Journal of Alloys and Compounds 346 (2002) 255–259 L

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Electrochemical properties of orthorhombic LiMnO 2 prepared by one-step

middle-temperature solid-state reaction
Z.P. Guo*, G.X. Wang, K. Konstantinov, H.K. Liu, S.X. Dou
Institute for Superconducting and Electronic Materials, University of Wollongong, Wollogong, NSW 2522, Australia
Received 8 March 2002; accepted 22 March 2002

Abstract

Orthorhombic LiMnO 2 with small grain size was successfully synthesised using a one-step middle-temperature solid-state reaction
(OSSS). Compared with the methods other researchers used, the OSSS method is much simpler. It is a one-step method without
intermediate regrinding or other treatments. The o-LiMnO 2 obtained showed a high initial capacity 180 mAh / g when cycled at a current
density of 0.5 mA / cm 2 at room temperature, and the rate capability was improved due to the smaller particle size. Therefore, the one-step
middle temperature solid-state reaction could be a promising method for o-LiMnO 2 compound synthesis.
 2002 Elsevier Science B.V. All rights reserved.

Keywords: Transition metal compounds; Electrode materials; Solid state reactions; Electrochemical reactions

1. Introduction synthetic process. For low temperature synthesis, most

groups used an excess amount of lithium salt of the
The layered oxide materials LiMO 2 (M5Co, Ni, lithium / sodium exchange reaction to form the homoge-
Mn . . . ) and the LiMn 2 O 4 spinel are the most widely neous LiMnO 2 phase. It requires a long reaction time and
studied cathode materials for lithium secondary batteries other reaction steps. Even for high temperature synthesis,
with high energy density [1–3]. The Mn-based materials very sensitive synthetic conditions and some treatments to
have attracted wide attention as intercalation cathode improve the reaction between the starting materials are
materials because of their low cost and nontoxicity. needed. Second, o-LiMnO 2 , which was synthesised at high
However, the LiMn 2 O 4 presents a significant capacity loss temperature, needed considerable time to reach the maxi-
when cycled in the 3 and 4 V region [4,5]. The onset of a mum discharge capacity at room temperature. Although it
collective Jahn–Teller distortion and the consequent struc- critically depends on current density and the cycle test
tural instability that occurs when Li x Mn 2 O 4 is discharged conditions, this indication is not desirable so far as use of
to an average Mn valence ,3.5 (i.e. when x.1) is this cathode material for lithium secondary batteries is
generally believed to be responsible for the rapid capacity concerned. Finally, although the o-LiMnO 2 synthesised at
loss when discharge reaches the 3 V plateau [6]. Ortho- low temperature has a high capacity, significant capacity
rhombic LiMnO 2 (space group Pmnm, hereafter referred to fade is reported upon cycling over both the 4 and 3 V
as o-LiMnO 2 ) shows better cyclability than LiMn 2 O 4 plateaus.
when both the 4 and 3 V plateaus are utilised [7,8]. On the other hand, Croguennec et al. have reported that
Orthorhombic LiMnO 2 of the ordered rock salt structure active material having a small grain size ,1 mm and
described by Johnston and Keikes [9] and Hoppe et al. [10] stacking faults induced a moderately enhanced discharge
has been studied by many research groups [11–15]. It has capacity up to 200 mAh / g [18]. According to their crystal
a capacity in the range of 30–250 mAh / g depending on structure analysis, the intercalation of the LiMnO 2 com-
the synthetic method and sintering temperature [11–20]. pound takes place primarily on the grain surface, and small
From a review of previous studies, we have found the grain size can induce rapid lithium diffusion between the
following problems. The first was the complexity of the bulk and its surface. Therefore, if an o-LiMnO 2 phase with
small grain size and with moderate stacking faults is
*Corresponding author. Fax: 161-2-4221-5731. successfully synthesised, specific discharge capacity and
E-mail address: zg04@[Link] (Z.P. Guo). cycle performance would probably be improved.

0925-8388 / 02 / $ – see front matter  2002 Elsevier Science B.V. All rights reserved.
PII: S0925-8388( 02 )00498-X
256 Z.P. Guo et al. / Journal of Alloys and Compounds 346 (2002) 255–259

Based on our previous research [21], we successfully compound was observed using a scanning electron micro-
synthesised MT-o-LiMnO 2 with a small grain size (,1 scope (SEM).
mm) using a one-step middle-temperature solid-state re- The electrochemical characterisations were performed
action (OSSS). Compared with the method other research- using PTFE cells. The cathode was prepared by mixing
ers used, the OSSS method is much simpler. We emphasise o-LiMnO 2 powder with 10 wt.% carbon black and 5 wt.%
that the LiMnO 2 in this study was synthesised by a PVDF (polyvinylidene fluoride) solution. The o-LiMnO 2
one-step method without intermediate regrinding or other and carbon black powders were first added to a solution of
treatments. The characteristics and electrochemical per- PVDF in N-methyl-2-pyrrolidinone (NMP) to make a
formance of the samples obtained were investigated and slurry with appropriate viscosity. Al foil was then used to
were compared with that of o-LiMnO 2 prepared by high coat the mixture. After the electrode was dried at 140 8C
temperature solid-state reaction (In this method, Li 2 CO 3 for 2 h in vacuum, it was compressed at a rate of about 150
and Mn 2 O 3 were used as starting materials, and the kg / cm 2 . PTFE test cells were assembled in an argon-filled
mixture were first calcined for 3 h at 650 8C, then fired at glove box, where the counter electrode was Li metal and
1000 8C for a further 24 h. The samples were reground the electrolyte was 1 M LiPF 6 dissolved in a 50:50 (v / v)
between firings). mixture of ethylene carbonate (EC) and dimethyl carbon-
ate (DMC). These cells were cycled between 2.0 and 4.4 V
at room temperature to measure the electrochemical re-
2. Experimental sponse.

The o-LiMnO 2 material was synthesised using

Mn(CH 3 COO) 2 ?4H 2 O (Aldrich 99.5%), LiOH?H 2 O (Al- 3. Results and discussion
drich 99.9%) and citric acid (Aldrich 99%) as starting
materials. The Li:Mn atomic ratio was 1.05:1, higher than 3.1. Crystal structure
the stoichiometric ratio of 1:1 to offset lithium loss by
Li 2 O evaporation during o-LiMnO 2 synthesis. These pow- The XRD patterns of the two types of o-LiMnO 2
ders were mixed and thoroughly ground in an agate mortar. compound are shown in Fig. 1. All XRD peaks except for
The mixture was loaded into alumina crucibles and cal- the marked peaks (attributed to the small amount of
cined in a tube furnace at 800 8C for 12 h under a flow of Li 2 MnO 3 ), are indexed on the basis of the orthorhombic
argon. phase with the space group Pmnm. Compared with the
Powder X-ray diffraction (1730 X-ray diffractometer) o-LiMnO 2 prepared by high temperature solid-state re-
using CuKa radiation was employed to identify the action (HT-o-LiMnO 2 ), some XRD peaks of o-LiMnO 2
crystalline phase of the synthesised materials. The lithium prepared by the one-step middle-temperature solid-state
and manganese concentrations in the resulting materials reaction (MT-o-LiMnO 2 ), broadened remarkably and / or
were analysed using an inductively coupled plasma spec- were characterised by a significant asymmetry, while some
trometer (ICP). The particle morphologies of the resulting lines remained unchanged. A full width at half-maximum

Fig. 1. X-ray diffraction patterns of o-LiMnO 2 materials. Above: HT-o-LiMnO 2 ; below: MT-o-LiMnO 2 .
 Z.P. Guo et al. / Journal of Alloys and Compounds 346 (2002) 255–259 257

(FWHM) in the (011) peak for HT-o-LiMnO 2 was 0.18, crystals. The particle size of MT-o-LiMnO 2 (0.3 mm) is
indicating that the HT-o-LiMnO 2 material is in a well- much smaller than that of HT-o-LiMnO 2 .
ordered orthorhombic structure, while MT-o-LiMnO 2 Other phenomena observed from XRD patterns are a
showed an increased FWHM to 0.1768, indicating that the decrease in the Li 2 MnO 3 impurity phase when using the
density of stacking faults has been increased, i.e. structural middle-temperature solid-state reaction. This is believed to
disorder [18]. This behaviour can also be observed in the be due to the existence of organic groups (citric acid and
increased broadening of the (120), (122) peaks. Croguen- CH 3 COO 2) in the reactant. These organic groups could
nec et al. proposed that the smaller the crystallites / crystals, react during sintering with free oxygen (possibly present in
the higher the number of stacking faults [18]. Therefore, small quantities due to inadequate furnace sealing) and
we can assume that the grain size of MT-o-LiMnO 2 is yield CO 2 , thus decreasing the density of oxygen and thus
smaller than that of HT-o-LiMnO 2 . To confirm this reducing the impurity phase Li 2 MnO 3 in the MT-o-
assumption, the particle morphologies (Fig. 2) of the LiMnO 2 . Tang et al. reported that the transformation of
compounds were observed using a SEM. A SEM mi- o-LiMnO 2 in a mixture of LiMn 2 O 4 and Li 2 MnO 3 was
crograph of the HT-o-LiMnO 2 compound is presented in accompanied by the absorption of oxygen gas during the
Fig. 2a and compared with the MT-o-LiMnO 2 compound calcination process (3LiMnO 2 11 / 2O 2 →Li 2 MnO 3 1
(Fig. 2b). The HT-o-LiMnO 2 compound has flake-shaped LiMn 2 O 4 ) [19]. The firing of citric acid could also lead to
particles with an average size of 2–15 mm, whereas the the temperature increasing very quickly in some areas,
MT-o-LiMnO 2 compound has similar spherical-shape thereby increasing the lithium evaporation and loss. An
ICP measurement verified this. The Li:Mn ratios in MT-o-
LiMnO 2 and HT-o-LiMnO 2 , are 96% and 99%, respective-
ly. The lower Li:Mn ratio may be another reason for the
smaller particle size in MT-o-LiMnO 2, as Croguennec et
al. believed that an excess of LiOH can act as a flux agent
favouring crystal growth.
The preparation methods also affect the overall con-
stants of o-LiMnO 2 . The lattice constants a, b and c for
HT-o-LiMnO 2 were calculated to be 2.806, 5.758 and
4.574 A,˚ respectively, while those of the MT-o-LiMnO 2
were 2.800, 5.766 and 4.582 A, ˚ respectively.

3.2. Electrochemical characteristics

PTFE cells containing o-LiMnO 2 materials were cycled

at room temperature. The cells were cycled in a voltage
window of 2.0–4.4 V at a constant current density of 0.5
mA / cm 2 . The first charge curves are shown in Fig. 3. The
two types of o-LiMnO 2 exhibited a slightly different
charging behaviour in the first charge. As shown in Fig. 3,
the HT-o-LiMnO 2 electrode was quickly charged from
OCV to 3.7 V and then followed an ascending plateau
between 3.7 and 4.4 V. For the MT-o-LiMnO 2 electrode,
charging the voltage from OCV to 3.7 V was relatively
slower, and the ascending plateau between 3.7 and 4.4 V
was lower. The first charging process consisted in remov-
ing Li from o-LiMnO 2 . The plateau recorded is charac-
teristic of a phase transition, as expected from the change
in the Mn electronic configuration (d3 instead of d4 in the
pristine phase) and from the removal of the Li ions from
the structure. It is obvious that the Li in MT-o-LiMnO 2 is
easier to remove because the charging plateau is lower.
This confirmed the theory of Crogunnec et al., i.e. the
smaller the sample crystal / crystallites, the more Li can be
removed [18].
Fig. 4 shows the evolution of the discharge specific
Fig. 2. (a) SEM image of HT-o-LiMnO 2 material. (b) SEM image of capacity vs. the number of cycles. Following the phase
MT-o-LiMnO 2 material. transition occurring at the first charge, several cycles
258 Z.P. Guo et al. / Journal of Alloys and Compounds 346 (2002) 255–259

Fig. 3. Galvanostatic mode first charge of o-LiMnO 2 samples. (1) HT-o-LiMnO 2 ; (2) MT-o-LiMnO 2 .

appear necessary for the materials to reach their optimal changes with n (Fig. 5). (Fresh cells were cycled until the
capacity, up to 40 cycles at a current density of 0.5 capacity reached a steady-state value first, then cells were
mA / cm 2 in the case of the HT-o-LiMnO 2 compounds. In cycled at different rates.) In agreement with a kinetic
contrast, the full capacity is obtained after only 3–4 cycles limitation, the capacity gain is more important for the
for the MT-o-LiMnO 2 materials. The initial capacity is HT-o-LiMnO 2 material than for MT-o-LiMnO 2 at low
180 mAh / g at room temperature. As can be seen, the need rates. For MT-o-LiMnO 2 , the specific capacity is about
for fewer cycles to reach the sample highest capacity is 81% of the best at C / 10, whereas it is only 48% for
correlated with the sample crystal / crystallite size. This is HT-o-LiMnO 2 . A slow discharge rate allows for the
likely to be correlated with kinetic reasons. Since the formation of the material in fewer cycles. All these results
crystal size of HT-o-LiMnO 2 is large, the inner area of the prove that the rate capability is better for the smaller
crystal may not be charged, although the surface area has crystal materials (MT-o-LiMnO 2 ).
already reacted. This means that the HT-o-LiMnO 2 sam- Therefore, we succeeded in synthesising a new type of
ples may contain a substantial amount of unreacted o- o-LiMnO 2 material by a one-step middle temperature
LiMnO 2 phase, probably in the crystal core, i.e. covered solid-state reaction with an excellent cycle performance as
by a spinel-type phase present at the crystal surface. well as a high initial discharge capacity at room tempera-
Experiments were then carried out at different rates (C /n ture. Further work is now in progress to test the high
with n . 10) in order to compare the reversible capacity temperature performance and more clearly reveal the

Fig. 4. Discharge specific capacity vs. cycle number of o-LiMnO 2 samples cycled at 0.5 mA / cm 2 in the 4.4–2.0 V range.
 Z.P. Guo et al. / Journal of Alloys and Compounds 346 (2002) 255–259 259

Fig. 5. Changes of normalised discharge capacity (C /Cmax ) for cells with active electrodes of o-LiMnO 2 at room temperature with a varying
charge–discharge rate.

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