The layered LiNi13Co13Mn13O2 system has recently drawn considerable interest for use as a cathode material for rechargeable lithium batteries. In order to investigate the charge-compensation mechanism and structural perturbations occurring in the system during cycling, in situ x-ray absorption spectroscopy (XAS) measurements were performed utilizing a novel electrochemical in situ cell specifically designed for long term x-ray experiments. The cell was cycled at a moderate rate through a typical Li-ion battery operating voltage range (2.9–4.7 V). The electrode contained 2.025 mg of LiNi13Co13Mn13O2 on a 25-μm Al foil and had an area of 0.79cm2. The x-ray absorption spectroscopy (XAS) measurements were performed at the Ni, Co, and the Mn edges at different states of charge (SOC) during cycling, revealing details about the response of the cathode to Li insertion and extraction processes. Changes of bond distance and coordination number of Ni, Co, and Mn absorbers as a function of the state of charge of the material were obtained from the extended x-ray-absorption fine structure (EXAFS) region of the spectra. The x-ray absorption near-edge structure (XANES) region was studied in order to characterize the oxidation states of the 3d transition metals during cycling (Li extraction/insertion). We found that oxidation states of transition metals in LiNi13Co13Mn13O2 are Ni2+, Co3+, and Mn4+, whereas during charging Ni2+ is oxidized to Ni4+ through an intermediate stage of Ni3+,Co3+ is oxidized almost to Co4+ and, utilizing Faraday’s calculation and XAS results, the Co was found to be at Co3.92+ at the end of the charge, while Mn was found to be electrochemically inactive and remains as Mn4+. The EXAFS data that were collected continuously during cycling revealed details about the response of the cathode to Li insertion and extraction. These measurements on the LiNi13Co13Mn13O2 cathode confirmed that the material retains its symmetry and good structural short-range order leading to superior cycling.

1.
A. G.
Ritchie
,
J. Power Sources
96
,
1
(
2001
).
2.
R.
Koksbang
,
J.
Barker
,
H.
Shi
, and
M. Y.
Saidi
,
Solid State Ionics
84
,
1
(
1996
).
3.
P. G.
Bruce
,
Chem. Commun. (Cambridge)
18
,
17
(
1997
).
4.
J.
Fan
and
P. S.
Fedkiw
,
J. Power Sources
72
,
165
(
1998
).
5.
A.
Manthiram
and
J.
Kim
,
Chem. Mater.
10
,
2895
(
1998
).
6.
C.
Delmas
 et al,
Electrochim. Acta
45
,
243
(
1999
).
7.
T.
Ohzuku
,
A.
Ueda
, and
M.
Nagayama
,
J. Electrochem. Soc.
140
,
1862
(
1993
).
8.
C.
Delmas
,
I.
Saadoune
, and
A.
Rougier
,
J. Power Sources
43
,
595
(
1993
).
9.
A. R.
Amstrong
,
R.
Gitzendanner
,
A. D.
Robertson
, and
P. G.
Bruce
,
Chem. Commun. (Cambridge)
1
,
1833
(
1998
);
A. R.
Amstrong
,
A. D.
Robertson
,
R.
Gitzendanner
, and
P. G.
Bruce
,
J. Solid State Chem.
145
,
549
(
1999
).
10.
X.
Zang
 et al,
J. Electrochem. Soc.
148
,
A463
(
2001
).
11.
Z.
Lu
,
D. D.
MacNeil
, and
J. R.
Dahn
,
Electrochem. Solid-State Lett.
4
,
A191
(
2001
);
Z.
Lu
and
J. R.
Dahn
,
J. Electrochem. Soc.
149
,
A815
(
2002
).
12.
T.
Ohzuku
and
Y.
Makimura
,
Chem. Lett.
30
,
642
(
2001
).
13.
J.-S.
Kim
,
C. S.
Johnson
, and
M. M.
Thackeray
,
Electrochem. Commun.
4
,
205
(
2002
).
14.
N.
Yabuuchi
and
T.
Ohzuku
, Extended abstract,
11th International Meeting on Lithium Batteries (IMLB 11), Monterey, CA, 23–28 June 2002
(unpublished).
15.
Z.
Lu
,
D. D.
MacNeil
, and
J. R.
Dahn
,
Electrochem. Solid-State Lett.
4
,
A200
(
2001
);
D. D.
MacNeil
,
Z.
Lu
, and
J. R.
Dahn
,
J. Electrochem. Soc.
149
,
A1332
(
2002
).
16.
K. M.
Shaju
,
G. V.Subba
Rao
, and
B. V.R.
Chowdari
,
Solid State Ionics
148
,
343
(
2002
).
17.
A.
Deb
,
U.
Bergmann
,
E. J.
Cairns
, and
S. P.
Cramer
,
J. Synchrotron Radiat.
11
,
497
(
2004
).
18.
G. N.
Goerge
and
I. J.
Pickering
,
EXAFSPAK: A suite of computer programs for analysis of x-ray absorption spectra
, Stanford Synchrotron Radiation Laboratory (SSRL), California,
1993
.
19.
M.
Newville
,
J. Synchrotron Radiat.
8
,
322
(
2001
).
20.
N.
Yabuuchi
and
T.
Ohzuku
,
J. Power Sources
119–121
,
171
(
2003
).
21.
Y.
Gao
,
M. V.
Yakovleva
, and
W. B.
Ebner
,
Electrochem. Solid-State Lett.
1
,
117
(
1998
).
22.
J. R.
Mueller-Neuhaus
,
R. A.
Dunlap
, and
J. R.
Dahn
,
J. Electrochem. Soc.
147
,
3598
(
2000
).
23.
Y.
Koyama
,
I.
Tanaka
,
H.
Adachi
,
Y.
Makimura
, and
T.
Ohzuku
,
J. Power Sources
119–121
,
644
(
2003
).
24.
I.
Saadoune
and
C.
Delmas
,
J. Solid State Chem.
136
,
8
(
1998
).
25.
T.
Ohzuku
and
A.
Ueda
,
J. Electrochem. Soc.
141
,
2972
(
1994
).
26.
D.-C.
Li
,
T.
Muta
,
L.-Q.
Zhang
,
M.
Yoshio
, and
H.
Noguchi
,
J. Power Sources
132
,
150
(
2004
).
27.
J. S.
Griffith
,
The Theory of Transition Metal Ions
(
Cambridge University Press
, Cambridge, England,
1961
).
28.
S.
Sugano
,
Y.
Tanabe
, and
H.
Kamimura
,
Multiplets of Transition-Metal Ions
(
Academic
, New York,
1970
), Vol.
1
, p.
73
.
29.
A.
Manceau
,
A. I.
Gorshkov
, and
V. A.
Drits
,
Am. Mineral.
77
,
1133
(
1992
);
B.
Poumellec
,
V.
Kraizman
,
Y.
Aifa
,
R.
Cortes
,
A.
Novakovich
, and
R.
Vedrinskii
,
Phys. Rev. B
58
,
6133
(
1998
);
O.
Sipr
,
A.
Simunek
,
S.
Bocharov
,
T.
Kirchner
, and
G.
Drager
,
Phys. Rev. B
60
,
14115
(
1999
).
30.
J. E.
Hahn
,
R. A.
Scott
,
K. O.
Hodgson
,
S.
Doniach
,
S. R.
Desjardins
, and
E. I.
Solomon
,
Chem. Phys. Lett.
88
,
595
(
1982
).
31.
M.
Belli
,
A.
Scafati
,
A.
Bianconi
,
S.
Mobilio
,
L.
Palladino
,
A.
Reale
, and
E.
Burattini
,
Solid State Commun.
35
,
355
(
1980
);
A.
Manceau
,
A. I.
Gorshkov
, and
V. A.
Drits
,
Am. Mineral.
77
,
1133
(
1992
).
32.
C. R.
Horne
,
U.
Bergmann
,
M. M.
Grush
,
R. C.C.
Perera
,
D. L.
Ederer
,
T. A.
Callcott
,
F. J.
Cairns
, and
S. P.
Cramer
,
J. Phys. Chem. B
104
,
9587
(
2000
).
33.
M.
Pouchard
,
A.
Villesuzanne
, and
J.-P.
Doumerec
,
J. Solid State Chem.
162
,
282
(
2001
).
34.
M. G.
Kim
,
Y. S.
Im
,
E. J.
Oh
,
K. H.
Kim
, and
C. H.
Yo
,
Physica B
229
,
338
(
1997
).
35.
A.
Chainani
,
M.
Mathew
, and
D. D.
Sarma
,
Phys. Rev. B
46
,
9976
(
1992
).
36.
Y.
Iwasawa
,
X-Ray Absorption Fine Structure for Catalyst and Surfaces
(
World Scientific
, Singapore,
1996
).
37.
G. J.
Colpas
,
M. J.
Maroney
,
C.
Bagyinka
,
M.
Kumar
,
W. S.
Willis
,
S. L.
Suib
,
N.
Baidya
, and
P. K.
Mascharak
,
Inorg. Chem.
30
,
920
(
1991
).
38.
A.
Bianconi
, in
X-Ray Absorption: Principles, Applications, Techniques of EXAFS, SEXAFS, and XANES
, edited by
D. C.
Koningsberger
(
Wiley
, New York,
1988
).
39.
J. A.
Victoreen
,
J. Appl. Phys.
19
,
855
(
1948
).
40.
D. C.
Koningsberger
and
R.
Prins
, in
X-Ray Absorption: Principles, Applications, Techniques of EXAFS, SEXAFS, and XANES
(
Wiley
, New York,
1988
).
41.
I.
Nakai
and
T.
Nakagome
,
Electrochem. Solid-State Lett.
1
,
259
(
1998
).
42.
I.
Nakai
,
K.
Takahashi
,
Y.
Shiraishi
,
T.
Nakagome
,
F.
Izumi
,
Y.
Ishii
,
F.
Nishikawa
, and
T.
Konishi
,
J. Power Sources
68
,
536
(
1997
).
43.
A.
Rougier
,
C.
Delmas
, and
A. V.
Chadwick
,
Solid State Commun.
94
,
123
(
1995
).
44.
I.
Nakai
,
K.
Takahashi
,
Y.
Shiraishi
,
T.
Nakagome
, and
F.
Nishikawa
,
J. Solid State Chem.
140
,
145
(
1998
).
45.
R. D.
Shannon
,
Acta Crystallogr., Sect. A: Cryst. Phys., Diffr., Theor. Gen. Crystallogr.
A32
,
751
(
1976
).
46.
A. N.
Mansour
,
J.
McBreen
, and
C. A.
Melendres
,
J. Electrochem. Soc.
146
,
2799
(
1999
).
47.
W. E.
O’Grady
,
K. I.
Pandya
,
K. E.
Swider
, and
D. A.
Corrigan
,
J. Electrochem. Soc.
143
,
1613
(
1996
).
48.
J.-M.
Kim
and
H.-T.
Chung
,
Electrochim. Acta
49
,
3573
(
2004
).
You do not currently have access to this content.