Jurnal Penelitian Fisika dan Aplikasinya (JPFA) Volume 8, Issue 2, December 2018

p-ISSN: 2087-9946 DOI: 10.26740/jpfa.v8n2.p84-90

e-ISSN: 2477-1775 https://journal.unesa.ac.id/index.php/jpfa

Research Article

The Effect of Temperature Variation on Conductivity Value of Cathode Lithium Ferro

Phosphate Carbon Composite

Metatia Intan Mauliana 1,a and Mochamad Zainuri 2,b

1
Informatics Engineering Departement, Faculty of Engineering, Universitas Muhammadiyah Sidoarjo
Jalan Mojopahit, Celep, Kecamatan Sidoarjo, Kabupaten Sidoarjo, Jawa Timur 61271, Indonesia
2
Physics Departement, Faculty of Mathematics and Natural Sciences, Institut Teknologi Sepuluh Nopember
Keputih Sukolilo Surabaya, Jawa Timur 60111, Indonesia

e-mail: a [email protected] and b [email protected]

Abstract
The lithium ferrous phosphate carbon composite (LFP/C) cathode material has been successfully
synthesized using solid-state reaction method by utilizing one of the natural sources of iron rocks in Tanah
Laut, Kalimantan, as the base material of Fe. Solid-state reaction method was done by using high energy
ball milling tool. The LFP cathode material was prepared using a base material (Li 2CO3), Fe3O4, and
(NH4)2HPO4 in a ratio of 3:6:2 and 5% wt. of Citric acid as a carbon source. There were some variations
of calcination temperature used under inert conditions at 400 °C, 500 °C, 600 °C, and 700 °C to determine
the effect on the phase structure and electrical conductivity produced by LFP/C cathode composites.
Characterization of phase structure was done by using X-ray powder diffraction (XRD), while the
conductivity value of the sample was tested using Electrochemical Impedance Spectroscopy (EIS). The
analysis of the diffraction pattern shows the largest composition of olivine structure formed at 700 °C at
93.3% wt. with Fe2O3 impurities of 6.7% wt. The highest conductivity value of LFP/C is shown by
sampling with 500 °C calcination temperature with a total conductivity value of 5.676 x 10-3 S.cm-1.
Keywords: iron rock, Cathode, solid-state reaction, LFP/C

Pengaruh Variasi Temperatur Terhadap Nilai Konduktivitas Katoda Lithium Ferro Phosphat
Carbon Composite

Abstrak
Material katoda lithium ferro phospat carbon composite (LFP/C) telah berhasil disintesis menggunakan
metode solid-state reaction dengan memanfaatkan salah satu sumber alam batuan besi Tanah Laut
Kalimantan sebagai sumber bahan dasar Fe. Metode solid state reaction dilakukan dengan menggunakan
alat high energy ball milling. Material katoda LFP dibuat dengan menggunakan bahan dasar (Li2CO3),
Fe3O4, dan (NH4)2HPO4 dengan perbandingan 3:6:2 serta ditambahkan asam sitrat 5%wt sebagai
sumber karbon. Pada penelitian ini digunakan variasi temperatur kalsinasi pada 400°C, 500°C, 600°C,
dan 700°C dalam kondisi inert untuk mengetahui pengaruh pada struktur fasa yang terbentuk dan
konduktivitas listrik, yang dihasilkan komposit katoda LFP/C. Karakterisasi struktur fasa yang terbentuk
dilakukan dengan menggunakan X-ray powder diffraction (XRD), sedangkan untuk mengetahui nilai
konduktivitas yang dihasilkan sampel dilakukan pengujian Electrochemical Impedance Spectroscopy

84
 Jurnal Penelitian Fisika dan Aplikasinya (JPFA), 2018; 8(2): 84-90

(EIS). Analisis pola difraksi sampel menunjukkan pada temperatur 700°C komposisi terbesar LFP
dengan struktur olivine terbentuk sebesar 93.3 %wt dengan impuritas berupa Fe2O3 sebesar 6.7 %wt.
Nilai konduktivitas LFP/C paling tinggi ditunjukkan oleh sampel dengan temperatur kalsinasi 500°C
dengan nilai konduktivitas total sebesar 5.676 10-3 S.cm-1.
Kata Kunci: Batu besi, katoda, solid-state reaction, LFP/C

PACS: 81.40.Rs, 81.10.-h, 81.10.Jt, 61.72.U-, 81.40.-z

© 2018 Jurnal Penelitian Fisika dan Aplikasinya (JPFA). This work is licensed under CC BY-NC 4.0
Article History: Received: March 14, 2018 Approved with major revision: July 3, 2018
Accepted: December 8, 2018 Published: December 31, 2018
How to cite: Mauliana MI and Zainuri M. The Effect of Temperature Variation on Conductivity Value of Cathode
Lithium Ferro Phosphate Carbon Composite. Jurnal Penelitian Fisika dan Aplikasinya (JPFA). 2018; 8(2): 84-90.
DOI: https://doi.org/10.26740/jpfa.v8n2.p84-90.

I. INTRODUCTION coating with conductive material to improve

The vast development of technology value of electronic conductivity [1, 2, 3]; (2)
and electronic devices, such as laptops and increase the Li-ion diffusion rate used doping
other portable communication devices, even with guest ions [4-6]; and (3) shorten the
electric-based vehicles, is currently being diffusion distance of Li-ion bulk by
intensively developed in developing countries, minimizing particle size [7-9].
including Indonesia. The trend has led to the A large number of studies have shown
need for more efficient, environmentally- that LFP/C cathode materials having high
friendly, high-capacity, economical, and porous/mesoporous and conductive structures
energy-efficient energy storage devices, can effectively strengthen the electrochemical
which are primarily derived from readily performance of battery during high
available raw materials. One type of efficient charge/discharge. Li and Kang [10] reported
battery is a secondary battery. Among the that LFP/C 3D network structures of multi-
types of secondary batteries on the market, the walled carbon nanotubes and such structures
most prominent is the Li-ion battery type. The are believed to have better electronic
LiFePO4 has been attractive because of good conductivity and discharge capacity [11].
cycle stability, high theoretical charging Some researchers employ polymers as the
capacity, environmentally friendly, and templates to create porous LFP/C with a pore
excellent thermal stability. However, the size of 4-50 nm, indicating the capacity of
LiFePO4 is generally have much lower discharge rates and excellent cycle stability
charge/discharge capacity than the theoretical [12]. However, the materials cannot withstand
value, especially at high current rates. low and high temperatures. The release rate
Moreover, it has two major disadvantages, with a specific capacity decreased to 60 mAh
namely slow diffusion of lithium ions and g-1 at 14.7 0C. Furthermore, a new porous
poor electronic conductivity. The numerous LFP/C microsphere has been developed by
researches have been carried out to develop Sun and Rajasekhara [13] using a new hot
both synthesis processes and modification solvent and the composite, and it has high tap
methods to improve the performance of density and exhibits excellent levels of ability,
LiFePO4 electrode. The most commonly used linking open 3D porous microstructure. In
strategies to improve the electrochemical addition, the increasing energy density of
performance of the battery are: (1) surface LIBs has been a major focus of recent

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researches. A lot of scientists are developing the iron sand was washed with N-butanol to
and improving cathode materials for example keep the surface clean of organic impurities.
with higher nickel contents and anode Fe element content is confirmed using X-ray
materials with silicon or tin composites for Fluorescence (XRF), and its oxide phase was
high voltage and high energy. Lithium-ion identified using X-Ray Diffraction (XRD).
batteries structured nanotechnology porous The LFP/C composite was made by a solid-
electrode materials have been the key to high- state method using high energy ball milling
performance rechargeable lithium batteries with a base material composition according to
due to their sustained advantages in fast the stoichiometry having 3:6:2 ratio for
charge/discharge rate [14]. Concurrently, Li2CO3, (NH4) 2HPO4, Fe3O4, and citric acid
reducing LIB production cost without as carbon source. The weight of carbon source
sacrificing cell performance is another focus is 5% wt. of the total composite raw material;
especially for further implementation, such as the material was milled for 4 hours with a ball-
electrical vehicles [15]. to-powder ratio in ethanol set at 5:1 and at the
LFP/C is synthesized by many methods rotational speed of 300 rpm. Calcination
such as solid-state method, sol-gel, co- temperature based on temperature calcination
precipitation, microwave heating, and vary by 500 °C, 600 °C, and 700 °C with a 10-
hydrothermal method [16-19]. In this study, hour hold time [20]. To prevent oxidation,
the solid-state reaction method was employed composite preparation of LFP/C was
by using high energy ball milling. The solid- performed in the N2 environment. After the
state reaction has several advantages over process, the composite sample was observed
other methods, such as it has simple synthesis using XRD to identify the formed phase, and
process and it is easy to control the unsure the conductivity value of the sample was
concentration and suitable for mass tested using Electrochemical Impedance
production. Spectroscopy (EIS). The measurements of
Another significant difference that has been conductivity were carried out by certain
used in this study is the iron rock of Tanah Laut, procedures. The component must be in the
Kalimantan, which is used as a precursor source of form of a battery cell. The first step after
Fe. Most of the elemental precursors usually use obtaining an active sample of the material
standard pro-analytical materials. This is due to an done was to make a salary, which is a mixture
iron rock in Tanah Laut showed high Fe content, and of Polyvinylidene Fluoride (PVDF) added
according to XRD results, it has that natural iron with DMAC, acetylene black, and active
rock contains Fe3O4 magnetite. The Fe3O4 mineral material. The mixing of PVDF, DMAC, and
will have potentiality as the main source of Fe- acetylene black was performed using a
source material for cathodes. Therefore, researchers magnetic stirrer at a rate of 150 rpm, while the
tried to utilize Fe3O4 natural iron as a Fe source to active material was mixed using mortar. The
form LFP/C to avoid high costs of Fe sources. mixed material was pasted on the grid or
aluminum sheet and dried for 24 hours in the
II. RESEARCH METHOD oven and compacted after that. The ready
Initially, the iron rock taken from Tanah sample was inserted into the battery cell
Laut, Kalimantan, has been mechanically following with an anode (lithium metal),
reduced to iron sand and sifted with size 170 separator and electrolyte to test its
Mesh; the iron sand was separated by the conductivity used EIS.
permanent magnet to obtain sand with high
iron content. After the magnetic separation,

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III. RESULTS AND DISCUSSION

The diffraction pattern of four samples
shows the qualitative and quantitative
differences. The increasing of calcination
temperature will increase the olivine phase
and reduce the impurity phase. At the
temperature of calcination 700 °C, the olivine
phase amount reached 93% with slight
hematite as impurities, while it is compared to
a lower calcination at temperature 600 °C, the
olivine ratio with impurities became 69% to
31%. The diffraction peak in the XRD pattern
revealed higher impurities in the sample that Figure 1. The XRD pattern of LFP/C composites
was in at calcination temperatures of 400 °C by solid-state reaction methods at 400°C, 500°C,
and 500 °C. The hematite phase appeared 600°C, and 700°C
along metastable phase of monoclinic
LiFeP2O7 at 400 °C. When the temperature The measurement of sample impedance
reached 500°C, the monoclinic LiFeP 2O7 values which has been given the variation of
phase vanished but hematite remained, but the calcination temperature was conducted by
hematite phase completely was removed at using Electrochemical Impedance
600°C. The peak of LiFePO4 was obtained at Spectroscopy (EIS). The EIS measurement
the temperature of 700 °C (ICDD no. 04-016- employs small AC signal of 20 mV and a DC
0416) with slightly impurities of hematite [20]. bias voltage of more than 3V in order to
The residual carbon in the LFP/C composite produce a curve that can form semi-circular
was amorphous because of carbon composite; arc patterns [3,21]. The frequency range used
apparently, it has no influence on the was at 0.1 Hz-10 KHz. The cole-cole curves
crystalline of the composite material. of EIS testing of the four samples can be seen
in Figure 2.

10000
9000
8000
7000
Z'' (Ohm)

6000
5000
4000
3000
2000
1000
0
0 10000 20000 30000 40000
Z' (Ohm)
LFP/C 400 LFP/C 500 LFP/C 600 LFP/C 700

Figure 2. Total impedance value curve of LFP/C composite material at various calcination temperature
(400 °C, 500°C, 600°C and 700°C)

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Table 1. The conductivity value of LFP / C composite material at various calcination temperature
Temperatures of Total resistivity Total Permittivity Total Conductivity
LFP/C (Ω) (Ω) (10-6 S/cm)
400oC 9483 334954 155.57
o
500 C 322 11388 5676.53
o
600 C 2568 90706 781.34
o
700 C 41758 1474921 33.50

Based on Figure 2, it shows that for samples the material with the best capacitive properties
at each temperature variation form a single is the sample with a 500 °C calcination
semicircle curve. The four samples have temperature. Capacitive properties are related
different semicircle diameters. The magnitude to the ability of materials to store Li ions in
of the semicircle diameter of the graph shows their structure. Furthermore, the conductivity
the impedance value, the larger the diameter value is shown in Table 2. Based on the table,
the higher the impedance value and the it is known that the sample with the largest
reverse. The highest impedance value is from conductivity value is shown by the sample at
the sample of 700 °C, while the lowest the temperature of 500 °C with a conductivity
impedance value is from the sample of 500 °C. value of 5.676 x 10-3 S.cm-1. This value is
The value of the impedance value can higher than the LFP material without carbon
affect the value of the conductivity of the which has low conductivity value (10-9 S.cm-
materials; the higher the impedance value, the 1) [3, 4, 6]. In the table, there is a tendency to
smaller the conductivity of the materials. decreasing conductivity value along with the
From the graph, it can be interpreted that the increase of calcination temperature. The
sample with the highest conductivity value is findings of this study have significant
from the sample of 500°C as it has the least implications in the field of material physics.
impedance value compared to other samples. The success of the synthesis of LFP/C by
Despite the fact that at the temperature of using raw material as a source of Fe will
700 °C also reaches highest purity, but it has a certainly be one of the beneficial alternatives
lower conductivity value compared to the to start utilizing natural resources in Indonesia.
sample 500 °C because at higher temperatures, Based on the results, further research is
there will be grain growth in LFP materials. expected to develop further in relation with
Therefore, coatings will usually be carried out the use of other natural resources, for example,
using carbon as in addition to increase the the raw material used as a carbon source,
conductivity, and carbon can also prevent or which is known that carbon has a significant
minimize the grain growth. But as the influence on the level of material conductivity.
temperature is increased, there will be a lot of
carbon that will oxidize to form CO2, so less IV. CONCLUSION
carbon is available to cover the LFP which in Lithium Ferro Phosphate Carbon
turn leads to decrease the conductivity. Composite (LFP/C) has been successfully
In addition, based on the peak height of made using solid-state reaction methods by
the semicircle curve, the capacitive properties utilizing one of the natural sources of iron
of each sample can be identified. The higher rocks of Tanah Laut, Kalimantan, as the base
the peak of the semicircle curve, the lower the material of Fe in inert condition. Based on the
capacitive properties it possesses (1/jωC). research, temperature variations influence the
Therefore, from the above cole-cole curves, formation of LFP/C crystallization but do not

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have a significant effect on the conductivity 02.

[9-10]. The conductivity level of LFP/C tends [5] Ruan YL. Effect of Doping Ions on
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ACKNOWLEDGMENT https://dx.doi.org/10.4028/www.scientific.ne
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supervisor of Department of Physics, Faculty [6] Zhang DY, Zhang L, Zhang PX, Lin MC,
of Mathematics and Natural Science, Institut Huang XQ, Ren XZ, and Xu QM.
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