Applied Mechanics and Materials Vol.

377 (2013) pp 141-145

Online available since 2013/Aug/30 at www.scientific.net
© (2013) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMM.377.141

Optimal Charge and Discharge Capacity Effects of the Sintering Process

on LiMn2O4 by the Solid-state Reaction Method

Yenchun Liu1, a, Maochieh Chi2,b and Mingcheng Liu 3

1,2,3
WuFeng University, 117, Sec 2, Chiankuo Road, Minhsiung, Chiayi County 62153, Taiwan
a
blliu@wfu.edu.tw, bjackchi@wfu.edu.tw

Keywords: sintering, spinel, solid-state reaction.

Abstract. This study investigates the optimal charge and discharge capacity of the sintering process
on the lithium battery spinel - LiMn2O4. Both Li2CO3 and Mn3O4 are utilized to synthesize the
cathode material LiMn2O4 using the solid-state reaction. Cathode materials are processed to fabricate
batteries at temperatures ranging from 800℃ to 900℃. Test results reveal that the highest initial
discharge capacity of 105.19 mAhg-1 (theoretically at 148 mAhg-1) has been obtained at the
temperature of 850℃ in the sintering process for synthesis of LiMn2O4. In addition, the initial
discharge capacity can be increased to 140.51 mAhg-1 with both overdosing the amount of lithium by
2% and increasing the range of operating voltage. The increasing of the charge voltage ranges from
4.5V to 4.8V and reducing of the discharge voltage ranges from 3.0V to 2.8V.

1. Introduction
Lithium battery technology is developing rapid, and is applied mainly for 3C products due to their
requirements of light weight and small dimension, so demand is rising rapidly. Lithium-ion secondary
batteries have the advantages of high energy density, high operating voltage and good cycling
stability. Thus, the lithium battery has generally replaced traditional nickel-cadmium and nickel metal
hydride batteries and is attracting much research. The cathode material synthesis is divided into two
types: the high temperature method and the low-temperature one. Since the starting material of the
high-temperature method is normally a solid, it is also known as the high-temperature solid-state
method. The low-temperature method is subdivided into precipitation, hydrothermal method and
sol-gel methods. The cost of high temperature production is lower and it is generally used in mass
industrial production. The cost of low temperature method fabrication is high and it is usually used in
the manufacture of high value-added, high purity or research and development processes. Lithium-ion
materials with high energy density, stable operating voltage and other advantages have been referred
to as "the most promising chemical power” [1]. Based on their structure, lithium-ion cathode
materials can be divided into the layer structure (LiCoO2 and LiNiO2), the spinel structure (LiMn2O4)
and the olivine structure (LiFePO4) [2]. Different materials have different lattice structure and
properties, which make their electrochemical properties different.
Currently, LiCoO2 is the most popular and easily synthesized material on the market [3,4].
However, it contains cobalt and has other problems, such as high cost, relatively limited availability
and environmental issues. One of the solutions is progressively using LiNiO2 and LiMn2O4 as lithium
ion cathode materials, although synthesizing LiNiO2 is difficult and the cycling life of LiNiO2 is short.
LiMn2O4 is the least toxic and cheapest of these materials, and it is much safer of it is overcharged [5].
But the Jahn-Teller effect on Mn2O4 will cause reducing capacity more quickly [6-8]. Doping with a
transition metal to replace part of the manganese and reducing the ion level of spinel will improve the
stability of the electrode during the life cycle. Meanwhile, reducing the capacity reduction is the focus
of recent research [9.10]. In lithium-ion materials, LiCoO2 belongs to the layer type with rock salt
structure. Theoretically its capacity can reach as high as 273.8 mAh/g, but if the X-values of the layer
structure LixCoO2 are lower than 5, the main structure will collapse due to lack of lithium ions to
support it. Only about half of the Li ions conducting reversible embedded in and out, and the actual
capacity is about 130~150 mAhg-1 [11]. Adding aluminum, nickel, manganese and other elements can

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142 Advances on Materials Engineering

increase the LiCoO2 capacity and improve cycling performance [12-15]. The capacity of LiMn2O4 is
affected by various lithium-ion battery materials, such as the dissolution of Mn in LiMn2O4, of which
main impact on LiMn2O4 is the reversible capacity. Electrolyte (LiPF6) will react with water
molecules and dissolved Mn. The trivalent and tetravalent conversion of Mn ions will then produce
the Jahn-Teller effect. At the same time, the solvent molecules on the anode surface will form a
passive film because of charge attraction. Overcharging will cause the electrolyte reduction and
battery self-discharge, resulting in reduced capacity [15,16]. Wakihara proposed an improved method
using nickel or chromium ions to replace the manganic ion in LiMn2O4 and increase the
electrochemical stability [17,18].
The solid-state reaction method is a traditional method with simple equipment requirement and
low cost, by which it is easy to achieve the large quantity and good qualify when synthesizing
LiNixMn2-xO4 as a cathode material [19-20]. The solid-state reaction method can prevent the
non-homogeneous sediment caused by high-temperature high-pressure reaction, thus reducing the
uniformity and impurity problems caused by the solution combustion method. This study synthesizes
LiMn2O4 powder by using different temperatures to synthesize LiNixMn2-xO4 by doping with nickel as
transition metal. The two three main purposes were to explore the nickel effect on the electronic and
chemical-electronic characteristics of the lithium-ion battery, and to obtain the optimum preparation
conditions and parameters for high capacity, and to improve the cycle performance of battery
material.

2. Experimental Procedures
2.1 Starting Materials and Measuring Tools. Lithium carbonate (Li2CO3), manganese tetraoxide
(Mn3O4), 1-methyl-2-pyrrolidone (NMP), polyvinylidene difluoride (PVDF) and other reagents were
used for synthesis, all of which were G.R. grade chemicals. An X-ray powder diffractometer (XRD)
with Cu Kα radiation (Rigaku D/Max-Ⅱ) was used to identify the crystalline phase of the LiMn2O4.
Particle morphological features were imaged by scanning electron microscope (SEM, JEOL JEM
200CX) with an accelerating voltage of 15kV. A battery automation test system ( Acc. Tech. System
Co., BAT-750 series) was used to test the charge capacity.
2.2 Experimental Procedures. This study synthesized LiMn2O4 with both Li2CO3 and Mn3O4
using a solid-state reaction method. In previous report [21], when the temperature is lower than 400
o
C, MnO2 will be generated and the Li-Mn-O composition will be located between Li2Mn4O9 and
Li4Mn5O12.In this study, the cathode material LiMn2O4 was synthesized at the temperature range of
800~900 ℃, and XRD and SEM were used to analyses its structure and observe the surface
morphology. Finally, a battery charging-discharging test was conducted to examine its charge and
discharge characteristics. In addition, at the optimal synthesis temperature, overdosing the amount of
lithium and increasing the range of operating voltage were used to test the capacity of LiMn2O4.
Based on different synthesis temperatures LiMn2O4 is milled, mixed with oxygen-rich atmosphere
and sintered. Finally, XRD and SEM were performed to analyses its structure and discuss its
charging-discharging characteristics based on different Ni doping concentration. Both Li2CO3 and
Mn3O4 were first mixed, and the mixtures were added then supplemented with acetone and zirconia
balls and placed in a planetary ball milling machine to mix completely for 2 hours. After mixing, the
mixtures were takenout, dried, and then placed in a high-temperature furnace with the temperature
increased to 900℃ at a speed of 5 ℃min-1. The sintering process lasted for 8 hours, followed cooling
down with the core temperature cooling. In order to obtain a finer powder of LiMn2O4, acetone and
zirconia ball, were added and milled for 1 hour. This was removed, dried, and screened with a 200
mesh, to yield LiMn2O4 powder. The synthesized LiMn2O4 was pressed into the battery and for the
charging and discharging test. For this the charge voltage was increased to 4.8V, and discharge
voltage decreased to 2.8V.
 Applied Mechanics and Materials Vol. 377 143

Scale 80% weight of LiMn2O4 and 10% of black carbon, placed into a ball milling machine and
milled for 2 hrs has until they were fully mixed. Them PVDF 10 %, was added and mixed with methyl
pyrrolidone they are completely dissolved. The mixture was placed in a ball milling machine for 2 hrs,
the uniform plasma was placed on aluminum foil, and a scraping cutter was uses to make a uniform
coating on aluminum foil. Using 120 ℃ temperature to remove residual solvent and rolling to adjust
the appropriate thickness, the aluminum foil was repeatedly rolled 4~6 times to obtain a final
thickness of about 0.5~0.3 mm. This was them cut to a diameter of 1.3cm as a circular anode plate, the
actual active substance weight was obtained, and it was placed into a glove box for balancing for at
least 12 hours and assembled them into a button-type battery. The finished button-type battery was
connected to 8 channel charging-discharging testing device for the battery charge and discharge test.
The first stage was to charge the battery at a constant current (C/20), until the voltage reached 4.5V.
The second stage was continuing charging until the current was less than 0.01mA using a constant
voltage 4.5V. When either using constant current charging or constant voltage charging is reached,
the battery is in fully charged state. The third stage is to discharge at constant current (C/20) until the
voltage has dropped to 3V.

3. Results and Discussion

3.1 XRD Pattern of the LiMn 2 O 4 Powder. The XRD patterns of LiMn2O4 at different temperatures
ranging from 800℃ to 900 ℃ are shown in Fig. 1. It can be seen that the peaks appear at diffraction
angle degrees of 18.6°, 36.2°, 37.9°, 44.0°, 48.2°, 58.2° and 64.1°, which are the same as the standard
of LiMn2O4 peaks. This indicates that the product is a single LiMn2O4 spinel structure, with no
impurity phase observed. However, Paulsen’s research mentioned that at low temperatures the
products would be the second phase of MnO2 and at high temperatures they would be the second
phase of Mn2O3, Mn3O4 and MnO, while the stable phase of LiMn2O4 was located at temperatures
ranging from 400 oC to 880oC. When the temperature is lower than 400 oC, MnO2 will be generated
and the Li-Mn-O composition will be located between Li2Mn4O9 and Li4Mn5O12 [21].
3.2 SEM Micro-structure of LiMn 2 O 4 . The SEM surface morphologies are shown in Figs. 2,
indicating that little difference was observed on LiMn2O4 with various sintering temperatures. All of
the powder particles are uniform and their diameters are approximately 2~3 µm when the sintering
temperatures are around 800oC to 900oC. This indicates that the temperature increase did not change
the particle sizes of LiMn2O4. The particles were generally spherical in the shape. However it can be
supposed that the size distribution for all samples is rather wide.
(111)

(400)
(311)

(440)
(511)
(331)
(222)

(531)

o
900 C
Intensity(a.u.)

o
875 C

o
850 C
o
825 C
o
800 C

LiMn2O4

20 40 60 80
2-Theta

Fig. 1 XRD patterns of the LiMn2O4 at different Fig. 2 SEM morphology of LiMn 2 O 4 powder
temperatures (800~900 ℃.) taken at 800℃for 8 hrs
3.3 Optimal Temperature of the Sintering Process for LiMn2O4. For the battery, LiMn2O4
powder produced at different temperatures was placed into a chamber with a constant temperature of
25 ℃ by control system. The charge and discharge current of 0.1C and cut-off voltages of 4.2 and 3.0,
5.2 and 3.3V were set to conduct continuous charge and discharge experiments and record the data of
144 Advances on Materials Engineering

voltage difference with the time. The initial charge and discharge capacity relating to cutoff voltage
on LiMn2O4 at different temperatures is shown in Figs. 3 and 4. It can be seen that the LiMn2O4 has a
higher discharge capacity of 105.19 mAhg-1 (theoretical 148 mAhg-1) when sintered at the
temperature of 850 ℃. The temperatures of 800 ℃ and 900℃ are both unable to obtain a high
capacity. The temperature of LiMn2O4 sintered at 800 ℃ does not have enough crystallinity, While
the temperature of 900 ℃ may cause the loss of the lithium ions and be in effective for enhancing the
capacity. Further, the rise of initial discharge capacity lasted at the sintering temperature of 850 ℃ and
then began to drop.

4.6 o o
800 C 825 C
o o 140
4.4
850 C 875 C
o
900 C
4.2 120

4.0

Capacity, mAh/g
Voltage, V

100
3.8

3.6
80
3.4

3.2 60

3.0 800 820 840 860 880 900

0 20 40 60 80 100 120 o
Sintering Temperature , C
Capacity, mAh/g

Fig. 3 Initial charge and discharge capacity of Fig. 4 Initial charge and discharge capacity
LiMn2O4 powder vs. voltage at different of LiMn2O4 powder at different
temperatures temperatures
3.4 Effect of Different Temperatures on LiMn 2 O 4. The initial discharge capacity relating to the
voltage at different temperatures is shown in Fig. 5. It can be seen that the increase of initial discharge
capacity is slow at the temperatures of 840 ℃, 850 ℃, and 860 ℃ because of the relaxation of the
operating voltage. The initial discharge capacity of cathode material Li1.02Mn2O4 is increased from
132.91 to 136.02, 137.67 to 140.52 and 130.20 to 133.24 mAh/g at the temperatures of 840 ℃, 850 ℃,
and 860 ℃, respectively.

o
5.4 840 C
o
850 C
5.1 o
860 C

4.8

4.5
Voltage, V

4.2

3.9

3.6

3.3

3.0
0 20 40 60 80 100 120 140
Capacity, mAh/g

Fig. 5 Initial discharge capacity of LiMn2O4 powder vs.

voltage at different temperatures

4. Conclusion
This study investigates the optimal charge and discharge capacity of LiMn2O4 by using a solid-state
reaction method at temperatures ranging from 800 oC to 900 oC. It is found that the pure LiMn2O4 has
the highest initial discharge capacity of 105 mAhg-1, at the temperature of 850 oC. In addition, both
lithium overdosing and increasing operating voltage have significant effect on the initial discharge
capacity at the temperature of 850 oC.
 Applied Mechanics and Materials Vol. 377 145

Acknowledgements
This work was supported by the professor C. H. Lin and the author gratefully acknowledges the
financially support of National Science Council of the Taiwan ( No. NSC100-2221-E-274-004).

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Advances on Materials Engineering
10.4028/www.scientific.net/AMM.377

Optimal Charge and Discharge Capacity Effects of the Sintering Process on LiMn2O4 by the Solid-
State Reaction Method
10.4028/www.scientific.net/AMM.377.141