Operando magnetic susceptibility measurements on the LixNi1/3Mn1/3Co1/3O2 cathode material during repetitive electrochemical cycling were performed, enabling a continuous and bulk sensitive monitoring of the charge compensation process. Upon charging and Li extraction down to the Li contents of x = 1/3, exclusively Ni undergoes oxidation in two consecutive steps, namely, Ni2+Ni3+ for x > 2/3 and Ni3+Ni4+ for 2/3 > x > 1/3 with a continuous transition in between. In the regime of low Li concentrations x < 1∕3, both Co- and O-ions contribute to the charge compensation. While the oxidation of Ni and O during charging is reversible, the Co oxidation is found to be irreversible.

1.
T.
Ohzuku
and
Y.
Makimura
,
Chem. Lett.
30
,
642
(
2001
).
2.
J. B.
Goodenough
and
Y.
Kim
,
Chem. Mater.
22
,
587
(
2010
).
3.
K.
Shaju
,
G. S.
Rao
, and
B.
Chowdari
,
Electrochim. Acta
48
,
145
(
2002
).
4.
C. F.
Petersburg
,
Z.
Li
,
N. A.
Chernova
,
M. S.
Whittingham
, and
F. M.
Alamgir
,
J. Mater. Chem.
22
,
19993
(
2012
).
5.
J.-M.
Kim
and
H.-T.
Chung
,
Electrochim. Acta
49
,
937
(
2004
).
6.
Y. W.
Tsai
,
B. J.
Hwang
,
G.
Ceder
,
H. S.
Sheu
,
D. G.
Liu
, and
J. F.
Lee
,
Chem. Mater.
17
,
3191
(
2005
).
7.
A.
Deb
,
U.
Bergmann
,
S. P.
Cramer
, and
E. J.
Cairns
,
J. Appl. Phys.
97
,
113523
(
2005
).
8.
M. G.
Kim
,
H. J.
Shin
,
J.-H.
Kim
,
S.-H.
Park
, and
Y.-K.
Sun
,
J. Electrochem. Soc.
152
,
A1320
(
2005
).
9.
H.
Kobayashi
,
Y.
Arachi
,
S.
Emura
,
H.
Kageyama
,
K.
Tatsumi
, and
T.
Kamiyama
,
J. Power Sources
146
,
640
(
2005
).
10.
X.
Liu
,
D.
Wang
,
G.
Liu
,
V.
Srinivasan
,
Z.
Liu
,
Z.
Hussain
, and
W.
Yang
,
Nat. Commun.
4
,
2568
(
2013
).
11.
B. J.
Hwang
,
Y. W.
Tsa
,
D.
Carlier
, and
G.
Ceder
,
Chem. Mater.
15
,
3676
(
2003
).
12.
Z.
Li
,
N. A.
Chernova
,
M.
Roppolo
,
S.
Upreti
,
C.
Petersburg
,
F. M.
Alamgir
, and
M. S.
Whittingham
,
J. Electrochem. Soc.
158
,
A516
(
2011
).
13.
W.-S.
Yoon
,
C. P.
Grey
,
M.
Balasubramanian
,
X.-Q.
Yang
,
D. A.
Fischer
, and
J.
McBreen
,
Electrochem. Solid State
7
,
A53
(
2004
).
14.
W.-S.
Yoon
,
M.
Balasubramanian
,
K. Y.
Chung
,
X.-Q.
Yang
,
J.
McBreen
,
C. P.
Grey
, and
D. A.
Fischer
,
J. Am. Chem. Soc.
127
,
17479
(
2005
).
15.
A.
Mauger
,
F.
Gendron
, and
C.
Julien
,
J. Alloy Compd.
520
,
42
(
2012
).
16.
E.
Shinova
,
R.
Stoyanova
,
E.
Zhecheva
,
G.
Ortiz
,
P.
Lavela
, and
J.
Tirado
,
Solid State Ionics
179
,
2198
(
2008
).
17.
M.
Labrini
,
I.
Saadoune
,
F.
Scheiba
,
A.
Almaggoussi
,
J.
Elhaskouri
,
P.
Amoros
,
H.
Ehrenberg
, and
J.
Brötz
,
Electrochim. Acta
111
,
567
(
2013
).
18.
S.
Miao
,
M.
Kocher
,
P.
Rez
,
B.
Fultz
,
Y.
Ozawa
,
R.
Yazami
, and
C. C.
Ahn
,
J. Phys. Chem. B
109
,
23473
(
2005
).
19.
D.
Mohanty
and
H.
Gabrisch
,
J. Power Sources
220
,
405
(
2012
).
20.
Y.
Koyama
,
I.
Tanaka
,
H.
Adachi
,
Y.
Makimura
, and
T.
Ohzuku
,
J. Power Sources
119–121
,
644
(
2003
).
21.
S.
Topolovec
,
H.
Kren
,
G.
Klinser
,
S.
Koller
,
H.
Krenn
, and
R.
Würschum
,
J. Solid State Electron.
20
,
1491
(
2016
).
22.
N.
Kizilitas-Yavuz
,
M.
Herklotz
,
A. M.
Hashem
,
H. M.
Abuzeid
,
B.
Schwarz
,
H.
Ehrenberg
,
A.
Mauger
, and
C. M.
Julien
,
Electrochim. Acta
113
,
313
(
2013
).
23.
J.
Kasnatscheew
,
M.
Evertz
,
B.
Streipert
,
R.
Wagner
,
R.
Klopsch
,
B.
Vortmann
,
H.
Hahn
,
S.
Nowak
,
M.
Amereller
,
A.-C.
Gentschev
,
P.
Lamp
, and
M.
Winter
,
Phys. Chem. Chem. Phys.
18
,
3956
(
2016
).
24.
B. B.
Berkes
,
A.
Jozwiuk
,
H.
Sommer
,
T.
Brezesinski
, and
J.
Janek
,
Electrochem. Commun.
60
,
64
(
2015
).
25.
D.
Kellerman
,
V.
Galakhov
,
A.
Semenova
,
Y.
Blinovskov
, and
O.
Leonidova
,
Phys. Solid State
48
,
548
(
2006
).
26.
C.-H.
Chen
,
B.-J.
Hwang
,
C.-Y.
Chen
,
S.-K.
Hu
,
J.-M.
Chen
,
H.-S.
Sheu
, and
J.-F.
Lee
,
J. Power Sources
174
,
938
(
2007
).
27.
W.-S.
Yoon
,
K.-B.
Kim
,
M.-G.
Kim
,
M.-K.
Lee
,
H.-J.
Shin
,
J.-M.
Lee
,
J.-S.
Lee
, and
C.-H.
Yo
,
J. Phys. Chem. B
106
,
2526
(
2002
).
28.
L.
Dahéron
,
R.
Dedryvére
,
H.
Martinez
,
M.
Ménétrier
,
C.
Denage
,
C.
Delmas
, and
D.
Gonbeau
,
Chem. Mater.
20
,
583
(
2008
).
29.
G.
Klinser
,
S.
Topolovec
,
H.
Kren
,
S.
Koller
,
H.
Krenn
, and
R.
Würschum
,
Solid State Ionics
293
,
64
(
2016
).
30.
K.
Ishidzu
,
Y.
Oka
, and
T.
Nakamura
,
Solid State Ionics
288
,
176
(
2016
).
You do not currently have access to this content.