Coherent x-ray diffraction imaging is used to map the local three dimensional strain inhomogeneity and electron density distribution of two individual LiNi0.5Mn1.5O4−δ cathode nanoparticles in both ex-situ and in-situ environments. Our reconstructed images revealed a maximum strain of 0.4%. We observed different variations in strain inhomogeneity due to multiple competing effects. The compressive/tensile component of the strain is connected to the local lithium content and, on the surface, interpreted in terms of a local Jahn-Teller distortion of Mn3+. Finally, the measured strain distributions are discussed in terms of their impact on competing theoretical models of the lithiation process.
REFERENCES
1.
A. S.
Andersson
and J. O.
Thomas
, J. Power Sources
97
, 498
–502
(2001
).2.
P.
Arora
, R. E.
White
, and M.
Doyle
, J. Electrochem. Soc.
145
(10
), 3647
–3667
(1998
).3.
J.
Cabana
, M.
Casas-Cabanas
, F. O.
Omenya
, N. A.
Chernova
, D.
Zeng
, M. S.
Whittingham
, and C. P.
Grey
, Chem. Mater.
24
(15
), 2952
–2964
(2012
).4.
H. N.
Chapman
, A.
Barty
, S.
Marchesini
, A.
Noy
, S. P.
Hau-Riege
, C.
Cui
, M. R.
Howells
, R.
Rosen
, H.
He
, J. C. H.
Spence
, U.
Weierstall
, T.
Beetz
, C.
Jacobsen
, and D.
Shapiro
, J. Opt. Soc. Am. A
23
(5
), 1179
–1200
(2006
).5.
Y.-T.
Cheng
and M. W.
Verbrugge
, J. Electrochem. Soc.
157
(4
), A508
–A516
(2010
).6.
J.
Christensen
and J.
Newman
, J. Electrochem. Soc.
153
(6
), A1019
–A1030
(2006
).7.
J.
Christensen
and J.
Newman
, J. Solid State Electrochem.
10
(5
), 293
–319
(2006
).8.
B.
Dunn
, H.
Kamath
, and J.-M.
Tarascon
, Science
334
(6058
), 928
–935
(2011
).9.
C. R.
Fell
, M.
Chi
, Y. S.
Meng
, and J. L.
Jones
, Solid State Ionics
207
, 44
–49
(2012
).10.
J. R.
Fienup
, Appl. Opt.
21
(15
), 2758
–2769
(1982
).11.
J. R.
Fienup
, J. C.
Marron
, T. J.
Schulz
, and J. H.
Seldin
, Appl. Opt.
32
(10
), 1747
–1767
(1993
).12.
E.
Fohtung
, J. W.
Kim
, K. T.
Chan
, R.
Harder
, E. E.
Fullerton
, and O. G.
Shpyrko
, Appl. Phys. Lett.
101
(3
), 033107
(2012
).13.
E. B.
Fohtung
, Ph.D. thesis, Universitätsbibliothek Freiburg
, 2010
.14.
R. E.
Garc ia
, Y.-M.
Chiang
, W. C.
Carter
, P.
Limthongkul
, and C. M.
Bishop
, J. Electrochem. Soc.
152
(1
), A255
–A263
(2005
).15.
R. J.
Gummow
, A.
De Kock
, and M. M.
Thackeray
, Solid State Ionics
69
(1
), 59
–67
(1994
).16.
J. Yu.
Huang
, L.
Zhong
, C. M.
Wang
, J. P.
Sullivan
, W.
Xu
, L. Q.
Zhang
, S. X.
Mao
, N. S.
Hudak
, X. H.
Liu
, A.
Subramanian
, H.
Fan
, L.
Qi
, A.
Kushima
, and J.
Li
, Science
330
(6010
), 1515
–1520
(2010
).17.
J.-H.
Kim
, S.-T.
Myung
, C. S.
Yoon
, S. G.
Kang
, and Y.-K.
Sun
, Chem. Mater.
16
(5
), 906
–914
(2004
).18.
J.-H.
Kim
, C. S.
Yoon
, S.-T.
Myung
, J.
Prakash
, and Y.-K.
Sun
, Electrochem. Solid-State Lett.
7
(7
), A216
–A220
(2004
).19.
S. J.
Leake
, R.
Harder
, and I. K.
Robinson
, New J. Phys.
13
(11
), 113009
(2011
).20.
X.
Li
, Y.
Xu
, and C.
Wang
, J. Alloys Compd.
479
(12
), 310
–313
(2009
).21.
S.
Marchesini
, H.
He
, H. N.
Chapman
, S. P.
Hau-Riege
, A.
Noy
, M. R.
Howells
, U.
Weierstall
, and J. C. H.
Spence
, Phys. Rev. B
68
(14
), 140101
(2003
).22.
Y.
Matsumura
, S.
Wang
, and J.
Mondori
, J. Electrochem. Soc.
142
(9
), 2914
–2918
(1995
).23.
A. A.
Minkevich
, T.
Baumbach
, M.
Gailhanou
, and O.
Thomas
, Phys. Rev. B
78
, 174110
(2008
).24.
A. A.
Minkevich
, E.
Fohtung
, T.
Slobodskyy
, M.
Riotte
, D.
Grigoriev
, T.
Metzger
, A. C.
Irvine
, V.
Novák
, V.
Holý
, and T.
Baumbach
, Europhys. Lett.
94
, 66001
(2011
).25.
M.
Morcrette
, Y.
Chabre
, G.
Vaughan
, G.
Amatucci
, J.-B.
Leriche
, S.
Patoux
, C.
Masquelier
, and J.-M.
Tarascon
, Electrochim. Acta
47
(19
), 3137
–3149
(2002
).26.
G.-A.
Nazri
and G.
Pistoia
, Lithium Batteries: Science and Technology
(Springer
, New York
, 2003
), pp. 361
–380
.27.
K.
Ozawa
, Lithium Ion Rechargeable Batteries: Materials, Technology, and New Applications
, (Wiley
, New York
, 2012
), pp. 11
–38
.28.
D.
Pavlov
, J. Power Sources
42
(3
), 345
–363
(1993
).29.
M. A.
Pfeifer
, G. J.
Williams
, I. A.
Vartanyants
, R.
Harder
, and I. K.
Robinson
, Nature
442
(7098
), 63
–66
(2006
).30.
I.
Robinson
and R.
Harder
, Nat. Mater.
8
(4
), 291
–298
(2009
).31.
D.
Sayre
, Acta Crystallogr.
5
(6
), 843
(1952
).32.
G. K.
Singh
, G.
Ceder
, and M. Z.
Bazant
, Electrochim. Acta
53
(26
), 7599
–7613
(2008
).33.
P. V.
Sushko
, K. M.
Rosso
, J.-G.
Zhang
, J.
Liu
, and M. L.
Sushko
, Adv. Funct. Mater.
23
, 5530
(2013
).34.
M. M.
Thackeray
, A.
de Kock
, M. H.
Rossouw
, D.
Liles
, R.
Bittihn
, and D.
Hoge
, J. Electrochem. Soc.
139
(2
), 363
–366
(1992
).35.
A.
Tripathi
, J.
Mohanty
, S. H.
Dietze
, O. G.
Shpyrko
, E.
Shipton
, E. E.
Fullerton
, S. S.
Kim
, and I.
McNulty
, Proc. Natl. Acad. Sci. U. S. A.
108
(33
), 13393
–13398
(2011
).36.
H.
Wang
, Y.-I.
Jang
, B.
Huang
, D. R.
Sadoway
, and Y.-M.
Chiang
, J. Electrochem. Soc.
146
(2
), 473
–480
(1999
).37.
B.
Xu
, D.
Qian
, Z.
Wang
, and Y. S.
Meng
, Mater. Sci. Eng., R
73
(56
), 51
–65
(2012
).38.
A.
Yamada
and M.
Tanaka
, Mater. Res. Bull.
30
(6
), 715
–721
(1995
).39.
M.-C.
Yang
, B.
Xu
, J.-H.
Cheng
, C.-J.
Pan
, B.-J.
Hwang
, and Y. S.
Meng
, Chem. Mater.
23
(11
), 2832
–2841
(2011
).40.
W.
Yang
, X.
Huang
, R.
Harder
, J. N.
Clark
, I. K.
Robinson
, and H.-K.
Mao
, Nat. Commun.
4
, 1680
(2013
).41.
X.
Zhang
, W.
Shyy
, and A. M.
Sastry
, J. Electrochem. Soc.
154
(10
), A910
–A916
(2007
).42.
J.
Xiao
, X.
Chen
, P. V.
Sushko
, M. L.
Sushko
, L.
Kovarik
, J.
Feng
, Z.
Deng
, J.
Zheng
, G. L.
Graff
, Z.
Nie
, D.
Choi
, J.
Liu
, J.-G.
Zhang
, and M. S.
Whittingham
, Adv. Mater.
24
(16
), 2109
–2116
(2012
).43.
See supplementary material at http://dx.doi.org/10.1063/1.4866030 for x-ray diffraction data, electrochemical data, and a description of the in–situ cell.
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