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Electrochemical performanceof LiMn2O4 with varying thickness of

cathode sheet
To cite this article: S Priyono et al 2019 J. Phys.: Conf. Ser. 1191 012022

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International Symposium on Frontier of Applied Physics IOP Publishing
IOP Conf. Series: Journal of Physics: Conf. Series 1191 (2019) 012022 doi:10.1088/1742-6596/1191/1/012022

Electrochemical performanceof LiMn2O4 with varying thickness

of cathode sheet

S Priyono1, *, S Hardiyani2, N Syarif2, A Subhan1 and A Suhandi1

1
Research Center for Physics, Indonesian Institute of Sciences, Kawasan PUSPIPTEK
Gedung 442, Serpong, Indonesia 15314
2
Department of Chemistry, Faculty of Mathematics and Natural Sciences, University
of Sriwijaya, Jl. Palembang Prabumulih Km. 32 Kabupaten Ogah Ilir, Sumatera
Selatan, Indonesia 30662

*E-mail: slam013@lipi.go.id

Abstract. Lithium-ion batteries are widely used as portable electrical energy storage devices
because they have high energy densities and long life cycles. One of the cathode active
materials used in the manufacture of Lithium-ion batteries is LiMn2O4 because of its easy and
cheap manufacturing, has a long life cycle, high power applications, safe, and low toxicity of
manganese basic materials. In this research, LiMn2O4 as cathode sheet has been made by
doctor blade coating. This method was carried out by mixing LiMn2O4 with polyvinylidene
fluoride (PVDF), Super P, and dimethylacetamide (DMAC) with weight ratio of 82.5 : 10 :
7.5, respectively, to obtain a well dispersed slurry. Slurry was superimposed on aluminum foil
surface with various thickness of 200, 300 and 400 μm. Coin cell was assembled using
electrodes, separator, lithium metal and electrolytes in the glove box. The cell battery was
characterized by using cyclic voltammetry, charge discharge and electrochemical impedance
spectroscopy in order to know the effect of active material thickness to cell battery
performances. The results showed that active material with 400 μm in thickness had the best
electrochemical performance due to a narrow and sharp reduction-oxidation peak pair, small
polarization value of 0.0335 V as well as having charge and discharge capacities of 1.1249
mAh and 1.0914 mAh, respectively. Moreover, EIS result showed that 400 μm thickness of
active material had highest conductivity value of 5.3922 × 10-5 Scm-1.

1. Introduction
Batteries are device that change chemical energy into electrical energy via electrochemical processes.
There are two common types of batteries such as primary (non-rechargeable) batteryand secondary
battery (refill or rechargeable). The secondary battery allows a reversible electrochemical reactionin
which electrical energy can convert back to chemical energy [1]. Among the types of secondary
batteries, lithium ion batteries have received special attention because they have higher energy density,
high capacity, slow self-discharge rate, low weight, high voltage, high specific energy and no memory
effect [2, 3].
The lithium battery consists of four components: positive electrode (cathode), negative electrode
(anode), electrolyte and separator. Separator is a porous membrane that serves to prevent the contact
between the electrodes. The main function of the electrolyte is to facilitate the flow of Li ions to be
regular and stable [4]. The electrolyte used in the battery is a mixture of lithium salts and organic

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International Symposium on Frontier of Applied Physics IOP Publishing
IOP Conf. Series: Journal of Physics: Conf. Series 1191 (2019) 012022 doi:10.1088/1742-6596/1191/1/012022

solvents. The anode receives the Li-ion during the charging cycle and transmits to the cathode during
the lifecycle [5].
Lithium manganese oxide or LiMn2O4 is one of electrode materials that have good structural
stability during the charge-discharge process. LiMn2O4 has a spinel structure with three-dimensional
intercalation capability. This causes the cathode material to be inserted lithium ion in three directions.
Lithium batteries are ion-based batteries with lithium ions as LiMn2O4 spinel drives show a lack of
lifecycle resistance and irreversible loss of rapid capacity at elevated temperatures [6]. Lithium
Manganese Oxide (LiMn2O4) is widely used as a cathode material for rechargeable lithium batteries. It
is considered to have the potential for cathode material because of its abundant availability,
environmentally friendly and affordable price, easy to manufacture, high specific theory capacity of
110 mAh/g, electrical conductivity of about 10-5 S/cm and large voltage range of 3.5-4.5 volt [7].
Another research reveals that LiMn2O4 synthesized with using Mn3O4 nano-crystal gives larger
capacity than theoretical value 122.7 mAhg-1 at 1 C rate [8].
The main challenge in the future deal with battery is how we get the highest capacity but it remain
small in size [9].There are so many factors affecting the capacity of the battery including the type of
active material, the composition of the sheet and the thickness of active material involved in the
electrochemical process [10]. Therefore, The increament thickness of active ingredients on the
electrode per unit area is importent in order to increase the capacity of the battery . However, addition
of large amount a As a results, The optimization the amount of active material involved in the
electrochemical reaction is required.Furthermore, the variations in the thickness of active materials in
the manufacture of battery cells will be explained in this paper.

2. Experimental Methods
This research uses LiMn2O4 powder as an active material and it was synthesized from previous result
containing more than 90 % deserved phase. Slurry was prepared by mixing an active material, binder,
and conductive carbon in ratio 82 : 10 : 7 to produce a cathode sheet. Polyvinylidene fluoride (PVDF)
as a binder was solved in hot dimetylacetamide (DMAC) until homogeny, afterward acetylene black as
a conductive agent was added dropwise during mixing followed by adding LiMn2O4 powder as an
active materials to yield uniform slurry. The slurry was coated into aluminum foil with varying coating
thickness of 200, 300, and 400 m. The samples were represented by LMO 2, LMO 3 and LMO 4.
The sheet sample was cut into a circle with diameter of 16 mm and it was arranged with separator,
electrolyte, metal Li and dropped by LiPF6 in Ar filled glove box to develop a half cell. LiPF6 acts as
electrolyte and metallic Li as counter electrode. The electrochemical impedance spectroscopy (EIS)
test is performed at a frequency of 0.120 kHz. The cyclic voltammetry (CV) test was performed at a
voltage range of 2.7  4.5 V with a scan rate of 160 mV/s while the charge-discharge (CD) was
performed at a voltage of 3.04.6 V with a speed of 0.1 C.

3. Results and Discussion

The chart of cyclic voltammetry (CV) indicates oxidation and reduction reactions. The presence of
some oxidation reduction buttons indicating a reversible reaction of a rechargeable sample that can be
used to make a secondary battery. These oxidation and reduction pairs occur in the present manganese
having oxidation numbers of +3 and +4 [12]. Each oxidation reduction reaction has two oxidation
peaks and two reduction peaks. The oxidation reaction is indicated at the upward-facing peak while the
reduction reaction at the top facing downward.
Figure 1 shows that all LMO samples had good electrochemical performance which was indicated
by the presence of two oxidation peaks and two reduction peaks formed. However, the LMO 4 sample
shows a narrower and sharper oxidation reduction counterpart than the LMO 2 and LMO 3 samples.
Therefore, the LMO 4 samples revealed rapid electrochemical reactions and caused the
intercalation/de-intercalation process of lithium ions to take place at a faster rate. Peak on the LMO 4
sample showed a higher peak thus having a larger capacity than other samples. This is due to the
amount of active material used is more. The results indicated that the more active material, the greater

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International Symposium on Frontier of Applied Physics IOP Publishing
IOP Conf. Series: Journal of Physics: Conf. Series 1191 (2019) 012022 doi:10.1088/1742-6596/1191/1/012022

of the current response because more mass of active materials involved in the oxidation reduction
process.

De-intercalation

Intercalation

Figure 1. Cyclic voltamogram of LiMn2O4 with different thickness

According to table 1, the results showed that the LMO 4 sample has the greatest polarization
voltage and the LMO 2 sample has the lowest polarization voltage. However, the large polarization
voltage has detrimental effect because decrease the battery performance. This is because the thicker
the layer of the active material, the greater the polarization voltage. There is a correlation between
longer diffusion and migration paths for lithium ions with the ohmic and mass transport because all
material as site for electron transport has inner resistivity. The thicker of electrode has more resistivity.
The longer cable the more energy we use to move electron in the cable, thus ohmic polarization will be
greater.
Figure 2 shows charge discharge patterns from LiMn2O4 with different thickness and all samples
were charged-discharged from voltage 3 V to 4.6 V. Each samples show two plateaus with voltage 3.9
V and 4.2 V indicating the working voltage of LiMn2O4. The charge discharge pattern of LiMn2O4
presented stair-like curve indicating transition of Mn3+/Mn4+ [13]. The results also showed that the
thicker of electrode, the higher of capacity because more active material contained in the sheet.
Sample LMO 2 and LMO 3 exhibit a capacity of about 0.5 mAh and it effect stable curves until 6
cycles. However, sample LMO 4 has higher capacity of about 1 mAh, however,it generate unstable
curve in cycle 6.
Electrodes of excellent EIS test results on the graph will form a semi-circle pattern (semi-circle)
and a straight line. The semi-circle on the EIS relates to the magnitude of the electron resistance (Re)
and the charge transfer (Rct) resistance. According to figure 3, it showed that the electrical conductivity
of the samples are sufficient because all samples showed a semicircle and slightly diffuses lithium ions.
The LMO 4 sample has the best electrical conductivity because it forms the smallest semicircle. It
revealed that the high amount of active materialcaused improving the electrical conductivity.

Table 1. Peak parameters of Cyclic Voltammetry test in LMO samples.

Vok1 Vok2 Vre1 Vre2 Vpol1 Vpol2 Ip1 Ip2 P1 P2
No Sample
(V) (V) (V) (V) (V) (V) (mA) (mA) (vmA) (vmA)
1 LMO 2 4.09 4.2 3.94 4.09 0.15 0.11 0.1756 0.1853 0.7182 0.77826
2 LMO 3 4.09 4.21 3.94 4.08 0.15 0.13 0.1656 0.1838 0.6773 0.7738
3 LMO 4 4.11 4.21 - 4.08 0.18 0.13 0.3674 0.3917 1.5100 1.6491

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International Symposium on Frontier of Applied Physics IOP Publishing
IOP Conf. Series: Journal of Physics: Conf. Series 1191 (2019) 012022 doi:10.1088/1742-6596/1191/1/012022

Figure 2. Charge-discharge chart of LiMn2O4

with different thickness (a) LMO 2, (b) LMO 3,
and (c) LMO 4.

Figure 3. Electrochemical impedance spectra (EIS) of

LiMn2O4 with different thickness.

Straight line indicates lithium ion diffusion or lithium intercalation and de-intercalation process.
The presence of a straight line indicates the lithium ions can move easily from cathode through
electrolyte and couple with electrons on anode. A more upright straight line signifies a faster diffusion
process. The conductivity value can be known by the following equation:
t
  (1)
Rct  A
Rct is a charge-transfer resistance, t is the sample thickness and A is the surface area of ​ ​ the
electrode.

Table 2. Electrochemical parameters calculated from EIS patterns

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International Symposium on Frontier of Applied Physics IOP Publishing
IOP Conf. Series: Journal of Physics: Conf. Series 1191 (2019) 012022 doi:10.1088/1742-6596/1191/1/012022

Thickness Re Rct Σ
No Sample
(mm) (ohm) (ohm) (S.cm-1)
1 LMO 2 0.06 11 172 1.6393 × 10-5
2 LMO 3 0.05 18 205 1.1211× 10-5
3 LMO 4 0.11 7 95 5.3922 × 10-5

According to table 2, it showed that the lowest conductivity value is identified in LMO 3 sample
with value of 1.1211 × 10-5 Scm-1 and the highest conductivity value is identified in LMO 4 sample
with value of 5.3922 × 10-5 Scm-1. The increament of thickness in active material will enhance
conductivity because of more carbon conductive contained in LMO 4 sheet.

4. Conclusions
LMO cathode sheets have been succesfully developed by mixing LiMn2O4, PVDF and Super P active
material with 82.5 %: 10 %: 7.5 % weight ratio and prepared with various thickness of 200 μm, 300
μm, and 400 μm. The LMO sample with a thickness of 400 μm had the best electrochemical
performance.According CV (Cyclic Voltammetry) test, it revealed that the LMO 4 sample had a high,
narrowand sharp peak oxidation reaction, therefore, LMO 4 had the best electrochemical performance.
According to CD test (Charge-Discharge), it revealed that the LMO 4 sample had the smallest
polarization voltage, henceLMO 4 had better battery performance than LMO 2 and LMO 3. According
EIS (electrochemical impedance spectroscopy) test, it showed that the LMO 4 sample had the best
conductivity eventhough having slow ion-lithium diffusion.

Acknowledgments
This research was supported by DIPA-research center for physics and partially co-funded by INSINAS
grant (No. 057/P/RPL-LIPI/INSINAS-1/III/2018) Ministry of Research Technology and Higher
Education of the Republic of Indonesia (Kemenristek-Dikti).

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