Journal of The Electrochemical Society, 156 共6兲 A417-A424 共2009兲 A417

0013-4651/2009/156共6兲/A417/8/$25.00 © The Electrochemical Society

Electrochemical Activities in Li2MnO3

Denis Y. W. Yu,*,z Katsunori Yanagida,* Yoshio Kato, and Hiroshi Nakamura*
Mobile Energy Company, SANYO Electric Company, Limited, Kobe, Hyogo 651-2242, Japan

Li2MnO3 is shown to be electrochemically active, with a maximum charge capacity of ⬃350 mAh/g and a discharge capacity of
⬃260 mAh/g at 25°C. A total of 1 mole of Li can be extracted from Li关Li1/3Mn2/3兴O2, and the first cycle efficiency is ⬃66%
regardless of state of charge. Larger charge-discharge capacity is obtained from materials with smaller particle size and larger
amount of stacking faults. Composition and structural analyses indicate that Li are removed from both the Li and transitional metal
layers of the material during charging. Results from X-ray-absorption fine-structure measurements suggest that the valence of Mn
remains at 4+ during charging but is reduced during discharging. Charging is accompanied by gas generation: at 25°C, oxygen is
the main gas detected, and the total amount accounts for ⬃1/8 mole of O2 generation from Li关Li1/3Mn2/3兴O2. At an elevated
temperature, amount of CO2 increases due to electrolyte decomposition. Li2MnO3 shows poor cycle performance, which is
attributed to phase transformation and low charge-discharge efficiency during cycling. Low first-cycle efficiency, gas generation,
and poor cycle performance limit the usage of Li2MnO3 in practical batteries.
© 2009 The Electrochemical Society. 关DOI: 10.1149/1.3110803兴 All rights reserved.

Manuscript submitted November 21, 2008; revised manuscript received February 4, 2009. Published April 3, 2009.

The study of Mn-based Li-excess layered cathode materials with
a formula Li关LixMnyMz兴O2 共where M represents one or more tran-
sition metal elements兲 has been gaining popularity because these
materials can give a discharge capacity ⬎200 mAh/g,1-16 much
higher than practical discharge capacity of common cathode mate-
rials, such as LiCoO2 and LiMn2O4. Successful application of these
materials can potentially increase energy density of Li-ion batteries.
One challenge that researchers face in the study of Li关LixMnyMz兴O2
materials is that there is almost an endless combination of systems,
depending on the additional element 共or elements兲 M and the ratio
of cations in the layered material. A change in composition is sure to
affect the electrochemical performance of the cathode material. In
addition, modifications such as acid treatment and surface coating
can further change material behavior.4,8,17-20 It is therefore difficult
to compare results from different publications due to differences in
material composition and processing techniques. Though, all of the
Li关LixMnyMz兴O2 materials share a common feature: a plateau at
4.5 V vs Li/Li+ during initial charging which is similar to the be-
havior of Li2MnO3. We therefore think it would be beneficial to
reinvestigate the fundamental mechanism of Li2MnO3 to help fur-
ther understanding of the properties of Mn-based Li-excess materi-
als.
Electrochemical properties of Li2MnO3 and acid-leached
Li2MnO3 were previously reported in the literature.4,5,8,21-30 How-
ever, the described discharge capacity varies from publication to
publication, with values ranging from a few to ⬃200 mAh/g. The
inconsistency in results is probably due to differences in synthesis
condition and test condition.25,29,30 In theory, Li2MnO3 has a capac-
ity of ⬃458 mAh/g 共with respect to the initial mass of the sample兲
if all Li can be extracted. In this study, we investigated the reasons
for the limited capacity observed in experiments and studied the
effect of physical parameters of Li2MnO3 on the discharge capacity
of the material by methods such as X-ray diffractometry 共XRD兲 and
scanning electron microscopy 共SEM兲.
It was originally thought that Li2MnO3 is electrochemically in-
active because Mn has a valence of 4+, and it is unlikely that Mn
will go to higher valence. Many researchers attributed the electro-
chemical activity of Li2MnO3 to the removal of Li2O from the ac-
tive material.2,4,8,25-28 However, there are few discussions on what is
the status of the oxygen atoms after charge-discharge. There is also
a lack of quantitative analysis on the correlation between the amount
of oxygen “lost” from the active material and the observed capaci-
ties, because direct measurement of oxygen stoichiometry is diffi-
cult. Armstrong et al.31 observed O2 gas generation from the initial
* Electrochemical Society Active Member.
z
E-mail: denis.yu@sanyo.com
charging of Li关Li0.2Ni0.2Mn0.6兴O2 material using an in situ differen-
tial electrochemical mass spectroscopy. Though, the amount of oxy-
gen gas cannot be determined by their method.
In this study, we used a quantitative approach aiming to under-
stand the fundamental mechanism of Li2MnO3, by tracking the
amount of Li in the active material by inductively coupled plasma
共ICP兲 atomic emission spectroscopy and the amount of oxygen gas
generated by gas chromatography 共GC兲. The change in valence of
Mn is studied qualitatively by X-ray absorption fine structure spec-
troscopy 共XAFS兲. The results are presented in this paper. In addi-
tion, the cycle performance of the active material and practical is-
sues of Li2MnO3 will be discussed. Throughout the paper, the
formula Li2MnO3 is used interchangeably with Li关Li1/3Mn2/3兴O2, a
notation that gives more information about the structure of the ma-
terial.
Experimental
Li2MnO3 powders were synthesized by a solid-state reaction
with LiOH · H2O and MnCO3 · nH2O 共n ⬃ 0.5兲 as precursors. The
starting materials were thoroughly mixed by milling in acetone for
1 h and then dried at 60°C. The resulting precursors were then
annealed at temperatures between 400 and 1000°C in air. Structure
of the powders was studied by XRD using a Cu K␣ source 共50 kV,
300 mA兲. Morphology and particle size information were obtained
from SEM. The surface area of the materials was determined using
an AUTOSORB-1 equipment by Quantachrome: ⬃0.5 g of material
was first dried at 150°C for 1.5 h and then the surface area was
determined by a five-point Brunauer–Emmett–Teller 共BET兲 method
with nitrogen as the adsorbate gas. ICP atomic emission spectros-
copy was used to study the amount of Li and Mn in the material
before and after charge-discharge.
For electrochemical evaluation, Li2MnO3 active material was
mixed with acetylene black and polyvinyl difluoride 共PVdF兲 in
1-methyl-2-pyrrolidone 共NMP兲 with a weight ratio of 80:10:10 to
form a slurry. The slurry was then coated onto a roughened alumi-
num current collector using a doctor blade. The electrodes were
rolled with a calender press to a packing density of about
2.2–2.3 g/cm3, with a typical thickness of 25–35 ␮m. These elec-
trodes were assembled in a glove box with Ar atmosphere using Li
metal as the counter and reference electrodes with a layer of sepa-
rator to make a flat laminated test cell. 1 M LiPF6 in ethylene
carbonate/diethylcarbonate 共EC/DEC兲 = 3:7 by volume was the
electrolyte used in the experiments. The electrodes were sandwiched
between glass plates to maintain contact of the electrodes, and the
cells were typically charged and discharged at room temperature
共25°C兲 between 4.8 and 2 V vs Li/Li+ with a constant current rate

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A418 Journal of The Electrochemical Society, 156 共6兲 A417-A424 共2009兲

Table I. Electrochemical properties of Li2MnO3 synthesized at different temperatures.

Annealing Charge Discharge Charge fwhm Avg. particle BET

conditions capacity capacity efficiency 18.7° peak sizea surface area
共°C兲 共h兲 共mAh/g兲 共mAh/g兲 共%兲 共001兲 plane 共nm兲 共m2 /g兲

400 共48兲 367.0 258.7 70.5 0.434 70 20.2

425 共10兲 355.0 251.8 70.9 0.368 70 18.0
600 共10兲 342.0 232.4 68.0 0.302 90 15.9
750 共10兲 294.8 197.2 66.9 0.252 110 10.7
800 共10兲 290.0 191.6 66.1 0.221 130 9.0
850 共10兲 206.7 135.4 65.5 0.180 140 6.6
900 共10兲 63.6 43.8 68.9 0.132 390 2.2
1000 共10兲 28.4 22.7 79.9 0.123 650 1.5
a
Measured from SEM images.

of 10 mA/g, unless stated otherwise. Charge-discharge capacities
were calculated with respect to the mass of Li2MnO3 before charg-
ing.
To study gas generation from the sample, an in situ measurement
was performed to monitor the change in cell thickness during
charge-discharge. The cells were disassembled after charging, and
the composition and total volume of the generated gas from the cells
were measured by GC.
Structural information of the material at different state of charges
was further investigated by an ex situ XAFS with the Mn–K edge in
transition mode using the BL08 beamline at SPring-8 in Hyogo
Prefecture, Japan. X-ray absorption near-edge spectroscopy
共XANES兲 was used to monitor the electronic structure of Mn and
extended X-ray absorption fine-structure 共EXAFS兲 was used to
monitor the interaction of Mn with surrounding atoms. To interpret
the XAFS results of Li2MnO3, XAFS of LiNi1/3Co1/3Mn1/3O2 and
LiMn2O4 were taken as references. Average particle size and BET
surface area of the reference materials were 10 ␮m and 2.0 m2 /g for
LiNi1/3Co1/3Mn1/3O2 and 13 ␮m and 0.35 m2 /g for LiMn2O4, re-
spectively.
Results and Discussion
Effect of synthesis conditions on electrochemical behavior of
Li2MnO3.— Annealing temperature was varied from 400 to 1000°C
to study the effect of synthesis condition on the electrochemical
performance of Li2MnO3 共see Table I兲. The materials were made
into test cells, and their electrochemical properties were tested. First
cycle charge-discharge profiles with a rate of 10 mA/g at 25°C of
several Li2MnO3 samples are shown in Fig. 1. An initial charge
plateau at ⬃4.5 V vs Li/Li+ is observed for all samples. Reducing
the synthesis temperature lowers the potential of the charge plateau
and leads to higher charge and discharge capacities. A maximum
charge capacity of about 350–370 mAh/g is obtained, correspond-
ing to the removal of ⬃1 mole of Li out of Li关Li1/3Mn2/3兴O2. In
return, a maximum discharge capacity of about 250–260 mAh/g is
obtained. First cycle efficiency 共FCE兲 is ⬃66% for most of the
samples, showing a reinsertion of only 2/3 of the extracted Li. The
discharge capacity is first of all limited by the charge capacity. Thus,
a larger discharge capacity is obtained from a sample with larger
charge capacity. In addition, the low FCE suggests that the discharge
capacity 共i.e., the reinsertion of Li兲 is limited by the structure of the
material. This will be further discussed in a later section together
with other analytical results.
To understand how the change in synthesis condition leads to a
change in electrochemical behavior of Li2MnO3, we first studied the
structure of the materials by XRD. XRD profiles of the different
samples are shown in Fig. 2. All samples show a layered structure
with a c2/m space group, with alternating Li layers and transitional
metal 共TM兲 layers separated by oxygen layers. The superlattice
peaks between 20 and 30° in the XRD profile 共with a Cu K␣
source兲, which are not observed in other layered materials, are due
to the ordering of Li/Mn in the TM layers. Figure 2 shows that
below a synthesis temperature of 600°C, only a single broad peak at
20.9° is observed. This broadening of the superlattice peak is attrib-
uted to an increase in the amount of stacking faults 共shifting of the
TM layers兲 perpendicular to the layered 共001兲 direction with a lower
synthesis temperature.32 The role of the stacking fault on the elec-
trochemical properties of the active material is unclear. From ther-
modynamics, a material without defects has the lowest energy state.
Introducing stacking faults and other defects in the material in-
creases the energy state of the material, which may lower the acti-
vation barrier for Li diffusion and allow Li to be extracted at a lower
potential. Further studies on the effect of defects on electrochemical
performance are in progress.
The effect of synthesis temperature on the particle size and mor-
phology was studied by SEM. Figure 3 shows the SEM pictures of

5 (001) (131)
1000°C 900°C 850°C 800°C 600°C 400°C
4.5 (130)
Potential (V vs. Li/Li+)

400°C
Intensity (a.u.)

3.5 600°C
800°C
3
850°C
2.5
10mA/g 900°C
2
1000°C 900°C 850°C 800°C 600°C 400°C first cycle 1000°C
1.5
0 100 200 300 400 15 25 35 45 55 65 75
Capacity (mAh/g) 2 θ (°)

Figure 1. 共Color online兲 First cycle charge-discharge profiles of Li2MnO3 Figure 2. 共Color online兲 XRD profiles of Li2MnO3 synthesized at different
synthesized at different temperatures. temperatures.

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 Journal of The Electrochemical Society, 156 共6兲 A417-A424 共2009兲
1000°C 900°C
1μm
800°C 400-600°C
1μm
Figure 3. 共Color online兲 SEM images of Li2MnO3 synthesized at different
temperatures.
the sample annealed at different temperatures. Average particle size
of the samples was determined by measuring the dimension of the
particles from the SEM images, and the results are shown in Table I.
Samples synthesized at a lower temperature have smaller particles
size: Li2MnO3 synthesized at 400°C has a particle size as small as
70 nm. Increasing temperature leads to larger particles. Significant
grain growth is observed for samples made at a temperature of
⬎850°C, particle size is ⬃650 nm when the sample is annealed at
1000°C. This is consistent with the decrease in the full width half-
maximum 共fwhm兲 of the XRD peaks with increasing synthesis tem-
perature 共see Table I兲. Figure 4 shows the relationship between dis-
charge capacity and particle size, showing larger capacity from
Li2MnO3 nanoparticles. We attribute this to a smaller diffusion path
for smaller particles, which allows the material to be charged to a
higher capacity.
Another consequence of reducing the annealing temperature is an
increase in surface area. The BET surface area of the Li2MnO3
samples was measured and the results are shown in Table I. An
inverse relationship between surface area and particle size is ob-
tained, the smaller the particle size, the larger the surface area. A
simple geometrical calculation shows that surface area per unit mass
共A/m兲 is related to the diameter of the particle 共d兲 by A/m = 6/␳d
for spherical particles, where ␳ is the density of the material. Our
result is consistent with the inverse proportionality between A/m and
d, suggesting that the increase in surface area of our Li2MnO3
BET surface area (m2/g)
0 5 10
300
Particle
Discharge capacity (mAh/g)
250 size
200
150
100
50
0
0 100 200 300 400
Particle size (nm)
Figure 4. 共Color online兲 Relationship between particle size, BET surface
area, and discharge capacity of Li2MnO3 samples.
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A419
2.0
1.8 LiNi1/3Co1/3Mn1/3O2
Normalized intensity (a.u.)
1.6
1.4
1.2
1.0 MnO6
0.8 connectivity Li2MnO3
1μm 450°C
0.6 600°C
0.4 750°C
1s → 3d 900°C
0.2
0.0
6535 6540 6545 6550 6555 6560 6565
Energy (eV)
Figure 5. 共Color online兲 XANES profiles of Mn K-edge of Li2MnO3 syn-
thesized at 450, 600, 750, and 900°C, all four profiles overlap on top of each
1μm other. XANES profile of LiNi1/3Co1/3Mn1/3O2 is also shown for comparison.
sample synthesized at a reduced temperature is a direct result of the
decrease in particle size, and not from other contributions, such as
surface roughening.
The effect of annealing temperature on the local environment of
Mn in as-made Li2MnO3 was studied by XAFS. Figure 5 shows the
results of Mn K-edge XANES of Li2MnO3 samples synthesized at
450, 600, 750, and 900°C. The double-peak near 6540 eV is attrib-
uted to a 1s-to-3d transition, which is expected to be weak for an
octahedral coordination of Mn.33,34 The shoulder at ⬃6548 eV is
associated with the connectivity of the MnO6 octahedral.35 No sig-
nificant change in the XANES Mn K-edge is observed with anneal-
ing temperature. Similarly, EXAFS, which gives information about
the interaction of Mn with neighboring atoms, does not depend on
synthesis condition 共EXAFS of one of the pristine samples is shown
in Fig. 12兲. These results suggest that annealing temperature does
not change the local environment of Mn.
In summary, electrochemical activity of Li2MnO3 is enhanced by
the reduction of particle size of the material and the increase in the
amount of stacking faults in the structure. Effect of particle size is
expected to be dominating since Li2MnO3 with poor crystallinity
but only gives discharge capacity ⬍100 mAh/g has been reported
elsewhere.29,30 Though the effect of stacking faults cannot be ruled
out because it was not possible to make small particles without
stacking faults with the current synthesis method. Li2MnO3 sample
synthesized at 425°C, which can give a charge and discharge capac-
ity of 350 and 250 mAh/g at 25°C, respectively, is used in subse-
quent studies to investigate the charge-discharge mechanism of
Li2MnO3.
Tracking Li atoms and structural change during charge-discharge
of Li2MnO3 at 25°C.— Li2MnO3 cells were charged and discharged
to different capacities, and the cells were disassembled and their
compositions were determined by ICP to correlate the measured
15 20 25
capacities from electrochemical tests with the amount of Li in the
material. Test results are shown in Table II. ICP results show that
pristine samples have a Li/Mn ratio of 2:1, according to the stoichi-
BET ometry of our starting precursors. By assuming that the amount of
Mn in the active material remains constant after charge and dis-
charge, we can calculate the amount of Li in the samples from ICP
measurements. Figure 6 shows the relationship between measured
capacity 共cumulative兲 and the amount of Li in LixMn2/3O2. The
dotted line in Fig. 6 represents the theoretical capacity at a given Li
content if all extracted Li contribute to the capacity. When the elec-
500 600 700 trochemical tests were performed at 25°C, measured capacities co-
incide with the Li contents in the material according to calculation.
This directly shows that the electrochemical activity of Li2MnO3 is
accompanied by Li extraction/insertion. When charging was per-
formed at 60°C, the measured capacity is ⬃50 mAh/g larger than
A420 Journal of The Electrochemical Society, 156 共6兲 A417-A424 共2009兲

Table II. Measured charge-discharge capacities and LiÕMn ratios.

Test Charge Discharge Cumulative x in

temperature capacity capacity capacitya Li/Mn LixMn2/3O2
Samples 共°C兲 共mAh/g兲 共mAh/g兲 共mAh/g兲 共ICP results兲 共calculated兲

Pristine — — — 0 2.00 1.33

A1 25 50.0 — 50.0 1.75 1.16
A2 25 99.7 — 99.7 1.66 1.10
A3 25 150.0 — 150.0 1.32 0.88
A4 25 248.8 — 248.8 0.95 0.64
A5 25 337.5 — 337.5 0.47 0.31
A6 25 336.2 125.0 211.2 1.05 0.70
A7 25 335.4 210.0 125.4 1.47 0.98
B1 60 429.2 — 429.2 0.40 0.27
a
Cumulative capacity = charge capacity − discharge capacity.

that corresponding to Li extraction. Other mechanisms, such as elec- effect, such as the presence of additional active sites on the large
trolyte decomposition, contribute to the excess capacity at an el- surface, or from accommodation of Li in the grain boundary or
evated temperature. defects such as stacking faults.
To further study the electrochemical behavior of Li2MnO3, the When the charge capacity is increased, the discharge capacity
electrodes were charged to different capacities and then discharged. also increases accordingly. At 25°C, a maximum charge capacity of
Figure 7 shows the charge and discharge curves of electrodes that 350 mAh/g is obtained, which corresponds to the extraction of
are initially charged to 0, 50, 150, 250, and 350 mAh/g 共fully 1 mole of Li out of Li关Li1/3Mn2/3兴O2. Not all of the Li can be
charged兲 共cutoff capacities during charging are marked by X兲. An extracted from the active material. During discharge, a maximum
electrode that is initially discharged 共without charging兲 gives a ca- capacity of 250 mAh/g is obtained, in which 229 mAh/g can be
pacity of ⬃20 mAh/g, suggesting that the as-made material can accounted for by the 4+/3+ transition of Mn. The remaining
accommodate some amount of Li. The amount of Li accommodated 21 mAh/g most likely corresponds to the capacity from Li accom-
from initial discharge decreases with synthesis temperature, with a modated on surface or defect sites, same as that obtained when the
capacity of ⬍2 mAh/g for Li2MnO3 synthesized at 900°C. We sus- material is initially discharged.
pect the initial discharge capacity originates from either a surface The discharge capacities of Li2MnO3 obtained from different
states of charge during first cycle is summarized in Fig. 8; all data
points lie on a straight line with a slope close to 0.66. This indicates
500 that the charge-discharge mechanism of Li2MnO3 is the same
∗ 60°C charge
Cummulative capacity (mAh/g)

450 electrolyte throughout the entire first cycle, regardless of the state of charge.
decompositio 25°C charge
400
25°C discharge
For every three Li extracted out of the lattice, only two can be
350 reinserted back into the lattice. This suggests that there is a struc-
300 tural limitation on the amount of Li reinserted, instead of a chemical
250 theoretical capacity of limitation from the redox reaction of Mn. In addition, Li extraction
Li[Li1/3Mn2/3]O2 is most likely not uniform throughout the particles, resulting in “re-
200
150
acted” and “not reacted” regions, similar to a two-phase transforma-
100
discharge pristine sample tion. The plateau at ⬃4.5 V vs Li/Li+ observed during charging
x=4/3
charge supports this hypothesis.
50
The change in structure of Li2MnO3 during charging and dis-
0
charging was monitored by XRD. A summary of the XRD profiles at
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6
different charged states is shown in Fig. 9. Upon charging, the over-
x in LixMn2/3O2 all intensity of XRD peaks decreases. The peak at 18.7°, which
correspond to the 共001兲 plane, is shifted to a larger angle, indicating
Figure 6. 共Color online兲 Plot of cumulative capacity with respect to Li
content in LixMn2/3O2 共dotted line represents the theoretical capacity at a
given Li content兲.
300
5 slope = 1
1st discharge capacity (mAh/g)

X 250
4.5 X X X
1st cycle
Potential (V vs. Li/Li+)

slope = 0.66
4 10mA/g 200

3.5 150
3
100
2.5 Li2MnO3
50
2 0 50 150 250 350
charged to
mAh/g mAh/g mAh/g mAh/g mAh/g
1.5 0
0 50 100 150 200 250 300 350 400 0 50 100 150 200 250 300 350 400
Capacity (mAh/g) 1st charge capacity (mAh/g)

Figure 7. 共Color online兲 Charge-discharge curves of Li2MnO3 by limiting Figure 8. 共Color online兲 First cycle discharge capacity of Li2MnO3 by lim-
the state of charge to 0, 50, 150, 250, and 350 mAh/g 共marked by X兲. iting the charge capacity.

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 Journal of The Electrochemical Society, 156 共6兲 A417-A424 共2009兲 A421

2.0
pristine pristine
1.8
LiNi1/3Co1/3Mn1/3O2

Normalized intensity (a.u.)

1.6 charged
* discharged
1.4
Intensity (a.u.)

1.2
1.0 charge
discharge charge
charge 0.8
C1 0.6
C2 discharge
C3 0.4
C4
discharge 0.2
D1
D2 0.0
17 19 21 35 37 39 41 43 45 62 64 66 68 70 6543 6548 6553 6558 6563
2 θ (°) Energy (eV)

Figure 9. 共Color online兲 XRD profiles of Li2MnO3 at different stages of Figure 10. 共Color online兲 XANES profiles of Mn K-edge in
charge. C1, C2, C3, and C4 correspond to a state of charge of 0, 150, 250, LiNi1/3Co1/3Mn1/3O2 during charging 共to 4.3 V兲 and discharging.
and 350 mAh/g, respectively. D1 and D2 correspond to a discharge of 125
and 210 mAh/g from a fully charged electrode.

LiNi1/3Co1/3Mn1/3O2 共i.e., that the valence of Mn remains 4+兲. After

discharge, as opposed to LiNi1/3Co1/3Mn1/3O2, the XANES profile
a decrease in lattice spacing between the layers with Li extraction.
of Li2MnO3 does not return to the original position. The overall
In addition, the intensity of superlattice peak 共between 20 and 25°兲
edge 共both the peak top and the edge position at ␮ = 0.4兲 is shifted
is reduced gradually upon charging, indicating that the Li/Mn order-
to a lower energy, indicating a decrease in valance of Mn during
ing in the transition metal layer is disrupted. This suggests that Li is
discharge. Shape of the discharged profile is similar to that of
extracted not only from the Li layer but also from the TM layer
LiMn2O4, as opposed to Li2MnO3. At this point, further quantitative
during charging. Because the charge mechanism is thought to be the
investigation on the change of valence of Mn is needed to further
same throughout the charging process, as shown in Fig. 8, we sus-
understand the charge-discharge mechanism. In addition, in situ
pect Li are extracted from both Li layer and TM layer at the same
XAFS measurements should be conducted to minimize reaction be-
time. At a fully charged state, almost all of Li atoms in the TM layer
tween the environment and the charged and discharged electrodes.
are removed, as the superlattice can hardly be seen.
EXAFS profiles of Li2MnO3 show that charging is accompanied
During discharging, there is a general shift for all major peaks to
with a reduction of both Mn-O and Mn–Mn Fourier transformation
smaller angles, indicating an increase in lattice constants with Li
共FT兲 peaks 共see Fig. 12兲 and this reduction in FT is also not revers-
insertion. The fully discharged state has a different XRD profile than
ible upon discharge. We attributed the results to a distortion around
that of the pristine sample: e.g., 共001兲 peak of the fully discharged
the Mn atoms associated with the removal of Li from the Li and TM
state is at a smaller angle and only one single peak is observed at
layers and the reduction of coordination number due to removal of
65°. These results suggest a change in lattice structure after dis-
oxygen from the lattice. Attempts to model the EXAFS results by
charge, with a XRD profile similar to a spinel structure. Intensity of
simulations codes, such as FEFF, are in progress to clarify the origin
the superlattice peak remains small after discharge. Because only
of the large change.
2/3 of the extracted Li can be reinserted, we suspect the atoms
reenter the Li layer, leaving Li vacancies in the TM layer.
Oxygen evolution during charge-discharge.— XAFS results sug-
Status of Mn during charge-discharge.— XAFS measurement gest that Mn valence remains 4+ during the charging of
was carried out to study the change in local environment of Mn Li关Li1/3Mn2/3兴O2. But ICP results show that Li atoms are removed
during charging and discharging. LiNi1/3Co1/3Mn1/3O2 is used as a from the active material. If charge compensation is accompanied by
reference to help interpret the XANES profile of Li2MnO3. The oxygen removal, as suggested by various researchers,2,4,8,25-28 the
reason for using LiNi1/3Co1/3Mn1/3O2 as a reference is that extraction of one mole of Li from Li关Li1/3Mn2/3兴O2 corresponds to a
Li2MnO3 and LiNi1/3Co1/3Mn1/3O2 shows similar Mn K-edge change in oxygen stoichiometry from 2 to 1.5. In this study, we
XANES profiles because both materials have a layered structure investigated how much of the change can be explained by gas gen-
with Mn in an octahedral coordination 共as shown in Fig. 5兲. After eration.
charge-discharge, the cells were disassembled and the cathode ma-
terials were removed from the Al collector for XAFS measurements.
Figure 10 shows the change in XANES profile of the reference 2.0
LiNi1/3Co1/3Mn1/3O2 material after charge and discharge. When pristine Li2MnO3
1.8 pristine
charged to 4.3 V, disappearance of the shoulder at ⬃6548 eV and
Normalized intensity (a.u.)

1.6 charged
the shift in the peak top to higher energy are attributed to the change * discharged
1.4
in the local environment of Mn from Li extraction, with the valence LiMn2O4 LiMn2O4
1.2
of Mn remaining 4+.34,36 The change in the shape and position of
the Mn XANES profile is reversible upon discharge. Quantitative 1.0
discharge charge charge
analysis of the XANES profile is difficult because of the shape 0.8
change during charge-discharge. An absorption intensity 共␮兲 of 0.4 0.6
discharge
is marked in Fig. 10 as a qualitative guide for the eye to show the 0.4
shift 共or the lack of shift兲 of the profiles. 0.2
Figure 11 shows the corresponding XANES profile of Li2MnO3. 0.0
During charging, a disappearance of the shoulder around 6548 eV 6543 6548 6553 6558 6563
and a gradual shift to higher energy of the peak top, similar to that of Energy (eV)
LiNi1/3Co1/3Mn1/3O2, are also observed. The edge position at ␮
= 0.4 hardly moves. These results suggest that the effect of charg- Figure 11. 共Color online兲 XANES profiles of Mn K-edge in Li2MnO3 during
ing of Li2MnO3 on the local environment of Mn is similar to that of charging 共to 4.8 V兲 and discharging.

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A422 Journal of The Electrochemical Society, 156 共6兲 A417-A424 共2009兲

14 50
Mn-O 25°C 45°C 60°C
pristine 45
12 1M LiPF6 EC/DEC=3:7
Mn-Mn charged 40
charge

Detected gas (ml/g)

10 * discharged 35
FT Magnitude

charge 30 H2
8 discharge 25 O2
discharge CO
6 20
CO2
15
4 10
5
2
0
0 150 250 350 350 350
0 1 2 3 4 5 6 Charge capacity (mAh/g)
R (Å)

Figure 14. 共Color online兲 Volume of gases collected from Li2MnO3 cells
Figure 12. 共Color online兲 EXAFS profiles of Mn K-edge 共FT兲 of Li2MnO3
with 1 M LiPF6 in EC/DEC = 3:7 charged at 25, 45, and 60°C.
during charging and discharging.

CO2 remain almost the same regardless of charge capacity, where as

First, a simple in situ test to monitor the change in cell thickness
of a flat laminated Li2MnO3 cell during charge-discharge was per-
formed. Figure 13 shows the variation of cell thickness and applied
current with time. The cell was initially charged at a rate of 30, 20,
and 10 mA/g with intermittent rest. Afterward, the “not-yet-fully-
charged” cell was discharged at 20 mA/g for 2 h and then recharged
again for 4 h. During initial charging, thickness of the test cell in-
creases with charging and remains unchanged during rest. The larger
the applied current, the larger is the rate of thickness change 关i.e.,
rate of gas generation 共see Fig. 13兲兴. Thus, gas generation is an
integral part of the charging process of Li2MnO3. Gas generation is
only observed during the initial charge of the active material. During
discharge, thickness does not change. Upon recharging, no change
in thickness is observed for the first 2 h 共which corresponds to the
removal of Li that was inserted in the previous discharge step兲. After
2 h, cell thickness increases again from the charging of the “not
reacted” Li2MnO3. This supports the hypothesis that Li is not ex-
tracted uniformly throughout the particles during first charge, as
suggested from the charge efficiency results in Fig. 8.
To determine the type of gases and the total volume generated,
cells were charged to a capacity of 150, 250, and 350 mAh/g at
25°C and the gas was collected and analyzed by GC. The results are
shown in Fig. 14 and summarized in Table III. H2, O2, CO, and CO2
are detected within the collected gas. The amounts of H2, CO, and
rest rest rest
Current (mA/g)
the amount of O2 increases with charge capacity. This confirms that
oxygen gas is generated during charging of Li2MnO3. About 44 mL
of gas per active-material mass is detected by GC when the elec-
trode is charged to a capacity of 350 mAh/g 共equivalent to the evo-
lution of ⬃1/8 mole of O2 gas during the removal of one mole of Li
from Li关Li1/3Mn2/3兴O2兲. This corresponds to a change in oxygen
stoichiometry from 2 to 1.75. Our result shows that the amount of
oxygen gas can account for half of the charge compensation. The
remaining oxygen atoms, if they are removed from the active mate-
rial, may have reacted with electrolyte or formed Li2O at the anode
and are therefore not accounted for in this study. A certain amount of
proton exchange may have also occurred during charging, resulting
in a smaller change in oxygen stoichiometry. A better tracing of
oxygen and hydrogen atoms in the system is needed to clarify the
full process.
Effect of test temperature on charge mechanism of Li2MnO3.—
Li2MnO3 cells were charged to 350 mA/g at 25, 45, and 60°C and
the composition of the resulting gas was determined by GC to study
the effect of test temperature on charge mechanism. The results are
shown in Fig. 14 and summarized in Table III. At 25°C, the main
gas after charging is O2. With increasing test temperature, a signifi-
cant reduction in the amount of O2 and an increase in the amount of
CO2 are observed. At 60°C, a small amount of CH4 is also detected,
but the signal overlapped with the O2 signal and therefore cannot be
isolated. CO2 generation is associated with electrolyte decomposi-
tion, and therefore, the test results suggest that there is a change in
rest rest charge mechanism of Li2MnO3 with temperature, from an oxygen-

30 loss process to the decomposition of electrolyte at a higher tempera-

20 ture.
10 The change in mechanism is also reflected in the material struc-
0 ture after charging. Li2MnO3 active materials were collected after
-10 charging at 25 and 60°C to 350 mAh/g and examined by XRD, and
-20 the profiles are shown in Fig. 15. Li2MnO3 charged at 25°C shows
a slight shift in the main peak from 18.68 → 18.80° 关the 共001兲
plane兴. This shift corresponds to the shrinking of the lattice plane
Thickness change (mm)

2hrs 2hrs
0.8 distance after Li is extracted from the layer. Material charged at
60°C shows a larger shift of the main peak from 18.68 → 19.02°
slope together with the growth of a peak at 38.3° 共marked by “x” in Fig.
0.6
=0.240 15兲. These features are characteristics of a P3 structure associated
slope slope
0.4 with hydrogen bonding between adjacent oxide layers,25,26 origi-
=0.080 =0.145 nated from the exchange of Li+ and H+ ions in the active material,
0.2 that are also seen after acid treatment of Li2MnO3.4,8,37 The protons
slope are likely to be generated from electrolyte decomposition. Note that
=0.145
0 the total amount of gas detected from the charged cell is smaller at
0 2 4 6 8 10 12 14 a higher test temperature 共see Table III兲. This is consistent with
Time (hour) electrolyte decomposition and proton exchange because the inter-
change of H+ and Li+ does not involve oxygen loss, and a larger
Figure 13. 共Color online兲 Change in Li2MnO3 cell thickness with charge and portion of the gas is absorbed in the electrolyte since the solubility
discharge. of CO2 is higher than that of O2.38,39

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 Journal of The Electrochemical Society, 156 共6兲 A417-A424 共2009兲 A423

Table III. Volume of detected gas per active material mass from charged Li2MnO3 cells at 25, 45, and 60°C (bracketed values refer to the
percentage).

Charge temperature 25°C 45°C 60°Ca

Charge capacity 150 mAh/g 250 mAh/g 350 mAh/g 350 mAh/g 350 mAh/g

Total detected 16.3 30.5 44.2 41.3 22.7

volume 共mL/g兲
H2 1.2共7.2%兲 1.4共4.5%兲 0.7共1.5%兲 1.4共3.4%兲 1.3共5.8%兲
O2 12.3共75.6%兲 26.4共86.5%兲 39.8共90.0%兲 28.2共68.4%兲 2.6共11.3%兲
CO 0.8共4.8%兲 0.8共2.6%兲 0.9共2.0%兲 1.5共3.7%兲 3.3共14.7%兲
CO2 2.0共12.4%兲 2.0共6.4%兲 2.9共6.5%兲 10.1共24.4%兲 15.4共67.8%兲
a
Small amount of CH4 is measured at 60°C but the signal overlaps with O2 signal from GC.

Our results show that oxygen loss is the dominating process at
25°C and electrolyte decomposition is more prominent at a higher
temperature, confirming the results of Robertson and Bruce.25 Both
mechanisms occurs at a similar potential of 4.5–4.6 V vs Li/Li+, and
therefore, a small change in test temperature can tip the balance in
favor of one mechanism over another. We suspect the contribution
from electrolyte decomposition will be reduced if a more oxidation-
resistant electrolyte is used in the cell and further tests are being
done to verify this.
Cycle performance of Li2MnO3 with different states of charge.—
Li2MnO3 electrodes were tested with different state of charges
共fixed by charge capacity兲, and the cycle performance was moni-
tored 共see Fig. 16兲. Electrodes charged to 4.8 V vs Li/Li+ or with a
charge cutoff of 250 mAh/g show poor cycle performance, where
the capacity reduces to below 100 mAh/g after 10 cycles. By reduc-
ing the state of charge to 150 mAh/g, the cycle life can be pro-
longed, but the discharge capacity eventually decays after 15 cycles.
The cycle efficiency 共ratio of discharge and charge capacities兲 is
⬃90% when the electrode is charged to 150 mAh/g. This suggests
that Li2MnO3 keeps on losing Li with cycling and eventually runs
to-spinel phase transformation during cycling, consistent with other
reports.25,29,30 The phase transformation is most likely facilitated by
the poor crystallinity of our sample, together with the removal of
oxygen from the lattice and the formation of Li vacancies in the TM
layer during charge-discharge.
Issues of Li2MnO3.— We have shown that Li2MnO3 made at a
low temperature is electrochemically active, with a discharge capac-
ity as large as 250–260 mAh/g. However, Li2MnO3 shows the fol-
lowing characteristics: first cycle efficiency is ⬃66%; gas is gener-
ated during the initial charging process; electrolyte decomposition is
observed at elevated temperature; and cycle performance is poor.
These limit the usage of phase-pure Li2MnO3 in practical Li-ion
batteries. Methods to increase first cycle efficiency, reduce gas gen-
eration and improve cycle performance are needed. One such
method that has been explored by numerous researches is to stabi-
300
4.8V cut
250
Discharge capcaity (mAh/g)

out of Li that leads to a capacity fade. Cycle performance can be

250mAh/g cut
improved by reducing the utilization of the electrode. For example,
200
an electrode with a charge cutoff of 50 mAh/g shows good cycle
performance with a cycle efficiency of close to 100%. However, this 150
is not a practical solution to improve cycle performance because we 150mAh/g cut
end up sacrificing the capacity. 100
The charge-discharge curves of a cycled electrode with a cutoff
capacity of 150 mAh/g are shown in Fig. 17. Discharge capacity 50mAh/g
50 cut
increases during the first few cycles, and the formation of discharge
plateaus around 4.0 and 2.9 V vs Li/Li+ is observed. These plateaus 0
are characteristics of spinel Mn, suggesting that there is a layered- 0 5 10 15 20 25
Cycle number

18.68° Figure 16. 共Color online兲 Cycle performance of Li2MnO3 with limited
18.80°
charge capacity.
Intensity (a.u.)

19.02° 5
10mA/g
1st
Intensity (a.u.)

4.5
Potential (V vs. Li/Li+)

2nd 5th
4 8th 150mAh/g
x 17 18 19 20 21 22 23
2θ charge cutoff
3.5
pristine 3

2.5
25°C charge increase of plateau 5th
2 with cycling
60°C charge 1st 2nd 8th
1.5
15 25 35 45 55 65 75 0 50 100 150 200
2 θ (°) Capacity (mAh/g)

Figure 15. 共Color online兲 XRD of Li2MnO3 materials charged at 25 and Figure 17. 共Color online兲 Charge-discharge curves of Li2MnO3 with a
60°C to 350 mAh/g. 150 mAh/g cutoff.

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A424 Journal of The Electrochemical Society, 156 共6兲 A417-A424 共2009兲

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