Professional Documents
Culture Documents
Effect of Synthesizing Method On The Properties of Lifepo /C Composite For Rechargeable Lithium-Ion Batteries
Effect of Synthesizing Method On The Properties of Lifepo /C Composite For Rechargeable Lithium-Ion Batteries
187-193
DOI: 10.1007/s13391-012-2131-x
Man-Soon Yoon,1 Mobinul Islam,1 Young Min Park,2 and Soon-Chul Ur1,*
1
Department of Materials Sci. and Eng./Research Center for Sustainable Eco-Devices and Materials (ReSEM),
Korea National University of Transportation, Chungju 380-702, Korea
2
Research Institutes of Industrial Science and Technology, Fuel Cell Project, Pohang 790-330, Korea
(received date: 6 August 2012 / accepted date: 21 September 2012 / published date: March 2013)
Olivine-type LiFePO4/C cathode materials are fabricated with FePO4 powders that are pre-synthesized by
two different processes from iron chloride solution. Process I is a modified precipitation method which is
implemented by the pH control of a solution using NH4OH to form FePO4 precipitates at room temperature.
Process II is a conventional precipitation method, of which H3PO4 (85%) solution is gradually added to a
FeCl3 solution during the process to maintain a designated mole ratio. The solution is subsequently aged
at 90°C in a water bath until FePO4 precipitates appear. In order to synthesize LiFePO4/C composites, each
batch of FePO4 powders is then mixed with pre-milled lithium carbonate and glucose (8 wt. %) as a carbon
source in a ball-mill. The structural characteristics of both LiFePO4/C composites fabricated using iron phospates
from two different routes have been examined employing XRD and SEM. The modified precipitation process
is considered to be a relatively simple and effective process for the preparation of LiFePO4/C composites
owing to their excellent electrochemical properties and rate capabilities.
Keywords: lithium iron phosphate, composite material, amorphous material, precipitation, industrial waste
release, for phosphorus removal, and as a sludge thickening, having the same composition as those in process I were syn-
conditioning and dewatering agent. The use of FeCl3 in the thesized in process II. For process II, a solution mixture was
electronics field is only a minor component. prepared with aqueous FeCl3 salts and H3PO4 (85%) solution
The objectives of the present study are to develop an inex- and the solution was stirred for 1 hour. The solution was sub-
pensive and simple route for synthesizing iron phosphates sequently aged at 90°C in a water bath until precipitates
from industrial by-product FeCl3 and to investigate the pro- appeared. The white colored precipitates fabricated from
cess effect on the properties of subsequent lithium iron phos- processes I and II were then isolated by filtration, and
phates. For these purpose, olivine-type LiFePO4/C cathode washed with distilled water and isopropyl alcohol. After
materials are fabricated with FePO4 powders pre-synthe- washing precipitates (FePO4·xH2O), a drying process was
sized by two different processes. This study provides useful carried out at 100°C for 6 hours. XRD analysis revealed that
process information on synthesizing iron phosphates and precipitates are of mostly an amorphous state.
subsequent olivine-type LiFePO4/C composites. FeCl3 (38%) Step II: LiFePO4/C was synthesized by a solid state reac-
solution, which was used in this study as an iron source, is an tion process using pre-milled Li2CO3 and pre-synthesized
industrial waste product and is the least expensive ($0.5/L) amorphous FePO4·xH2O powders. Appropriate amounts of
among all other iron sources. Synthesis of LiFePO4/C com- precursors and glucose (8 wt. %) were weighed and ball-
posite by using this precursor with other low priced precur- milled with a ZrO2 media in ethanol for 24 hours. The mix-
sors such as H3PO4 and glucose is reported here for the first ture was then dried at 80°C for 4 hours. The dried powders
time. Two different precipitation methods for synthesizing were then fired at 700°C for 4 hours under an N2 atmosphere
LiFePO4/C composite are highlighted in this study by using to prevent the oxidation of Fe2+ and to coat the surface of
an inexpensive precursor FeCl3 solution rather than focusing LiFePO4 particles with carbon.
on their electrochemical properties.
2.3 Structural characterization
2. EXPERIMENTAL PROCEDURE To observe phase information and possible second phase
formation in precursor states, the amorphous FePO4·xH2O
2.1 Materials powders were heat treated in air at 600°C - 700°C for
The starting materials used for synthesizing amorphous 3 hours to obtain crystalline FePO4 powders. Thermo gravi-
FePO4 were FeCl3 solution (38%, AR), H3PO4 (85%, AR) metric analysis (TGA) and differential scanning colorimetric
solution and NH4OH (25% - 30%, AR). Li2CO3 (99%, AR) analysis (DSC) were conducted using a thermal analysis sys-
and glucose (98%) were used with pre-synthesized FePO4 tem (NETZSCH 449C) with a heating rate of 10°C min−1.
for fabricating the LiFePO4/C composite. The glucose and The powder x-ray diffraction (XRD, Rigaku, D/MAX-
H3PO4 solution were purchased from Samchun pure chemical 2500H) analysis with Cu Kα radiation was used to identify
Co., Ltd., while Li2CO3 was purchased from SQM. The FeCl3 the crystalline phases of the prepared materials. In order to
solution was supplied by Dea Myoung Chemical. All the observe the microstructures, e-SEM (FEI, Quanta-400) and
chemicals were used as received without further purification. FE-SEM (Jeol, JSM-6700F) were employed.
Fig. 1. XRD patterns of FePO4 before and after heat treatments; (a) synthesized by process I and; (b) synthesized by process II.
Fig. 2. SEM micrographs of as-synthesized FePO4; (a) by process I and; (b) by process II.
Fig. 5. SEM micrographs of LiFePO4/C composites; (a) fabricated with the pre-synthesized FePO4 by process I, before heat treatment; (c) as for
(a), but after heat treatment; (b) fabricated with the pre-synthesized FePO4 by process II, before heat treatment, and; (d) as for (b), but after heat
treatment.
Powder Technol. 212, 327 (2011). Power Sources 184, 444 (2008).
13. G. K. Marasinghe, M. Karabulut, C. S. Ray, D. E. Day, M. 16. S. A. Needham, A. Calka, G. X. Wang, A. Mosbah, and H.
G. Shumsky, W. B. Yelon, C. H. Booth, P. G. Allen, and D. K. Liu, Electrochem. Commun. 8, 434 (2006).
K. Shuh, J. Non-Crystalline Solids 222, 144 (1997). 17. L.-L. Xie, K.-Q. You, X.-Y. Cao, C.-F. Zhang, D.-W. Song
14. C. Delacourt, C. Wurm, M. Morcrette, and C. Masquelier, and L.-B. Qu, Electron. Mater. Lett. 8, 411 (2012).
J. Chem. Mater. 15, 5051 (2003). 18. M. M. Rashad and M. I. Nasr, Electron. Mater. Lett. 8, 325
15. Y. Lin, M. X. Gao, D. Zhu, Y. F. Liu, and H. G. Pan, J. (2012).