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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
LiM0.03Fe0.97PO4
x < 0.05
Cu
Raman Intensity
1022
Cu
Ti
Ti
Cr
Cr
Al
Al
500
1000
500
1000
-1
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)
1124
1080
1064
1019
960
911
7.2
9.5
9.8
92
9.0
9.0
104
100
126
263
66
58
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
LixFePO4
x=0.04
Absorption
1024
x=0.11
x=1
400
800
1200
Wave number
(cm-1)
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
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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