Beruflich Dokumente
Kultur Dokumente
DOI 10.1007/s10008-013-2221-1
ORIGINAL PAPER
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
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
Experimental
High purity or analytical grade chemicals, namely lithium
nitrate (Aldrich), manganese nitrate tetrahydrate (Aldrich),
b ()
c ()
()
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)
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
Sample
40
Conditions of preparation
Quantity of N2 adsorbed / cm g
-1
S4
S5
S6
S8
S5A2
(iv)
20
(iii)
(ii)
(i)
0
0.0
0.3
0.6
0.9
o
0.0006
-1
dVol/dDia / cm g nm
-1
0.0003
(iv)
(iii)
(ii)
(i)
Microemulsion400 C heating
Microemulsion500 C heating
Microemulsion600 C heating
Microemulsion800 C heating
Microemulsion500 C heating
2 h acid treatment
S5A6
Microemulsion500 C heating
6 h acid treatment
S5A12
Microemulsion500 C heating
12 h acid treatment
S5A24
Microemulsion500 C heating
24 h acid treatment
S5A2H3 Microemulsion500 C heating
2 h acid treatment3 h heating
at 300 C
S5A6H3 Microemulsion500 C heating
6 h acid treatment3 h heating
at 300 C
S5A12H3 Microemulsion500 C heating
12 h acid treatment3 h
heating at 300 C
S5A24H3 Microemulsion500 C heating
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
61
3.6 and 7
44
42
3.7
0.0000
30
60
90
120
150
Pore diameter / nm
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
-1
120
-1
100
(ii)
(i)
80
(iii)
60
40
(iv)
20
0
10
11
Cycle number
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
a
120
Quantity of N2 adsorbed / cm g
-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
a
-100
-2
-50
Current / mA cm
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
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
Intensity / a.u
10
20
30
40
50
60
70
80
2 / degree
150
Quantity of N2 adsorbed / cm g
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
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
Specific discharge capacity / mAh g
c
Specific discharge capacity / mAh g-1
-1
300
250
200
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
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