ITREC2017 - Subkhan Alfaruq

PERFORMANCE OF LITHIUM IRON PHOSPHATE CATHODE WITH
VANADIUM DOPING AND BAMBOO ACTIVATED CARBON COATING
Nofrijon Sofyan1, Subkhan Alfaruq1, Anne Zulfia Syahrial1*, and Ahmad Subhan 2
1
Department of Metallurgical and Materials, Faculty of Engineering, Universitas Indonesia, Depok-
West Java 16424, Indonesia
2
Tropical Renewable Energy Centre (TREC)-Faculty of Engineering, Universitas Indonesia, Depok-
West Java 16424, Indonesia
Coresponding Author : [email protected]
ABSTRACT
LiFe1-xVxPO4/activated carbon positive electrode materials have been successfully
prepared using hydrothermal synthesis. The effect of vanadium doping and activated carbon
coating on the performance of LiFePO 4 has systematically been investigated with
simultaneous thermal analysis, X-ray diffraction, scanning electron microscopy, and
electrochemical impedance spectroscopy. As-prepared LiFePO4 showed that the transition
temperature at 639 C which is phase formed has an olivine-based structure with
orthorhombic groups and exhibits peak shift due to the vanadium doping. The agglomerated
morphology of LiFePO4 decreases with increasing levels of vanadium doped. EIS showed
that there was an increase of conductivity from 2.02x10 -5 S/cm at 0% vanadium to 4.37x10 -
5
S/cm in 5% vanadium which it have higher conductivity than glucose carbon coating in
previous research. Vanadium doping and bamboo activated carbon coating are promising
candidate for high performance Li-ion batteries.
Keywords: bamboo activated carbon; cathode battery; hydrothermal method; LiFePO4;

vanadium doping
1. INTRODUCTION
With the cumulative problems of global warming has strengthened, efforts have been made
to replace the non-renewable fossil fuels by other sustainable green energy sources, like
solar, wind, hydroelectric, and nuclear power. Different from the conventional fossil fuels,
most of these ecofriendly energy sources suffer from their uncontrollable complicated
situation and intermittent nature. This problem brings a great research interest in material
development for energy storage. LIBs have been considered as an effective, convenient and
simple system, gaining much attention from the world wide scientists because of its high
density and relatively simple mechanism.
A lithium ion battery can work as the energy storage device by converting electric energy
into electrochemical energy. There are four key components in a LIB system: cathode,
anode, separator and electrolyte. The electrochemical performance of cathode materials is
indisputably significant to the comprehensive property of LIBs and more over the cost
nearly twice as much as the anode, thus the researches about the developments and
optimizations of cathode material have never been stopped (Xu et al. 2013). Generally, the
cathode materials for commercial LIBs are mainly occupied with transition metals oxides
or phosphates active material, such as LiCoO 2, LiMn2O4 and LiFePO4. Compared with
conventional layered LiCoO2 and spinel-type LiMn2O4, the specific characteristics of
olivine LiFePO4 such as excellent cyclic stability, non-toxic, environmental friendliness,
low cost, higher working voltage and excellent thermal stability are the most promising
cathode material for their outstanding complex electrochemical performance. However,
LiFePO4 usually shows a poor rate capability because of its low intrinsic electronic
conductivity (10-9 Scm-1) and low diffusion coefficient of Li + are the main problem that
limited its application in industry (Chen, Wu, and Pang 2013).
Carbon coating such as, carbon nanotube, activated carbon, carbon black, and acetylene
black is the most promising method to improve the electronic conductivity on the surface of
LiFePO4 particles. In a recent work, showed that the presence of activated carbon inside
these composite electrodes improves the electronic conductivity and high performance at
high current density of the LFP (Bckenfeld et al. 2012). Another advantages of activated
carbon as coating is their relative low cost and easy to produce due to its source from
natural cellulose such as bamboo, rice straw, coconut shell and much more. Li ion diffusion
can be improved by supervalent metal ion doping or substitution at Fe-site of LiFePO 4.
Vanadium substitution can significantly improve the electrochemical performance of
LiFePO4 cathode material for lithium ion battery. Because V doping create a vacancy and
disorder lattice into the crystal structure of LiFePO 4, therefore Li ion can move easier
between cathode materials (Chiang et al. 2012).
In this study, we present the influence on the electrochemical behavior of cathode materials
due to vanadium doping and activated carbon coating from bamboo. V-substituted LiFePO 4
(LiFe1-xVxPO4, 0 x 0.07) samples were prepared via a hydrothermal method and coating
by activated carbon from bamboo via solid state reaction. The physicochemical properties
and electrochemical performances have been studied using X-ray diffraction (XRD),
scanning electron microscopy (SEM), simultaneous thermal analysis (STA), and
electrochemical impedance spectra (EIS).
2. EXPERIMENTAL METHODS
2.1. Materials
The starting material used in this work are LiOH (99% Merck), NH4.H2SO4 (99%
Merck), FeSO4.H2O (99%, Sigma Aldrich), NH4VO3 (99% Merck), ethanol (99%, Merck),
and Bambusa balcoa or locally known as bambu Jawa which was purchased from
traditional market in South Jakarta, Indonesia.
2.2. Preparation of Activated Carbon
Bamboo that has been cut into small pieces was dried in an oven at 105C for 24 h to
remove all moisture and obtain a bamboo charcoal. The bamboo charcoal was crushed
down in the ball mill machine. Chemical activation was carried out by initially carbonizing
the precursor under inert atmosphere from room temperature to carbonization temperature
of 400C for 1 hour under a closed system, activation using 30% phosphoric acid (H3PO4)
solution with impregnation ratios of 4: 1 (w/w) for 24 h of soaking duration. Then, sample
was dried into the oven at 105 o C for 20 hours. The dried sample was then pyrolysed for
activation at temperatures of 500C. Sample then neutralized with NaOH and successively
rinsed with distilled water until the filtrate reached a stable pH of 6. Finally, to remove the
moisture sample was heated at 105 o C for 20 hours and bamboo activated carbon powder
ready to be characterized.
2.3. Preparation of LiFePO4/V/AC

LiFePO4 is synthesized via hydrothermal method. NH4H2PO4, LiOH and FeSO4.7H2O
powder are taken as starting materials with the molar ratio of 1:2:1. The materials
dissolved in the deionized water and then mixed by magnetic stirrer. The resulting solution
is placed in Teflon-lined stainless steel autoclave and the hydrothermal reactions are
performed at 170 o C. LFP formed by the reaction:
6LiOH (l) +3NH4H2PO4 (l) + 3FeSO4.7H2O (l) 3LiFePO4 (s) + 3H2SO4 (l) + 13H2O +
3Li+ + 3NH2-
The products were cooled to room temperature and washed with distilled water until reach
pH 6-7. Product then dried at temperature 150 o C to obtain LFP powder. Here, ammonium
metavanadate (NH4VO3) was used as vanadium source. LFP powder was mixed with
NH4VO3 using ball mill machine for 20 minutes. The next process, bamboo activated
powder was added into the ball mill chamber as a coating and then mixed for 20 minutes.
The percentage ratio of LFP, NH4VO3, and activated carbon is (97-x): 4: x %wt, were x =
0, 3, 5, and 7 %. The resulting product was sintered at temperature 800 o C in a nitrogen
atmosphere for 4 h. Finally, the product were cooled down to room temperature and ready
to be characterized.
3. RESULTS AND DISCUSSION

3.1 X-Ray Diffraction Characterization
The XRD patterns of synthesized LiFePO 4, LiFePO4/AC, and vanadium doped
LiFePO4 samples are shown in Fig.1. All sample are crystallized and the main phase of all
prepared materials can be indexed as Pnma orthorhombic structure of synthetic triphylite
LiFePO4 structure. No peak appears for crystallized carbon because the carbon contained is
crystallized phase exists to be detected by XRD (Long et al. 2015). The carbon in this
composite does not affect the structure of LiFePO4. Fig.1. It can be found that there are a
regular shift of the lattice parameters of orthorhombic phase in the prepared samples
increase with amount of V substitution up to x 0.07. The regular shifts of the lattice
parameters imply that the alien elements V has been successfully occupied 4c sites of Fe 2+
in the LiFePO4 structure to form solid solution LiFe1-xVxPO4.
Fig. 1. XRD patterns of LiFe1-xVxPO4/AC (0 < x < 0.07). The vertical lines (on
the bottom of graphs) mark reference diffraction patterns of LiFePO4 (with Pnma space
specified in the International Center for Diffraction Data (ICDD) database with PDF-2 code
00-019-0721.
3.2 SEM and EDS Characterization

SEM characterization was carried out in order to evaluate the effect of V doped on
the morphology and particle size distribution of LiFePO4/C. according to the SEM images
in Fig. 2, it can be found that LFP powders are mainly fine particles between 50 and 100
nm sizes, which pure LFP particle has an agglomerate structure with the hexagonal-shaped
particles. Than doped LFP shows the spherical-shaped particles and less agglomerate,
which is we expected because vanadium doping at Fe site has a great effect on the structure
and beneficial to the enhancement of LFP electronic inductivity (Zhang et al. 2012). As
seen from Figure 3, the EDS results showed that as-prepared sample had the elements,
such as Fe, P, O, C, and V, and all of the elements were distributed uniformly, indicating
that C and V dispersed in LiFePO4 evenly.
Fig. 2. SEM image of LFP with (a) 0%wt and (b) 5%wt vanadium doped
Fig.3. EDS image of LFP with (a) 0%wt and (b) 5%wt vanadium doped
3.3 EIS Characterization

To compare the effect of vanadium doping and activated carbon coating on electrochemical
performance of the LFP cathode, the electrochemical impedance measurements were
carried out. Fig.3 Shows Nyquist plots of the prepared samples. The values of the cross
point of the semicircle on the horizontal axes represent the charge transfer resistance. The
straight line represents the Warburg impedance, which is associated with the lithium-ion
diffusion in the inner of LiFePO4 particles. The charge transfer resistance will now be
thoroughly discussed, which has a close relationship between composition and
conductivity of the interface. As shown in Fig.3 and table 3, the V doped sample shows
superior electrochemical performance than the undoped sample due to higher conductivity
and better electrode kinetics related to the synergistic effect of V3+ in the lattice (Pietrzak et
al. 2013).
Fig.4 Nyquist plots of LFP/CA with 0%V, 3%V, 5%V and 7%V materials
4. CONCLUSION
In this study, the relationship between the enhanced electrochemical properties and the
structure of LFP/V/AC is described. By adding NH 4VO3 into LiFePO4, better conductivity
of Li1xVxFePO4 is found relative to LiFePO4 without vanadium doped and the structure
shows more spherical-shaped particles and less agglomerate, because of vanadium doping
at Fe site has a great effect on the structure and beneficial to the enhancement of LFP
electronic inductivity. Activated carbon coating on LFP particles can increase the external
conductivity.
5. ACKNOWLEDGEMENT
We would like to thank to Ministry of Research and Higher Education Republic of
Indonesia for funding this research through Program Hibah PITTA.
6. REFERENCES tidak boleh ada et al, tulis semua nama author

Bckenfeld, N et al. 2012. Electrochimica Acta The Influence of Activated Carbon on the
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Chen, Mao Sung, She Huang Wu, and Wei Kong Pang. 2013. Effects of Vanadium
Substitution on the Cycling Performance of Olivine Cathode Materials. Journal of
Power Sources 241: 69095. http://dx.doi.org/10.1016/j.jpowsour.2013.04.022.
Chiang, Ching-yu et al. 2012. Vanadium Substitution of LiFePO Cathode Materials to
Enhance the Capacity of LiFePO -Based Lithium-Ion Batteries Vanadium Substitution
of LiFePO 4 Cathode Materials to Enhance the Capacity of LiFePO 4 -Based Lithium-
Ion Batteries.
Long, Yun-Fei et al. 2015. Enhanced Rate Performance of LiFePO4/C by Co-Doping
Titanium and Vanadium. Solid State Sciences 48: 10411.
http://linkinghub.elsevier.com/retrieve/pii/S1293255815300157.
Pietrzak, Tomasz K. et al. 2013. Novel Vanadium-Doped Olivine-like Nanomaterials with
High Electronic Conductivity. Solid State Ionics 251: 4046.
Xu, Jiantie, Shixue Dou, Huakun Liu, and Liming Dai. 2013. Cathode Materials for next
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ITREC2017 - Subkhan Alfaruq

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PERFORMANCE OF LITHIUM IRON PHOSPHATE CATHODE WITH

VANADIUM DOPING AND BAMBOO ACTIVATED CARBON COATING

Keywords: bamboo activated carbon; cathode battery; hydrothermal method; LiFePO4;

2.3. Preparation of LiFePO4/V/AC

3. RESULTS AND DISCUSSION

3.2 SEM and EDS Characterization

3.3 EIS Characterization

6. REFERENCES tidak boleh ada et al, tulis semua nama author

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