Abstract
The functioning of a positive electrode in a lithium battery is based on the reversible intercalation of lithium. In some cases, such a reaction can lead to important structural modifications and therefore to an amorphization of the material. A theoretical approach is presented here that leads to structural predictions and simulations of electrochemical behaviour of positive electrode materials. In the first part, DFT (Density Functional Theory) formalisms and the respective advantages of FLAPW (Full potential Linearized Augmented Plane Waves) and PP/PW (Pseudopotential / Plane Waves) methods are discussed. In the second part are given some fundamental electrochemistry considerations related to the intercalation process, thermodynamics aspects and relationships with electronic structure. Then, an approach combining experimental data and geometry optimisation of structural hypotheses is given. This approach was first applied to a model compound LiMoS{sub 2}, and has been then generalised to systems of industrial interest such as Li{sub x}V{sub 2}O{sub 5} (0 {<=} x {<=} 3). The simulated X-ray diagrams of the optimised structures for LiMoS{sub 2} and {omega} - Li{sub 3}V{sub 2}O{sub 5} are in good agreement with experimental data. In the case of Li{sub x}V{sub 2}O{sub 5}, the first discharge curves starting from {alpha} - V{sub 2}O{sub 5}
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Citation Formats
Rocquefelte, X.
First principles simulation of the electrochemical behaviour of lithium battery materials; Modelisation du comportement electrochimique de materiaux pour batteries au lithium a partir de calculs de premiers principes.
France: N. p.,
2001.
Web.
Rocquefelte, X.
First principles simulation of the electrochemical behaviour of lithium battery materials; Modelisation du comportement electrochimique de materiaux pour batteries au lithium a partir de calculs de premiers principes.
France.
Rocquefelte, X.
2001.
"First principles simulation of the electrochemical behaviour of lithium battery materials; Modelisation du comportement electrochimique de materiaux pour batteries au lithium a partir de calculs de premiers principes."
France.
@misc{etde_20520213,
title = {First principles simulation of the electrochemical behaviour of lithium battery materials; Modelisation du comportement electrochimique de materiaux pour batteries au lithium a partir de calculs de premiers principes}
author = {Rocquefelte, X}
abstractNote = {The functioning of a positive electrode in a lithium battery is based on the reversible intercalation of lithium. In some cases, such a reaction can lead to important structural modifications and therefore to an amorphization of the material. A theoretical approach is presented here that leads to structural predictions and simulations of electrochemical behaviour of positive electrode materials. In the first part, DFT (Density Functional Theory) formalisms and the respective advantages of FLAPW (Full potential Linearized Augmented Plane Waves) and PP/PW (Pseudopotential / Plane Waves) methods are discussed. In the second part are given some fundamental electrochemistry considerations related to the intercalation process, thermodynamics aspects and relationships with electronic structure. Then, an approach combining experimental data and geometry optimisation of structural hypotheses is given. This approach was first applied to a model compound LiMoS{sub 2}, and has been then generalised to systems of industrial interest such as Li{sub x}V{sub 2}O{sub 5} (0 {<=} x {<=} 3). The simulated X-ray diagrams of the optimised structures for LiMoS{sub 2} and {omega} - Li{sub 3}V{sub 2}O{sub 5} are in good agreement with experimental data. In the case of Li{sub x}V{sub 2}O{sub 5}, the first discharge curves starting from {alpha} - V{sub 2}O{sub 5} and {gamma}' - V{sub 2}O{sub 5} were then successfully simulated. A chemical bond analysis was carried out to help understand the origin of the distortion in LiMoS{sub 2} and the voltage variations in the electrochemical curves of Li{sub x}V{sub 2}O{sub 5}. This study clearly demonstrates that an approach combining first-principle calculations and available experimental data is invaluable in the structure determination of poorly crystallized compounds. Such a procedure contributes to the understanding of the phase transitions induced by the lithium intercalation in vanadium oxide compounds and can really be used in the research of new battery materials. (author)}
place = {France}
year = {2001}
month = {Oct}
}
title = {First principles simulation of the electrochemical behaviour of lithium battery materials; Modelisation du comportement electrochimique de materiaux pour batteries au lithium a partir de calculs de premiers principes}
author = {Rocquefelte, X}
abstractNote = {The functioning of a positive electrode in a lithium battery is based on the reversible intercalation of lithium. In some cases, such a reaction can lead to important structural modifications and therefore to an amorphization of the material. A theoretical approach is presented here that leads to structural predictions and simulations of electrochemical behaviour of positive electrode materials. In the first part, DFT (Density Functional Theory) formalisms and the respective advantages of FLAPW (Full potential Linearized Augmented Plane Waves) and PP/PW (Pseudopotential / Plane Waves) methods are discussed. In the second part are given some fundamental electrochemistry considerations related to the intercalation process, thermodynamics aspects and relationships with electronic structure. Then, an approach combining experimental data and geometry optimisation of structural hypotheses is given. This approach was first applied to a model compound LiMoS{sub 2}, and has been then generalised to systems of industrial interest such as Li{sub x}V{sub 2}O{sub 5} (0 {<=} x {<=} 3). The simulated X-ray diagrams of the optimised structures for LiMoS{sub 2} and {omega} - Li{sub 3}V{sub 2}O{sub 5} are in good agreement with experimental data. In the case of Li{sub x}V{sub 2}O{sub 5}, the first discharge curves starting from {alpha} - V{sub 2}O{sub 5} and {gamma}' - V{sub 2}O{sub 5} were then successfully simulated. A chemical bond analysis was carried out to help understand the origin of the distortion in LiMoS{sub 2} and the voltage variations in the electrochemical curves of Li{sub x}V{sub 2}O{sub 5}. This study clearly demonstrates that an approach combining first-principle calculations and available experimental data is invaluable in the structure determination of poorly crystallized compounds. Such a procedure contributes to the understanding of the phase transitions induced by the lithium intercalation in vanadium oxide compounds and can really be used in the research of new battery materials. (author)}
place = {France}
year = {2001}
month = {Oct}
}