Partial exchange of the Li{sup +}, Na{sup +} and K{sup +} alkaline cations in the HNi(PO{sub 4}).H{sub 2}O layered compound
Journal Article
·
· Journal of Solid State Chemistry
- Dpto de Quimica Inorganica, Facultad de Ciencia y Tecnologia, Apdo. 644, E-48080 Bilbao (Spain)
- Dpto. de Mineralogia y Petrologia, Facultad de Ciencia y Tecnologia, Apdo. 644, E-48080 Bilbao (Spain)
The exchange of the Li{sup +}(1), Na{sup +}(2) and K{sup +}(3) alkaline cations in the layered HNi(PO{sub 4}).H{sub 2}O was carried out starting from a methanolic solution containing the Li(OH).H{sub 2}O hydroxide for (1) and the M(OH) (M=Na and K) hydroxides together with the (C{sub 6}H{sub 13}NH{sub 2}){sub 0.75}HNiPO{sub 4}.H{sub 2}O phases for (2) and (3). The compounds are stable until, approximately, 280{sup o}C for (1) and 400 deg. C for phases (2) and (3), respectively. The IR spectra show the bands belonging to the water molecule and the (PO{sub 4}){sup 3-} oxoanion. The diffuse reflectance spectra indicate the existence of Ni(II), d{sup 8}, cations in slightly distorted octahedral geometry. The calculated Dq and Racah (B and C) parameters have a mean value of Dq=765, B=905 and C=3895cm{sup -1}, respectively, in accordance with the values obtained habitually for this octahedral Ni(II) cation. The study of the exchange process performed by X-ray powder diffraction indicates that the exchange of the Li{sup +} cation in the lamellar HNi(PO{sub 4}).H{sub 2}O phase is the minor rapid reaction, whereas the exchange of the Na{sup +} and K{sup +} cations needs the presence of the intermediate (C{sub 6}H{sub 13}NH{sub 2}){sub 0.75}HNiPO{sub 4}.H{sub 2}O intercalate in order to obtain the required producth the sodium and potassium ions. The Scanning electronic microscopy (SEM) images show a mean size of particle of 5{mu}m. The Li{sup +} exchanged compound exhibits small ionic conductivity ({omega}cm{sup -1} is in the 10{sup -8}-10{sup -9} range) probably restrained by the methanol solvent. Magnetic measurements carried out from 5K to room temperature indicate antiferromagnetic coupling as the major interaction in the three phases. Notwithstanding the Li and K phases show a weak ferromagnetism at low temperatures.
- OSTI ID:
- 20900918
- Journal Information:
- Journal of Solid State Chemistry, Journal Name: Journal of Solid State Chemistry Journal Issue: 12 Vol. 179; ISSN 0022-4596; ISSN JSSCBI
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
36 MATERIALS SCIENCE
ANTIFERROMAGNETISM
CATIONS
CLATHRATES
COUPLING
FERROMAGNETISM
HYDROXIDES
INFRARED SPECTRA
IONIC CONDUCTIVITY
LITHIUM IONS
NICKEL PHOSPHATES
POTASSIUM IONS
SCANNING ELECTRON MICROSCOPY
SODIUM IONS
SOLVENTS
SPECTROSCOPY
TEMPERATURE RANGE 0000-0013 K
TEMPERATURE RANGE 0013-0065 K
TEMPERATURE RANGE 0065-0273 K
TEMPERATURE RANGE 0273-0400 K
X-RAY DIFFRACTION
ANTIFERROMAGNETISM
CATIONS
CLATHRATES
COUPLING
FERROMAGNETISM
HYDROXIDES
INFRARED SPECTRA
IONIC CONDUCTIVITY
LITHIUM IONS
NICKEL PHOSPHATES
POTASSIUM IONS
SCANNING ELECTRON MICROSCOPY
SODIUM IONS
SOLVENTS
SPECTROSCOPY
TEMPERATURE RANGE 0000-0013 K
TEMPERATURE RANGE 0013-0065 K
TEMPERATURE RANGE 0065-0273 K
TEMPERATURE RANGE 0273-0400 K
X-RAY DIFFRACTION