Surface degradation of Li1–xNi0.80Co0.15Al0.

05O2 cathodes: Correlating charge

transfer impedance with surface phase transformations
S. Sallis, N. Pereira, P. Mukherjee, N. F. Quackenbush, N. Faenza, C. Schlueter, T.-L. Lee, W. L. Yang, F.
,
Cosandey, G. G. Amatucci, and L. F. J. Piper

Citation: Appl. Phys. Lett. 108, 263902 (2016); doi: 10.1063/1.4954800

View online: http://dx.doi.org/10.1063/1.4954800
View Table of Contents: http://aip.scitation.org/toc/apl/108/26
Published by the American Institute of Physics
 APPLIED PHYSICS LETTERS 108, 263902 (2016)

Surface degradation of Li1–xNi0.80Co0.15Al0.05O2 cathodes: Correlating charge

transfer impedance with surface phase transformations
S. Sallis,1 N. Pereira,2 P. Mukherjee,3 N. F. Quackenbush,4 N. Faenza,2 C. Schlueter,5
T.-L. Lee,5 W. L. Yang,6 F. Cosandey,3 G. G. Amatucci,2 and L. F. J. Piper1,4,a)
1
Materials Science and Engineering, Binghamton University, Binghamton, New York 13902, USA
2
Energy Storage Research Group, Department of Materials Science and Engineering, Rutgers University,
North Brunswick, New Jersey 08902, USA
3
Department of Materials Science and Engineering, Rutgers University, North Brunswick, New Jersey 08902,
USA
4
Department of Physics, Applied Physics and Astronomy, Binghamton University, Binghamton, New York
13902, USA
5
Diamond Light Source Ltd., Harwell Science and Innovation Campus, Didcot, Oxfordshire OX11 0DE,
United Kingdom
6
Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA
(Received 18 May 2016; accepted 14 June 2016; published online 27 June 2016)
The pronounced capacity fade in Ni-rich layered oxide lithium ion battery cathodes observed when
cycling above 4.1 V (versus Li/Liþ) is associated with a rise in impedance, which is thought to be due
to either bulk structural fatigue or surface reactions with the electrolyte (or combination of both).
Here, we examine the surface reactions at electrochemically stressed Li1–xNi0.8Co0.15Al0.05O2 binder-
free powder electrodes with a combination of electrochemical impedance spectroscopy, spatially
resolving electron microscopy, and spatially averaging X-ray spectroscopy techniques. We circumvent
issues associated with cycling by holding our electrodes at high states of charge (4.1 V, 4.5 V, and
4.75 V) for extended periods and correlate charge-transfer impedance rises observed at high voltages
with surface modifications retained in the discharged state (2.7 V). The surface modifications involve
significant cation migration (and disorder) along with Ni and Co reduction, and can occur even in the
absence of significant Li2CO3 and LiF. These data provide evidence that surface oxygen loss at the
highest levels of Liþ extraction is driving the rise in impedance. Published by AIP Publishing.
[http://dx.doi.org/10.1063/1.4954800]

Nickel-rich layered oxides as positive electrodes within
lithium ion batteries offer high theoretical capacities but
suffer from irreversible capacity fading with cycling at
the highest levels of charge. The substitution of metals to
stabilize the structure (Al3þ, Ti4þ, Mn3þ, and Co3þ) along
with synthesizing in lithium excess conditions have circum-
vented bulk issues, such as Ni/Li inter-site mixing and
Ni2þ formation, that hinder the capacity and cyclability
of LiNiO2.1 Indeed, Li1–xNi0.8Co0.15Al0.05O2 (NCA) and
Li1–xNixMnyCozO2 (NMC) compounds are among the best-
in-class commercial cathodes capable of delivering high dis-
charge capacities of up to 200 mAhg1, which are considered
promising for electric vehicle applications.2 However, this is
still far below its theoretical capacity exceeding 265 mAhg1
because significant capacity fading occurs when charged
beyond 4.1 V (vs. Li/Liþ).
Increasing evidence has determined that the capacity
retention issues in Ni-rich layered oxides are largely due to
interactions at the electrode–electrolyte interface (EEI) that
occur in the highly reactive delithiated phase.3–9 This is in
keeping with reports of dramatically improved capacity
retention for layered oxide electrodes protected by surface
coatings, especially insulating Al oxides.10–12 Moreover,
classical electrochemical impedance spectroscopy (EIS) has
long identified the formation of a surface film on layered ox-
ide cathodes as a source of the observed impedance rise
a)
Electronic mail: lpiper@binghamton.edu
upon cycling,13 which has since been shown to be true for
NCA.14 Unfortunately, the EEI associated with the positive
electrode is less understood than for the negative electrode.15
At the negative electrode, a solid electrolyte interface (or
SEI) layer is formed due to the electrochemical reduction of
the electrolyte, and the composition of the SEI layer is
mostly carbonates and LiF.15 However, Li2CO3 and LiF spe-
cies are still observed at cathode surfaces, including
NCA.6,9,15,16 This is surprising since electrolyte reduction
should not occur at the cathode, and even electrolyte oxida-
tion is not expected for most layered cathode materials based
on the location of the highest occupied molecular orbital of
most commercial electrolytes.15 These surface species likely
originate from undesired chemical reactions due to either air
exposure (Li2CO3) or reactions with HF from decomposed
salt and residual water in the electrolyte (LiF).15,16 While
these species can harm the electrochemical performance and
capacity retention,17 pronounced phase transformations
resulting in a “rocksalt-like” surface phase must also be
accounted for.3–9 Accelerated cycling tests at elevated tem-
peratures have shown that Ni-rich layered oxides electrodes
(including NCA) undergo significant power fading that coin-
cide with the formation of electrochemically inactive NiO-
like rocksalt phases at particle surface thought to be due
to loss of oxygen.18,19 Recent transmission electron micros-
copy studies employing electron energy loss spectroscopy
(STEM-EELS) have revealed that the formation of the NiO-
like layer occurs sooner than previously thought, i.e., at 50%

0003-6951/2016/108(26)/263902/4/$30.00 108, 263902-1 Published by AIP Publishing.

263902-2 Sallis et al. Appl. Phys. Lett. 108, 263902 (2016)

depth of charge in the first cycle.8 However, the presence of Figure 1 shows the EIS spectra evolution with time over
Li2CO3 and LiF species makes it difficult to determine 5 weeks at constant voltage after charge to 4.1, 4.5, and
whether the surface species induce the phase transformations 4.75 V. As expected, the impact of state of charge and poten-
or if the surface phase transformations are inherently due to tial is substantial. While the EIS spectra recorded remains
surface oxygen loss. Understanding this distinction between fairly constant at low potential (i.e., up to 4.1 V), significant
extrinsic chemical and intrinsic electrochemical origins is development of charge transfer impedance is apparent by the
important for the rational design of next-generation high evolution of the semicircle associated with the R3 intercept
capacity-retention positive cathodes. over time above 4.1 V. The degree to which NCA is delithi-
Here, we present results of electrochemically stressed ated, as affected by the increase in voltage, clearly dictates
binder-free NCA powder electrodes from EIS, spatially the immediate and subsequent evolution of impedance with
resolving transmission electron microscopy (TEM), spatially time.
averaging X-ray absorption spectroscopy (XAS), and X-ray XPS studies of reference electrodes at various states of
photoelectron spectroscopy (XPS). We present evidence of a charge (SOC) immediately ruled out the build-up of organic
correlation between impedance rise and electrochemically EEI species, such as LiF and Li2CO3, as the origin of the im-
induced surface phase transformations involving Ni (and Co) pedance growth. The Li 1 s and C 1 s core-level XPS analysis
reduction and Ni migration in the absence of organic build- of our NCA electrodes is provided in the supplementary
up. The observation of surface phase transformations in the material (Fig. S2). Although LiF was observed in the held
absence of traditional EEI components (such as Li2CO3 and (and discharged) NCA electrodes, the LiF signal is almost
LiF) reveals that surface oxygen loss is the driving mecha- below detectable limits for electrodes 4.5 V (SOC), i.e.,
nism for the surface phase transformations that contribute to when the impedance growth is occurring in Fig. 1. Moreover,
the impedance rise. Li2CO3 was undetectable in all of the electrodes (except for
Our studies employed powder electrodes of commer- the 3.6 V SOC electrode).
cially available NCA active material with 2.5 wt. % carbon No evidence of electrochemically induced phase trans-
black. The preparation and characterization of the NCA pow- formations were observed in our TEM studies of NCA pow-
der electrodes is provided in the supplementary material. For der electrodes held at 4.1 V for 2 weeks (supplementary
the LiCoO2 parent material, polyvinylidene fluoride (PVDF) material, refer to Fig. S3), consistent with the corresponding
binder in slurry electrodes has been shown to significantly impedance spectra showing very little impedance build up
accelerate surface Co reduction and dissolution into the elec- for this voltage (refer to Fig. 1(a)). Selected area electron
trolyte when employing a lithium hexafluorophosphate
(LiPF6) salt in ethylene carbonate and dimethyl carbonate
(EC:DMC) electrolyte.20 As a result, the PVDF-binder has
been excluded from the electrode preparation of this study in
order to circumvent chemically induced surface reduction
reactions and provide optimal samples for post electrochem-
istry characterization. We note that the absence of PVDF-
binder did not harm the electrochemical performance of our
powder electrodes in this study. The charge and discharge
capacities for all the electrodes studied by TEM/XPS/XAS
presented here are provided in the supplementary material
(Tables SI-SIV). Table I shows that the results obtained in
this study are consistent with results obtained with electrodes
fabricated with PVDF-binder. Samples held at a constant
voltage above 4.1 V for 2 weeks exhibit charge capacities
in excess of the 265 mAhg1 theoretical capacity (at 0.05 Li
content) of NCA due to corrosion. Finally, we also would
like to note that the electrochemical performance was
highly reproducible between duplicate batches for the
TEM/XPS/XAS measurements.

TABLE I. Representative electrochemical data of NCA powder electrodes.

Voltage held Duration Charge capacity Discharge capacity Li

(V) (weeks) (mAhg1) (mAhg1) content

3.6 0 16.4 … 0.94

4.1 2.18 232.2 170.1 0.78
4.5 0 231.2 … 0.17
4.5 2.18 324.0 184.4 0.71
4.75 0 255.6 … 0.08 FIG. 1. Impedance spectra recorded every 12 h over 5 weeks at constant
4.75 2.18 375.5 215.1 0.82 voltage after charge to 4.1 V, 4.5 V, and 4.75 V. Only selected representative
spectra were plotted for clarification.
263902-3 Sallis et al.
diffraction (SAED) patterns from the interior (1) and surface
(2) of the particle shown in Fig. S3 both display the layered
R3m diffraction pattern expected for NCA.
In contrast, the NCA particle electrodes held at 4.5 V
exhibited two additional distinct phases to the layered R3m
phase at their surfaces. Figure 2 displays TEM images of three
different surfaces of a representative NCA particle held at
4.5 V for 2 weeks before discharging to 2.7 V. Based on our
SAED analysis, two of the surfaces displayed layered (R3m)
phases while the third shows a spinel (Fd3m) phase. We note
that a subsurface spinel phase has previously been reported
for Ni-rich layered oxides.4,8,19 Further inspection of the third
surface revealed a rocksalt NiO-like surface layer that was re-
stricted to 2–3 nm of the surface, based on our HR-TEM and
EELS analysis. The observation of surface phase transforma-
tions at this voltage agrees well with the observed onset in im-
pedance rise with time at this voltage (Fig. 1).
Extended disordered phases are significantly more pro-
nounced in the electrode held at 4.75 V. They are found to
extend up to 30 nm from the surface. Figure 3 displays two
distinct high resolution HAADF-STEM images highlighting
considerable cation migration into the Li layer (top figures)
and with complete cation disordering (bottom figures). In the
former, diffraction spots from Ni in the Li layer can be easily
identified (note that these weaker interlayer spots due to Ni
migration are absent for surfaces 1 and 2 of Fig. 2). The for-
mation of insulating disordered phases would significantly
hinder Liþ transport and would contribute to the massive
increase in impedance observed at this voltage (Fig. 1).
FIG. 2. TEM and SAED images of a NCA electrode particle held at 4.5 V.
Three distinct phases can be identified between the interior, subsurface, and
surface. Three surfaces are shown (top left), with surfaces 1 and 2 displaying
a layered (R3m) phase up to the surface. Surface 3 displays a spinel (Fd3m)
phase, with a disordered rocksalt phase in the first 2–3 nm (top right).
Appl. Phys. Lett. 108, 263902 (2016)
FIG. 3. High-resolution HAADF-STEM images of two subsurface structures
of a representative NCA electrode particle held at 4.75 V. (Top left) Layered
R3m structure with extensive cation migration into the Li layer and (bottom
left) cation disordered phase with “rocksalt like” contrast observed up to
30 nm from the surface. Enlarged respective figures with highlighted struc-
ture R3m and Fm 3m models are shown on the right.
High-resolution surface sensitive total electron yield
(TEY) mode XAS was employed to obtain oxidation state in-
formation, to complement the TEM studies. Figure 4 displays
the O K-edge, Ni and Co L3,2-edge XAS with an effective
probing depth of 5 nm, determined from our epitaxial oxide
studies.21 Before discussing these data we note that the elec-
trode held at 4.1 V for 2 weeks (and discharged to 2.7 V) is
spectroscopically indistinguishable from a reference powder
electrode at a SOC of 3.6 V (refer to supplementary material,
Fig. S4) in either TEY or bulk-sensitive total fluorescent yield
(TFY) detection (refer to supplementary material, Fig. S4).
This is expected for these electrodes since they should be lay-
ered R3m phase throughout. This also confirms that the held
electrodes recover to the nominally Ni3þ line-shape in the
bulk, consistent with their discharged Li contents (refer to
supplementary material, Fig. S4 and Tables SIII and SIV). As
a result, any differences in the TEY mode XAS between the
held electrodes held above 4.1 V must reflect electrochemi-
cally induced surface phase transformations.
The Ni L3,2-edge in Fig. 4 shows increased relative
spectral weight at 853 eV for electrodes held at 4.5 V and
4.75 V (compared with 4.1 V), which reflects surface Ni2þ.
This observation is consistent with the extended cation disor-
dered phase with “rocksalt-like” contrast seen in the TEM
studies for the NCA surfaces held at these voltages (Figs. 2
and 3). Further support is provided by closer inspection of
the corresponding TEY mode O K-edge XAS spectra. The O
K-edge can probe the hybridization between the unoccupied
O 2 p and metal 3 d and 4sp states, and provides the same in-
formation as O K-edge EELS. Previous studies have
employed O K-edge STEM-EELS to identify a “rocksalt
NiO”-like surface phase in NCA.4,8,19 Here, the TEY mode
XAS provides better instrumental resolution while being
highly surface-sensitive. In Fig. 4 the main peak at 529 eV
263902-4 Sallis et al.
is related to the O 2 p and Ni eg (and Co eg) hybridization of
NCA. The spectra for the electrodes held at 4.5 V and 4.75 V
display an additional feature at 532 eV (compared with the
4.1 V), which is attributed to the formation of surface NiO-
like oxygen environment based on direct comparison with
reference NiO thin films.
In addition, our XAS in Fig. 4 present evidence of sur-
face Co reduction occurring in tandem with surface Ni
reduction. We note that the 4.1 V held electrode reflects a
Co3þ lineshape, expected for the discharged state. The
appearance of additional multiplet features is consistent with
coexisting Co2þ containing surface species (most likely spi-
nel Co3O4 and related phases). Similar evidence of surface
Co2þ species have been reported in NMC electrodes.5
Evidence of Co surface reduction at NCA electrodes has
been suggested previously,4,19 but Co reduction is rarely
considered in recent studies of phase transformations of
NCA.8 As a result, the extended cation disordered surface
phase may contain significant Co2þ contributions and must
be accounted for in computational studies. We note that Co
reduction (and dissolution into the electrolyte) at LiCoO2
surfaces is known to cause impedance growth.22
To conclude, we present combined impedance, electron
microscopy, and X-ray spectroscopy results of electrochemi-
cally stressed NCA electrodes. We observe the formation of
an extended surface cation disordered phase with reduced Ni
and Co surface species above 4.1 V, which correlates well
with a pronounced impedance rise above this voltage. We
note that our observed phase transformations occur at higher
voltages than reported for slurry electrodes,8 which we at-
tribute to PVDF accelerating surface reduction in the latter.
The use of binder-free powder electrodes also reveal that sur-
face phase transformations can occur in the absence of sig-
nificant chemically induced electrode-electrolyte species,
such as Li2CO3 and LiF. This highlights surface oxygen loss
at high levels of Liþ extraction as the driving mechanism for
the surface phase transformations and resultant charge trans-
fer impedance growth. The formation of an extended cation
disordered phase near the surface is likely to severely impede
transport. In addition, the reduction and possible subsequent
dissolution of Ni2þ and Co2þ into the electrolyte could also
poison the counter electrode, as seen for Co-rich layered
oxides.
See the supplementary material for a full description of
the electrode preparation and electrochemical characteriza-
tion along with details regarding the XPS, TEM, and XAS.
Additional XPS, TEM, and XAS analysis is provided.
Appl. Phys. Lett. 108, 263902 (2016)
FIG. 4. High resolution TEY mode
XAS of the (left) Ni L3,2, (middle) O K-,
and (right) Co L3,2-edges of three elec-
trodes held at 4.1 V, 4.5 V, and 4.75 V
for 2 weeks and measured in the dis-
charged state of 2.7 V vs. Li/Liþ. A ref-
erence NiO film is included as a
reference Ni2þ lineshape. The arrows
indicate evidence of surface NiO and
Co2þ contributions for electrodes held at
4.5 V and 4.75 V.
We thank Professor Gerbrand Ceder for discussions.
This work was supported as part of NECCES, an Energy
Frontier Research Center funded by the U.S. Department of
Energy, Office of Science, Office of Basic Energy Sciences
under Award No. DE-SC0012583. XAS experiments were
performed at beamline 8.0.1 at the ALS and beamline I09 at
Diamond Light Source. The work at ALS was supported by
the Office of Basic Energy Sciences, of the U.S. Department
of Energy under Contract No. DE-AC02-05CH11231. We
thank Diamond Light Source for access to beamline I09
(SI12764) that contributed to the results presented here.
1
A. Manthiram, J. C. Knight, S. T. Myung, S. M. Oh, and Y. K. Sun, Adv.
Energy Mater. 6, 1501010 (2015).
2
M. S. Whittingham, Chem. Rev. 104, 4271 (2004).
3
J. Li, L. E. Downie, L. Ma, W. Qiu, and J. R. Dahn, J. Electrochem. Soc.
162, A1401 (2015).
4
S. Zheng, R. Huang, Y. Makimura, Y. Ukyo, C. a. J. Fisher, T. Hirayama,
and Y. Ikuhara, J. Electrochem. Soc. 158, A357 (2011).
5
F. Lin, I. M. Markus, D. Nordlund, T.-C. Weng, M. D. Asta, H. L. Xin,
and M. M. Doeff, Nat. Commun. 5, 3529 (2014).
6
M. Shikano, H. Kobayashi, S. Koike, H. Sakaebe, E. Ikenaga, K.
Kobayashi, and K. Tatsumi, J. Power Sources 174, 795 (2007).
7
L. Baggetto, D. Mohanty, R. a. Meisner, C. a. Bridges, C. Daniel, D. L.
Wood III, N. J. Dudney, and G. M. Veith, RSC Adv. 4, 23364 (2014).
8
S. Hwang, W. Chang, S. M. Kim, D. Su, D. H. Kim, J. Y. Lee, K. Y.
Chung, and E. A. Stach, Chem. Mater. 26, 1084 (2014).
9
S. Watanabe, M. Kinoshita, T. Hosokawa, K. Morigaki, and K. Nakura,
J. Power Sources 258, 210 (2014).
10
S. T. Myung, K. Izumi, S. Komaba, Y. K. Sun, H. Yashiro, and N.
Kumagai, Chem. Mater 17, 3695 (2005).
11
A. T. Appapillai, A. N. Mansour, J. Cho, and Y. Shao-Horn, Chem. Mater.
19, 5748 (2007).
12
L. Daheron, R. Dedryvère, H. Martinez, D. Flahaut, M. Menetrier, C.
Delmas, and D. Gonbeau, Chem. Mater. 21, 5607 (2009).
13
M. G. S. R. Thomas, P. Bruce, and J. B. Goodenough, J. Electrochem.
Soc. 132, 1521 (1985).
14
T. Hayashi, J. Okada, E. Toda, R. Kuzuo, N. Oshimura, N. Kuwata, and J.
Kawamura, J. Electrochem. Soc. 161, A1007 (2014).
15
M. Gauthier, T. J. Carney, A. Grimaud, L. Giordano, N. Pour, H.-H.
Chang, D. P. Fenning, S. F. Lux, O. Paschos, C. Bauer et al., J. Phys.
Chem. Lett. 6, 4653 (2015).
16
K. Edstr€om, T. Gustafsson, and J. O. Thomas, Electrochim. Acta 50, 397
(2004).
17
D.-H. Cho, C.-H. Jo, W. Cho, Y.-J. Kim, H. Yashiro, Y.-K. Sun, and S.-T.
18
Myung, J. Electrochem. Soc. 161, A920 (2014).
A. M. Andersson, D. P. Abraham, R. Haasch, S. MacLaren, J. Liu, and K.
Amine, J. Electrochem. Soc. 149, A1358 (2002).
19
D. P. Abraham, R. D. Twesten, M. Balasubramanian, J. Kropf, D. Fischer,
J. McBreen, I. Petrov, and K. Amine, J. Electrochem. Soc. 150, A1450
(2003).
20
E. Markevich, G. Salitra, and D. Aurbach, Electrochem. Commun. 7, 1298
(2005).
21
N. F. Quackenbush, H.-J. Paik, J. C. Woicik, D. A. Arena, D. G. Schlom,
and L. F. J. Piper, Materials 8, 5452 (2015).
22
G. Amatucci, Solid State Ionics 83, 167 (1996).