Advanced Materials Research Vols.

236-238 (2011) pp 552-555

Online available since 2011/May/12 at www.scientific.net
© (2011) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.236-238.552

Preparation and Characterization of a New Type Lithium

Hexafluorophosphate Complex
Hailan Yang, Zhiye Zhang, Lin Yang,
Benhe Zhong, Lingyun Li, Xiaoxia Huang, Xinlong Wang*
School of Chemical Engineering, Sichuan University, Chengdu 610065, China
*email: corresponding author: wangxl@scu.edu.cn

Keywords: Lithium-ion secondary battery; 1,2-dimethoxyethane lithium hexafluorophosphate;

preparation; characterization
Abstract. In this paper, a new type lithium hexafluorophosphate (LiPF6) complex was prepared with
a new method using phosphorus pentachlorine (PCl5), lithium fluoride (LiF) and
1,2-dimethoxyethane (C4H10O2). The structure of the complex was carefully characterized by FTIR,
TG-DTG, 1H NMR and 31P NMR. FTIR results indicate that the synthesized complex is consisted of
LiPF6 and C4H10O2. Chemical analysis shows that the content of LiPF6 in the complex is about 45%,
which could infer that the mole ratio of LiPF6 and LiPF6(C4H10O2)2 in the complex is 1:2. The results
of 1H NMR and 31P NMR further confirm the composition of the complex and determine the
structure. The molecular formula of the LiPF6 complex is LiPF6(C4H10O2)2. Thermal analysis shows
that the strong decomposition peaks of the complex appear at 75˚C and 175˚C. LiPF6(C4H10O2)2 may
be used in the electrolyte of the lithium ion battery which 1,2-dimethoxyethane is permitted or broke
down into LiPF6 after further preparation.

Introduction
Lithium hexafluorophosphate (LiPF6) is the most widely used salt in electrolyte for commercial
lithium-ion batteries; the most merit of LiPF6 is that it can form SEI film on the carbon anode and
appropriate set of fluid to achieve effective passivity for current collector of Al.
Traditional method for preparing LiPF6 is HF solvents method which have the advantage of high
yield, however, it need proper anticorrosion material and idea of removing the extra HF because of the
use of corrosive HF, PF5 in this method. This disadvantage limited the development and for solvent
method. In the past few years, research on the preparation of LiPF6 has dramatically increased, but it
still can not avoid the use of high corrosive HF and PF5. Given increasing demand for LiPF6 in the
world market, the design of a safer and environmentally friendly way for production of this salt is of
great importance.
LiPF6 has poor thermal stability, and it is very sensitive to water, it react and release corrosive
gases HF while meeting a trace of water (such as environmental water is greater than or equal to
10ppm)[1]，the reaction is as the following formula (1)
LiPF6 + H2O → LiF + POF3 + 2HF (1)
The active characteristics of LiPF6 bring about great difficulties for the preparation and
purification of LiPF6. At present, the main method for LiPF6 is still traditional method[2]. However,
the method is still not suitable for mass production because of the complicated and unstable
techniques and the high cost. Therefore the emphasis of present studies is to develop a simple and
environmentally friendly method which can be fit for the industrialization of synthesis of LiPF6.
These years, complex method that uses some organic solvent to prepare LiPF6 was studied by many
researchers and the literature[3-5] has proved the possibility and superiority of this method, but few
studies about the intermediate complex of the solvent and LiPF6 were reported.
In this paper, a new method using PCl5, LiF and DME is studied and the structure of the
intermediate complex of LiPF6 and DME is characterized. Compared with the other method, PCl5,
LiF and DME used as the raw material in this method have lower toxicity and corrosion than HF or
PF5 which is widely needed in the traditional way; moreover, it cost less than others.

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 Advanced Materials Research Vols. 236-238 553

Experimental
Materials and the preparation of the LiPF6 complex
PCl5, LiF, C4H10O2(DME), C5H12 were all supplied by Tianjin Kemiou Chemical Reagent Co.,
China. nitron(99.9%) was a product of Tokyo Kasei Kogyo Co., Ltd.(TCI); High purity (99.999%)
Argon gas was supplied by the fourth Aero Station Plant in Chengdu; the glove box was provided by
Dellix industry co., LTD in Chengdu. The Monel reactor is self-made.
Preparation of the LiPF6 complex
Calculated PCl5 and LiF were sealed in a self-made Monel metal reactor which had been mixed well
in a glove box with no H2O and CO2. The temperature of the reactor was controlled at 200˚C~250˚C
for 2h and another 4h at 80~100˚C. Then amount of C4H10O2 was then used to extract LiPF6 from the
mixture made in previous step, LiPF6 complex was crystallized from the filtrated solvent and washed
several times with normal pentane. The final product was dried and kept in the glove box until the
analysis was performed.
Characterization
emical analysis
The yield of LiPF6 in the complex was measured by the gravimetric analysis of nitron.
FTIR spectroscopy
The infrared spectrum was record on SpectrAA220FS FT-IR instrument provided by Uniscience
Company in USA. 1~2 mg complex was grinded in an agate mortar for 5min, and then mixed well
with a amount of white oil, the mixture was then sealed between two pieces of KBr for measurement
in the FTIR instrument. White oil as the blank samples was measured in the same condition.
31
P, 1H NMR spectroscopy
The 31P, 1H NMR of the product and 1H NMR of C4H10O2 were conducted in AXANCE300 NMR
spectrometer with CDCl3 as the solvent to characterize the structure of the LiPF6 complex with
Infrared spectrum and TG measurements.
XRD analysis
X-ray diffraction(XRD) measurement on the LiPF6 complex powder and the standard LiPF6 were
recorded with the Philips k-Alphecl X-ray diffraction instrument, Cu-Kα radiation was used.
Thermal analysis
TG measurements were conducted using the TGA 2910 instrument. The LiPF6 complex sample was
measured from 0 to 400˚C with the average heating rate of 5˚C⋅min-1 and the N2 flow of 50ml⋅min−1.

Results and Discussion

Chemical analysis
The yield of LiPF6 in the LiPF6 complex is 45%±0.5 measured by the gravimetric analysis of nitron.
Infrared spectrum characterization

Fig.1. FT-IR spectra of the LiPF6 complex Fig.2. FT-IR spectra of the white oil
554 Application of Chemical Engineering

The FT-IR spectrum of the LiPF6 complex and the white oil are shown in Fig.1 and Fig.2. After
subtracted the absorption peaks of the white oil in figure 2, the main absorption peaks in figure 1 are
876.46cm-1, 563.01cm-1, 1419.20cm-1, 1305.14cm-1, 1100cm-1, 3435.98cm-1. According to the
relevant literature[6] that absorption peaks of LiPF6 should appear at 820~860cm-1 and 550~565cm-1,
strong absorption at 876.46cm-1, 563.01cm-1 can be confirmed that there is LiPF6 in the received
production. The signal at 1419.20cm-1, 1305.14cm-1, 1100cm-1 is due to δC-H and δC-O of C4H10O2.
The signal at 3435.98cm-1 may be due to νR―OH caused by the possible water during testing or the
absorption peak of νLi–O which needed more other characterization. Therefore, it can be confirmed
that the complex was comprised of LiPF6 and C4H10O2, but it cannot be determined the location of
coordination bond of the LiPF6 complex.
1
H, 31P NMR spectrum
NRM 1H and 31P pattern of the LiPF6 complex are showed in Fig.3 and Fig.4, NRM 1H pattern of
C4H10O2 is showed in Fig.5. A few of inferrences are got from NRM results[7,8]. According to Fig.3,
31
P spectrum with seven peaks is the 31P-19F coupling ( JP-F ) that is in line with the law n +1, and δp:
-144.03ppm, JP-F: 708.4Hz, the coupling constant of 31P and other six 19F is basically the same by
calculating from the experimental data results, each one is JP-F: 708.4Hz, and only the octahedral
structure model is consistent with these results. This is also corresponded with the results provided by
Dillon and others that 31P-NMR of PF6- in CD2Cl2 solvents showed seven peaks, and δp: -145.1ppm,
JP-F: 714Hz. The ether bond with the lone pair electrons of 1, 2-dimethoxyethane is inferred not be
coordinated with the P as P is with 6 F in PF6-, or the fluoride, because an unpaired electronics at the
second layer orbit in 2S22P5 of F and 3S23P33d of P are formed six-coordinated octahedral complex
structure after S2P3d2 hybrid and F has no track to accommodate the lone pair electronics at
ether-oxygen bond. Then it is obvious that a SP3 hybrid of coordination compound is formed by Li+
and 4 -O- Li+. δC 3.27ppm and δC 3.44ppm is the chemical shifts of methylene in -CH2-O- and methyl
in CH3-O-, the amplified map showed between two single peaks in Fig.4 may be due to coupling of
1
Li and 1H. The structure of C4H10O2 remain the same in the complex except the ether bond because
δC 3.37ppm from CH3 and δC 3.22 ppm from -CH2- is basically consistent with the hydrogen spectrum
of C4H10O2 showed in Fig.5, and the structure of the complex is concluded in Fig.6.

Fig.3 NRM 1H pattern of LiPF6 complex Fig.4 NRM 31P pattern of LiPF6 complex
H

H
H
H

H H
H
O
H
H
H H
H

H Li
O H O
H
O
H
H H

H F
H

F
P
F

1
Fig.5 NRM H pattern of C4H10O2 Fig.6 the structure of LiPF6 complex
 Advanced Materials Research Vols. 236-238 555

XRD Characterization
XRD pattern of LiPF6 and LiPF6 complex are showed in Fig.7 and Fig.8.

Fig.7 XRD pattern of LiPF6 Fig.8 XRD pattern of the obtained crystal
The XRD patterns showed significant difference. Through calculating the grain sizes of the crystal
cell by Scherrer equation, the average grain size of pure LiPF6 is 81.39nm and that of the synthetic
LiPF6 complex is 101.26nm.
Thermal analysis
The thermal decomposition curve of LiPF6 complex is
shown in Fig.9. It can be seen that the strong decomposition
peaks of the complex appear at 75˚C and 175˚C, and the
mass loss is 55% and 45% respectively. As it is reported in
Refs[9] that the peak temperature of the decomposition of
LiPF6 varied from 192.93˚C (average heating rate
2.0˚C/min) to 223.83˚C (average heating rate 20.0˚C/min),
it is speculated that the decomposition of the complex is
divided into two steps: 1) Li(C4H10O2)2PF6 → C4H10O2 +
LiPF6 2) LiPF6 → LiF + PF5. The thermal stability of Fig.9 TG-DTG curve of LiPF6
self-synthesized complex is lower than the LiPF6. complex

Conclusion
(1) PCl5, LiF, and C4H10O2 were successfully used to synthesize LiPF6 complex with powder crystal.
(2) The structure and composition of synthetic complex was dissected to LiPF6(C4H10O2)2 by means
of FT-IR, H NMR, P NMR, X-Ray and TG testing methods.
(3) The LiPF6(C4H10O2)2 could be used in the electrolyte which 1,2-dimethoxyethane is permitted or
become pure lithium hexafluorophosphate after purification.

References
[1] Teng X G, Li F Q, Ma P H, et al. Thermochimica Acta, 2005, 436: 30-34
[2] Eguchi T,Hashimoto T. JP Patent, 09-268005, 1997-10-14
[3] Patrick Willmann. US Patent. 5993767. Nov.30, 1999
[4] Teng X G, Dai J C, Ma P H. Inorg Chem., 2004, 20(9): 1109~1111
[5] Liu J W, Li X H, Wang Z X, et al. Trans. Nonferrous Mct. Soc.China, 2010, 20(2): 344-348
[6] Yikan Ke, Huiru Dong. Handbook of Analytical Chemistry. vol.3, Beijing: Chemical Industry
Press. 1998: 51-59
[7] Xinyue Wei, Zhihua Mao. Acta Chemical Sinica (Huaxue Xuebao). 2004, 64: 969-974
[8] Ruili Liu, Yao Xu. Acta Chemical Sinica (Huaxue Xuebao). 2004 (62): 22-27
[9] Zhenhai Liu. Introduction for Thermal Analysis. Beijing: Chemical Industry Press, 1991: 54~77
Application of Chemical Engineering
10.4028/www.scientific.net/AMR.236-238

Preparation and Characterization of a New Type Lithium Hexafluorophosphate Complex

10.4028/www.scientific.net/AMR.236-238.552