Electrochimica Acta 48 (2003) 2813 /2821 www.elsevier.

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In situ X-ray diffraction study on MmNi3.85Mn0.27Al0.37Co0.38 as negative electrode in alkaline secondary batteries
R. Baddour-Hadjean a,*, J.P. Pereira-Ramos b, M. Latroche c, A. Percheron-Guegan c
a b

LADIR, UMR 7075, CNRS-Paris VI, 2 rue Henri Dunant, 94320 Thiais, France LECSO, UMR 7582, CNRS-Paris XII, 2 rue Henri Dunant, 94320 Thiais, France c LCMTR, UPR 209, CNRS, 2 rue Henri Dunant, 94320 Thiais, France

Received 13 January 2003; received in revised form 6 May 2003; accepted 9 May 2003

Abstract This paper reports an in situ XRD study on the multisubstituted intermetallic compound MmNi3.85Mn0.27Al0.37Co0.38 during an electrochemical charge /discharge reaction. Structural data are available through the evolution of the lattice parameters as electrochemical hydrogen absorption desorption proceeds within 0 B/x 5/4.3 H per formula unit and a satisfactory agreement is obtained with ex situ neutron diffraction data previously reported for the parent compound LaNi3.55Mn0.4Al0.3Co0.75. Preliminary results show the existence during discharge of a less expanded b? phase compared with the fully charged b phase. # 2003 Elsevier Ltd. All rights reserved.
Keywords: Intermetallic alloys; In situ XRD; NiMH batteries

1. Introduction The electrochemical performances of secondary batteries are mainly governed by the nature, the magnitude and the reversibility of the structural changes occurring in electrode materials during the discharge and charge processes. Therefore, the knowledge of these structural changes are of the utmost importance for a better understanding of the reaction mechanisms and then for improving the electrochemical properties, especially the cycle life. In addition to conventional ex situ X-ray diffraction experiments of cathode or anode materials after working, in situ XRD measurements are of interest to provide structural information when possible changes in the oxidation state and in the material structure due to chemical reactions in air can occur. Scatter between data from several samples or from repeated mounting can be reduced markedly. Finally, kinetics of structural changes can be also studied.
* Corresponding author. E-mail address: badour@glvt-cnrs.fr (R. Baddour-Hadjean). 0013-4686/03/$ - see front matter # 2003 Elsevier Ltd. All rights reserved. doi:10.1016/S0013-4686(03)00416-X

Many works have been devoted to lithium intercalation compounds including transition metal sulfides, selenides [1 /3], transition metal oxides for 3V [5 /9] and 4V application [4,11 /13] but also anode materials such as the carbon electrode [10]. Surprisingly very few experiments using in situ XRD have been performed on cathode and anode materials working in alkaline batteries except the work reported on electrochemical insertion of protons in g MnO2 [14]. As far as metal hydrides are concerned, the first in situ XRD investigation was reported on LaNi5 [15] for which phase transitions occurring during solid/gas absorption /desorption experiments have been evidenced using a high-pressure XRD cell. Only very recent studies on phase transitions in LaNi4Co during electrochemical cycling [16] and in LaNi5 and La Ni4.75Al0.25 during the initial activation process [17] have been reported. In the first case, the formation of an intermediate g phase hydride between the hydrogen solid solution a phase and the fully hydrided b phase was clearly observed during absorption and desorption while changes in the crystallite size and the lattice strains have been investigated in the latter case.

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In fact the main contribution about structural changes in LaNi5-related metal hydrides electrodes comes from in situ neutron diffraction experiments on the single substituted compounds LaNi4.5Al0.5, LaNi4.5Mn0.5, LaNi4Co and the trisubstituted alloy MmNi3.55Mn0.4Al0.3Co0.75 [18 /20]. Use of Mischmetal (Mm) instead of lanthanum is for economical purpose since this rare earth mixture is cheaper than lanthanum. In spite of the quality of the structural information drawn from this kind of experiment based on a bulk analysis of the sample, the large amount of active material needed for this technique combined with the use of a deuteride electrolyte and a difficult access to an appropriate neutron beam make this method hard for practical use in a laboratory. Therefore, we have searched to develop a specially designed cell allowing simultaneously electrochemical and in situ XRD experiments. In this paper, we report for the first time an in situ XRD study on the multi-substituted intermetallic compound MmNi3.85Mn0.27Al0.37Co0.38 during the electrochemical charge /discharge reaction.

2. Experimental The alloy was prepared by induction melting of the Misch metal (Mm 0/La0.53Ce0.33Nd0.11Pr0.015Zr0.015) and the pure components (nickel, manganese, aluminum, cobalt (99.99%)) in a water-cooled copper crucible. The sample was melted several times and was annealed before quenching to ensure good homogeneity. Stoichiometry and homogeneity were controlled both by metallographic examination and microprobe analysis. According to the EPMA results, the alloy is slightly understoichiometric (AB4.88) and single phase. The sample was ground to an average particle size of about 40 mm and stored under vacuum. X-ray diffraction patterns were recorded on an Inel diffractometer equipped with a curved position sensitive detector (CPS 120) using Cu Ka radiation. Conventional hydrogen gas PC isotherms were measured with a Sieverts type apparatus using calibrated and thermalized volumes. Electrodes were made from the intermetallic active material mixed with carbon black and PTFE in the weight ratio of 90:5:5. The mixture was spread out in sheet 0.25 mm thick and compressed on a nickel grid (3 cm diameter) which plays the role of current collector. Around 800 mg of active material was available in each electrode; the latter was impregnated under primary vacuum in 7 M KOH before any electrochemical test. A special electrochemical cell was constructed to perform in situ XRD experiments. Its shape is similar to that constructed by Y. Sato [7]. The working electrode was covered by a thin Mylar foil (0.1 mm thick) giving rise to only one large diffraction peak located around 268 2u.

The counter electrode was constructed of a 0.5 mm thick nickel plate parallel to the working electrode. Exposure of the working electrode to oxygen produced at the counter electrode is minimized by efficient argon bubbling in electrolyte. An Hg/HgO/7 N KOH reference electrode was used to measure the potential of the metalhydride during charging and discharging. The half-cell body containing the auxiliary electrode was made of glass while the half-cell containing the working electrode was made of Plexiglas. The electrolyte volume was around 30 cm3 and the cell was used in the horizontal position. XRD data were analyzed using the PEACKOC software. Prior to in situ XRD measurements, the electrode was galvanostatically charged and discharged at 30 mA/g (C/10 rate) for ten cycles. This activation step is associated both with the reduction of the passive oxide layer and the developing of the surface area (particle size reduction) of the negative electrode to reach its optimal discharge. The depths of charge and discharge are expressed in Faraday per mol. (F/ mol) in the case of electrochemical experiments. In situ XRD measurements were performed after constant current periods (10 mA/g for charge, 5 mA/g for discharge), which allows to describe the structural changes occurring during a complete charge /discharge process.

3. Results The XRD pattern of the electrode material before starting the electrochemical absorption /desorption experiments is reported in Fig. 1. The main diffraction lines observed can be indexed in the hexagonal symmetry (P6/mmm space group) with the following unit cell parameters a0/5.000 (1) A and c 0/4.034 (1) A. We have examined the evolution of the XRD signal in the 2u domain 28 /468 which includes the main five diffraction lines of the alloy, the 111 peak exhibiting the highest intensity. It appears that the curved position sensitive detector (CPS 120) is well adapted to such in situ measurements as a time duration of 500 s is long enough to get well defined diffraction peaks. However, spectra recorded after 120 or 180 s already provides some valuable information. Fig. 2 reports the electrochemical and solid/gas isotherm curves at 25 8C for MmNi3.85Mn0.27Al0.37Co0.38. The electrochemical isotherm (Fig. 2a) has been approached from the tenth cycle of a MmNi3.85Mn0.27Al0.37Co0.38 electrode, charged and discharged at very low rate (C/10, D/20). The solid gas isotherm (Fig. 2b) has been obtained by converting the hydrogen pressure into equilibrium potential using the Nernst relation. As illustrated by Fig. 2, there is a very good agreement between the two sets of data, both in

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Fig. 1. In situ XRD pattern of the starting material MmNi3.85Mn0.27Al0.37Co0.38.

term of equilibrium potentials and hydrogen content. Starting from the rest potential, (/845 mV (Fig. 2a) the potential decreases continuously down to (/920 mV. Then the working potential exhibits a voltage plateau between /0.5 and 3.2 H/mol of alloy; this composition

range characterized by a mid-charge potential of (/925 mV corresponds to the expected coexistence of the a and b phase. This quasi-voltage plateau is followed by a change in the E versus x curve. This last part of the charge corresponds to the composition range of the b

Fig. 2. Comparison of electrochemical (a) and solid /gas (b) isotherm curves at 25 8C for MmNi3.85Mn0.27Al0.37Co0.38.

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phase, 3.2 /4.2 H/mol of alloy. Ideally, the electrode is completely loaded at this stage of the charge. Then the potential remains constant at (/950 mV, which corresponds to the second reduction process, commonly attributed to the hydrogen evolution potential. Subsequently, discharging process gives rise to a quantitative and symmetric curve with a hysteresis between charge and discharge of about 20 mV, corresponding to a pressure ratio Pabs/Pdes /4.3. The middischarge potential observed during this period is (/906 mV and a high specific capacity of 270 mAh/g is obtained. Hence from these electrochemical experiments, the maximum hydrogen content which can be absorbed by the intermetallic compound is 4.2 H/mol, which corresponds to the hydride formula MmNi3.85Mn0.27Al0.37Co0.38H4.2. This value is very closed to that expected at 1 bar from solid gas data (4.45 H/mol). We have checked the cycling behavior of MmNi3.85Mn0.27Al0.37Co0.38 at a sustained C/6/D/6 rate. Fig. 3 reports the evolution of the discharge capacity as a function of the number of cycles. After the first seven cycles for which an increase of the capacity corresponds to the activation process, a maximum specific capacity of 280 mAh/g is obtained, then the reversible capacity slightly decreases at a rate of about 0.6 mAh/g per cycle. However, a capacity of 240 mAh/g is still available after 70 cycles, showing the attractive properties of this alloy as negative electrode for rechargeable alkaline batteries. Fig. 4 shows the XRD patterns of the negative electrode for low hydrogen contents corresponding to faradic yields of 0.2, 0.3 and 0.4 F/mol. We observe a progressive and slight shift of the 101, 110, 200, 111, 002 diffraction lines towards lower 2u values with increasing

hydrogen content, which means qualitatively an increase of the a and c parameters in the a phase as hydrogen absorption proceeds. The composition range corresponding to the a phase is in good accord with electrochemical data showing a solid solution chronopotentiometric behavior between 0 and 0.5 F/mol (Fig. 2). However, the shoulder observed for 0.2 F/mol (Fig. 4b) around 42.58 and a new peak located at 42.788 for 0.3 F/mol can be both assigned to the 002 b line. This result indicates that the local formation of some b phase grains can occur, even at the early stage of the absorption process. A detailed discussion of XRD peak intensities is therefore difficult, probably due to the presence of instantaneous lattice strains, dislocations and possible local heterogeneous hydrogenation phenomenon. However XRD peaks positions give valuable information about the evolution of the lattice parameters with the hydrogen content. The coexistence of the a and b phases is illustrated in Fig. 5, which reports the XRD patterns obtained for 1.8, 2.5 and 3 F/mol. As a matter of fact, as shown in Fig. 5a, the 002 and 200 a lines practically disappear from 2.5 F/ mol while the intensity of the main 111 diffraction line of the a system is strongly reduced for a higher faradic yield of 3 F/mol. At the same time, the 200 and 111 b lines increase from 1.8 to 2.5 F/mol. The 002 b peak at 3 F/mol increases and shifts to lower 2u when compared with 2.5 and 1.8 F/mol, which reflects an increase in the c parameter with the hydrogen content for the b phase. In the lower 2u region, the progressive disappearance of the a phase is illustrated by the significant decrease of the 101 and 110 lines of the a system.

Fig. 3. Evolution of the specic capacity of the MmNi3.85Mn0.27Al0.37Co0.38 compound as a function of the number of cycles in the potential range (/ 0.7/(/0.960 V (C/6, D/6 rate).

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Fig. 4. XRD patterns of the hydride at different depths of charge (0.2, 0.3 and 0.4 F/mol of alloy).

When the electrode is theoretically fully charged and overcharged (Fig. 6) i.e. for faradic yields of 4.4 and 5.5 F/mol, respectively, the XRD spectra only exhibit the b phase fingerprint where the 110, 200 and 111 lines increase in intensity. These results are in good agreement with electrochemical data. Therefore, an overcharge

seems necessary to optimize the amount of b phase grains while no change in the unit cell parameters occurs. The maximum content of hydrogen in MmNi3.85Mn0.27Al0.37Co0.38 cannot exceed 4.2 H/mol. under atmospheric pressure (Fig. 2). Hence, the XRD spectrum

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Fig. 5. Evolution of the XRD patterns for 1.8, 2.5 and 3 F/mol of alloy.

recorded for a coulombic charge of 5.5 F/mol corresponds to that of the hydride with formula MmNi3.85Mn0.27Al0.37Co0.38 H4.2. This overcharge is necessary to ensure a quantitative hydride formation, after which hydrogen evolution takes place at the same potential.

After charging, the electrochemical oxidation at constant current leads to hydrogen desorption according to the discharge curve reported in Fig. 2. For a faradic yield of 1 F/mol involved in the oxidation reaction (noted as (/1 F/mol in Fig. 7a),

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Fig. 6. Evolution of the XRD patterns for 4.4 and 5.5 F/mol of alloy.

the 110, 200 and 111 b lines shift significantly towards higher 2u values (Fig. 7a). This result indicates a decrease of the cell volume for the hydride phase involved in discharge. For a faradic yield of 5.5 F/mol involved in the oxidation reaction (noted as (/5.5 F/mol in Fig. 7b), the XRD pattern of the pristine material is completely recovered, as shown in Fig. 7b.

4. Discussion These XRD data as electrochemical hydrogen absorption and desorption proceed are directly related to structural changes in MmNi3.85Mn0.27Al0.37Co0.38 electrode, which are summarized in Fig. 8. The pristine electrode material incorporates the first all hydrogen with a slight increase of parameters a and c (less than 1%) for a hydrogen content corresponding to a faradic yield between 0 and 0.4 F/mol. A little amount of b phase is detected in some grains, but rapidly disappears for higher hydrogen content due to hydrogen diffusion in the compound. Then, above 1 F/mol, we observe the emergence of a new phase in the same hexagonal system, with larger lattice parameters. The a parameter changes from 5.04 A for the a phase to 5.35 A for the b phase ($/6%) and

the c parameter changes from 4.06 A for the a phase to 4.22/4.24 A for the b phase (i.e. $/4% expansion). These new values of unit cell parameters indicate the emer gence of the b phase (V 0/104.7 A3) which coexists with the a phase up to a coulombic charge of 3 F/mol (Fig. 5). However for the highest depth of charge values, only the b phase is clearly evidenced with the three main diffraction lines 110b, 200b, 111b (Fig. 6) without any evidence for the presence of the a phase, showing the quantitative transformation a/b takes place. No significant change in the unit cell volume and lattice constant of b phase is seen, even after an overcharge. These different values of unit cell parameters are in good agreement with that usually reported for these phases [20,21]. Finally, the discharge process provides information on the reversibility of the structural changes. The shifts observed in Fig. 7a between the b phase observed in charge (for 4.2 H) and the hydrogen rich phase observed in discharge (for 3.2 H) indicate the existence of a new set of lattice parameters for the hydride phase observed in discharge (noted b?). Indeed, the lattice parameters decrease from 5.36 A (b phase) to 5.22 A (b? phase) for the a parameter and from 4.23 A (b phase) to 4.19 A (b? phase) for the c parameter. It comes out a lower unit cell volume for the b? phase (99 A3 against 104 A3 for the b phase), which could be explained by the

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Fig. 7. XRD patterns of the discharged alloy after a complete charge (5.5 F/mol); (a) 1 F/mol, (b) 5.8 F/mol.

lower hydrogen concentrations usually observed in desorption [19]. For a quantitative discharge process (Fig. 7b), the XRD pattern of the pristine alloy is completely recov-

ered with unit cell parameters of 5.000 and 4.025 A, which gives evidence for the good structural reversibility of the electrochemical hydrogen absorption/desorption reaction.

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from this latter, a satisfactory agreement is obtained if considering the two set of data drawn from in situ XRD [16] and ex situ neutron diffraction data for LaNi3.55Mn0.4Al0.3Co0.75 [21].

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Fig. 8. Evolution of the unit cell parameters of MmNi3.85Mn0.27Al0.37Co0.38 during the charge process and discharge process as a function of the faradic yield (F/mol of alloy).

5. Conclusion The present work provides for the first time XRD data on a multisubstituted intermetallic compound during the electrochemical charge /discharge reaction. Indeed, except the phase transitions investigated in LaNi4Co during electrochemical cycling through an in situ XRD study [14], most efforts have been focused on in situ neutron diffraction applied to the study of LaNi4.5Al0.5 [18], LaNi3.55Mn0.4Al0.3Co0.75 [19] and MmNi4.3(xMn0.3Al0.4Cox (x 0/0.36 and 0.69) [20]. Even if the chemical composition of our alloy differs