Ion exchange and structural ageing in the layered perovskite phases H1-xLixLaTiO4

Thomas Yip, Eddie Cussen

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

Grinding together the solid acid HLaTiO¬4 with stoichiometric quantities of lithium hydroxide monohydrate gives the solid solution H1-xLixLaTiO4. The structures of these crystalline phases have been refined against neutron powder diffraction data to show that all of these compounds crystallise in the centrosymmetric space group P4/nmm. The protons and lithium cations occupy sites between the perovskite layers; the former in hydroxide groups that hydrogen-bond to adjacent layers whilst Li+ is in four-coordinate sites that bridge the perovskite slabs with a geometry intermediate between square-planar and tetrahedral. The reaction proceeds rapidly but the unit cell size continues to evolve over the course of days with a gradual compression along the interlayer direction that can be modelled using a power law dependence reminiscent of an Ostwald ripening process. On heating, these materials undergo a mass loss due to dehydration but retain the layered Ruddlesden Popper structure up to 480°C before a substantial loss of crystallinity on further heating to 600°C. Impedance spectroscopy studies of the dehydrated materials shows that Li+ mobility in these materials is lower than the LiLaTiO4 end member, possibly due to microstructural effects causing large inter-grain resistance through the defective phases.
LanguageEnglish
Pages6985-6993
Number of pages9
JournalInorganic Chemistry
Volume52
Issue number12
Early online date28 May 2013
DOIs
Publication statusPublished - 2013

Fingerprint

Ion exchange
Aging of materials
lithium hydroxides
heating
Ostwald ripening
grinding
dehydration
hydroxides
Heating
interlayers
crystallinity
ions
slabs
Neutron powder diffraction
solid solutions
lithium
impedance
hydrogen bonds
Dehydration
Lithium

Keywords

  • perovskite
  • ion exchange
  • structural ageing
  • structural aging
  • layered perovskite phases

Cite this

Yip, Thomas ; Cussen, Eddie. / Ion exchange and structural ageing in the layered perovskite phases H1-xLixLaTiO4. In: Inorganic Chemistry. 2013 ; Vol. 52, No. 12. pp. 6985-6993.
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Ion exchange and structural ageing in the layered perovskite phases H1-xLixLaTiO4. / Yip, Thomas; Cussen, Eddie.

In: Inorganic Chemistry, Vol. 52, No. 12, 2013, p. 6985-6993.

Research output: Contribution to journalArticle

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T1 - Ion exchange and structural ageing in the layered perovskite phases H1-xLixLaTiO4

AU - Yip, Thomas

AU - Cussen, Eddie

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AB - Grinding together the solid acid HLaTiO¬4 with stoichiometric quantities of lithium hydroxide monohydrate gives the solid solution H1-xLixLaTiO4. The structures of these crystalline phases have been refined against neutron powder diffraction data to show that all of these compounds crystallise in the centrosymmetric space group P4/nmm. The protons and lithium cations occupy sites between the perovskite layers; the former in hydroxide groups that hydrogen-bond to adjacent layers whilst Li+ is in four-coordinate sites that bridge the perovskite slabs with a geometry intermediate between square-planar and tetrahedral. The reaction proceeds rapidly but the unit cell size continues to evolve over the course of days with a gradual compression along the interlayer direction that can be modelled using a power law dependence reminiscent of an Ostwald ripening process. On heating, these materials undergo a mass loss due to dehydration but retain the layered Ruddlesden Popper structure up to 480°C before a substantial loss of crystallinity on further heating to 600°C. Impedance spectroscopy studies of the dehydrated materials shows that Li+ mobility in these materials is lower than the LiLaTiO4 end member, possibly due to microstructural effects causing large inter-grain resistance through the defective phases.

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