V. Serin
1,2
, C. Magen
2,3
, R. Serra
1
, M. R. Ibarra
2,3
, M.J. Hÿtch
1,2
, J. Zhang
4
, L. Lemort
4
, M.
Latroche
4
, B. Knosp
5
, and P. Bernard
5
1 CEMES-CNRS, TALEM, 29 rue Jeanne Marvig, 31055 Toulouse, France
2 TALEM, CNRS-Universidad de Zaragoza, 29 rue Jeanne Marvig, 31055 Toulouse, France
3 Instituto de Nanociencia de Aragón, Departamento de Física de la Materia Condensada,
Universidad de Zaragoza, 50009, Zaragoza, Spain
4 CMTR, ICMPE-CNRS, 2-8 rue Henri Dunant 94320 Thiais, France
5 SAFT, Direction de la Recherche, 111-113 bld. Alfred Daney, 33074 Bordeaux France
corresponding author: serin@cemes.fr
Applications for Ni-MH batteries are driven by increased energy density. Hydride forming
compounds such as La–Mg–Ni ternary compounds show improved performance, in particular new
crystallographic phases of A
2
B
7
type [1,2,3]. Such compounds can be described as the growth along
the c axis of two different sub-units [AB
5
] (C layer) and [A
2
B
4
] (L layer), where A is a rare earth or
an alkali earth and B is a transition metal, forming either a rhombohedral [3R] (R-3m) or hexagonal
[2H] (P6
3
/mmc) crystallographic structure. A series of compounds in this family of materials has
been prepared by spark plasma sintering (SPS) and characterized by X-ray, microprobe and TEM
analysis.
Here we present analysis of a La
0.65
Nd
0.15
Mg
0.20
Ni
3.5
compound by HREM, HAADF and STEM
EELS in order to identify the local structure and defects. HRTEM observations were performed on
an image-corrected FEI Tecnai (SACTEM-Toulouse) operating at 200 kV and HAADF imaging and
STEM EELS on a probe-corrected FEI Titan 60-300 microscope operating at 300 kV (Zaragoza).
Assuming the intensity of the columns can be related to the Z atomic numbers of the different
elements in presence (Nd:60, La:57, Ni:28, Mg:12), the structure can be interpreted readily from the
HAADF image from Fig. 1. In particular, the highest intensity can be identified as the rare-earth
columns, and the layers lacking contrast the nominally Mg
2
Ni
4
layers. The fact that the Mg
2
Ni
4
layer
are visible at all, suggests that rare-earth elements are indeed also present here. This is confirmed by
X-ray analysis showing that Mg partially substitutes rare-earth elements only in the [A
2
B
4
] layer.
The contrast allows us to identify the structure in this grain as the rhomohedral [3R] structure in
agreement with the majority phase determined from Rietveld analysis of the X-ray diffraction
patterns. As expected, the Ni sublattice is less identifiable, though the columns with two superposed
Ni atoms in the unit cell are clearly visible. The intensity profile along the Ni atom line (in red on
Fig 1), which is superimposed to the HAADF image, is of help to discriminate single and
superposed Ni atoms. The simulation fits quite well the image, but the exact position of La and Nd
atoms remains unclear (close Z values). Spatially resolved STEM EELS cartography will be
presented to conclude on that point and on the chemical nature of occasional changes in the
sequence of stacking. The spatially resolved EELS analysis will be helpful to accurately interpret the
contrast in the HAADF images.
References
[1] T. Kohno et al., Journal of Alloys and Compounds 311 (2000) L5.
[2] E. Akiba, H. Hayakawa, and T. Kohno, Journal of Alloys and Compounds 408-412 (2006) 280.
[3] R. V. Denys et al., Journal of Solid State Chemistry 181 (2008) 812.
[4] This work is supported by the ANR program MAHYA (n° ANR-07-STOCK-E-MAHYA-07-01).
788
doi:10.1017/S1431927611004818
Microsc. Microanal. 17 (Suppl 2), 2011
© Microscopy Society of America 2011
https://doi.org/10.1017/S1431927611004818
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