Polymer Template-Assisted Microemulsion Synthesis of Large PDF

J Solid State Electrochem
DOI 10.1007/s10008-013-2221-1
ORIGINAL PAPER
Polymer template-assisted microemulsion synthesis of large

surface area, porous Li2MnO3 and its characterization
as a positive electrode material of Li-ion cells
Tirupathi Rao Penki & D. Shanmughasundaram &
N. Munichandraiah
Received: 20 June 2013 / Revised: 6 August 2013 / Accepted: 9 August 2013

# Springer-Verlag Berlin Heidelberg 2013
Abstract Lithium-rich manganese oxide (Li2MnO3) is prepared by reverse microemulsion method employing Pluronic
acid (P123) as a soft template and studied as a positive
electrode material. The as-prepared sample possesses good
crystalline structure with a broadly distributed mesoporosity
but low surface area. As expected, cyclic voltammetry and
chargedischarge data indicate poor electrochemical activity.
However, the sample gains surface area with narrowly distributed mesoporosity and also electrochemical activity after
treating in 4 M H2SO4. A discharge capacity of about
160 mAh g1 is obtained. When the acid-treated sample is
heated at 300 C, the resulting porous sample with a large
surface area and dual porosity provides a discharge capacity of
240 mAh g1. The rate capability study suggests that the sample
provides about 150 mAh g1 at a specific discharge current of
1.25 A g1. Although the cycling stability is poor, the high rate
capability is attributed to porous nature of the material.
Keywords Lithium-ion cell . Mesoporous . Lithium excess
manganese oxide . Microemulsion route . Polymer template .
High rate capability
Introduction
Lithium-ion batteries have attracted global interest from both
consumers and researchers during the past a couple of decades
[1, 2]. The interest has arisen because of the extended applications, which are successful in small sizes at present and
anticipated in large sizes in the future. Although the energy
density of the present Li-ion batteries is greater than that of
T. R. Penki : D. Shanmughasundaram : N. Munichandraiah (*)
Department of Inorganic and Physical Chemistry, Indian Institute of
Science, Bangalore 560012, India
e-mail: muni@ipc.iisc.ernet.in
Pb-acid batteries by about four times, future requirements

such as electric vehicle applications require still greater energy
density. The next generation Li-ion batteries thus need novel
electrode materials which can provide greater discharge capacity than the materials in use at present, in addition to the
need that they should be safe, inexpensive, non-toxic, and
environmental-friendly.
The present Li-ion batteries employ positive electrode materials of the categoryLiCoO2, LiMn2O4, and LiFePO4
either in their pure state or with partial substitutions of the
transitional metals. The discharge capacity values of LiCoO2,
LiMn2O4,and LiFePO4 are 140, 130, and 170 mAh g1, respectively [3]. Li-ion batteries with greater energy density
than the present batteries require positive electrode materials
of greater discharge capacity. Compounds which can store
more than one lithium atom per transition metal atom are
expected to provide enhanced discharge capacity. Li2MnO3
belongs to this category of materials [4]. Li2MnO3 is considered isostructural to layered LiCoO2 and its formula can also
be represented as Li(Li0.33Mn0.67)O2. One third of the octahedral sites meant for Mn in the crystal lattice are occupied by Li
atoms. On the basis of extraction of the total available Li in
Li2MnO3, a discharge capacity of 456 mAh g1 is expected,
provided the compound is electrochemically active. Li2MnO3
was synthesized in single-phase from the reaction of LiOH
and MnO2 [5]. By treating the compound with H2SO4 or
HNO3, a discharge capacity of 199 mAh g1 was obtained
in the first chargedischarge cycle, which decreased rapidly to
143 mAh g1 in the eighth cycle. Following this report, several
publications have appeared with varying capacity values
[614]. Initial discharge capacity values are generally high
for the activated phases of Li2MnO3, but cycling instability is
observed in all reports.
In addition to the high discharge capacity, an electrode
material needs to possess high rate capability for the purpose
of fast charge or/and discharge. Porous materials are expected
a
100
(iv)
9 % loss
(ii)
Weight loss / %
80
(iii)
I region
60
II region
59 % loss
40
8 % loss
(i)
20
170 C 240 C
455 C
0
100
200
300
400
500
600
700
800
Temperature / C
(202)
(060)
(330)/(061)
(201)
(132)
(130)
(020)
(110)
Intensity / a.u.
(131)
(001)
(iv)
(iii)
(ii)
(i)
10
20
30
40
50
60
70
80
2 / degree
Fig. 1 a Thermogravimetry recorded at a heating rate of 10 C min1 of

precursor gel (i ), sample S5 (ii ), sample S5A6 (iii ), and sample
S5A6H3 (iv ); and b powder XRD pattern of samples S4 (i ), S5 (ii ),
S6 (iii ), and S8 (iv )
to possess high rate capability because the electrolyte can

creep into particles and enhance the contact area of the
electroactive surface with the electrolyte [15]. As a result,
the material can withstand an enhanced specific current during
chargedischarge cycling. To the best of the authors' knowledge, there are no reports on the synthesis of porous Li2MnO3.
In the present study, the lithium excess oxide is prepared by
inverse microemulsion route assisted by soft polymer template, namely, Pluronic acid (P123). By treatment in dilute
acid and heating, the compound gains a large surface area and
dual mesoporosity, which result in providing a high initial
discharge capacity and also a high rate capability.
Experimental
High purity or analytical grade chemicals, namely lithium
nitrate (Aldrich), manganese nitrate tetrahydrate (Aldrich),
Pluronic acid [P123, poly(EO)20-poly(PO)70-poly(EO)20,

where EO and PO are ethylene oxide and propylene oxide
units, respectively; molecular weight, 5,800] (Aldrich), lithium dodecylsulfate (LDS, Aldrich), cyclohexane (Merck), nbutanol (SD Fine Chemicals), H2SO4 (SD Fine Chemicals),
lithium ribbon (0.75 mm thickness, Aldrich), acetylene black
(AB, Alfa Aesar), poly(vinylidene fluoride) (PVDF, Aldrich),
1-methyl-2-pyrrolidinone (NMP, Aldrich) and 1 M LiPF6
dissolved in ethylene carbonate, diethyl carbonate and
dimethyl carbonate (2:1:2v/v) electrolyte (Chameleon) were
used as received.
Li2MnO3 was prepared by reverse microemulsion route
employing P123 as a soft template. The oil and aqueous
phases were prepared separately. For the oil phase, 1.0 g
P123 was dissolved in a mixture consisting of 51.2 ml cyclohexane and 6.2 ml n -butanol by stirring for 2 h. Then, 0.225 g
LDS was added and stirred for 3 h to get a transparent
solution. Lithium nitrate (0.84 g) and manganese nitrate
tetrahydrate (1.074 g) were dissolved in 15 ml doubledistilled water. About 20 % of excess of lithium nitrate than
the stoichiometric quantity was used. The aqueous phase was
transferred to the oil phase and stirred for 12 h at ambient
temperature. The emulsion was slowly evaporated at 110 C.
A white gel was obtained. Samples of gel were calcined in air
at 400, 500, 600, 800 C for 6 h. Red colored powder samples
were obtained.
For activation of Li2MnO3, 1.0 g of a sample was added to
100 ml of 4 M H2SO4 and stirred at ambient conditions for
different durations from 2 to 24 h. The powder was separated
from the acid by centrifugation and washed with doubledistilled water thrice, finally rinsed with acetone, and dried
at 110 C for about 12 h. A black colored powder was
obtained. The acid-treated Li2MnO3 samples were heated at
either 300 or 500 C in air for 4 h. The color of the samples
remained black.
The powder X-ray diffraction (XRD) patterns were
recorded using a Bruker AXS D8 Advance X-ray diffractometer at 40 kV and 30 mA using Cu Ka ( =1.5418 ) radiation
source. Nitrogen adsorptiondesorption isotherms were
recorded at 196 C by using Micromeritics surface area
analyzer model ASAP 2020. The specific surface area was
calculated using the BrunauerEmmettTeller (BET) method
Table 1 Unit cell parameters obtained from XRD pattern

Sample a ()
b ()
c ()
()
Cell volume (3)
S4
S5
S6
S8
S5A6
8.523 (4)
8.534 (5)
8.530 (2)
8.537 (5)
8.672 (6)
5.008 (4)
5.015 (4)
5.022 (2)
5.026 (4)
5.045 (4)
109.14 (4)
109.20 (2)
109.12 (1)
109.27 (2)
110.29 (3)
199.29 (2)
199.35 (2)
199.49 (1)
199.87 (2)
206.90 (3)
4.942 (3)
4.934 (4)
4.929 (2)
4.935 (3)
5.042 (4)

Fig. 2 Scanning electron
microscopy images of Li2MnO3
samples a S4, b S5, c S6, and d
S8
in the relative pressure (p/p 0) range 0.050.25 from adsorption branch of the isotherm. The pore size distribution was
calculated by BarrettJoynerHalenda (BJH) method from
desorption isotherm. The morphology was examined using a
FEI Co scanning electron microscope (SEM) model Sirion.
The chemical composition was analyzed by inductive coupled
plasma atomic emission spectroscopy using Varion inductively couple atomic emission spectrometer model Vista-PRO.
The elemental analysis for C and H was carried out by using
a Thermo Finnigan FLASH EA 1112 CHN analyzer.
Thermogravimetric analysis (TGA) was recorded from ambient temperature to 800 C at a heating rate of 10 C min1
under the flow of O 2 gas by using thermal analyzer
NETZSCH model TG 209 FI.
For fabrication of electrodes, the active material (80 wt%),
AB (15 wt%) and PVDF (5 wt%) were mixed in a mortar and
few drops of NMP were added to obtain a slurry. Stainless
steel disks (16 mm diameter) were cleaned with water, etched
in 30 % dilute HNO3, rinsed with double-distilled water
followed by acetone and air-dried. The slurry was applied on
a pre-treated stainless steel disk and dried at 110 C under
vacuum for 12 h. The mass of active material was 3
5 mg cm2. Lithium metal foil was used as a counter cum
reference electrode and Celgard porous polypropylene
membrane (2400) was used as a separator. A commercial

electrolyte of 1 M LiPF6 dissolved in ethylene carbonate,
diethyl carbonate and dimethyl carbonate (2:1:2v/v) was used
as the electrolyte. Coin-type cells CR2032 (Hohsen Corporation, Japan) were assembled in an argon-filled MBraun glove
box.
The cells were galvanostatically cycled in the voltage range
from 1.5 to 4.4 V at different current densities at room temperature. Cyclic voltammetry and chargedischarge cycling
experiments were carried out using an EG&G potentiostat
model Versastat and Biologic potentiostat/galvanostat model
VMP3. Rate capability with different current densities was
examined by using Bitrode battery cycling unit in an airconditioned room at 221 C.
Results and discussion

Soft chemical synthesis by inverse microemulsion route provides a control over particle size of the product. By dispersing
a small volume of aqueous phase consisting of the reactants in
a large volume of non-aqueous phase, the reactants are confined to micrometer sized reaction zones and particles of the
products are limited to the size of the aqueous droplets, which
Sample
40
BET surface pore

area (m2 g1) diameter
(nm)
Conditions of preparation
Quantity of N2 adsorbed / cm g
-1
Table 2 Conditions of preparation, BET surface area and pore diameter

of different samples
S4
S5
S6
S8
S5A2
(iv)
20
(iii)
(ii)
(i)
0
0.0
0.3
0.6
0.9
o
Relative pressure (p/p )

0.0009
0.0006
-1
dVol/dDia / cm g nm
-1
0.0003
(iv)
(iii)
(ii)
(i)
Microemulsion400 C heating
2 h acid treatment
S5A6
6 h acid treatment
S5A12
12 h acid treatment
S5A24
24 h acid treatment
S5A2H3 Microemulsion500 C heating
2 h acid treatment3 h heating
at 300 C
6 h acid treatment3 h heating
at 300 C
12 h acid treatment3 h
heating at 300 C
24 h acid treatment3 h
heating at 300 C
5.8
5.6
5.3
2.6
115
1045
1025
1030
1050
3.9
89
3.9
78
3.7
74
3.5
49
3.6 and 6.1
61
3.6 and 7
44
2.4 and 3.7
42
3.7
0.0000
30
60
90
120
150
Pore diameter / nm
Fig. 3 a Nitrogen adsorption/desorption isotherms and b pore size

distribution BJH curves of Li2MnO3 samples S4 (i), S5 (ii), S6 (iii),
and S8 (iv) samples. In a, curves (ii), (iii), and (iv) are, respectively,
vertically shifted by 5, 10, and 15 units of y-axis scale relative to the
position of curve (i)
are stabilized by surfactant molecules. Sub-micrometer/

nanosized product particles are synthesized by this route
[16]. The presence of polymeric templates such as P123 in
the reaction medium facilitates the product particles to develop porosity. The presence of hydrophilic EO block and hydrophobic PO block is considered to be responsible for generating porosity on the product particles [17]. By combining
the salient features of inverse microemulsion and polymeric
templates, synthesis of porous, sub-micrometer sizes cathode
materials, namely, LiFePO4 and LiNi1/3Mn1/3Co1/3O2, were
synthesized in our laboratory [1820]. A similar procedure
was adopted for preparation of Li2MnO3 in the present work.
The gel obtained after evaporation of solvents at 110 C
was subjected to thermal analysis (Fig. 1a, curve i). There is a
continuous loss of mass between ambient and about 240 C
due to the removal of solvents and decomposition of nitrates
and organic matter. About 58 % of weight loss is observed at
240 C. The mass of the sample is fairly constant between 240
and 450 C. There is about 8 % loss of mass between 240 and

450 C followed by stability up to 800 C. Therefore, samples
of the gel were heated at several temperatures from 400 to
800 C for 6 h. The samples prepared at 400, 500, 600, and
800 C are hereafter referred to as S4, S5, S6 and S8, respectively. Thermogravimetric analysis of the heated samples
(Fig. 1a, curve ii shown typically for sample S5) indicates
thermal stability of the compounds in the temperature range
from ambient to 800 C.
Powder XRD patterns of the samples prepared at different
temperatures are shown in Fig. 1b, which are similar for all
samples. The structure of Li2MnO3 was determined by using
single crystal X-ray diffraction by Strobel and LamberAndron [21]. Li2MnO3 was described as Li[Li1/3Mn2/3]O2
Table 3 Elemental analyses. Mn and Li were estimated by inductive
coupled plasma atomic emission spectroscopy; C and H by CHNS
analysis, and O is the balance
Sample
S5
S5A6
S5A6H3
Weight % of elements
Mn
Li
39.09
49.06
51.79
7.78
4.70
4.55
1.28
0.894
0.407
0.78
1.31
0.67
51.07
44.03
42.57
a
4.5
st
1 ch
st
2 ch
Potential / V Vs Li/Li
4.0
3.5
3.0
2.5
2.0
st
1 dis
1.5
0
20
40
60
80
100
Specific discharge capacity / mAh g

120
-1
120
-1
100
(ii)
(i)
80
(iii)
60
40
(iv)
20
0
10
11
Cycle number
Fig. 4 a Chargedischarge curves of Li 2 MnO 3 sample S5 at

100 A cm2 (specific current 33 mA g1) and b discharge capacity
variation of Li2MnO3 samples S4, S5, S6, and S8 on repeated charge
discharge cycling at a specific current of 3033 mA g1
structure of O3-type where the octahedral sites of inter-slab

are occupied by lithium-ion and octahedral sites of the slab by
lithium and manganese ions in 1:2 ratio. The XRD patterns
(Fig. 1b) agree well with the standard pattern of layered
structure (JCPDS file No. 841634). The (020) and (110)
reflections in 2 range 2023 indicate LiMn ordering in
the mixed cation layer and these superstructure reflections are
signatures for Li2MnO3. The XRD patterns of all samples
(Fig. 1b) were indexed to Li2MnO3 and lattice constants were
obtained (Table 1). Lattice constants are close to those reported in the JCPDS file 841634 (a =4.937 ; b =8.532 ; and
c =5.03 ). Similar agreement in lattice constants was
reported for Li2MnO3 prepared from aqueous sol gel method [22]. The average crystallite size of Li2MnO3 samples
were calculated from diffraction peaks of (001), (201), and
(131) planes using Scherrer equation [23] and the average
crystallite size was 140 nm. The unit cell parameters and
also the crystallite size were nearly the same for all S4S8
samples (Table 1).
SEM micrographs of the as-prepared samples of Li2MnO3

are presented in Fig. 2. The S5 sample appears to have layerlike morphology with several layers aggregated together and
edges projecting upwards. The thickness of layer is about
23 nm and length is about 190 nm. With an increase in
temperature of preparation, morphology changes to porous
sponge-like at 600 C (S6 sample) and plate-like morphology
at 800 C (S8 sample). Thus, the temperature of preparation
influences the morphology, particle nature, and as well as the
size.
Nitrogen adsorption/desorption isotherms and BJH porosity curves are presented in Fig. 3. The adsorption and desorption branches do not merge in the pressure region p/p 0 between 0.50 and 0.99 for all samples suggesting porous nature
of the samples. The amount of N2 adsorbed at p/p 0 =0.99 is
about 40 cm3 g1, which is considered as high. This is attributed to porosity of the materials. The porous nature is also
reflected in BJH curves (Fig. 3b). There is a broad distribution
of pores around 1040 nm diameter. The BET surface area and
average pore diameter obtained for all samples are listed in
Table 2. The surface area of S5 samples is 5.5 m2 g1 with
pore diameter of 1020 nm. There is a marginal decrease in
surface area by increasing the temperature of preparation
(Table 2). The porosity acquired by the Li2MnO3 samples is
attributed to the presence of the polymeric template in the
reaction medium of preparation.
Results of elemental analysis and the calculated composition for S5 sample, typically, are provided in Table 3. It is
likely that the origin for C and H is the polymer P123. The
composition is calculated assuming that Mn is present as per
the intended composition of Li2MnO3. The deficiency of Li
(1.57 against intended 2.0) is probably due to loss of Li in the
process of synthesis. It is reported that the XRD patterns of
compounds with Li/Mn ratio less than 2 also correspond to the
pattern of stoichiometric Li2MnO3 [24].
Cyclic voltammograms (not shown) of Li2MnO3 prepared
at different temperatures suggested poor electrochemical activity of the compound. In general, the positive electrode
materials of Li-ion cells exhibit well-defined reduction and
oxidation current peaks of cyclic voltammograms [25]. In the
present study, redox current peaks were absent for all asprepared samples. Poor electrochemical activity is also
reflected in galvanostatic charge/discharge cycling (Fig. 4a).
The electrodes were subjected to chargedischarge cycling
between 1.50 and 4.40 V at a specific current of 33 mA g1.
Although Li2MnO3 was reportedly [14] cycled between 1.50
and 4.80 V, the potentials greater than 4.50 V are expected to
be undesirable due to the possibility of decomposition of the
electrolyte and evolution of gases inside sealed cells. Hence,
the upper limit of cycling is limited to 4.40 V in the present
study, similar to the studies reported on Li2MnO3 electrodes
which were cycled between 1.50 and 4.50 V in order to avoid
decomposition of the electrolyte [26]. The discharge capacity

Fig. 5 a Powder XRD pattern
and b SEM image of sample
S5A6
Intensity / a.u.
10
20
30
40
50
60
70
80
2 / degree
obtained at a specific current of 33 mA g1 rate is in the range
95115 mAh g1 for S4, S5 and S6 samples (Fig. 4). The
capacity of S8 sample is only about 22 mAh g1. On repeated
chargedischarge cycling (Fig. 4b), the discharge capacity of
S5 sample is fairly stable at 100 mAh g1, whereas the
capacity of S4 and S6 samples decreases gradually. The
capacity of S8 sample is stable at about 10 mAh g1. These
values are considerably lower than the theoretically expected
value of 456 mAh g1. The poor electrochemical of Li2MnO3
samples is because Mn is already in +4 oxidation state and
delithiation of it during charging process necessitates an increase in the oxidation state to +5, which is unlikely to exist
[5]. As the discharge capacity to the extent of 100 mAh g1 is
obtained from the S4, S5, and S6 samples, it is presumed that
these compounds are non-stoichiometric (Table 3) although
the XRD patterns (Fig. 1b) match with the standard pattern. It
is likely that the temperature of preparation influences stoichiometry of the compound. It was reported that discharge capacity of Li2MnO3 depended on the method of synthesis [25].
An initial capacity of about 70 mAh g1 was obtained when
Li2MnO3 was prepared from Mn3O4 at 900 C whereas less
than 20 mAh g1 was obtained when it was prepared from MnOOH precursor [26].
It is known that Li2MnO3 can be converted into electrochemically active phase by treatment in acid [5]. By treatment
in acid, the Li2MnO3 undergoes a partial dissolution of Li2O
thereby facilitating the insertion of Li+ ion into the resulting
sample during discharge. Thus, the sample gains electrochemical activity. As the quantity of removable Li2O depends on
duration of acid treatment, it was attempted to activate the
mesoporous Li2MnO3 samples by treatment in 4 M H2SO4
solution for different durations. The S5 and S8 samples were
treated in 4 M H2SO4 for a few hours, and then tested for

electrochemical activity after washing and drying. It was
found that both the samples delivered higher discharge capacity than the as-prepared samples, but the S5 sample delivered
higher capacity than the S8 sample after acid treatment.
Hence, detailed investigations were carried out with S5 sample of Li2MnO3. Sample S5 was subjected to treatment in 4 M
H2SO4 for different durations. Samples of S5, which were
treated for 2, 6, 12, and 24 h are hereafter referred to as
S5A2, S5A6, S5A12, and S5A24, respectively. The
thermogravimetry data S5A6 sample (Fig. 1a, curve iii) suggests a mass loss of 10 wt% at about 170 C. It is thus inferred
that the sample gains protons or H2O to the extent of about
10 wt%. There is a gradual mass loss between 170 and 800 C.
The sample retains about 75 % of its initial mass at 800 C.
Powder XRD pattern of S5A6 sample is shown in Fig. 5a.
There are some changes observed in the XRD pattern (Fig. 5a)
in comparison with the patterns of as-prepared samples
(Fig. 1b). The (001) reflection exhibits a split, the superlattice
structure is slightly altered at 2 =23, a new peak is developed next to (130) reflection and the (131) peak is diminished
(Fig. 5a). Nevertheless, the unit cell parameters of S5A6
sample calculated on the basis of Li2MnO3 structure are listed
in Table 1. There is a marginal increase in the values of a, b,
, and unit cell volume. Significant changes are not observed
in morphology (Fig. 5b) when compared with the data of the
as-prepared S5 sample (Fig. 2). However, marked changes are
observed in N2 adsorption/desorption isotherms and BJH
porosity curves (Fig. 6). BET surface area measured from
adsorption isotherms are significantly greater than the values
measured for the as-prepared sample (Table 2). The loop
between adsorption and desorption isotherms (Fig. 6a) is
a
120
-1
140
100
80
60
40
(iv)
(iii)
(ii)
20
(i)
0
0.0
0.2
0.4
0.6
0.8
1.0
b
0.03
0.02
(ii)
-1
dVol/dDia / cm g nm
-1
(i)
0.01
(iii)
(iv)
0.00
10
12
14
Pore diameter / nm
Fig. 6 a Nitrogen adsorption/desorption isotherms and b BJH curves of

samples S5A2 (i), S5A6 (ii), S5A12 (iii), and S5A24 (iv). In a, curves
(ii), (iii), and (iv) are, respectively, vertically shifted by 5, 10, and 15 units
of y-axis scale relative to the position of curve (i)
wider in relation to the data of the as-prepared samples

(Fig. 3). The quantity of N2 adsorbed by the acid-treated
samples at p/p 0 =0.99 is about 120 cm3 g1 (Fig. 6a), which
is three times greater than the corresponding values for the asprepared samples (Fig. 3). Pore diameter decreases to a narrow
range at about 4 and pore volume is also greater (Fig. 6b)
than the as-prepared samples (Fig. 3). The increased surface
area and pore volume are thus attributed to the acid treatment
of Li2MnO3, which is already mesoporous before subjecting
to the acid treatment. The chemical analysis of S5A6
sample (Table 3) indicates a decrease in the Li content
and also in C and O contents. The quantity of H has increased
due to acid treatment, which is also reflected in TGA data
(Fig. 1a, curve iii).
The electrochemical results of acid-treated samples of
Li2MnO3 are presented in Fig. 7. Cyclic voltammogram of
S5A6 sample (Fig. 7a) shows an oxidation current peak at
3.20 V and a reduction current peak at 2.80 V. Thus, the peak
potential separation is about 0.40 V, which is an indication of

an irreversible nature of electrode process. In addition to the
major oxidation current peak observed at 3.20 V, there
is a minor oxidation peak at 4.20 V. Thus, the cyclic
voltammogram indicates that the inactive phase of the asprepared Li2MnO3 is converted into electrochemically active
phase on treating in 4 M H2SO4 for a few hours, although the
peak potential separation is 0.40 V. The chargedischarge
curves (Fig. 7b) contain potential plateaus at 3.20 and
2.80 V for charge and discharge process, respectively. The
discharge capacity calculated from Fig. 7b is 196 mAh g1 for
sample S5A6. This value is significantly greater than the value
obtained from the as-prepared sample (Fig. 4b). The variations
of discharge capacity of acid-treated samples on repeated
cycling at a specific current of 30 mA g1 are shown in
Fig. 7c. The discharge capacity values of samples S5A2,
S5A6, S5A12, and S5A24 in the first cycle are 179, 196,
183, and 182 mAh g1, respectively, and the corresponding
values in the tenth cycle are 135, 146, 161, and 110 mAh g1.
The coulombic chargedischarge efficiency throughout the
cycle-life test is greater than 95 % (Fig. 7c curve v, typically
for the sample S5A6). After mild acid treatment, thus,
Li2MnO3 samples gain electrochemical activity, but the cycling stability is poor. A gradual change in crystallographic
structure is perhaps responsible for the cycling instability.
As thermogravimetry of the acid-treated sample (S5A6)
indicated the presence of impurities which were removed at
170 C (Fig. 1a, curve iii), attempts were made to heat this
sample and to examine the electrochemical properties. Samples of S5A6 were heated for 4 h at 300 and 500 C, and tested
for chargedischarge capacity. The sample heated at 300 C
provided greater discharge capacity than the sample heated at
500 C. Therefore samples of S5A2, S5A6, S5A12, and
S5A24 were heated at 300 C for 4 h. The resulting samples
are hereafter referred as S5A2H3, S5A6H3, S5A12H3, and
S5A24H3, respectively. The thermogravimetry (Fig. 1a, curve
iv) of sample S5A6H3 indicates that the sample is stable up to
800 C and the impurities present in sample S5A6 were
removed by heating at 300 C for 4 h.
Powder XRD pattern of the S5A6H3 sample, typically, is
shown in Fig. 8a. The patterns of the other heated samples are
similar to this pattern. The patterns of these samples are
different from the patterns of the as-prepared samples
(Fig. 1b). Yu and Yanagida reported detailed structural analysis of Li2MnO3 and related compounds, recently [24]. During
acid treatment, there was a gradual reduction of O3 peaks
(ABCABC stacking) and an increase in the P3 peaks
(AABBCC stacking) as supported by a shift of the main
XRD peak from 2 =18.7 to 19.15, and also by the emergence of a peak at 2 =38.3 [24]. On the basis of XRD
patterns, Raman spectra, and TGA results, it was concluded
that after acid treatment and heating, Li2MnO3 transforms into
spinel Li4Mn5O12 phase [24]. The SEM image (Fig. 8b)
a
-100
-2
-50
Current / mA cm
Fig. 7 a Cyclic voltammogram

of sample S5A6 at a sweep rate of
0.05 mV s1, b chargedischarge
curves of sample S5A6 at a
specific current of 30 mA g1, and
c variation of specific discharge
capacity of samples S5A2 (i),
S5A6 (ii), S5A612 (iii), and
S5A24 (iv). Variation of
coulombic efficiency is shown as
curve (v), typically, for sample
S5A6
0
50
100
150
1.5
2.0
4.5
2.5
3.0
3.5
+
Potential / V vs Li/Li
4.0
4.5
st
1 ch
2
Potential / V Vs Li/Li+
4.0
nd
ch
3.5
3.0
2.5
2.0
2
1.5
0
50
100
nd
dis
150
st
1 dis
200
-1
100
200
80
(iii)
150
(ii)
(i)
(iv)
100
40
50
60
Coulombic efficiency / %
-1
(v)
20
shows that the morphology of S5A6H3 sample is nearly the

same as S5 and S5A6 samples (Fig. 2 and 5b). Nevertheless,
significant changes are observed in N2 adsorption/desorption
5
6
7
Cycle number
10
0
11
isotherms and BJH curves (Fig. 9). The gap between the
adsorption and desorption isotherms has increased (Fig. 9a).
The quantity of N2 adsorbed at p /p 0 =0.99 by S5A6H3

Fig. 8 a Powder XRD pattern
and b SEM image of sample
S5A6H3
Intensity / a.u
10
20
30
40
50
60
70
80
2 / degree
150
3 -1
100
(iv)
50
(iii)
(ii)
(i)
0
0.0
0.2
0.4
0.6
0.8
1.0
b
0.014
-1
-1
dVol/dDia / cm g nm
sample is about 160 cm3 g1, which is greater than the volume
(120 cm3 g1) adsorbed by S5A6 sample (Fig. 6a) and significantly greater than the volume (40 cm3 g1) adsorbed by the
as-prepared S5 sample (Fig. 3a). Furthermore, the presence of
two kinds of pores is observed in BJH curves (Fig. 9b). Pores
of narrow size distribution around 4 nm are present on all
samples S5A2H3S5A24H3, similar to the acid-treated samples (Fig. 6b). Additionally, another pore with broad distribution around 510 nm has evolved. Initiation of the secondary
pore is clearly visible for S5A2H3 sample (Fig. 9b, curve i).
Formation of the secondary pore around 7 nm is clearly
observed for S5A6H3 sample (Fig. 9, curve ii). For the sample
S5A12H3, the secondary pore diameter decreases to 6 nm
with decreased pore volume (Fig. 9b, curve iii) and it decreases further for the S5A24H3 sample (Fig. 9b, curve iv).
Dual porosity is beneficial for electrode materials because the
pores allow the electrolytes to creep and tolerate volume
expansion/contraction during chargedischarge cycling.
Thus, both the time of acid treatment and heating influence
to the formation of dual porosity. The chemical analysis of
S5A6H3 sample (Table 3) indicates a decrease in H and C
content in relation to S5A6 sample. However, the Mn and Li
contents in the samples are nearly the same.
Electrochemistry results are presented in Fig. 10. Cyclic
voltammogram of S5A6H6 sample recorded at a sweep rate of
0.05 mV s1 indicates sharp reductionoxidation pair of peaks
in the potential region 2.803.20 V (Fig. 10a). In addition to
this pair of peaks, there is another pair of small broad peaks
appearing at 4.204.50 V region. This is perhaps due to the
presence of some quantity of LiMn2O4 phase in the sample.
The discharge profiles (Fig. 10b) of S5A6H3 sample provides
a minor potential plateau at about 4.0 V and a major constant
0.007
(ii)
(iii)
(iv)
(i)
0.000
10
12
14
16
18
20
Pore diameter / nm
Fig. 9 a Nitrogen adsorption/desorption isotherm and b BJH curves of

samples S5A2H3 (i), S5A6H3 (ii), S5A12H3 (iii), and S5A24H3 (iv). In
a, curves (ii), (iii), and (iv) are, respectively, vertically shifted by 5, 10,
and 15 units of y-axis scale relative to the position of curve (i)
Current density / mA cm
-2
600
400
200
-200
-400
1.5
2.0
2.5
3.0
3.5
4.0
4.5
Potential / V vs Li/Li+
4.5
st
1 ch
nd
ch
Potential / V Vs Li/Li
4.0
3.5
3.0
2.5
2.0
2
1.5
0
50
100
dis
st
1 dis
200
250
nd
150
-1
300
100
90
-1
200
150
80
250
200
70
(i)
(iii)
150
60
100
(ii)
(iv)
50
50
0
0
10
11
40
Cycle number
100
30
20
50
10
0
10
15
20
25
30
Cycle number
35
40
45
50
Coulombic efficiency / %
300
250
c
Specific discharge capacity / mAh g-1
Fig. 10 a Cyclic voltammogram

of at a sweep rate of 0.05 mV s1,
b chargedischarge curves at a
specific current of 30 mA g1, and
c cycle-life data of sample
S5A6H3. Cycle-life data of
S5A2H3 (i), S5A6H3 (ii),
S5A12H3 (iii), and S5A24H3
(iv) samples for 20 cycles at a
specific current of 30 mA g1 are
shown as inset in c
sample provides about 150 mAh g1 at a specific discharge

current of 1.25 A g1. Further work is in progress on dualporosity lithium-rich electrochemically stable composites of
Li2MnO3.
-1
300
250
200
Acknowledgments The authors thank Renault Nissan Technology and

Business Centre India Pvt. Ltd. for financial support, and Dr. Subramani
and Dr. Arockia Vimal for helpful discussions. The authors also thank Dr.
C. Shivakumara for his help in analysis of XRD patterns.
150
100
28
57
84
249
112
381
753
518
1250
1121
50
References
0
5,0
5,0
5,0
5,0
5,0
5,0
5,0
5,0
5,0
Cycle number
Fig. 11 Rate capability of sample S5A6H6. Current density in milliampere per gram is indicated. For each current density, a fresh cell was used
potential plateau at 2.80 V, which are followed by a gradual

potential fall from 2.80 to 1.50 V. The major charge and
discharge plateaus observed in 2.803.00 V region agree with
the results reported by Yu and Yanagida [24] for acid-treated
and heated samples. The discharge capacity obtained from the
first cycle is about 240 mAh g1. However, there is a rapid
capacity decrease on repeated chargedischarge cycling
(Fig. 10c). Similar results are obtained from all heated samples
(Fig. 10c inset).
The results of rate capability study are presented in Fig. 11.
For each current density, a fresh cell was employed and it was
subjected to five chargedischarge cycles. At each current,
there is a decrease in capacity similar to the data presented in
Fig. 10c. There is a gradual capacity decrease by increasing
the specific current. It is interesting to observe that about
150 mAh g1 of initial capacity is delivered as a specific
current as high as 1.25 A g1. This high rate capacity is
attributed to the porous nature of the samples.
Conclusions
Lithium-rich manganese oxide (Li2MnO3) was prepared by
reverse microemulsion method employing P123 as a soft
template and studied as a positive electrode material. The asprepared sample possessed good crystalline structure with a
broadly distributed mesoporosity with poor electrochemical
activity. However, the sample gained surface area with narrowly distributed mesoporosity and also electrochemical activity after treating in 4 M H2SO4. A discharge capacity of
about 160 mAh g1 was obtained. When the acid-treated
sample was heated at 300 C, the resulting sample with a large
surface area and dual porosity provided a discharge capacity
of 240 mAh g1. The rate capability study suggested that the
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