<i>Ab initio</i>calculation of the lithium-tin voltage profile

Courtney, I. A.; Tse, John S.; Mao, Ou; Häfner, J.; Dahn, J. R.

doi:10.1103/physrevb.58.15583

Cited by 270 publications

(236 citation statements)

References 24 publications

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“…First principles calculations have been used extensively to predict important properties of Li-insertion materials such as the average potential 4,5,6,7,8,9,10,11,12,13,14 and potential profile 15,16 for Li insertion, phase stability 17,18,19 and Li diffusion 20 . While this has led to considerable success in predicting the trends of Li insertion voltages 4 and even new phases 15 , it has been noted that LDA or GGA can give relatively large errors for the average Li insertion potential 4,21 .…”

Section: Introductionmentioning

confidence: 99%

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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Section: Introductionmentioning

confidence: 99%

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

et al. 2004

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“…This definition is widely used as the sole voltage estimate in the LIB theory literature. [56][57][58][59] At equilibrium, when the voltage is pinned at the redox potential of Li-insertion reactions, V e must be equal to V i . Thus V i should be considered a self-consistent criterion at interfaces.…”

Section: Introductionmentioning

confidence: 99%

How Voltage Drops Are Manifested by Lithium Ion Configurations at Interfaces and in Thin Films on Battery Electrodes

Leung

Leenheer

2015

J. Phys. Chem. C

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Battery electrode surfaces are generally coated with electronically insulating solid films of thickness 1-50 nm. Both electrons and Li + can move at the electrode-surface film interface in response to the voltage, which adds complexity to the "electric double layer" (EDL). We apply Density Functional Theory (DFT) to investigate how the applied voltage is manifested as changes in the EDL at atomic lengthscales, including charge separation and interfacial dipole moments. Illustrating examples include Li 3 PO 4 , Li 2 CO 3 , and Li x Mn 2 O 4 thin-films on Au(111) surfaces under ultrahigh vacuum conditions. Adsorbed organic solvent molecules can strongly reduce voltages predicted in vacuum. We propose that manipulating surface dipoles, seldom discussed in battery studies, may be a viable strategy to improve electrode passivation. We also distinguish the computed potential governing electrons, which is the actual or instantaneous voltage, and the "lithium cohesive energy"-based voltage governing Li content widely reported in DFT calculations, which is a slower-responding self-consistency criterion at interfaces. This distinction is critical for a comprehensive description of electrochemical activities on electrode surfaces, including Li + insertion dynamics, parasitic electrolyte decomposition, and electrodeposition at overpotentials. keywords: lithium ion batteries; voltage prediction; density functional theory; computational electrochemistry

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“…An approximation made in these calculations is that the transformation from reactant to product is in two phases, so an average voltage can be defined [5]. Courtney et al [6] used the ab initio pseudopotential plane-wave method and the approximation by Aydinol et al [5] to calculate the average voltage for the anode material tin-oxide (in particular, lithium -tin, Li x Sn y ). Deiss et al [4] calculated the energy density and cell voltages of LiC 6 /LiMoO 2 (anode/cathode) and LiC 6 /NiO 2 using the average voltage between the fully charged and the discharged states.…”

Section: Introductionmentioning

confidence: 99%