Unravelling structural ambiguities in lithium- and manganese-rich transition metal oxides

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Although Li- and Mn-rich transition metal oxides have been extensively studied as high-capacity cathode materials for Li-ion batteries, the crystal structure of these materials in their pristine state is not yet fully understood. Here we apply complementary electron microscopy and spectroscopy techniques at multi-length scale on well-formed Li1.2(Ni0.13Mn0.54Co0.13)O2 crystals with two different morphologies as well as two commercially available materials with similar compositions, and unambiguously describe the structural make-up of these samples. Systematically observing the entire primary particles along multiple zone axes reveals that they are consistently made up of a single phase, save for rare localized defects and a thin surface layer on certain crystallographic facets. More specifically, we show the bulk of the oxides can be described as an aperiodic crystal consisting of randomly stacked domains that correspond to three variants of monoclinic structure, while the surface is composed of a Co- and/or Ni-rich spinel with antisite defects.

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### ARTICLE

Received 29 May 2015 | Accepted 23 Sep 2015 | Published 29 Oct 2015 DOI: 10.1038/ncomms9711 OPEN
## Unravelling structural ambiguities in lithium- and manganese-rich transition metal oxides

Alpesh Khushalchand Shukla 1, Quentin M. Ramasse 2, Colin Ophus 3, Hugues Duncan 1,
Fredrik Hage 2 & Guoying Chen 1

Although Li- and Mn-rich transition metal oxides have been extensively studied as

high-capacity cathode materials for Li-ion batteries, the crystal structure of these materials in

their pristine state is not yet fully understood. Here we apply complementary

electron microscopy and spectroscopy techniques at multi-length scale on well-formed

Li1.2(Ni0.13Mn0.54Co0.13)O2 crystals with two different morphologies as well as two
commercially available materials with similar compositions, and unambiguously describe the

structural make-up of these samples. Systematically observing the entire primary particles

along multiple zone axes reveals that they are consistently made up of a single phase, save for

rare localized defects and a thin surface layer on certain crystallographic facets. More

specifically, we show the bulk of the oxides can be described as an aperiodic crystal

consisting of randomly stacked domains that correspond to three variants of monoclinic

structure, while the surface is composed of a Co- and/or Ni-rich spinel with antisite defects.

1 Energy Storage and Distributed Resources Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA. 2 SuperSTEM Laboratory,
SciTech Daresbury Campus, Daresbury WA4 4AD, UK. 3 National Center for Electron Microscopy, Molecular Foundry, Lawrence Berkeley National
Laboratory, Berkeley, California 94720, USA. Correspondence and requests for materials should be addressed to A.K.S. (email: [akshukla@lbl.gov).](mailto:akshukla@lbl.gov)

ayered transition metal oxides (LiMO2, where M is usually
Co, Mn, Ni or some combination thereof) are presently used
as cathode materials for secondary lithium-ion batteries in
# L
consumer electronics, as they provide reversible capacities from
about 140 to 190 mAh g � 1 . It is known that increasing the
lithium and manganese contents in these materials to a general
composition of Li1 þ xM1 � xO2 can lead to much higher capacities,
typically 4250 mAh g � 1 (ref. 1). Although this class of Li- and
Mn-rich transition metal oxides (referred to as LMRTMOs
hereafter) was introduced nearly a decade ago, their commercial
application has been hindered by severe shortcomings in the
materials, including a large first-cycle irreversible capacity loss 2,
voltage and capacity fade 3, d.c. resistance rise at a low state of
charge and transition metal dissolution 4 . Studies have attributed
these issues to the structural changes occurring during first-cycle
activation and prolonged cycling, yet the crystal structure of the
pristine oxides is still a matter of debate. Much of the research
efforts have been focused on electrochemistry 5–9 and phase
transformation 10–13 studies, and several attempts that have been
made to solve the crystal structure of the pristine material in the
past have led to conclusions in three categories: (1) intermixed
nano-domains of two phases that are trigonal LiMO2 (where M
represents all the transition metals present in the compound) and
monoclinic Li2MnO3 (refs 11,14–18), (2) a single monoclinic
phase in the entire sample 19–21 and (3) a single trigonal phase or
a ‘solid solution’ with the presence of a superstructure 19,22 . Bulk
techniques such as powder X-ray or neutron diffraction are
traditionally used for phase identification. However, the
experimental neutron and X-ray diffraction patterns of
LMRTMOs can be fitted to all three proposed models 19,23 .
Conversely, methods such as aberration-corrected scanning
transmission electron microscopy (STEM) provide high spatial
resolution and have been used to suggest a single-phase nature of
the oxides (for instance by Jarvis et al. 20,21 ), but the results were
to our knowledge always derived from small fields of view and
therefore cannot exclude the possibility that other phases were
present within the primary particles. It is unclear whether the
report of three types of structure is a result of different synthesis
conditions and/or compositions used by the various research
groups, both of which have been shown to heavily influence the
crystal structure of the oxides.

Furthermore, structural changes on the surface layers of
LMRTMO were recently attributed to the effects of cycling 24 .
Such transition metal-rich surface layers, however, have
also been observed in pristine materials as reported in
recent studies on Li1.2Ni0.2Mn0.6O2 (ref. 17) and Li1.2Ni0.175
Mn0.525Co0.1O2 (ref. 25).

Thus, a better understanding of structural changes and phase
stability of the cathodes demands comprehensive studies that
unfold both the bulk structure and surface composition in
LMRTMO. In this paper, we report structural and spectroscopic
analyses performed on a variety of LMRTMO samples, including
two crystal samples with discrete, well-formed primary particles
and two commercial samples from different sources, by using
complementary capabilities offered by aberration-corrected
STEM, electron energy loss spectroscopy (EELS) and X-ray
energy-dispersive spectroscopy (XEDS). We present unambiguous evidence that LMRTMOs are composed of a monoclinic
single phase with three different variants in the bulk and a
Co- and/or Ni-enriched spinel surface layer that is crystallographic facet dependent. Our study is mainly based on primary
particles prepared using a molten-salt method with a composition
of Li1.2(Ni0.13Mn0.54Co0.13)O2 having needle and plate morphologies as shown in Supplementary Fig. 1. This synthesis technique
utilizes a liquid reaction medium to enable atomic-level mixing of
the reactants and to allow for a homogeneous nucleation and

growth of crystals from the flux at a relatively low temperature.
Synthesis using this technique results in discrete primary particles
that are impurity-free, making them ideal candidates for
performing fundamental characterization using advanced highspatial resolution techniques such as aberration-corrected STEM.
For comparison, we also studied two commercial samples: TODA
HE5050 having a composition of Li1.2Mn0.55Ni0.15Co0.1O2 and
HCMR XLE2, which has a proprietary composition with a
general formula LiyMO2, where y41, M ¼ Mn, Co and Ni and
Mn4Ni4Co. For all the samples, we obtained three-dimensional structural information by imaging them using multiple
zone axes, thus eliminating the ambiguities that can arise from
the fact that materials with different structures can give similar
two-dimensional projections. It should be emphasized that the
present study is based on results obtained from LMRTMO that
consists of Ni, Mn and Co as the transition metals and have
relatively high amount of lithium. The species in the transition
metal oxides (for example, elements other than Ni, Mn and Co)
and the amount of lithium and/or manganese (for example, in
case of LMRTMO with lithium content closer to stoichiometric
LiMO2) can potentially have an effect on the structure of
LMRTMO.

Results
Observation of monoclinic domains using STEM imaging. To
determine whether the primary particles consist of single phase or
multiple phases using atomic-resolution images, it is necessary to
check whether the projections that are unique to the respective
structure are continuous throughout the primary particle.
Figure 1a shows a high-angle annular dark field (HAADF) image
that consists of bright columns corresponding to the transition
metals. As seen in the micrograph, projections corresponding to

[100], [1 � 10] and [110] directions of the monoclinic phase, shown
in the structural models in Fig. 1d–f, are found in the same field
of view with the flips between the domains occurring on the (001)
plane. It should be noted that HAADF images in this zone axis
consist of doublets of transition metal columns. This projection of
transition metals is unique to the monoclinic phase and impossible for a crystal consisting of a trigonal LiMO2 phase to produce
in any orientation. Domains consisting of these three variants of
the monoclinic phase are shown in orange, blue and green colours in a lower-magnification image in Fig. 1b. HAADF images
taken in this direction have been reported in recent publications 26–28, albeit with small fields of view covering only a small
portion of the primary particles. In this study, we were able to
take atomic-resolution images showing this structure throughout
the primary particles, as shown in Fig. 1g taken from the needleshaped sample, thus eliminating any doubts of presence of other
phases in the primary particle. This was particularly obvious in
the needle sample, where due to the small thickness of the
particle, we were able to image the entire width of the primary
particle in atomic resolution and images along the entire length of
the particle unambiguously proved that although the particle is
made of domains corresponding to the monoclinic variants, it
entirely consists of a single phase. It should be noted that both the
size and stacking of these domains in the direction normal to the
transition metal layer have no apparent order, and the lattice
cannot be translated along the z-direction although it can be
translated along x- and y-directions. It can thus be said that these
LMRTMOs have two-dimensional periodicity. The material is
crystalline, but primary particles are not single crystals. Generally
speaking, these materials can therefore be referred to as aperiodic
crystals according to the modern definition of crystals 29,30 . It can
also be seen from Fig. 1b that the domains usually flip between

[100]M and [110]M or [1 � 10]M, where the subscript M refers to the

b c d

[100]

Transition
metal

Lithium

Oxygen

[100]

[11–0]

2 nm

[11–0]

[110]

2 nm 5 nm

[110]

20 nm 10 Å

Figure 1 | HAADF STEM images taken from the needle sample. (a) HAADF image showing the structure of LMRTMO needles. (b) Colour-coded HAADF
image showing the variants of the monoclinic phase. (c) HAADF image with a larger field of view showing that domains of a single-phase, monoclinic
structure are present throughout the primary particle. (d–f) Model showing the monoclinic structure in [110], [1 � 10] and [110] directions, respectively. (g)
HAADF image showing that the structure is observed over the entire primary particle. Occasionally, transition metal-rich defects are observed as shown in
the inset, which corresponds to the defect shown in the red oval.

monoclinic unit cell, although occasionally reflection twins (flips
between [110] and [1 � 10]) were also observed, consistent with
observations made by Jarvis et al. 27 . Similar observations were
also made on the commercial HCMR XLE2 and TODA HE5050
materials as shown in Supplementary Figs 2b and 3b, respectively,
where the variants of the monoclinic phase were found
throughout the primary particles, except for some infrequently
observed areas consisting of defects.

Further studies on the bulk structure of the materials were
performed by observing the samples in [103]M (normal to the
shared (001)M plane) and the [001]M directions. Figure 2a shows
a HAADF image from the needle sample tilted to [103]M zone
axis. The criss-cross pattern of rows of transition metal columns
corresponds to the presence of three projections of [103]M (as
shown in the lower right inset in Fig. 2b), although two of them
are more prominently present in this example, as also evident
from the diffractogram shown in the inset of Fig. 2a. Several
particles, both from needles and plates, exhibited areas where
only one variant was prominent, as demonstrated in Fig. 2b, that
was taken from the plate sample. Similar results were also
observed in the commercial TODA HE5050 sample, as shown in
Supplementary Fig. 3c. It is interesting to note that in a recent
study on TODA HE5050 material, Mohanty et al. 23 concluded
that this material was more likely a composite of trigonal and
monoclinic phases based on results from temperature-based
magnetic susceptibility measurements, which is contradictory to
the conclusions from this study that clearly shows the absence of
a composite structure based on direct observation using various
zone axes.

While certain directions as shown in the above two examples
uniquely show the presence of variants of monoclinic phase in the
bulk, images taken in some directions can be quite misleading,
which we believe has led to some of the contradicting reports in
the literature. Figure 3 shows an interesting example of a
plate that provided areas with the three variants in varying
amounts due to the presence of terraces on them, as shown in the
lower-magnification image in Fig. 3a. When a single variant is

100 nm

2 nm 2 nm

Figure 2 | Projection of LMRTMO in [103] direction. (a) HAADF image
taken from the needle sample showing all three variants, although only two
of them are the prominently present as shown in the Hanning-masked FFT
image. The inset also shows a STEM image simulated by multislice method
under similar conditions (b) HAADF image taken from the plate sample
where only one variant was prominent as also evident from the Hanningmasked FFT. Model showing projection of transition metals in the
monoclinic structure in [103] direction is also shown in the inset.

imaged in the [001]M direction, a honeycomb or graphene-like
projection is observed. Figure 3b shows a HAADF image from an
area that predominantly consisted of a single variant. Closer
inspection of the image shows that the centre of the hexagon
exhibits some intensity, which is due to the fact that the column
has shared Li and TM occupancy. In some areas, this intensity is
higher. This higher intensity is not due to higher concentration of
transition metals in lithium columns, but simply due to the effect
of stacking of the variants as shown in Fig. 3c, where a
honeycomb-like structure is observed on the top-right corner
(corresponding to the region with a predominantly single variant)
of the image, while a hexagonal-like image is observed in the
bottom-left corner (corresponding to a thicker area where two or
three variants are present). Thus, if a small area with two or three

50 nm 2 nm

2 nm 2 nm

Figure 3 | HAADF images taken in [001]M zone axis. (a) a lowmagnification image showing a terraced plate. (b) Image showing a
honeycomb structure similar to monoclinic Li2MnO3 with predominantly a
single variant. (c) Image from an area corresponding to different levels of
stacking. Note the honeycomb-like structure and hexagonal-like structure in
the top-right and bottom-left regions of the micrograph, respectively.
(d) Image taken from the thick region shown in the bottom-left corner of a,
indicating a region consisting of all three regions and showing a different
structure on the surface.

variants is observed in projection, as shown in the Fig. 3d
corresponding to the thick area, it is possible to mistakenly assign
them to the trigonal phase. Note that Figs 2a and 3d show the
presence of a different phase on the surface that is discussed later
in the paper.

Characterization using EELS and XEDS. To confirm the
presence of a single phase throughout the primary particle, and
particularly the lack of Mn-rich domains as previously reported,
we studied the elemental distribution of transition metals using
both EELS and XEDS. Atomic-resolution EELS maps as shown in
Fig. 4 were obtained on several regions in a primary particle, and
the experiments were repeated on several particles from both
needle and plate samples. Since the material is quite electronbeam sensitive, relatively low doses (o40 pA of current, which is
lower than often used for EELS mapping but still high by comparison with true low-dose experiments 31 ) of electrons were used
and an improved signal-to-noise ratio was obtained using
principal component analysis, which allowed the clear
localization of transition metal atomic columns in the EELS
maps 32 . Oxidation states of transition metals were calculated
from the core-loss ionization edge intensities. L edges in
transition metals result from excitations of 2p electrons into
empty bound states and feature two white lines due to spin–orbitsplit 2p3/2 and 2p1/2 levels to the available states in the 3d band.
The ratio of intensity of these lines, called L23 ratio increases with
decrease in oxidation states for 3d metals. By taking the L3/L2
ratio of the white lines (by applying a cross-section step function
and then integrating the area under the peak corresponding to the

HAADF Mn Co Ni MnCoNi

HAADF 20 nm Mn 40 nm Co 40 nm Ni 40 nm Mn Co Ni

Figure 4 | EELS and XEDS. (a) atomic-resolution EELS maps for the needle
sample and (b) higher field-of-view XEDS maps taken on the plate sample
showing uniform distribution of transition metals.

L3 and L2 edges) as described by Pearson et al. 33, the oxidation
states of the elements present in our samples were found to be
consistent with 4 þ, 3 þ and 2 þ for Mn, Co and Ni,
respectively, as expected 33 . The EELS maps taken throughout
the particle did not exhibit areas with relatively higher manganese
concentration, which would be expected if the particle were a
composite of Li2MnO3 and LiMO2 in the bulk of the particle.
EELS maps taken using other zone axes also did not reveal any
segregation of Mn in the bulk. The uniformity of transition metal
distribution was confirmed by taking XEDS maps with large fields
of view as shown in Fig. 4b, which was taken from a plate sample.
Interestingly, the XEDS maps show that the surface layer on the
edge of the particle, which imaging alone suggested may consist
of a different crystallography than the bulk, exhibits clear cobalt
segregation (with slightly higher than average Ni content). The
structure and composition in this surface layer, as well as the
oxidation states of transition metals therein, will now be discussed
in detail.

Analysis of the surface layer. Figure 5a shows a HAADF image
of the plate sample in the orientation [001]supercell, equivalent to

[103]M. In this plate, only one variant of the monoclinic structure
is predominantly present, similar to the image shown in Fig. 2b,
whereby the dark regions in the striped pattern correspond to
rows of lithium columns, although some intensity from the
presence of transition metals is observed due to the presence of
other variant(s) in a small amount. In the surface layer, these
rows of lower intensities are filled up, making a hexagonal pattern. This phase is typically B2 nm thick and is present on
(010)M facets, as shown in Fig. 5a, and at 120 degrees to (010)M
plane that corresponds to the other two variants of monoclinic
(Fig. 5b), but is also seen on facets normal to (010)M as shown on
the lower part of the image in Fig. 5c. One possible interpretation,
based on the intensities of these extra columns in the HAADF
images, is that the lithium atoms are replaced by transition metal
atoms and the intensities are due to the presence of antisite
defects. However, after examining several particles in different
orientations we were able to conclude that the surface layer had a
different crystal structure, that of a spinel. In particular, the
commercial HCMR XLE2 and TODA HE5050 materials have
primary particles with an equiaxed morphology, which allowed us
to view the primary particles in [010]supercell or the equivalent

[010]M direction. HAADF images taken in this orientation, such
as the one shown in Fig. 5d for the XLE2 material confirmed the

110 111
112

010 103
100

100
nm

111 110
112

301 010
001

103 010

2 nm 100 2 nm

110 111 112 111
112 110

310 103
110

100 103
010

1 nm 1 nm 010 1 nm

111

110

301 010 111 112
001 110

301 001
010

112

Transition metal

Li + transition metal

1 nm

Figure 5 | HAADF images alongside the STEM simulation image and model of the interface. (a) The surface layer is spinel viewed in [111]S zone axis,
while the bulk shows predominantly a single variant of the monoclinic structure. The interface is (010)M. (b,c) Spinel surface on other facets on the same
particle, at 120 degrees from (010)M as shown in c but also seen on facets normal to (010)M, as shown in the upper part of the image in c. (d,e) Spinel
surface and the bulk in [110] and [010] zone axes, respectively. (f) Surface spinel in [112] zone axis and the bulk in the orientation equivalent to [001]M.
Only one variant of the monoclinic structure is shown in the model and STEM simulation. HAADF images in a, b, c and f were recorded from the plate
sample, while those in d and e were recorded from the commercial HCMR XLE2 sample.

presence of a spinel structure on selected surface facets of the
particle. Figure 5d was used to deduce the orientation relationship
between the bulk and the surface spinel, which is described below.

ð001ÞMk ð1 � 11ÞS; ½010�Mk ½110�S

A model of the interface was prepared using this orientation
relationship and it matched with experimental HAADF images
taken with all other zone axes as shown in Fig. 5a–c,f. The zone
axis for the spinel surface layer shown in Fig. 5a–c is [111]S, while
that for Fig. 5f is [112]S. Interestingly, Fig. 5d–f shows that the
crystallographic planes on which these surface layers terminate
are {111}, which are known to be stable facets for spinels in
general according to the Wulff theorem 34,35 .

EELS spectrum imaging revealed interesting changes that shed
light on the structure of the bulk vis-a`-vis that of the surface.
These changes are observed via features in the spectra, such as the
L23 ratio of transition metal white lines and the fine structure of O
K and Mn L2,3 edges. Figure 6a shows a series of EEL spectra
covering EELS edges from O to Ni, corresponding to surface and
bulk regions of areas such as the one shown in Fig. 5a, where each
spectrum was averaged from an area with three rows of atomic
columns to improve signal-to-noise ratios. Figure 6c–e shows the
L23 ratio for the transition metals. Although the exact valence is
difficult to quantify precisely, the trends clearly show that the
oxidation state of Mn and Co decreases as we approach the
surface. The oxidation state of Ni stays constant at 2 þ, as
expected.

Figure 6b shows an expanded view of the spectra close to the
Mn edge, which shows that the Mn L3 edge corresponding to the
surface is at a lower energy loss, compared with that of the bulk,
indicating decrease in oxidation state at the surface. Moreover,
the fine structure of the L3 shows a shoulder corresponding to the
eg � t2g split, which is associated with Mn þ 4 species with
octahedral coordination 36 . The Mn L3 edge corresponding
to the surface, on the other hand, does not clearly show this

split as commonly observed in compounds with Mn in lower
oxidation states. The overall signature of the bulk and the surface
regions also corresponds to layered oxides and spinels,
respectively. A higher oxidation state in the bulk is also
indicated by the higher O pre-peak intensity observed in the
bulk, compared with that in the surface, whose O signature
resembles that of a spinel 37 . EELS spectrum imaging also revealed
segregation of Co and Ni in the plates and needle samples on the
surface. EELS spectrum imaging was also performed in the lowloss region, and analysis of the Li K-edge revealed that Li was
present in these surfaces, although the concentration was lower
than that observed in the bulk.

It should be noted that lithium-containing oxides, and
specifically spinels are very susceptible to electron beam damage,
and it has been recently shown that exposure to electron beam
can also reduce the oxidation states of Mn and Co 38,39 . We also
observed that the use of a higher dose or current led to the
formation of antisite defects, with transition metals replacing Li
atoms. This makes EELS experiments on such surfaces very
challenging as also noted in a recent study on a similar LMRTMO
material 25 . However, we were able to get reliable EELS data by
performing spectrum imaging at 100 kV voltage with lower
current (o40 pA) and short exposures and then improving the
signal-to-noise ratio using principal component analysis 32 .
Furthermore, as mentioned earlier, these surface layers were
found only on certain crystallographic facets, and we confirmed
that the change in oxidation state was not due to the effect of the
electron beam by observing that the oxidation state of Mn and Co
did not noticeably change when we scanned across surfaces that
did not have these spinel domains using similar imaging
conditions. Although the dose used was sufficient to provide us
information on the decrease in oxidation states of transition
metals and segregation of Co and Ni at the surface, we were not
successful in localizing the atomic columns as we did in the case
of the bulk regions (as shown in Fig. 4a), as the acquisition of

1.6×10 5

1.4×10 5

1.2×10 5

1×10 5

8×10 4

6×10 4

4×10 4

2×10 4

0
500 550 600 650 700 750
Energy loss (eV)

800 850 900

5 5

2 3 4 3 4 5 6 3 4 5 6

Mn L3/L2 Co L3/L2 Ni L3/L2

5×10 4

4×10 4

3×10 4

2×10 4

1×10 4

Surface
Bulk

0
635 640 645 650 655 660

Energy loss (eV)

1 2 3 4 3 4 5 6

Figure 6 | Analysis of EELS data. (a) series of EEL spectra showing the surface (top) and the bulk (bottom) corresponding to the HAADF image in
Fig. 5a, (b) Mn L3 and L3 edges for the bulk and the surface, showing the presence of eg � t2g split corresponding to the bulk region and the chemical shift to
lower energy corresponding to the surface. (c,d,e) L3/L2 ratio corresponding to Mn, Co and Ni, respectively, showing decrease in oxidation states for Mn
and Co at the surface.

such data sets required much higher dose rates (longer pixel dwell
times) that in turn led to damage of the surface.

Further characterization of the spinel surface was achieved
using XEDS mapping. Figure 7 shows an XEDS line scan across
the surface shown in Fig. 4. Elemental information obtained from
XEDS experiments confirmed that there was a lower concentration of oxygen at the surface, along with confirming the
segregation of Co and Ni at the expense of Mn. It was also
found that the relative concentration of Co and Ni on the surface
depends on the original bulk composition. For example, the
commercial HCMR XLE2 and TODA HE5050 materials, which
had a higher Ni content exhibited higher concentration of Ni
(compared with that of Co) on the surface, as shown in
Supplementary Fig. 3.

Finally, the HAADF STEM image in Fig. 8 taken from the plate
sample shows the last piece of the puzzle, which represents
certain areas (shown in the red rectangle) that showed an
apparently different structure than that of a conventional spinel.
As seen in the HAADF image, higher intensities were observed at
distances twice that of adjacent columns, creating a ‘superstructure’. This was only observed occasionally on thin and
tapered areas. We considered three possibilities that could
potentially explain this anomaly. First, this could simply be the
effect of thickness on the variation of intensities for different
columns. STEM simulation indeed showed the effect of thickness
as shown in Supplementary Fig. 5, but the intensities in the
calculated HAADF images do not closely match those of the
experimental images. Second, these antisite defects might also be
formed due to exposure to the electron beam. We ruled out this

0
0 50 100 150

Position (nm)

Figure 7 | XEDS line scan across the spinel surface. These line scans
corresponding to images in Fig. 4b for the plate sample show segregation of
Co and Ni and depletion of O and Mn on the surface, relative to the bulk.

possibility by observing such areas even when we rastered the
beam to fresh areas by quickly moving the sample. This leaves us
with the third possibility and the presence of antisite defects in
the spinel structure, whereby some lithium sites are occupied by
transition metals. This is also supported by results obtained
by low-loss EELS, which showed a lower concentration of lithium
at the surface. We can thus conclude that the pattern observed
in these thin areas is due to a combination of the presence of
antisite defects and the lower thickness. These antisite
defects might also be present in the thicker regions such as the

120

100

Mn-KA

Co-KA

Ni-KA

O-KA

2 nm

Figure 8 | Antisite defects on the surface. (a) HAADF STEM image
showing an apparently different structure in the thin areas (shown in the
red-coloured rectangle). (b) A slightly tilted projection of spinel in [111]
direction. The circled regions are the columns with mixed Li and TM atoms,
which correspond to columns with antisite defects (TM in Li sites), giving
higher intensity in HAADF images.

Table 1 | Summary of results.

Monoclinic single variant Monoclinic three variants

[100] [010] [103] [100] [010] [001]

Transition
metal
Lithium
Oxygen

Technique Conclusion

HAADF STEM
imaging and [111]

HAADF STEM Spinel structure on the surface based on [010], [121]
imaging and [111] zone axes, some antisite defects in the

spinel.
Core-loss EELS O-edge signature and L3/L2 ratios indicate lower
oxidation states of Mn and Co.
Li K edge/low- Li is present, but in lower concentration compared
loss EELS with the bulk.

Li K edge/low- Li is present, but in lower concentration compared
loss EELS with the bulk.

Li K edge indicates a spinel structure in the surface
and layered in the bulk.
XEDS Co and Ni segregation on the surface, Mn and
O depletion.

EELS, electron energy loss spectroscopy; HAADF, high-angle annular dark field; STEM, scanning
transmission electron microscopy; XEDS, X-ray energy-dispersive spectroscopy.

flat facet shown on the left side of Fig. 8a as evidenced by the nonuniform intensities in these regions, but the effect is less obvious
due to the higher thickness in these regions. It should be noted
that the antisite defects we are referring to indicate the presence
of transition metals in the (tetrahedral) Li sites in the spinel
structure found on the surface, and not to antisite defects found
in the parent structure as proposed by Dixit et al. 25 in a recent
study on Li1.2Ni0.175Mn0.525Co0.1O2. The results from different
microscopy and spectroscopy techniques are summarized in
Table 1.

Discussion
On the basis of the three-dimensional information obtained by
HAADF images taken using various zone axes and supporting
evidence from XEDS and EELS data, we can now conclude that
the bulk of the primary particles is composed of domains that
correspond to three different variants of monoclinic phase.
Supercells generated by using a single variant of monoclinic unit
cell and by randomizing monoclinic domains that are rotated 120
degrees and stacked on (001)M planes are shown in Fig. 9a,b,
respectively. The directions and their equivalence to a single
crystal of the monoclinic structure are summarized in
Supplementary Table 1. It is worth mentioning that the projection
of the particle with three variants of the monoclinic structure in

Figure 9 | Structural model for LMRTMO. (a) LMRTMO with a single
monoclinic variant and (b) three monoclinic variants in [100], [010] and

[001] directions.

[010]supercell direction and its equivalent directions (rotated 120
degrees along the z-direction) is indistinguishable from a trigonal
structure, for example, in case of stoichiometric LiMO2 with R � 3m
symmetry (when viewed in [010] or [100] directions) and also
from a single crystal of the monoclinic phase. This is true not only
for the projection of the transition metals as observed in HAADF
images, but also for the projection of lighter oxygen and lithium
atoms, as can be seen in annular bright-field images, which have
been used to infer the presence of domains with trigonal structure
in Li-rich-layered materials in recent studies 11,18 . For example, a
projection similar to that shown in Supplementary Fig. 3d can
also be obtained from a single crystal consisting of Li2MnO3 or
LiNi0.33Mn0.33Co0.33O2 when observed in equivalent directions,
and analysis using several zone axes is required to reveal the true
structure of the material.

It has been shown that LMRTMOs convert to spinel 11 or
‘spinel-like’ 24 upon cycling. More recently, it has been shown
that surface layers with a different composition than that of the
bulk are present even in pristine materials and are facet
dependent 17,25, which calls for careful consideration of facets
and orientations of the particles when comparing pristine
and cycled materials. The structure of this surface layer has not
been solved in previous studies, to our knowledge. Gu et al.
suggested that the surface layer in LiNi0.5Mn0.5O2 has the same
structure as the bulk but with a different orientation, while more
recently Dixit et al. 25 suggested that the surface layer consisted of
antisite defects with transition metals substituting on Li sites
based on their study on Li1.2Ni0.175Mn0.525Co0.1O2. We believe
that these discrepancies and ambiguities in the analysis of the
surface layer structure arise due to the fact these conclusions are
based on projections obtained from a single orientation and
several different structures can give the same projections,
especially in the [010]M direction. To this end, we have
observed the surface layer from different orientations to provide
a complete, three-dimensional picture on the surface layer
and its orientation relationship with the bulk structure. Using a
multiple-technique approach, we deduced that the surface

of Li-rich-layered oxides is a Co- and Ni-rich spinel with several
antisite defects.

In conclusion, we have shown unambiguously by the use of
electron probe-based techniques applied over a wide range of
length scales that the bulk structure consists of variants of the
monoclinic phase throughout the particles, except on the surface
of certain facets, where B2-nm layers of spinel structure were
found. The bulk structure was confirmed in four different
samples with different morphologies and compositions, which
indicates that this structure is commonly observed in this class of
materials. This study not only solves the ambiguity in the
structure determination of these materials but it also highlights
the importance of atomic-resolution imaging and spectroscopy
performed on multiple zone axes when carrying out such
investigations. It should be emphasized that these results are
relevant to LMRTMOs, and it will be interesting to see whether
and how the bulk structure changes as the amount of Li and Mn
is decreased and we plan to study this effect in the future. We
hope that results from this study on pristine LMRTMOs will
provide new directions to researchers studying the phase
transformations in this class of materials and can be applied to
potentially solve the problems such as voltage and capacity fade
that are related to the surface and bulk structure. Indeed, the
voltage profiles of initial charge/discharge of LMRTMOs have
been so far conveniently divided into two regions where Li is
removed from the two ‘components’, namely, LiMO2 and
Li2MnO3. The substantial proof on a single phase presented in
this study calls for revisiting the interpretation of the voltage
profiles. Furthermore, with a now clearer understanding of the
surface structure, the facets where they are formed and their
orientation relationship with the bulk, we can attempt to
understand the effect of delithiation and cycling on different
facets by using electron- and X-ray-based tomography techniques 40–43 that can provide both chemical and morphological
information in a wide length scale. Ultimately, such studies can
guide us to engineer primary particles with tailored facets that
would minimize the change of structure and hence the stress and
strain in the cycled material.

Methods
Synthesis. Both needle and plate samples were prepared using the molten-salt
synthesis method. Stoichiometric amounts of LiNO3, Mn(NO3)2 � 4H2O,
Co(NO3)2 � 6H2O and Ni(NO3)2 � 6H2O and of the flux (KCl for needles and CsCl
for plates) were mixed in a flux to a total transition metal molar ratio of 8 and 2,
respectively. The mixture was dissolved in a small amount of water, which was
removed by mild heating under agitation. The dried powder was transferred into
an alumina crucible with a lid, heated at a rate of 3 �C min � 1 and then soaked for
8 h at 800 �C for needles and 900 �C for plates before cooling to room temperature
at a controlled cooling rate.

HCMR XLE2 material was obtained from Envia Systems. According to the
manufacturer, it was prepared using a co-precipitation technique as described in
patent number US 8,741,485. In this process, LMRTMO is prepared using a solidstate method, whereby a lithium source is added to a metal carbonate that is
precipitated from an aqueous solution of metal salts and then calcined at 900 �C.
TODA HE5050 material was obtained from TODA KOGYO Corp.

Electron microscopy. The needles and plate samples were studied using a probecorrected microscope operating at 100 kV accelerating voltage using a convergence
angle of B30 mrad and a collection angle for HAADF images that was calibrated at
82–190 mrad. The commercial samples (Envia and Toda) were observed using a
probe-corrected microscope operating at 80 kV accelerating voltage using a convergence angle of B30 mrad and a collection angle for HAADF images of
60–180 mrad, except for the images in Supplementary Fig. 3a,b,d, which were taken
using the same microscope at 300 kV accelerating voltage, a convergence angle of
B17 mrad and a collection angle of 68–340 mrad. XEDS maps with sub-nanometre
resolution were obtained at 120 kV accelerating voltage using an FEI Titan
microscope equipped with a quad-detector system. Samples for electron microscopy were prepared by drop casting a sonicated solution of LMRTMOs and
anhydrous ethanol. HAADF STEM simulations were performed using a custom
code that was prepared using details provided in ref. 44.

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Acknowledgements
This work was supported by the Assistant Secretary for Energy Efficiency and Renewable
Energy, Office of Vehicle Technologies of the US Department of Energy under Contract
DE-AC02-05CH11231 under the Batteries for Advanced Transportation Technologies
(BATT) Program. Work at the Molecular Foundry was supported by the Office of Science,
Office of Basic Energy Sciences, of the US Department of Energy under Contract No.
DE-AC02-05CH11231. We also acknowledge support from SuperSTEM, Daresbury, UK,
which is the National Facility for Aberration-Corrected Scanning Transmission Electron
Microscopy, supported by the Engineering and Physical Science Research Council. We
thank Dr Robert Kostecki and Dr Subramaniam Venkatachalam for providing the TODA
HE5050 and Envia HCMR XLE2 materials, respectively, Dr Despoina-Maria Kepaptsoglou
for training A.K.S. on the Nion UltraSTEM microscope and Dr Karen Bustillo for her help
with the analysis of the XEDS data. We sincerely thank Dr Amith Darbal, Dr Partha Pratim
Das, Dr Sonia Estrade, Mr Joan Mendoza, Dr Lluis Yedra and Dr Stavros Nicolopoulos for
providing insights into the structural ambiguities of LMRTMO via precession electron
diffraction experiments. We also thank Dr Philippe Moreau, Dr Saravanan Kuppan,
Dr Ulrich Dahmen and Professor Dan Shechtman for useful discussions.

Author contributions
H.D. and G.C. synthesized the plate and needle samples. A.K.S., Q.M.R. and F.H.
performed aberration-corrected STEM imaging and EELS experiments on them. A.K.S.
performed aberration-corrected STEM imaging experiments on the commercial
materials. A.K.S. performed XEDS experiments and analysed microscopy and spectroscopy data from all the samples with inputs from Q.M.R. and C.O. C.O. performed
theoretical calculations and simulations and helped relate the experimental results with
simulations. A.K.S. wrote the manuscript with contributions from all the authors.

Additional information
Supplementary Information accompanies this paper at [http://www.nature.com/](http://www.nature.com/naturecommunications)
[naturecommunications](http://www.nature.com/naturecommunications)

Competing financial interests: The authors declare no competing financial interests.

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How to cite this article: Shukla, A. K. et al. Unravelling structural ambiguities in
lithium- and manganese-rich transition metal oxides. Nat. Commun. 6:8711
doi: 10.1038/ncomms9711 (2015).

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