Volume 7, Issue 12, December – 2022 International Journal of Innovative Science and Research Technology

ISSN No:-2456-2165

Synthesis and Characterization of LiFePO4/CNT

Composites with Variation of Calcination Time as
Battery Cathode
Gunawan, Eko Siswoyo, Faisal Aprialdi, Ngadiwiyana, Roni Adi Wijaya
Department of Chemistry, Faculty of Science and Mathematics, Diponegoro University
Semarang, Indonesia

Abstract:- Synthesis of LiFePO4/CNT composite with preparation of the LiFePO4 composite was carried out using the
various calcination times as a battery cathode material has sol-gel method and the addition of CNT was carried out using
been successfully carried out. LiFePO4 synthesis was the doctor's blade method and then calcined with various
obtained by the sol-gel method and the addition of CNT heating times. Furthermore, LiFePO4/CNT characterization
was carried out by the doctor blade method. The effect of was carried out using SEM-EDS and XRD and its conductivity
variations in calcination time and the addition of CNT to was measured to determine the maximum potential condition
the synthesis results were observed. Observations using of the material as a battery cathode.
SEM-EDS showed successful synthesis with a
homogeneous surface morphology with the appropriate II. EXPERIMENTAL
element content. The XRD results also showed standard-
compliant nano crystalline peaks with increasing A. Materials
crystallinity by addition of CNT and duration of The materials used in this study were copper sheet (MTI,
calcination. In addition, the conductivity also increased in Malaysia), LiOH p.a, FeCl3.5H2O p.a (Merck, Germany),
the presence of CNT and the longer the calcination time. distilled water, NH4OH p.a (Merck, Germany), H3PO4. CNT
This shows that the resulting LiFePO4/CNT has the powder prepared using the spray pyrolysis method as a result
potential as a battery cathode material. of previous studies[8] was used as an electrode material.
Ethanol (Merck, Germany), terpineol (Sigma Aldrich, USA),
Keywords:- LiFePO4/CNT, Calcination, Battery. ethylcellulose (Sigma Aldrich, USA), monoethanolamine
(Merck, Germany), and iso-propanol (Merck, Germany) were
I. INTRODUCTION used unrefined.

Batteries have been used for energy storage because they B. Synthesis of LiFePO4/CNT
have the principle of storing electricity to produce energy. The LiOH and Fe2O3 powders were mixed until
need for compact, high-energy, environmentally friendly, and homogeneous, and then the mixture was poured into H3PO4.
rechargeable batteries has been developed from lithium-ion The result is a gel powder heated by calcination at 400 ºC in
battery concept. Currently, LiFePO4 is studied extensively and argon gas for 5 hours. Ethylcellulose was dissolved in ethanol
is a good candidate for Li-ion battery cathode material, because (2% by mass) and stirred for 10 minutes, followed by mixing
of its high theoretical capacity (170 mAh/g), stability of with 1.6 g of terpineol to form the binder. CNT and LiFePO4
charging cycle, low cost, and environmental friendliness [1,2]. were dispersed into the binder with stirring for 10 minutes.
Then, the paste was deposited onto the Cu foil substrate using
However, the disadvantages remain that the low the doctor blade method and dried at calcination heating
electronic conductivity and low lithium ion diffusion rate temperature with different times of 2, 4, and 6 hours.
during the discharge process impair the performance of the
diffusion rate, and cause the storage capacity to decrease C. Characterization
rapidly. Important features responsible for the low-rate ability The surface structure of the electrode was characterized
are considered to be intrinsically poor electronic conductivity by X-ray diffraction spectroscopy (XRD, Philip Analytical X-
(10–9 S cm-1) and low Li+ ion diffusion due to its olivine crystal Ray BV) with Cu Kα radiation (λ = 1.5418 Å) at 40 kV,
structure significantly limiting its performance at high charge Scanning Electron Microscopy (SEM), EDS (Energy
and discharge rates [3–5]. Dispersive Spectroscopy), and a multimeter (SANWA-
multimeter) was carried out to study the conductivity.
To overcome this problem, many reports state that the
electrical performance of LiFePO4 can be improved by ion III. RESULT AND DISCUSSION
doping [6], particle size, cation doping, and modification of the
phase surface [7]. Carbon materials such as graphite, graphene, The results of Scanning Electron Microscopy (SEM) are
and carbon black have been studied as cathode electrodes to find out the morphology of pure LiFePO4 and
because of their corrosion resistance, and high conductivity. LiFePO4/CNTs as shown in figure 1. The surface area
Recently, carbon nanotubes (CNTs) have been of interest for morphology of pure LiFePO4 indicated that the material had
their increased conductivity, and high electron storage, which homogeneous particle sizes (Fig. 1a), further addition of CNT
influences fast charging characteristics [8]. In this study the (Fig. 1b) morphologically patched LiFePO4 material onto the

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Volume 7, Issue 12, December – 2022 International Journal of Innovative Science and Research Technology
ISSN No:-2456-2165
CNTs. However, the morphology of LiFePO4/CNT is not The crystal size of pure LiFePO4 is 101.6 nm and
limited, based on the composite material results. decreases when CNT is added. Then the decrease in crystal size
was directly proportional to the calcination time, the results at
2, 4, and 6 hours were 60.07; 34.74; and 15.93 nm, respectively.
The crystal sizes obtained are summarized in table 1. It is
known that the effect of addion of CNT and increasing the
calcination time decreases the crystal size.

Fig 1. SEM for pure LiFePO4 (a), LiFePO4/CNT (b).

Testing using EDS (Energy Dispersy Spectroscopy) is to

identify the composition of the sample. The EDS of pure
LiFePO4 as shown in Figure 2a is dominated by the elements
Li, Fe, P, and O with a composition of 41.01, 27.63, 18.41, and
12.68% respectively. Furthermore, the EDS yield of CNT-
doped LiFePO4 as a whole is dominated by carbon, namely
83.73% (figure 2b).

Fig 3. LiFePO4/CNT XRD results at various calcination times.

Conductivity measurements were measured on a battery

prototype with a voltage of 0.2 V used and tested using a
Fig 2. EDS for pure LiFePO4 (a), LiFePO4/CNT (b). multimeter to identify resistance (R). Conductivity can be
calculated by equation 2.
Figure 3 shows the adjusted diffraction pattern with
𝑡
reference to the powder Diffraction Standard program. The 𝜎= (2)
𝑅.𝐴
carbon type detected in the reference (JCPDS number 020-456)
seems to be dominated by the peak at 2θ from 26.29º - 26.39º.
It exhibits a type of carbon with (002) oriented hexagonal where t, R and A are the thickness, resistance and surface
structure of graphite. The diamond structure is dominated by a area of the electrode[8]
peak at 2θ from 43.44 º - 43.91º with reference number JCPDS
060 675 with orientation (111) [8]. The crystalline phase of Table 1 and Figure 4 show the relationship between
LiFePO4 is olivine. LiFePO4 material and its peaks were temperature variations during heating and conductivity. From
detected by JCPDS card no. 40-1499. The peak of LiFePO4 is Figure 4 it can be seen that increasing the linear conductivity
shown at 2θ slightly less than 30º and (211) and (020) reflection value of LiFePO4 doped with CNT is the highest conductivity
of FePO4 is shown at 2θ slightly greater than 30o. This peak can value. Therefore, a longer time for the heat of calcination will
be used to distinguish these two phases and the fractions of the have an impact on increasing conductivity of CNT-doped
different phases present in a multiphase mixture (311) LiFePO4 [10–12]. The addition of CNT in LiFePO4 makes the
reflection phase LiFePO4 (35.6o) phase FePO4, reflection (121) crystal size smaller because during the calcination process the
phase LiFePO4 (36.5o) indicates FePO4 phase (36.7o). The peak decrease in LiFePO4 crystals is affected by porous carbon
area of crystal orientation is used for calculations in materials, so it will disturb the smallest size [13,14].
determining crystal size by using dominant and strong peaks Furthermore, the addition of calcination time will generate
with high-intensity peaks. Crystallite size was calculated using activation energy in crystal vibrations and also release
the Scherer equation [9] as in equation 1. boundary atoms to diffusion motion and substitution for other
atomic lattice transformations. The increase in conductivity
𝐾𝜆
𝐿= (1) will affect the increase in fast charging characteristics of
𝛽 𝐶𝑜𝑠 θ
lithium-ion batteries.
where L is nano crystallite size (nm), λ is the X-ray
wavelength in nanometer (nm), β is the peak width of the Table 1. Crystallization size and conductivity (pure LiFePO4
diffraction peak profile at half maximum height resulting from and LiFePO4/CNT heated at various times).
small crystallite size in radians and K is a constant related to Crystal size Conductivity
Sample
crystallite shape, normally taken as 0.9. (nm) (S/m) (10-7)
LiFePO4 pure (2h) 101.64 1.881
LiFePO4/CNT (2h) 60.07 2.451

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Volume 7, Issue 12, December – 2022 International Journal of Innovative Science and Research Technology
ISSN No:-2456-2165
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