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Solid State Ionics 177 (2006) 1021 1025

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A new insight into the LiFePO4 delithiation process


V. Lemos a,, S. Guerini a , J. Mendes Filho a , S.M. Lala b , L.A. Montoro b , J.M. Rosolen b
a

Departamento de Fsica, Universidade Federal do Cear, Centro de Cincias, Caixa Postal 6030, Campus do Pici, 60455-970 Fortaleza, Cear, Brazil
b
Departamento de Qumica, FFCLRP, Universidade de So Paulo, 14040-901 Ribeiro Preto, SP, Brazil
Received 8 November 2005; received in revised form 14 February 2006; accepted 7 March 2006

Abstract
Raman and Fourier transform infrared measurements for LixM0.03Fe0.97PO4, M = Cr, Cu, Al, Ti were performed. The spectra for delithiated
samples to a low content of lithium extraction are practically the same as those of LiFePO4. For a high content of lithium extraction, the spectra
repeat that of FePO4. In the case of the Li0.11FePO4 oxide the spectra cannot be reproduced just by the superposition of the end member profiles.
An additional broad band contribution is found in both Raman and infrared spectra probably due to a disordered structure present in the mixture.
This suggests that the well accepted two-phase model for the delithiation process in LiFePO4 is incorrect. The model should be revised to include
the new phase as detected here for a particular level of lithium extraction close to that of complete oxidation of the Fe2+ ions to Fe3+.
2006 Elsevier B.V. All rights reserved.
Keywords: LiFePO4 delithiation; Metal doped LiFePO4; Lithium intercalated compounds; Lithium batteries; Vibrational spectroscopy

1. Introduction
The compound LixFePO4 has been currently proposed as the
most beneficial cathode for rechargeable lithium battery since it is
inexpensive and environment-friendly [17]. Used as an anode,
the related compound FePO4.2H2O was found to surpass the
electrochemical properties attained before by producing an
increased capacity by a 45 time factor [8,9]. Ion-storage applications were hindered in the past because of a poor electronic
conductivity intrinsic to this family of compounds. It has been
found recently, however, that the doping of LixFePO4 with a metal
super valent to Li+, enhances the electronic conductivity by eight
orders of magnitude [1012]. As a consequence, the performance
of the battery charging can be severely increased. This fact makes
the metal doped LixFePO4 the most promising candidate for a
low-power rechargeable lithium battery.The exact mechanism for
the increased electronic conductivity, however, is still a subject of
research. Some arguments favor the doping effect as a relevant
influence on the conductivity increase through the modification of

Corresponding author. Tel.: +55 85 4008 9925; fax: +55 85 4008 9450.
E-mail address: volia@fisica.ufc.br (V. Lemos).
0167-2738/$ - see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.ssi.2006.03.008

the electronic structure of LiFePO4 [13]. Other arguments favor a


low-valency iron derivative as responsible for the high conductivity in these compounds rather than the doping effect [14].
Evidences for the latter are given in a recent publication where the
presence of a nanophase phosphide network within the grain
boundaries of LiFePO4 is proposed to be formed during heat
treatment and to act as an efficient electrical conduit [15]. However, this proposal is inconsistent with the previous results on a
scanning electron microscopy showing that phosphide particles
do not form a continuous network [16]. Such controversies on the
subject cannot be solved by using the data available in the literature to date and many other investigations are required within
the departure from stoichiometry focus. This departure may be
achieved, for instance, in the delithiation of LiFePO4 to FePO4.
The model for lithium extraction/insertion in LixFePO4 is generally adopted as a two-phase process [1720]. This process was
highly evidenced in the observation of FePO4 Raman bands with
increased intensities upon LixFePO4 delithiation [20]. The Raman
positions were observed to be independent of the lithium content
allowing for a single-phase formation to be ruled out [20]. No
further alternative was put forward except for the existence of
LixFePO4 solid solutions, such existence, however, restrained to
higher temperatures (T 150 C), as proposed recently [21]. An
argument for a possible additional phase in the delithiation

V. Lemos et al. / Solid State Ionics 177 (2006) 10211025

process was raised by our group based upon a distribution of sites


found in the analysis of Mossbauer transformed patterns [22].
Therefore, it is fundamental to look for new evidences in the
three-phase-process for lithium extraction including the additional phase state of crystallinity. To achieve this goal, it is necessary
to investigate the vibrational properties of lithium containing
compounds, and particularly the metal doped LixFePO4.
Here, Raman scattering and Fourier transform infrared (FTIR)
spectroscopy studies were performed for a series of olivine-type
LixM0.03Fe0.97PO4, M = Cr, Cu, Al, Ti. The close to end members
compounds behave like their x = 1 and x = 0 counterparts. When
lithium is extracted from the Li-rich phosphates, a new phase with
poor crystallinity is formed. This phase gives strong contribution
to broad bands in the FTIR and Raman spectra, for the particular
x = 0.11 level of lithium extraction.
2. Experimental
The LiFePO4 samples were prepared using the LiCl (from
Aldrich) and FeCl2.H2O (from AlfaAesar) compounds left to
dry in a pre-evacuated chamber (vacuum of 106 Pa) in phosphor
pentaoxide atmosphere for 72 h. The material was then mixed
with H3PO4 (from Synth) solution. The solution was stirred for
2.5 h in nitrogen flux and dried in nitrogen atmosphere. The
obtained powder was then crushed in an argon containing
(H2O b 3 ppm) glove-box and submitted to a heat treatment under
an argon/hydrogen (9/1 v/v) flux. The heating was a two-step
procedure using a (Lindberg/Blue) tubular oven: (i) Increasing
temperature at a rate of 10 C/min up to 350 C and keeping this
temperature constant for 5 h; (ii) Increasing temperature at a rate
of 5 C/min up to 600 C and keeping this temperature constant
for 24 h. The visual aspect of the powder was a light grey color,
the characteristic of Fe2 presence. The powder was then ball
milled in an agate mortar for a period of 24 h.
The LixM0.03Fe0.97PO4 preparation followed the same procedure as described before, adding the metal dopant M (M = Cr, Cu,
Al, Ti) in molar fractions obeying the proportion 1:0.03:0.97:1 for
Li, M, Fe,P, respectively. In the case of Cu and Al doping the
anhydrous salts (from AlfaAesar), Cu(OOCCH3)2 and Al2O
(OOCCH3)4, were employed, respectively. In the remaining cases
the metallic Cr and Ti were previously mixed in a HCl solution (1/
1 v/v). The mixture was then rinsed in deionized water and heated
to dry, a process that was repeated at least three times to remove
the HCl in excess.
The lower Li content samples were obtained from those by
chemical delithiation in Na2S2O8 solution. In the delithiation
process to Li0.11FePO4, Na2S2O8 was employed at the concentration of 0.2 M for a period of time of 48 h. In the case of the
preparation of LixM0.03Fe0.97PO4, x b 0.05, we used a Na2S2O8
solution at 1 M and reaction time of one week. The delithiated
samples were filtered, abundantly rinsed (with deionized water
and acetone) for complete removal of soluble impurities, dried
and stored into glove-box. The lithium concentration achieved
was determined with a flame emission spectroscopy. Characterization using an X-ray diffraction associated with a qualitative criteria of color indicate the absence of extraneous
components.

The Raman spectra were acquired by using a T64000 Jobin


Yvon triple spectrometer operating in the double subtractive
configuration. Detection was through a nitrogen cooled CCD
(Charged Coupled Device). The 514.5 nm (2.41 eV) line of an
Ar+ -ion laser was employed as exciting radiation. The laser beam
was focused using a 50 times objective and an OLYMPUS BH-2
microscope to a spot size of about 2 m diameter. The incident
power density was kept well below 105 W/cm2 to avoid heating
the sample. All measurements was performed in the backscattering geometry and at a room temperature. The spectral resolution
imposed bythe equipment was 0.6 cm 1.
3. Results and discussion
Raman scattering studies were performed for the complete
series of phosphates. The assignments of LiFePO4 Raman modes
were performed previously by using a simulation as a basis,
through a detailed analysis of the spectra [23]. Raman spectra for
LiM0.03Fe0.97PO4, M = Al, Cr, Ti, Cu, are shown in Fig. 1 (left
panel). The spectra are practically the same in all cases except for
small differences in the relative intensities. In particular, the Ag-3
modes at 996 cm 1 and 1068 cm 1 have a decreased
intensity rate in the case of chromium doping. In this case of a
high Li content the Raman spectra reproduce fairly well the results
for the undoped LiFePO4 published before by some of us [23].
The fact that all four spectra in this figure are basically the same
indicates that metal doping causes negligible differences in the
vibrational properties of LiFePO4. Moreover, those spectra
reproduce the spectrum for the undoped LixFePO4 compound,
when 0.96 1 [22,23]. Fig. 1 (right side) shows spectra for
LixM0.03Fe0.97PO4, M = Al, Cr, Ti, Cu, in the case when the
lithium extraction is almost complete (x b 0.05). Again, it is
possible to observe that the spectra do not differ appreciably from
the spectrum of undoped FePO4 as can be checked by examining
a previous published work by Burba and Frech [20]. There is a
striking similarity among the four spectra, also in this case of a
low lithium content, indicating the negligible effects of a low level
metal doping on the FePO4 vibrations. Notice that the FePO4
LixM0.03Fe0.97PO4

LiM0.03Fe0.97PO4

x < 0.05
Cu

Raman Intensity

1022

Cu
Ti
Ti
Cr
Cr
Al

Al
500

1000

500

1000

-1

Wave number (cm )


Fig. 1. Raman spectra from LiM0.03Fe0.97PO4, and Lib 0.05M0.03Fe0.97PO4,
M = Al, Cr, Ti, Cu.

V. Lemos et al. / Solid State Ionics 177 (2006) 10211025

Raman scattering being much stronger than that of LiFePO4, so is


that of the closely related Lib 0.05M0.03Fe0.97PO4, M = Al, Cr, Ti,
Cu, phosphates. A comparison of these results with those found
for the high lithium content phosphates suggests a two-crystalline
phases co-existing in the intermediate range of lithium content in
agreement with the literature. A two-crystalline-phase mixture
was proposed to form based on spectroscopic studies of
phosphates in relatively close steps of lithium delithiation [20].
The authors failed to observe any other modification in spectra
that could be tracked to the formation of a new phase in this
mixture. The lowest lithium content studied by Burba and Frech
[20] was for the phosphate Li0.38FePO4, a Li-composition that left
a far important gap from the limiting FePO4 compound. To fill in
this gap data for an intermediate level of lithium extraction, such
as for LixFePO4, with x = 0.2 or 0.1, is required. For this reason the
phosphate Li0.11FePO4 was prepared by us and studied in
comparison with the end members LiFePO4 and FePO4. The full
Raman spectrum for this sample was published elsewhere [22]. In
this spectrum no narrow bands was observed in addition to those
of the LiFePO4 and FePO4 crystals in agreement with the two
crystalline phases argument. On the other hand, a broad band is
present in the [Ag-3, Ag-1] spectral range as shown in Fig. 2.
This spectral range was fit with a set of six bands with Lorentzian
line shape. The result of this fitting is given in Table 1. The table
shows that among the six lines, only one is broad, the line that is
centered at 1019 cm 1, with a half-line width of about 92 cm 1.
Surprisingly, this line width is about ten times greater than the
values found in the remaining lines. It should be noted also, in this
table, that the integrated area for the broad line surpasses the
others by a factor of 25 times. Since it is the strongest feature in
the spectrum, it cannot be neglected. Being broad, it indicates a
structural disorder. Actually, previous Moossbauer results show
the existence of a new doublet in addition to those assigned to the
crystals LiFePO4 and FePO4. The question of how a new phase
segregates in the mixture was answered by performing a
transformed pattern analysis of the Mossbauer results. The

LixMFePO4

Raman Intensity

x = 0.11

1000

Wave number

1200

(cm-1)

Fig. 2. Raman spectrum from Li0.11FePO4 and its fitting to a set of six bands
with Lorentzian line shape.

1023

Table 1
Parameters from the fittingof the Li0.11FePO4 phosphate Raman spectrum in the
[7001350] cm 1 range to a set of six bands with Lorentzian line shape
(cm 1)

(cm 1)

Integrated area (a.u.)

1124
1080
1064
1019
960
911

7.2
9.5
9.8
92
9.0
9.0

104
100
126
263
66
58

particular spread profile of this doublet transformed pattern


suggested the associated micro environment to be poorly
crystallized generating a disordered phase in the phosphate in
addition to the two crystalline phases [22]. Considering the
experimental evidence for the existence of a new disordered
phase, LixFePO4 can no longer be interpreted as a two-crystalline
phase mixture. This finding greatly contrasts with the welldocumented two-phase behavior of this system at room
temperature [1720]. We, thus, believe that the two phase process
for transformation of LiFePO4 into FePO4 upon lithium extraction
includes a pathway where a highly disordered phase is generated.
Although the exact nature of this phase is impossible to precise
based on our data, no evidence for the formation of iron
phosphocarbide, as suggested by Herle et al., [15] was found. For
instance, our previous published results on Mossbauer spectroscopy, [22] strongly differ from the characteristic spectrum of
Fe75P15C10 taken at a room temperature [24]. Those results are not
consistent with the presence of Fe2P in the sample, either, because
the Mossbauer characteristic spectrum and related parameters
are beyond comparison [25].
At this point it should be reminded that the two-phase model
was considered to proceed including the formation of a layer of
FePO4 around each LiFePO4 particle. As lithium ions are
extracted the distance from the center of the particle and the
FePO4/LiFePO4 boundary decreases. The interface surface area
decreases, in consequence, causing inhibition of further lithium
diffusion [7,1720]. Our Li0.11FePO4 spectroscopic data do not
fit in this process. In order to check this aspect, we performed Xray diffraction experiments for all samples. The X-ray results do
not show a selective behavior for the Li0.11FePO4 phosphate
(not shown here). A possible explanation for the lack of signs of
disorder in the X-ray diffraction from this sample is the new
structure to be formed as a minority phase, such as a network
grain boundary phase as proposed previously [15]. X-ray
profiles of all samples failed to show any foreign diffraction line
that could be attributed to the formation of sizable amounts of
iron phosphide or other impurity phase. Moreover, the
qualitative criteria of color described previously, [26] indicates
that, if present, the content of Fe3 is negligible. Therefore,
further research is required to elucidate this point, particularly
simulations that include a disordered phase segregation. It
should be remained, however, that the existing first-principles
calculations employing either the local density or the generalized density approximation were found to fail in detecting phase
separation in LixFePO4 for the complete range of lithium
extraction [27].

V. Lemos et al. / Solid State Ionics 177 (2006) 10211025

The FTIR results are given in Fig. 3 left and right panel for the
high and the low lithium content compounds, respectively. The
plots show that the spectra are nearly identical to those of LiFePO4,
whether the lithium extraction was limited to a low level, or to
FePO4 if not. In the case of a high lithium content the similarity with
LiFePO4 is preserved up to the value x =0.79. On the other hand, for
a high content of lithium extraction, the FTIR spectrum does not
differ appreciably from that of the end member FePO4 spectrum.
There are minor differences between the spectra presented here for
the low doping level with several metals. The differences that are
worth mentioning are mainly: (i) The increased relative intensity of
the middle frequency range features [400700] cm 1 as compared
with those for the high frequency range, in the case of the
LiCr0.03Fe0.97PO4 phosphate. (ii) The increased relative intensity of
the high frequency range features [7001250] cm 1 as compared
with those for the middle frequency range, in the case of the
Li0.03Cu0.03Fe0.97PO4 phosphate. As the differences are intensity
related only, it is possible to conclude that the FTIR results also
indicate a negligible effect of doping in the vibrational properties
for the small concentrations of metal treated here. As the metal
doping effects are negligible we analyze the undoped Li0.11FePO4
phosphate FTIR in the search of the disorder effect to result in
significant differences as compared with high lithium content
phosphates. We selected the Li0.11FePO4 sample to compare,
because in this case, the differences are extraordinary. They are
evident in Fig. 4 where we plot the FTIR spectra for LiFePO4,
Li0.11FePO4 and Li0.04Cr0.03Fe0.97PO4. We denoted the upper curve
LixFePO4, x = 0.04, for simplicity, because the spectrum for
Li0.04Cr0.03Fe0.97PO4 was found to reproduce exactly that of a
pure FePO4, as published before [20]. Fig. 4 shows that
Li0.11FePO4 FTIR spectrum could not be reproduced by the superposition of the end members spectra, the upper and lower curves in
this figure. The analysis of Fig. 4 reveals also a striking distinguishing feature in the Li0.11FePO4 FTIR spectrum for which a
very broad feature appears, selectively, in this case. It should be said
that no such a broad band appear for the doped phosphates with a
low lithium content, as shown in Fig. 3. In order to better describe
this point we performed a fitting procedure of all spectra. The

LiM0.03Fe0.97PO4

LixM0.03Fe0.97PO4
x < 0.05

Cu

Absorption

Cu
Ti

Ti
Cr

Cr
Al
500

Al
1000

500

1000

Wave number (cm-1)


Fig. 3. FTIR spectra for LiM0.03Fe0.97PO4, and Lib 0.05M0.03Fe0.97PO4, M = Al,
Cr, Ti, Cu.

LixFePO4

x=0.04

Absorption

1024

x=0.11

x=1

400

800

1200

Wave number

(cm-1)

Fig. 4. Comparison of LiFePO4, Li0.11FePO4 and Li0.04Cr0.03Fe0.97PO4 FTIR


spectra, this latter being representative for the FePO4 spectrum.

results for the set of three samples, LiFePO4, Li0.11FePO4 and


Li0.04Cr0.03Fe0.97PO4, are given in Table 2 including the
comparison with previous published LiFePO4 infrared active
mode wave numbers [20]. It is seen in this table that the IR wave
numbers agree with those found by Burba and Frech for LiFePO4,
[20] within 5 cm 1 at most. The two remaining columns list data for
Li0.11FePO4 and Li0.04Cr0.03Fe0.97PO4, the latter being representative for FePO4, as explained previously. The comparison shows that
the frequencies found for the Li0.11FePO4 IR-modes in the bending
Table 2
FTIR wave numbers, i, in units of cm 1 and line width, i, in units of cm 1
LiFePO4

LiFePO4

Ref. [20]
#
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22

Our
i
468
501

546
576
636
647

945

i
467
502

548
578
635
648

942

i
22
37

14
22
11
22

Li0.11FePO4

Li0.04FePO4

Our

Our

i
467
502

548
578
635
648

965
1043

78
57

1065

1070

43

1096

1099

36

1139

1144

37

22
37

14
22
11
22

926

32

956

24

1066

187

1078

35

57

964
1046

530
534

19
39

577

19

652
682

30
13

946

47

1085

43

1129

96

The column labeled Li0.04FePO4, corresponds to measurements made on the Cr


low doping level phosphate as explained in the text.

V. Lemos et al. / Solid State Ionics 177 (2006) 10211025

motion region reproduces those of the LiFePO4 phosphate. In


Raman scattering the coincidence was found to be with FePO4
frequencies, mainly. This is not surprising since Raman scattering is
much stronger for FePO4 than for LiFePO4. The surprise in the
present comparison comes from the fact that Li0.11FePO4 IR-modes
in the stretching region do not reproduce LiFePO4 or FePO4 wave
numbers. Although modes listed as 16 and 17 in the table have
close wave numbers, their line width differs considerably, the first
being more than four times broader. It is reasonable, therefore, to
assume all four bands (11, 13, 16, and 18 in the table) to represent
motions in a structure that differ from the end members structures,
and list the data in separate lines accordingly. Those marked differences give a hint to the segregation of a new phase, besides the
crystalline structures of LiFePO4 and FePO4 in the mixture. A solid
solution is improbable because the only experimental evidence for a
solid solution of LixFePO4, (0 1) found to date required a very
high temperature (450 C) of stabilization [21]. The quite striking
feature in the FTIR spectrum for the Li0.11FePO4 compound is the
broad band listed as mode 16 in Table 2. Its line width value is well
superior to any other line width, as can be checked out in this table.
This broad band should be interpreted as due to the presence of the
disordered phase in the mixture, thus reinforcing the fact that a twophase model is, at least, incomplete in describing the lithium
extraction process in LiFePO4. The data is much more consistent
with a new segregated phase with poor crystallinity. This finding
reinforces the previously proposed segregation of a disordered
phase based on Mossbauer results [22]. The fact that the X-ray
failed to detect it indicates a minority phase formed during lithium
extraction. Some authors speculate on an amorphous phosphocarbide magnetic phase intermediate between Fe3P and Fe3C with
high conductivity being a candidate to form a continuous network
upon processing [15]. Although our findings agree with an
amorphous nature of the new structure and possibly the formation
of a network connecting the LiFePO4 particles, the exact compound
being iron phosphate or other is unsupported so far. Therefore, our
results bring about a warning as how lithium extraction in LiFePO4
exactly proceeds is still an open question.
4. Conclusions
A detailed investigation using Raman and FTIR spectroscopy
was performed for LixM0.03Fe0.97PO4, M =Cr, Cu, Al, Ti, in the
complete range of lithium extraction. The vibrational properties of
these compounds were found to be independent of the metal
doping. The lithium extraction, on the other hand, greatly modifies
the spectra due to the segregation of crystalline phases in the
phosphate. In contrast with Raman results, some Li0.11FePO4 FTIR
features are displaced, beyond experimental errors, from either the
LiFePO4 or the FePO4 bands. The overall results fail to support the
well accepted two-crystalline-phase mixture model for a lithium
extraction. They point to the formation of an additional disordered
phase, as indicated the observed Raman and FTIR broad bands for
the particular Li0.11FePO4 phosphate. No evidence for such a phase
was found in the doped LiFePO4 spectra. Our X-ray diffraction data

1025

failed to detect this phase most probably due to its being a minority
phase, possibly a network grain boundary phase.
Acknowledgments
The authors would like to thank the Spectroscopy and
Microscopy Laboratories from the Instituto de Geocincias da
UNICAMP for allowing us to use the Raman scattering facilities.
Financial support was received from the Fundaco de Amparo
Pesquisa do Estado de So Paulo (FAPESP) and the Conselho
Nacional de Desenvolvimento Cientfico e Tecnolgico (CNPq).
CNPq grants are acknowledged byV.L. for DCR 303818/034
and byJ.M.R. for 3049993/20034.
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