Li intercalation, electronic and thermodynamic properties in H2Ti3O7 bulk: A theoretical study

JUAN, JULIÁN; FERNÁNDEZ-WERNER, LUCIANA; BECHTHOLD, PABLO; JASEN, PAULA V.; FACCIO, RICARDO; GONZÁLEZ, ESTELA A.

COMPUTACIONAL MATERIALS SCIENCE

Elsevier

Lugar: Amsterdam; Año: 2023 vol. 228

0927-0256

We performed DensityFunctional Theory calculations with Hubbard methodology (DFT+U) in order tostudy Li intercalation in H2Ti3O7 and theelectronic and thermodynamic properties of this doped system. The calculated voltagesfor the three doped systems considered were found to be stable and withpromising values. Their electronic structure presented a small magnetic momentinduced due to the asymmetry present in the spin up and spin down contributionto the densities of states. Also, the systems present a type-n semiconductorbehaviour. A charge transfer of 0.7e- from Li to titanate was observed. Phonondensities of states show the presence of H and O peaks at high frequencies inthese systems. A novel theoretical thermodynamic study on Li intercalation inthis titanate was performed, finding that the doped systems have stable andpromising properties. The calculated bulk’s Gibbs free energy difference was of−252 kJ⋅mol−1. The NudgedElastic Band (NEB) methodology and on- the-fly force field machine learning(MLFF) from ab initio molecular dynamics (AIMD) were applied to determine thestability sites for Li. From selected diffusion paths for Li, we found thatthere is one in the structure with an energy barrier of 0.33 eV. Consequently,this study presents innovative and significant results as a guide for futuretheoretical and experimental works on this potentially Li-ion battery anodematerial. @font-face{font-family:"Cambria Math";panose-1:2 4 5 3 5 4 6 3 2 4;mso-font-charset:0;mso-generic-font-family:roman;mso-font-pitch:variable;mso-font-signature:-536870145 1107305727 0 0 415 0;}@font-face{font-family:Calibri;panose-1:2 15 5 2 2 2 4 3 2 4;mso-font-charset:0;mso-generic-font-family:swiss;mso-font-pitch:variable;mso-font-signature:-536859905 -1073732485 9 0 511 0;}p.MsoNormal, li.MsoNormal, div.MsoNormal{mso-style-unhide:no;mso-style-qformat:yes;mso-style-parent:"";margin:0cm;margin-bottom:.0001pt;mso-pagination:widow-orphan;font-size:12.0pt;font-family:"Calibri",sans-serif;mso-ascii-font-family:Calibri;mso-ascii-theme-font:minor-latin;mso-fareast-font-family:Calibri;mso-fareast-theme-font:minor-latin;mso-hansi-font-family:Calibri;mso-hansi-theme-font:minor-latin;mso-bidi-font-family:"Times New Roman";mso-bidi-theme-font:minor-bidi;}.MsoChpDefault{mso-style-type:export-only;mso-default-props:yes;font-family:"Calibri",sans-serif;mso-ascii-font-family:Calibri;mso-ascii-theme-font:minor-latin;mso-fareast-font-family:Calibri;mso-fareast-theme-font:minor-latin;mso-hansi-font-family:Calibri;mso-hansi-theme-font:minor-latin;mso-bidi-font-family:"Times New Roman";mso-bidi-theme-font:minor-bidi;}div.WordSection1{page:WordSection1;}