication, we predict the potential of LiNiPO 4 , LiMnSiO 4 , LiFeSiO 4 , LiCoSiO 4 and LiNiSiO 4 using the highly accurate GGA+U method.The electrochemical activity of LiFePO 4 [10] and Li 3 V 2 (PO 4 ) 3 [11][12][13][14] has spawned considerable interest in materials with poly-anion groups, as they may be considerably more stable than close-packed oxides at the end of charging. Currently, LiFePO 4 and Li 3 V 2 (PO 4 ) 3 are of commercial interest, though the rather low potential of LiFePO 4 gives it too low an energy density to compete with layered oxides in applications where volumetric or gravimetric energy density is most important. In this communication we use ab-initio computations to predict the potential of other phosphates and silicates in the olivine structure. While ab-initio methods have previously been used to predict the potential of insertion electrodes, we use a more accurate quantum mechanical approach in this work, allowing us to predict the insertion potentials within 0.1-0.2V. We find that of the compounds investigated, LiFePO 4 actually has the lowest potential. Among the phosphate compounds, the potential of LiNiPO 4 is found to be too high to be of practical interest. LiMnSiO 4 , LiFeSiO 4 , LiCoSiO 4 and LiNiSiO 4 also have high potentials, with only the Mn and Fe material just below 5V.

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Section: Resultssupporting

confidence: 76%

The Li intercalation potential of LiMPO4 and LiMSiO4 olivines with M=Fe, Mn, Co, Ni

Zhou

Cococcioni

Kang

et al. 2004

Electrochemistry Communications

418

315

View full text Add to dashboard Cite

show abstract

“…Early examples from the literature are the simulation of the room-temperature voltage profile of the Li-Al alloy by Reimers and Dahn, 78 and the investigation of lithium-vacancy orderings in Li x CoO 2 by Van der Ven et al 55,59 Wolverton and Zunger also applied first-principlesbased cluster expansion to cation (Li/Co) and lithium-vacancy ordering in Li x CoO 2 , reproducing the experimentally observed layered ground state and reporting the temperature-dependence of the voltage profile. 79,80 Van der Ven and Ceder used MC simulations based on a cluster expansion Hamiltonian to compute the temperature dependence of the lithium intercalation voltage profile of Li(Ni 1/2 Mn 1/2 )O 2 ( Figure 2b). 81 As seen in Figure 2b, temperature effects mainly smooth out the voltage steps that are present in the 0-K approximation, resulting in a continuous voltage slope instead, so that the difference between finitetemperature and 0-K voltage profiles are often small.…”

Section: 56mentioning

confidence: 99%

Computational understanding of Li-ion batteries

2016

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Over the last two decades, computational methods have made tremendous advances, and today many key properties of lithium-ion batteries can be accurately predicted by first principles calculations. For this reason, computations have become a cornerstone of battery-related research by providing insight into fundamental processes that are not otherwise accessible, such as ionic diffusion mechanisms and electronic structure effects, as well as a quantitative comparison with experimental results. The aim of this review is to provide an overview of state-of-the-art ab initio approaches for the modelling of battery materials. We consider techniques for the computation of equilibrium cell voltages, 0-Kelvin and finite-temperature voltage profiles, ionic mobility and thermal and electrolyte stability. The strengths and weaknesses of different electronic structure methods, such as DFT+U and hybrid functionals, are discussed in the context of voltage and phase diagram predictions, and we review the merits of lattice models for the evaluation of finite-temperature thermodynamics and kinetics. With such a complete set of methods at hand, first principles calculations of ordered, crystalline solids, i.e., of most electrode materials and solid electrolytes, have become reliable and quantitative. However, the description of molecular materials and disordered or amorphous phases remains an important challenge. We highlight recent exciting progress in this area, especially regarding the modelling of organic electrolytes and solid-electrolyte interfaces.

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“…A variety of investigations on lithium vacancies and cation intermixing have been reported for layered oxides. [5] In contrast, few experimental details showing the atomic-scale point defects in olivine-type lithium metal phosphates LiMPO 4 (where M = Fe, Mn, Ni, Co), are yet available, although these phosphates have attracted a great deal of attention as alternative cathode materials in lithium-ion batteries over the past decade.…”

mentioning

confidence: 94%

Orientation‐Dependent Arrangement of Antisite Defects in Lithium Iron(II) Phosphate Crystals

et al. 2008

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The distribution and local concentration of point defects in crystal lattices such as dopants and atomic vacancies have been recognized as significant factors that govern the overall electrical and optical properties of inorganic crystals. [1][2][3] The intentional use of impurities in semiconductors [1] and the formation of ionic vacancies in ion-conducting metal oxides [2] are well-known examples of displaying the correlation between atomic-scale chemical variations and resulting physical properties. Furthermore, as the chemically different environment induced by point defects leads to breaking of the ordered arrangement of atoms in crystals, mass and charge transport behaviors are also considerably affected by the presence of the defects. [4] In many lithium intercalation compounds, an ordered array of lithium is usually maintained. Therefore, the control of point defects, including cation disorder, is of major significance for application to electrodes in rechargeable batteries. A variety of investigations on lithium vacancies and cation intermixing have been reported for layered oxides.[5] In contrast, few experimental details showing the atomic-scale point defects in olivine-type lithium metal phosphates LiMPO 4 (where M = Fe, Mn, Ni, Co), are yet available, although these phosphates have attracted a great deal of attention as alternative cathode materials in lithium-ion batteries over the past decade.[6] As illustrated in Figure 1a, the lithium and the metal (M) ion in LiMPO 4 having an ordered olivine structure occupy different octahedral inter-

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Cation and vacancy ordering inLixCoO2

Cited by 137 publications

References 36 publications

The Li intercalation potential of LiMPO4 and LiMSiO4 olivines with M=Fe, Mn, Co, Ni

The Li intercalation potential of LiMPO4 and LiMSiO4 olivines with M=Fe, Mn, Co, Ni

Computational understanding of Li-ion batteries

Orientation‐Dependent Arrangement of Antisite Defects in Lithium Iron(II) Phosphate Crystals

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