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J. MATER. CHEM., 1995,5(11), 1919-1925 1919

Preparation, Physical and Structural Characterization of LiMnO,

Samples with Variable Cationic Disorder
Laurence Croguennec,*aPhilippe Deniard: Raymond Brecaand Andre Lecerf
aLaboratoire de Chimie des Solides, I.M.N. (C.N.R.S.),2 rue de la Houssiniere, 44072, Nantes cedex 03,
France
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Laboratoire de Chimie des Solides, I.N.S.A. de Rennes, 20 avenue des Buttes de Couesmes, 35073
Rennes cedex, France

Orthorhombic LiMnO, samples, synthesized at high temperatures from a mixture of LiOH.H20 and Mn203 under a
reducing atmosphere, have been fully characterized. The morphology showed that important differences exist between
two sets of materials: A-type materials prepared with a deficiency of LiOH with respect to the LiMnO, stoichiometric
composition and B-type materials prepared with an excess of LiOH. Bulk density variations were interpreted in terms
of the occurrence of several lithium and/or manganese salt impurities. From Rietveld refinements, and contrary to the
previously described LiMnO, structures, the present LiMnO, samples exhibit a cationic disorder on the lithium and
manganese sites, with occupancy variations ranging from 3 to 12%. Finally, the frequently occurring abnormal widening
of the second diffraction line could be modelled and attributed to the mixing of a regular diffraction peak of the phase
under study [the (110) reflection] and of some poorly crystallized unreacted Mn203.These structural results can be
used to explain the electrochemical behaviour of the samples when employed as cathodes in rechargeable lithium
batteries.

Over the last 20 years, the LiMnO, phases have been the b-MnO, and Li,C03 between 600 and 650°C in a first step
subject of many studies because, like LiNiO, and LiCoO,, to eliminate CO,, followed by heating the sample between
they are very active cathodic materials, often used in 800 and 1000 "C under an argon flux. The improved perform-
rechargeable electrochemical lithium batteries. The intense ances have been observed, but not explained.
research on the manganese phases has also been motivated We recently prepared a new high-temperature orthorhombic
because manganese is non-toxic and its oxides are cheap. In LiMnO, according to a newly patented p r ~ c e d u r e . ~
addition, Mn presents the advantage of exhibiting the Preliminary results have shown that this compound which is
oxidation state IV in MnO,, allowing for good stabilization used as a cathode in LiMnO,/Li electrochemical systems,
of the oxidized LiMnO,. presents a mean discharge potential of around 3.5 V, with the
The search for electrochemically highly reactive phases led best batteries reaching a capacity higher than 160 mA h 8-l
many groups to imagine new soft chemistry ways to prepare with rather good ~yclability.~ Because the phase atomic
manganese dioxides (with or without lithium). So, a new low- structure characteristics are believed to be the key to the
temperature (300 < T/"C <450) synthesis of orthorhombic unexpectedly high electrochemical energy of this new high-
LiMnO, was implemented by Ohzuku et al.' It consisted of temperature-formed manganese oxide, a complete and
heating a pressed pellet of an equimolecular mixture of thorough structural and physical study of LiMnO, has
manganite (y-MnOOH) and lithium hydroxide (LiOH.H,O) been undertaken. This article reports the full characteriza-
under nitrogen for 15 h. More recently, Reimers et a1.' pro- tion of this phase.
posed an improvement of the Ohzuku method. They showed
that LiMnO, could be readily prepared at very low tempera-
ture (100"C) through an ion-exchange reaction. LiMnO, Synthesis
The compounds synthesized at higher temperatures The synthesis of the orthorhombic LiMnO, phase has been
(T/> 450 "C) generally present electrochemical capacities performed by mixing Mn203 (prepared by thermolysis of
smaller than the phases obtained at low temperature. The MnO, under air at 700 "C) and LiOH.H20 (commercial
improved electrochemical properties of the low-temperature product used as received) in l/ca. 2 proportions. The synthesis
phases have been tentatively attributed to disorder (ie. to consists of successive grindings and heatings at 300, 500 and
stacking faults), a characteristic which would be responsible 700°C. The final temperature of 700°C is maintained for 4 h
for the poor crystallization state of the phases [wide diffraction before allowing the sample to cool slowly to room tempera-
peaks in the X-ray diffraction (XRD) diagrams]. A higher- ture. The preparation cannot be made under air, because the
temperature synthesis (600< T/"C < 620) has been used by phase reacts with oxygen to give a mixture of Li2Mn0, and
Gummow et aL3 to prepare an orthorhombic LiMnO,. The LiMn204.The synthesis was hence performed under an inert
phase was prepared under argon from a mixture of y-MnO, gas (argon for instance) or under a mildly reducing atmosphere
and LiOH, with carbon as a reducing agent. Poor electro- (nitrogen mixed with hydrogen). The nominal Li/Mn chosen
chemical reactivity led to a capacity of only 70 mA h g-' ratios ranged from 0.95 to 1.10 in order to try to obtain
when the phase was put into use in a lithium battery. This various non-stoichiometries around the LiMnO, composi-
result reinforced the idea that high-temperature-prepared tions. This corresponded to two series of samples with
LiMnO, materials were not appropriate as cathodic materials Li/Mn < 1 (labelled A) and Li/Mn > 1 (labelled B) totalling
for use in lithium rechargeable batteries. However, recently six samples in all. The Mn and Li elemental analyses per-
Davidson et aL4 prepared the same orthorhombic lithium- formed on the samples revealed ratios slightly different from
manganese dioxide at high temperature, and, unexpectedly, the nominal values (Table 1). In addition, redox analyses
the phase showed rather elevated specific capacities of about demonstrated the absence of MnIVand Mn" species, pointing
140 mA h 8-l. The synthesis consists of firing a mixture of to a LiMnOz stoichiometry in the preparations. Accordingly,
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1920 J. MATER. CHEM., 1995, VOL . 5

Table 1 Analytical Li/Mn ratio [( Li/Mn),,,,J, density and overall characteristics of the XRD diagrams us. targetted compositions [( Li/Mn)no~nal]
for the LiMnO, samples; [the thickness of the (110) diffraction line and the resolution of the (310)/(230) doublet indicate a better definition of
the diagram and larger crystal size in agreement with SEM observations]

A-type samples B-type samples

MN389 MN384 MN386 MN399 MN4 12 MN40 1

0.98 1.oo 1.06 1.08 1.10

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(LWn)nominal 0.95
(Li/Mn)obs 0.96 0.98 1.oo 1.03 1.05 1.06
density 4.246(5) 4.224( 1) 4.223(3) 4.179( 1) 4.157(3) 4.038( 1)
(110) line wide wide thin thin thin thin
(3 lo)/(230) peak not resolved not resolved not resolved resolved resolved resolved

the various samples will be labelled LiMnO, throughout carbonation of LiOH) was also confirmed by the neutron
the paper. diffraction study and by differential scanning calorimetry
Hoppe et aL6 prepared an orthorhombic modification of (Fig. 2 ) showing, in the latter case, a phase transition at 723 "C
LiMn02, a material reported to be stoichiometric, with a corresponding well to Li2C03fusion.
brown-black colour. The materials prepared according to the
above method5 are light-green or black. The light-green colour
Physical Characterization
corresponds to A-type materials and the black colour to the
B-type ones. Colour is therefore the first visible criterion that Morphology
allows the differentiation between the Hoppe phases and some A scanning electron microscopy (SEM) study performed with
of those of the present study. The differences may originate a JEOL 6400F instrument allowed comparison of the A- and
either in the composition of the phases (departure from B-type materials. The former group presents a homogeneous
LiMnO, stoichiometry) or in a grain size effect, well known, size distribution of regular, elongated grains, parallelepipedic
for instance, in pigments. in shape (Fig. 3). The grain sizes span from ca. 0.2 to 1 pm.
The presence of some impurities (Li,C03, Li,SO, and The latter group shows (Fig. 4) a large grain size distribution
MnO) was clearly demonstrated in the LiMnO, samples with very ill-defined shapes. Whereas the large grains are
prepared according to ref. 5. MnO was detected by XRD in embedded within one another, the smaller grains are scattered
the materials referenced MN389 and MN384 [revealed around the larger ones (diameter of large grains, ca. 10 pm,
through a small peak at the foot of the (011) line (28=35") and of small grains, ca. 1 pm). Thus the larger grains of the
and another one at 28=59']. The occurrence of lithium B-type samples are about ten times the size of those of the
sulfate and carbonate was demonstrated by IR spectroscopy A-type samples. Note that the green samples correspond, as
and elemental analysis. The IR spectra show vibrations expected, to the smaller grains.
characteristic of lithium sulfate at 1150 and 1000cm-l and
of lithium carbonate at 1490, 1430 and 860 cm-' (Fig. 1). The
analysis of C, S, Li and Mn yielded a maximum content of Density
about 0.2 and 4 wt.% for the sulfate and the carbonate, Density measurements have been made with an automated
respectively. There was no hydrogen, as also confirmed by ACCUPYC 1330 pycnometer. The data show that the A-type
the absence of incoherent scattering in the powder neutron samples have very similar densities [identical within three
diffraction diagrams, which were recorded at the Laboratoire estimated standard deviations (ESD)]. The densities of the
Leon Brillouin (Laboratoire commun CEA-CNRS, Saclay, B-type materials, notably lower than those of the other group,
France). The presence of lithium carbonate (resulting in the decrease with the observed Li/Mn bulk ratio (Table 1).

Description of the LiMnOz Model Structure

The stoichiometric, orthorhombic LiMnO, compound pre-
sents a Pmnm space group, with Z = 2 , Mn and Li being in
the 2a special position (on a symmetry element) with an
octahedral coordination of oxygen atoms (in the 2b special

1 8 I I I I I I 1

4000 3600 3200 2800 2400 2000 1600 1200 800 400
wavenumberlcm
Fig. 1 IR spectrum of sample MN412. Arrows indicate the vibrations
attributed to two impurities often found in the LiMnO, samples. For
this particular example, the maximum weight concentrations of Fig.2 Differential thermal analysis of sample MN412 showing the
Li2S04 and Li,CO, are ca. 0.2 and 4%. fusion of Li,C03 at 723 "C
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J. MATER. CHEM., 1995, VOL . 5 1921

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Fig. 4 Morphology of the B-type samples. A large grain size

distribution can be observed (grain size ca. 10-1 pm). (a) MN399,
( b ) MN412, (c) MN401.
Fig. 3 Morphology of the A-type samples. A homogeneous grain size
distribution is observed (grain size ca. 0.2-1 pm). (a) MN389,
(b) MN384, (c) MN386.

Fig. 5 shows a projection of the structure along

the c axis. The structure is built up from MnO, octahedra
sharing apices along the u axis and edges along the c axis, so
that the structure exhibits a succession of corrugated (MnO,),
and (Li06), slabs. As previously reported by Reimers et aL2
it can be described as a cation superlattice structure of a rock
salt structure of MnO.
Considering that !ithiurn and mangFnese are similar sized
ions (ri(Mniii)= 0.645 A and ritLii)= 0.76 A)7 and that they play
a perfectly symmetrical role in the structure, a lithium/
manganese substitution can be envisaged within the hypoth-
esis of cationic disorder. Within the same slab, there could be
LiO, and MnO, octahedra simultaneously present. Such a
hypothesis has not been considered in the LiMnO, structures
published to date.' 4.h L0 0 a
X-Ray Diffraction Study of the LiMnO, Phases OMn O L i
Characterizationof the Powders Fig. 5 Projection of LiMnO, along the c axis. The two-dimensional
The X-ray powder diffraction diagrams of the different arrangement is made up of corrugated slabs of MnO, and LiO,
LiMnO, samples were obtained on a SIEMENS D5000 octahedra sharing edges and corners.
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1922 J. MATER. CHEM., 1995, VOL . 5

Table 2 Full pattern matching LiMnO, refined parameters: the cell parameters values can be compared with those obtained by Hoppe et aL6

A-type samples B-type samples

MN389 MN384 MN386 MN399 MN412 MN40 1 HoPPe

~~ ~ ~~~~~~~

44 4.5777( 2) 4.5807 (2) 4.5824(2) 4.5758(9) 4.5753( 1) 4.5770( 9) 4.572

b/+ 5.7480(3) 5.7487(4) 5.7524( 3) 5.7516(2) 5.7504(2) 5.7559( 1) 5.757
CIA 2.8052( 1) 2.8048 (2) 2.8067( 1) 2.8062( 1) 2.8061( 1) 2.8076( 1) 2.805
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VIA3 73.83( 1) 73.86( 1) 73.99( 1) 73.85(2) 73.84(1) 73.97(2) 73.8

I I I , ' I 1 I 1 nations. The experimental data necessary for the calculations

1 1 MNQOI are the peaks widths at half maximum (FWHM) and the

i d
1 .
Gaussian-Lorentzian q mixing factors for the sample reflec-
tions and those of LaB, used as standard. These data were
MN412 obtained from the PROFILE program." Table 3 presents the
results obtained. The samples MN384 and MN389 are charac-
I MN399
1
terized by grain size anisotropy (longer along b), correspond-
ing to the small and well shaped crystals observed by SEM
and to the wider diffraction lines (non-separated peak at 28=
MN386
c A 1 63"). In addition, the growth axes of the needle-like crystals
(Fig. 3) do correspond to b. For the other materials, the
MN384 anisotropy is less obvious in agreement with the larger, not
so well shaped crystals, with more well resolved XRD patterns.
140 This is in accord with the fact that the samples MN399 and
MN389
1 A 1 . MN401 present grain or crystallite sizes about one order
20 40 60 80 100 larger than those of MN389, MN384 and MN386.
28ldegrees

Fig. 6 General features of the X-ray powder diffraction diagrams of

Structure Refinement of the LiMnOz Samples from the Hoppe
the LiMnO, samples. Note the large width of the 2 8 ~ 2 8 "peak Model
[( 110) line] of some samples.
When it proved necessary, i.e. for the MN389 and MN384
samples, the ( 110) reflection (28 z 24.8') was removed from
diffractometer in reflect@ geometry, without 5 monochroma- the powder diffraction Rietveld refinement. In effect, the
tor (Cu-K,, = 1.540598 A, Cu-K,, = 1.544390 A). The param- abnormal width of this very intense reflection did not allow
eters refined with a full pattern matching program' are given for classical Cagliotti linewidth refinement as a function of
in Table 2 and the XRD diagrams are shown in Fig. 6. 28 [( FWHM), =u t 8 8 + vtg8 + w]. As discussed later, this
The ( 110) reflection (28 =24.8') is sometimes very wide abnormal line is not due to LiMnO, only. This point allowed
compared with the other peaks of the diagram (Table 1) and us to suppress this ill-defined line.
its intensity varies regularly from sample to sample on going In a first step, the XRD data were refined using the Hoppe
from MN389 to MN401. In addition, around 28 = 63', a peak, structural model6 with atomic position 2a for manganese and
with (310)/(230) indexing, appears either as a singlet or a lithium, and 2b for oxygen. Because the atomic displacement
doublet. In some phases, the doublet is perfectly separated, parameters (ADP) were difficult to refine (even Hoppe refine-
but in others not at all (Table l), depending on the crystallite ment from single-crystal data led to non-homogeneous ADPs,
sizes. Clearly, the (110) and (310)/(230) diffraction lineshapes see Table4 captiop), the isotropic ADYs of the refinements
give qualitative indications of thz state of crystallinity of the were fixed at 0.5A2 for Mn and 1.00A2 for Li and for 0.
phase. Indeed, as observed by SEM (Fig. 4), larger grains (B- (For Mn, the value corresponds to that generally found for
type samples) give a thinner (110) line and a better separation this element in single-crystal studies and that for lithium
of the (310)/(230) doublet. corresponds to the lower value obtained in other similar
In the case of oxygen, the calculated Bisovalues
vary wildly from 0.5 to >4.0 A,; an intermediate value bas
Grain Size Anisotropy
been chosen, such that a small variation around it (k0.5A')
Because of the non-monotonic variation of the reflection induced little change in the structural results. Table 4 summar-
linewidths with 26 for the LiMnO, samples [a problem linked, izes the values of the cell parameters and of the atomic
in particular, to the (110) line at 28=24.8'], the grain size positions obtained with this model. Note that the cell volumes
anisotropy was studied by the Warren-Averbach m e t h ~ d . ~ are very similar, suggesting that the compounds all present
This method has been put in use with the WIN-CRYSIZE LiMnO, stoichiometry.
software," to allow crystallite size and microstrain determi- As the results show, these values are not significantly

Table 3 Crystallite size determination obtained with the Warren-Averbach method in the u , b and c directions of the LiMnO, cells (for MN412
the crystallite size cannot be determined by the Warren-Averbach method because it is too highly crystalline)

A-type samples B-type samples

MN389 MN384 MN386 MN399 MN412 MN401

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J. MATER. CHEM., 1995, VOL . 5 1923

Table 4 Cell parameters and atomic positions of the Rietveld-refined LiMnOz samples with an ordered model based on Hoppe6 results’
A-type samples B-type samples

MN389 MN384 MN386 MN399 MN412 MN40 1 HoPPe

a14 4.5780( 2) 4.5810( 2) 4.5826(3) 4.5758( 1) 4.5751(1) 4.5771( 1) 4.572

blA 5.7486(4) 5.7487(5) 5.7523(4) 5.7516( 2) 5.7506( 1) 5.7561(2) 5.757
44 2.8053( 1) 2.8O46(2) 2.8068(2) 2.8062(1) 2.8061(1) 2.8076( 1) 2.805
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V/A3 73.82( 1) 73.86(1) 73.99(1) 73.85( 2) 73.829(6) 73.97(2) 73.8

Y (Mn) 0.6317(7) 0.6385(7) 0.6352( 8) 0.6363( 5) 0.6361(5) 0.6352(6) 0.6347(2)
Y (Li) 0.092(8) 0.103 (5) 0.121(8) 0.097 (5) 0.099(5) 0.097(5) 0.926(4)
Y CO(1)I 0.132(3) 0.139(4) 0.138(3) 0.126(2) 0.131(2) 0.128( 3) 0.144(1)
Y [I0(2)1 0.617(3) 0.608( 3) 0.610(3) 0.604(2) 0.603(2) 0.601(2) 0.602(1)
X2 5.71 1.98 3.95 4.42 2.72 4.01 -
Rv 6.19 4.14 4.15 4.72 3.65 4.26 6.68

a A’
Theoisotropic ADP! were fixed at Ob5 for Mn and l.OoA’ for Li and 0. (Those of the Hoppe single-crystal refinement were Biso(&)=
0.27 A’, BIso(Lit=
1.8 A’, Biso[o(l),=0.3A’ and BisoI,~,,l=1.1 A’.)

different from those obtained by Hoppe.6 Despite the very

good reliability factors, this structural model was not found
to be the most appropriate for the LiMnO, materials synthe-
sized according to the method of ref. 5. In effect, certain
diffraction regions still remained poorly modelled. Since the
lithium and manganese ions have a similar size and fill the
same type of octahedral site, Li/Mn substitution was
attempted. In such a hypothesis, a single slab will then contain
MnO, and LiO, groups and the model will thus correspond
to cationic disorder.

Structure Refinement with Cationic Disorder

Within the frame of cationic disorder, the occupation ratios
-2m[,
4000
.m-1 a
20 40 60

28/degrees
80 100 120

of lithium and manganese on each site have been refined and

normalised with respect to the other cation. Similarly, the Fig. 7 X-Ray powder diffraction Rietveld refinement diagram of
substitution rates of Li and Mn on the Mn and Li sites, sample MN412 taking into account the disorder between lithium and
manganese. A satisfactory refinement is achieved for this compound,
respectively, have been constrained to be equal. On the same as well as with all the other LiMnO’ phases (see Table 5).
site, the Mn and Li atoms were indeed constrained to have
the same atomic positions, with the ADPs fixed at the above
values. Table 5 lists the cell parameters, atomic positions and
occupation ratios using the disordered model. quality of the Rietveld refinement) is to be attributed to an
The reliability factors (Table 5 ) and fitting of the XRD increase in the number of variables or to the amelioration of
patterns (see Fig. 7 for MN412 as an example) are clearly the structural model. The deviance, D, is defined as follows:
better with the introduction of Li/Mn substitution. However,
it was necessary to check the validity of the procedure, since
the improved results could be due simply to the increase in
the number of refined parameters. Using the deviance test’ where yi and yci are the observed and calculated intensities
(analogous to the Hamilton test used in single-crystal structure and N is the number of recorded data points. The deviance
determinations) it is possible to determine whether the lower- thus takes into account the quality of the refinement model
ing of x2 (the goodness-of-fit factor used to evaluate the and the number of parameters used. The deviance criterion,

Table 5 Cell parameters and atomic positions of the Rietveld-refined LiMnO, samples with a disordered model (a sizeable improvement of the
fit is observed with a measurable and significant site substitution)

A-type samples B-type samples

MN389 MN384 MN386 MN399 MN412 MN401

4.5780(2) 4.5809(2) 4.5825( 2) 4.5758( 1) 4.5752( 1) 4.5771( 1)

5.7488(3) 5.7487(4) 5.7526(3) 5.7517(1) 5.7506( 1) 5.7561(2)
2.8054(1) 2.8047(2) 2.8067( 1) 2.8062(1) 2.8061( 1) 2.8076( 1)
73.83( 1) 73.86( 1) 73.99( 1) 73.86(2) 73.829( 6) 73.97(2)
0.630( 1) 0.633( 1) 0.6303(8) 0.6322(4) 0.6339( 5 ) 0.6323( 5)
0.099(5) 0.095( 5) 0.093 (3) 0.07 1(2) 0.084( 3) 0.078(3)
0.132(6) 0.134( 4) 0.139( 3) 0.116( 1) 0.126(2) 0.121 (2)
0.612( 5) 0.605(3) 0.607(3) 0.593( 1) 0.597(2) 0.593( 2)

7.1(3) 6.5(3) 9.9(2) 6.0(2) 3.3(2) 4.2( 2)

5.50 3.67 3.35 4.26 3.50 4.08
4.50 1.55 2.57 3.59 2.51 3.70
21 22 35 19 8 8
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1924 J. MATER. CHEM., 1995, VOL . 5

Q, is defined as: pound Mn203, one of the precursors of the synthesis of the
LiMnO, samples. The high-temperature phase LiMnO, syn-
Q = D +uprnax thesized by Davidson et aL4 also exhibits the same anomal-
where P,, is the number of refined parameters and a = 2 ously wide peak. This kind of preparation does not use Mn,O,
or In Pmax.8 as a precursor, but it may be present as an intermediary phase
The model presenting the lowest Q value is considered the during the reduction of the manganese dioxide.
better to describe the structure. The results obtained for the The theoretical density of stoichiometric LiMnO, is 4.213.
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six studied materials (Table 6) show that, with a substantially All the A-type compounds show similar densities within three
lower Q value, we are justified in choosing the Li/Mn substi- ESDs, but slightly higher than 4.213. As Li,CO, has been
tution model to describe the structure of the phases under detected in these compounds, one should expect a lower
study. The simultaneous refinement of X-ray and neutron density than the stoichiometrically expected value. Since the
diffraction data later confirmed the cationic disorder. Li/Mn phases are, within error, necessarily stoichiometric (see syn-
substitution thus appears to be an original characteristic thesis and structure refinement sections) the only way to
which differentiates the present materials from those pre- explain this discrepancy is to take into account another
viously ~ t u d i e d . ' - ~It. ~has not been possible to prove whether impurity having a higher density than LiMnO,. This material
other high-temperature-prepared materials present the same should be Mn203: it explains the broad line observed in the
feature. Structural calculations carried out on Hoppe single- XRD diagrams and it does not introduce another oxidation
crystal data6 proved inconclusive. state for manganese (only an oxidation state of 111 is found
for Mn in all the syntheses). For the B-type materials, the
density decreases on going from MN399 to MN401, in
Modelling of the Abnormal Reflection Line (110)
accordance with the increase in Li,C03 content and the quasi-
The superposition of two lines could explain the anomalously absence of Mn203, as observed by XRD. This means that
wide peak situated at 28 = 24.8'. For instance, one of the lines some excess of LiOH is necessary to consume Mn,O, fully;
could be that of the LiMnO, samples themselves, the other this excess probably plays the role of a melt, favouring crystal
possibly being attributable to a badly crystallized impurity. growth and explaining the occurrence of the larger single
The line has thus been modelled by two peaks using the crystals of the B-type samples and their better defined XRD
program PROFILE" for the material MN384. The profile patterns (see above).
parameters obtained during the XRD data refinement (with
the zone around 28=24.8' indeed excluded) allowed the
theoretical profile of the (110) peak to be modelled. From the Conclusion
difference peakobs-peakcalc, a second peak was obtained Through various and accurate measurements, it has been
(Fig. 8),owhichcould correspond to an interatomic distance possible to demonstrate that the LiMnO, samples prepared
of 3.58 A, attributable to an Mn-Mn distance in the com- at high temperature and under reducing atmospheres do show
the same Pmnm space group as previously reported for the
Table6 Values of the deviance criteria obtained for the ordered (Q) LiMnO, compounds. However, whereas these latter materials
and disordered (Q') structure arrangements of the LiMnO, phases have been described as ordered compounds, the LiMnO,
(see text for a definition of Q) samples prepared according to ref. 5 exhibit a significant
degree of Li/Mn substitution (between 3 and 12%). The
sample Q Q' disorder introduced to improve the modelling of the powder
A-type samples XRD data is in line with the behaviour of lithium, the size of
MN389 18000 14200 21 which allows such a substitution as often observed in oxides.
MN384 6100 4840 20 Clearly, the presence of manganese within the lithium sheets
MN386 12300 8050 35 may improve the electrochemical behaviour of the disordered
B-type samples materials compared with that of the ordered phases. On the
MN399 14200 11600 18 other hand, it is also possible that too high a substitution
MN4 12 6950 6430 7 rate may hamper the lithium diffusion throughout the struc-
MN40 1 12500 11600 7
ture17 and modify the phase-transition mechanism expected
upon lithium deintercalation of LiMnO, . Electrochemical
studies are at present under way to attempt to link the
electrochemical activity (capacity, energy and reversibility) to
the stoichiometry, substitution ratio and morphology of this
new LiMnO, material.

Thanks are due to Alcatel Alsthom Research for financial

support.

References
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Fig. 8 Decomposition of the 2 0 ~ 2 4 . 8 "X-ray diffraction line of the A. Lecerf, P. Biensan and S. Baudry, Fr. Pat. Brevet FR, 9308484.
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of the phase (110) line and of an impurity wider peak (pocrly 1975,417, 1.
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J. MATER. CHEM., 1995, VOL . 5 1925

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Paper 5/02130H; Received 3rd April, 1995