Li ions segregated on anatase powders: Surface excess and ionic conductivity in the natural adsorbed water

Autor(es)

Caldeira, Giovanna Jaques ; Bernardes, Andre Avancini ; Martins, Vitor L. ; Schneider, Jose Fabian ; Goncalves, Renato V. ; Gouvea, Douglas

• Tipo de documento: Artigo Científico
• Fonte: Journal of the American Ceramic Society; v. N/A, p. 15-pg., 2025-03-22.

Resumo

The exploration of doped titanium dioxide (TiO2) materials presents significant potential for advancing technologies in energy storage, catalysis, and electronics. Among various dopants, lithium (Li) ions have attracted considerable interest due to their role in lithium-ion batteries. However, the understanding of lithium-ion distribution within the bulk and at the interfaces (surface and grain boundaries) of anatase TiO2 nanoparticles remains limited and poorly understood. The lithium concentrations examined in this study were 0.0, 0.7, 3.2, 6.5, and 16.7 mol%. The specific surface area increased notably for lithium concentrations above 3.2 mol%, indicating the segregation of lithium ions on the TiO2 surface. This segregation was demonstrated using several techniques, including x-ray photoelectron spectroscopy, nuclear magnetic resonance (NMR), and diffuse reflectance infrared Fourier transform spectroscopy (FTIR-DRIFT). NMR, in particular, provided novel insights into the proportions of lithium segregated on the surface and at grain boundaries. Impedance spectroscopy measurements revealed that overall electrical conductivity increases proportionally with the excess of lithium ions on the surface, whereas it decreases in dry atmospheres. This suggests that the segregated lithium ions dissolve in the naturally adsorbed water layer on the nanoparticle surfaces, contributing to ionic conductivity. This study offers valuable insights into the effects of lithium distribution in the nanostructure of TiO2. (AU)

• Processo FAPESP: 13/07793-6 - CEPIV - Centro de Ensino, Pesquisa e Inovação em Vidros
• Beneficiário: Edgar Dutra Zanotto
• Modalidade de apoio: Auxílio à Pesquisa - Centros de Pesquisa, Inovação e Difusão - CEPIDs
• Processo FAPESP: 19/12885-3 - EMU concedido no processo 2013/07793-6: espectrômetro de ressonância magnética nuclear em estado sólido
• Beneficiário: José Fabián Schneider
• Modalidade de apoio: Auxílio à Pesquisa - Programa Equipamentos Multiusuários
• Processo FAPESP: 19/26309-4 - Além de íon-Li: desenvolvimento de baterias reversíveis de metal-ar não-aquosas
• Beneficiário: Vitor Leite Martins
• Modalidade de apoio: Auxílio à Pesquisa - Jovens Pesquisadores
• Processo FAPESP: 20/15230-5 - Centro de Pesquisa e Inovação de Gases de Efeito Estufa - RCG2I
• Beneficiário: Julio Romano Meneghini
• Modalidade de apoio: Auxílio à Pesquisa - Programa Centros de Pesquisa em Engenharia
• Processo FAPESP: 14/50279-4 - Brasil Research Centre for Gas Innovation
• Beneficiário: Julio Romano Meneghini
• Modalidade de apoio: Auxílio à Pesquisa - Programa Centros de Pesquisa em Engenharia