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Which of the nickel-rich NCM and NCA is

Cite this: J. Mater. Chem. A, 2021, 9,
13540
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structurally superior as a cathode material for
lithium-ion batteries?
Bo Wang,ab Fei-long Zhang,ab Xin-an Zhou,a Peng Wang,ab Jie Wang,a Hao Ding,a
Hong Dong,a Wen-biao Liang,a Ning-shuang Zhangabc and Shi-you Li *abc

Received 6th February 2021
Accepted 10th May 2021
DOI: 10.1039/d1ta01128f
rsc.li/materials-a
As two typical layered nickel-rich ternary cathode materials, NCA and NCM are expected to be
commercialized in lithium-ion power batteries. However, there is still a lack of systematic research on
the pros and cons of these two nickel-rich materials in industry. Herein, LiNi0.85Co0.1Al0.05O2 and
LiNi0.8Co0.1Mn0.1O2 were synthesized by the co-precipitation method. It is found that
LiNi0.85Co0.1Al0.05O2 delivers a better cycling stability than LiNi0.8Co0.1Mn0.1O2, even with a higher nickel
content. Characterization of the internal structure and the chemical composition of materials after
cycles indicated serious Mn dissolution in LiNi0.8Co0.1Mn0.1O2 during the long cycles. The Mn dissolution
will lead to more serious Li/Ni mixing and Ni dissolution, which would finally cause the worse structural
stability of LiNi0.8Co0.1Mn0.1O2. Besides, first principles calculations were used to calculate the difficulty
of generating oxygen vacancies in LiNi0.85Co0.1Al0.05O2 and LiNi0.8Co0.1Mn0.1O2 during cycling, and the
result showed that the formation energy of vacancy defects of O adjacent to the dopant atoms in the Al
doped structure is higher than that of the Mn doped structure. The existence of oxygen vacancies
provides a channel for the migration and dissolution of transition metal atoms. Finally, it is calculated and
proved that the Al–O bonding stability under the TM–O octahedral coordination system is much greater
than the Mn–O bonding stability.

NCA materials and the high energy density of more than

Introduction
With the widespread application of lithium-ion power batteries
in the automotive industry, the lack of cruising range has
gradually become an important factor restricting electric vehi-
cles' popularization. Among all factors, the energy density of
a power battery which depends on the specic capacity of the
cathode material is the key factor affecting the range of electric
vehicles. Therefore, in recent years, a large number of research
studies have mainly focused on the development of new
cathode materials with high specic capacity.1 In the current
power battery cathode material system, nickel-rich layered
materials (LiNi1
xMxO2, M ¼ Co, Mn, and Al) have become the
mainstream cathode materials for commercial power batteries
due to their high specic capacity and low cost advantages,2
such as the low nickel materials represented by LiNi1/3Co1/3Mn1/
3O2 and the nickel-rich materials represented by LiNi0.8Co0.15-
Al0.5O2. Drawing on the more than 80% nickel molar content in
a
College of Petrochemical Technology, Lanzhou University of Technology, Lanzhou
730050, PR China. E-mail: lishiyoulw@163.com
b
Gansu Engineering Laboratory of Cathode Material for Lithium-ion Battery, Lanzhou
730050, PR China
c
Gansu Key Laboratory of Low-Carbon Energy and Chemical Engineering, Lanzhou
730050, PR China
300 W h kg
1, in recent years, the molar content of nickel in
NCM materials has gradually increased to more than 80%, such
as LiNi0.8Co0.1Mn0.1O2 (NCM811).3 Compared with NCA, nickel-
rich NCM has a similar discharge specic capacity of above
190 mA h g
1 and almost the same raw material cost, but
slightly lower process cost. At present, there is no clear
conclusion on the cycling stability of the two materials and the
decline mechanism in industry.4 Nickel-rich NCM and NCA are
both nickel-rich layered oxides which face some common
problems of nickel-rich materials in the recycling process: (1) in
the lithium deintercalation process, the cations of the transi-
tion metal layer and lithium layer will exhibit the anti-occupying
phenomenon due to the mutual occupation of Li+ and Ni2+,
which will cause the generation of lithium vacancies and nickel
vacancies, as well as microscopic local irreversible phase tran-
sitions, and ultimately damage the channel of lithium ion
migration;5,6 (2) due to the different kinetics, the nickel
concentration of the cathode will increase from the surface to
the inside during the delithiation process, which will eventually
lead to serious nickel dissolution on the surface of the material
and more nickel ions would migrate from the inside of the
cathode particle to the surface;7 (3) the Ni4+ produced in the
deep delithiation state is easily reduced to Ni3+ spontaneously
due to thermodynamic instability. During the reduction

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process, O will be precipitated owing to the charge conservation
of the material, which will cause the destruction of the material
structure.8,9 In addition to the above three internal structural
damage mechanisms, another main reason for the decline of
nickel-rich materials is the serious side reactions on the surface
during the cycles. The high oxidation state Ni4+ remaining on
the material surface in the high delithiation state can oxidize
the electrolyte to generate electrochemically inert by-products
and corrosive acids, resulting in a sharply raised impedance
of the material/electrolyte interface and further corrosion of the
material surface, which can promote the dissolution of transi-
tion metals in the material and produce more inactive
substances.10,11 Although many scholars have done a lot of
research studies on the decline mechanism of nickel-rich NCM
and NCA in recent years, most of the studies are biased towards
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the study of the two materials separately, and there are few
studies that link these two materials to carry out a comparative
systematic study. As a result, there is still erce debate in
industry about which nickel-rich material is a more suitable
cathode for the next-generation lithium-ion power batteries.
Wangda Li et al.12 studied the long-term cycling stability of
LiNi0.8Co0.15Al0.5O2 and LiNi0.7Co0.15Mn0.15O2 in a graphite full
battery system. It is found that LiNi0.8Co0.15Al0.05O2 with
a higher nickel content has better stability during long-term
charge and discharge cycles. However, the thermodynamic
and kinetic factors that produce the difference in the stability of
the two materials have not been studied in depth. In this work,
it is also found that the long-term cycling stability of nickel-rich
NCA with higher nickel content is better than that of nickel-rich
NCM. This gives us a revelation worth pondering that the
stability of NCA may be better than that of NCM with the same
nickel content in long-term cycling. In terms of elemental
composition, both these materials have Ni and Co, and the
difference is most likely caused by the difference in the role of Al
and Mn.
In order to further explore the gaps le by academics and
resolve the current disputes regarding nickel-rich cathode
materials in the lithium-ion battery industry, a comparative test
has been designed to investigate the stability of LiNi0.85Co0.1-
Al0.05O2 (NCA8515) and NCM811 materials at high temperature
and under long cycles. Under the common voltage window of
a half-cell system (2.7–4.3 V vs. Li+/Li) for 500 charge–discharge
cycles, it is found that NCA8515 delivers a better cycling stability
than NCM811 even with higher nickel content. Based on this
anomalous phenomenon, this work explores the reasons for the
difference in the structural stability of the nickel-rich NCA and
NCM during cycles in terms of the elemental composition and
crystal microstructure. In this process, eld emission scanning
electron microscopy (SEM), X-ray diffractometry (XRD), cold
eld emission transmission electron microscopy (TEM),
inductively coupled plasma-optical emission spectroscopy (ICP-
OES), X-ray photoelectron spectroscopy (XPS), and density
functional rst-principles calculations have been utilized to
study the mechanism of structural degradation of NCA8515 and
NCM811 materials during cycling. Finally, thermodynamic
structural stability differences between the two nickel-rich NCA
and NCM materials are found, and the advantages of nickel-rich
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NCA and NCM as the next-generation cathode materials of
lithium-ion power batteries in commercial applications are
explained, respectively.
Results and discussion
Differences in electrochemical performance of NCA8515 and
NCM811 during long cycles at 55  C
Fig. 1 shows the long-term cycling performance of NCA8515 and
NCM811 in lithium metal half-cells. It can be seen from Fig. 1(a)
that the capacity retention rates of NCA8515 and NCM811 are
57% and 44% aer 500 cycles at 55  C with 0.5C rate, respec-
tively. Obviously, the capacity of NCM811 decays faster than
that of NCA8515, but the coulomb efficiencies of the two
materials remain above 95%. The median voltage of NCA8515
and NCM811 at the beginning of discharge is above 3.77 V, and
the voltage attenuates to 0.2427 V and 0.2794 V aer 500 cycles,
respectively. The platform voltage retention ability of NCA8515
is better than that of NCM811, as shown in Fig. 1(b). Fig. 1(c)
and (d) show the interval charge–discharge curves of the two
materials during 500 cycles at 55  C. It can be seen that the rst
charge–discharge capacities of NCA8515 are 212.4 mA h g
1 and
198.8 mA h g
1 which are higher than those of NCM811 due to
the higher nickel content. Aer 500 cycles, the capacity of
NCA8515 and NCM811 decayed to 112.6 mA h g
1 and
110 mA h g
1, respectively, with a discharge capacity loss of
88.8 mA h g
1 aer long cycles. While the rst charge and
discharge capacities of NCM811 at high temperature are
197.7 mA h g
1 and 190.9 mA h g
1, the charge and discharge
capacities aer 500 cycles are 85.7 mA h g
1 and 84.1 mA h g
1,
respectively, with a capacity loss of 106.8 mA h g
1 aer cycles.
It is worth noting that although NCA8515 has a higher nickel
content than NCM811, it has better stability than NCM811
during cycles. This is inconsistent with the conclusions of
numerous current research studies, because it is generally
Fig. 1 Long-term cycling performance of NCA8515 and NCM811 in
lithium metal half-cells. Evolution of (a) specific discharge capacity and
(b) medium charge and discharge voltages over 500 cycles, and (c and
d) voltage profiles at the 1st, 100th, 200th, 300th, and 500th cycles at
55  C, 0.5C rate. 1C is equal to 180 mA g
1.
J. Mater. Chem. A, 2021, 9, 13540–13551 | 13541

Journal of Materials Chemistry A
believed that the higher the Ni content in a nickel-rich material,
the more unstable the structure of the material.13,14 In this work,
NCA8515 and NCM811 have the same Co content, and the main
reason for the difference in stability of the two materials may be
related to the difference in the effects of Mn and Al.
EIS impedance spectroscopy was used to describe the
dynamic process of the cathode/electrolyte interface during
battery cycles.15 Fig. 2 shows the impedance of NCA8515 and
NCM811 aer the rst, 200, and 500 discharges with a voltage
window of 2.7–4.3 V at 55  C. The impedance spectrum is
composed of a small semicircle in the high-frequency region
and a semicircle in the low-frequency region. The semicircle in
the high-frequency region represents the active material contact
impedance (Rf), including the lm impedance of the active
material surface and the contact impedance of the material
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particles, conductive carbon and current collector. The low-
frequency region is the charge transfer resistance (Rct) of the
interface between the material and electrolyte, including the
transfer resistance of the charge and ions at the material/
electrolyte interface.16 Fig. 2(a) shows the impedance of the
two materials at the completion of the rst discharge. It can be
seen that the Rf of NCM811 is slightly larger than that of
NCA8515, which may be related to the byproducts produced
from the reaction between the material and electrolyte during
the rst cycle. The slightly smaller Rct of NCM811 may be due to
the doping of Al in NCA8515 which leads to a lower electronic
conductivity, so a larger charge transfer resistance is reected at
the interface between the material and electrolyte.17 Fig. 2(b)
and (c) show the two materials' impedance tests aer 200 and
500 cycles of discharge. It is found that the Rf and Rct of NCM811
increase faster than those of NCA8515. Aer 200 cycles, the Rct
of NCM811 is much greater than that of NCA8515. The Rf values
of NCM and NCA show no obvious difference, indicating that
the charge transfer ability of the material/electrolyte interface of
NCM811 decreases more severely than that of NCA8515 during
long cycles at high temperature. Combined with the
Fig. 2 EIS analysis of NCA8515 and NCM811 at high temperature for
the first time (a), after 200 cycles (b), and after 500 cycles (c) and
impedance simulation values (d) after different cycles.
13542 | J. Mater. Chem. A, 2021, 9, 13540–13551
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illustrations in Fig. 2(b) and (c), it can be seen that the
increased Rct value in the low-frequency region is much larger
than the Rf in the high-frequency region. Obviously, the
impedance of the half-cell corresponding to the two materials is
mainly Rct's contribution during the long cycles, indicating that
NCM811 can produce a thicker electrochemically inert layer on
its surface during cycles, which may be related to the phase
change of the material surface. Fig. 2(d) shows the impedance
simulation values of the two samples under different cycles,
corresponding to the results of Fig. 2(a)–(c).
The dQ/dV curve reects the subtle changes in the charge
and discharge platform of the material. It reveals the relation-
ship between the phase change and voltage of the material
during the cycles. Generally, a nickel-rich ternary material's
capacity platform is caused by the change in the valence of the
transition metal ions in the material, and the price change of
metal ions is directly related to the phase change of the mate-
rial.18 Fig. 3 shows the dQ/dV curves of NCA8515 and NCM811 at
a voltage window of 2.7 V to 4.3 V. Fig. 3(a) and (b) show the rst,
second, third, and seventh time differential capacity curves of
the activation process of the two samples with an activation rate
of 0.1C. It is found that the phase change will occur from
hexagonal H1 to monoclinic M and from hexagonal H2 to H3 in
the rst two cycles, therein, the phase change from H1 to M is
reversible, while the phase change from H2 to H3 is partially
irreversible.19,20 Moreover, it can be seen from Fig. 3(a) and (b)
that the peak shi during the rst and second charging of
NCM811 is larger than that of NCA8515, indicating that
NCM811 has a slight overcharging phenomenon during the rst
charging. This result may be related to the different ratios of
transition metal elements in the two samples. The capacity
platform of the two samples remains unchanged from the third
to the seventh cycle, indicating that the phase changes of the
two samples tend to be stable, and the reversibility performance
Fig. 3 The dQ/dV curves of NCM8515 (a and c) and NCA811 (b and d)
activated in the 1st, 2nd, 3rd, and 7th cycles (a and b) at 25  C with 0.1C
and in the 8th, 9th, 10th, 11th, 209th and 509th cycles (c and d) at 55  C
with 0.5C.
This journal is © The Royal Society of Chemistry 2021

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is improved. Fig. 3(c) and (d) show the differential capacity
curves of the two samples at the 8th cycle of adjusting the
magnication, the 9th cycle at 55  C, and the subsequent 10th,
11th, 209th, and 509th cycles. It is found that the phase tran-
sition of the two samples from the hexagonal H1 phase to the
monoclinic M phase near 3.6 V and from the hexagonal H2 to
H3 phase near 4.2 V increased slightly aer sub-adjusting the
rate at the 8th cycle.21 However, the increase degree of NCA8515
is greater than that of NCM811, which may be related to the
higher Ni content in NCA8515. In the 9th cycle, high tempera-
ture is used, compared with the 10th and 11th cycles, and the
peak intensities of NCA8515 near 3.6 V and 4.2 V are almost the
same, indicating that the state of deintercalation of NCA8515
under the high temperature is almost the same as that of
normal temperature with no signicant phase transition, while
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the phase transition of the NCM811 material around 3.6 V and
4.2 V is more obvious. Taking into account the lower Ni content
and the same Co content of NCM811, it is believed that the
different electrochemical performances of these two samples in
the rst cycle at high temperature may be the result of the slight
structural stability difference between the two materials being
amplied under the fast kinetic process. Furthermore, from the
differential capacity curves of the 200th and 500th cycles at high
temperature, it can be seen that the voltage plateaus of the two
samples are both polarized during the cycling process.22
However, the polarization of NCM811 is more serious than that
of NCA8515, which shows that the structural stability of
NCM811 is worse than that of NCA8515 during high tempera-
ture and long cycles.
The mechanism of the difference in stability between
NCA8515 and NCM811 during long cycles
Fig. 4 shows the SEM images of the electrode slices of NCM811
and NCA8515 materials before and aer 500 cycles. As shown in
Fig. 4 NCA8515 (a–d and i) and NCM811 (e–h and j) materials before
the cycles (fresh pole piece; a, b, e and f) and after 500 cycles (c, d, g
and h). SEM image and XRD surface distribution of the secondary
particles of the pole piece material.
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Fig. 4(a), (b), (e), and (f), the morphologies of the two samples
are very similar before the cycling. It can be seen that the two
samples’ particles are secondary particles with a particle size of
around 10 mm with a complete shape and good sphericity. Aer
500 cycles, the secondary particles of these two samples have
cracks or are even broken. In comparison, the NCM811 (Fig. 4(c)
and (d)) particles are broken more slightly than NCA8515
particles (Fig. 4(g) and (d)). The possible reason for faster
capacity decay of NCM811 under high temperature and long
cycles may be its more serious irreversible cracks and particle
breakage. The secondary particle nickel-rich material synthe-
sized by the co-precipitation method will show internal cracks
in the particles due to the volume shrinkage and expansion
during the charge and discharge process. Previous mainstream
reports revealed that the internal cracks of NCM/NCA materials
are caused by the accumulation of internal grain boundary
defects in the secondary particles during long cycles.23 But
recent studies have shown that the long cycle is not the main
factor which promotes the generation of internal cracks.
Internal cracks will occur due to lattice expansion during the
rst charging process and become more serious with the
deepened charging depth. The initial crack is reversible and will
gradually close during the discharge process, but the long cycle
mainly affects the reversibility of the crack.24 Besides, irrevers-
ible cracks will extend along the inside to the surface of the
material, leading to the entry of the electrolyte which causes
more severe material/electrolyte interface side reactions. As
a result, the impedance increases sharply, and the contact of the
particles distributed inside the material will be lost due to the
lack of conductive substances, resulting in inability to provide
capacity.25 The occurrence of irreversible cracks is directly
related to the stability of the internal boundary of the material.
The more serious particle fragmentation phenomenon of
NCM811 shows that the stability of the internal grain boundary
during the high temperature and long cycle process is far worse
than that of NCA8515. The reason for this phenomenon may be
that the primary grain surface layer of NCM811 can produce
a more serious irreversible phase change layer, which needs to
be further conrmed in the subsequent characterization.
Although it is suspected that an irreversible phase change layer
will appear on the grain surface of the material aer a long
cycle, it is considered that the content of the phase change layer
in the entire material is minimal, so the main structure of the
two materials may still be unchanged aer the long cycle.12 It is
still a layered structure with the space group R3 m, which can be
seen from the cracking degree of the (006)/(012) peak in the XRD
continuous fast-scan spectrum.26 In addition, as shown in
Fig. 4(i) and (j), the increased ratio of (003) and (104) peak
intensities indicates that the cation mixing of the two materials
increases aer long cycles,27 but in the NCM811 material, it is
more serious. Continuous XRD quick trace can only provide
a simple qualitative analysis of the material structure, and the
quantitative analysis of its delicate structure is carried out in the
following characterization.
Fig. 5 is the Rietveld renement processing results of the
XRD slow point scan data of NCA8515 and NCM811 materials
before and aer 500 cycles. It can be seen that the main phase
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Journal of Materials Chemistry A
Fig. 5 Rietveld refinement maps of XRD stepwise slow scan data for NCA8515 and NCM811 before and after 500 cycles: (a) and (c) represent the
original material; (b) and (d) represent the material after the cycles; the black cross, red line and blue line represent the directly observed data
points, calculated fitting data points, calculation results and error of the observed results, respectively. The light green line represents the Bragg
position of the R3m space group.
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structure of the two materials has not changed aer the cycles.
Both of them show a layered structure with the R3 m space
group, which is consistent with the conclusion of the previous
XRD quick scan data. This is in line with the current main-
stream conclusion of phase transition research studies on
nickel-rich ternary cathode materials: the phase transition
mainly occurs on the material surface during the cycles. The
renement results revealed the changes in the lattice parame-
ters of the two materials before and aer the cycles. It is found
that the lattice parameters a and c of the fresh NCA8515 and
NCM811 are similar. Aer the cycles, the lattice parameter
a showed a slight decrease with the amplitudes of 0.01442 Å and
0.01636 Å, respectively. The lattice parameter c increases
signicantly with the increasing amplitudes of 0.0231 Å and
0.05394 Å aer cycles, as shown in Table 1. It can be seen that
the lattice parameter c of NCM811 and NCA8515 has increased
drastically aer the long cycling process. This may be the actual
reason for the volume expansion of the material during the
cycling process,28 which is consistent with the previous SEM
characterization results. NCM811 has a more serious volume
expansion effect during the cycles. NCA8515 and NCM811 also
have a signicant difference in the values of the lattice param-
eter c/a before and aer the cycles, which increased by 0.0331
and 0.0471 aer 500 cycles, respectively, as shown in Table 1. In
general, the value of c/a directly reects the degree of distortion
of the lattice. The increased c/a value indicates that the material
lattice has been stretched irreversibly along the direction
perpendicular to the plane of the Li layer. This irreversible
stretch is related to the generation of lithium vacancies in the
material during the lithium insertion process.29 Hence, the
NCM811 material has a greater degree of lithium vacancy
generation than the NCA8515 material aer long cycles. The
Table 1 The lattice parameters of the XRD data of NCA8515 and NCM811 materials before and after 500 cycles after Rietveld refinement
Sample a-Axis [Å] c-Axis [Å]
Pristine NCA8515 2.8661(0) 14.1781(4)
500-times cycled NCA8515 2.8516(8) 14.2012(4)
Pristine NCM811 2.8756(1) 14.2064(4)
500-times cycled NCM811 2.8592(5) 14.2603(8)
13544 | J. Mater. Chem. A, 2021, 9, 13540–13551
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generation of lithium vacancies may be the result of the disso-
lution of transition metal elements caused by the changed
chemical environment of the oxygen atoms at both ends of the
lithium layer, thereby promoting the migration of Li+ to the TM
site. From the rened results in Table 1, it can be seen that the
Li-occupied Ni site defect in NCA8515 (6.1%) is much smaller
than that in NCM811 (9.4%) aer the long cycles, indicating
that there may be more serious transition metal element
dissolution in NCM811. In addition, the full width at half
maximum (FWHM) of the (003) and (104) diffraction peaks of
NCM811 aer cycling increased more obviously than that of
NCA8515. The increased FWHM indicates that the crystallinity
of the material decreases during the cycles accompanied by the
destructed lithium-ion insertion sites in the crystal lattice as
well as the irreversible lithium-ion migration.12
Fig. 6 shows the high-resolution TEM images and selected
area electron diffraction (SAED) images along the h010i direc-
tion of a part of the NCA8515 and NCM811 secondary particle
section aer cycles. It is found that the thickness of the Fm3 m
rock salt layer (hexagonal H3 phase) below the surface of the
primary NCA8515 particles reaches 30–40 nm, as shown in
Fig. 6(a–c). Fig. 6(d) is the Fourier transform images of different
micro-regions. As shown in Fig. 6(d), an obvious boundary layer
between the rock salt phase and the R3 m layered phase
(hexagonal H1 phase) can be observed near 40 nm depth, and
a small amount of the Fm3 m spinel phase (hexagonal H2 + H3
phase) area runs through their boundary layers. Almost all the
regions below 40 nm show obvious lattice fringes, indicating
that these regions are layers without phase change states
(Fig. 6(e)). The arrangement of h006i, h003i and h101i points in
the SAED image also proves the existence of the Fm3 m region
 30
above 40 nm and the R3m region below 40 nm, as shown in
Li/Ni mixing FWHM (003) FWHM (104)
c/a [%] [ ] [ ]
4.9468 3.0 0.1726 0.2174
4.9799 6.1 0.2159 0.2603
4.9403 2.8 0.1735 0.2216
4.9874 9.4 0.3387 0.3492
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stability of the two materials. However, NCA8515 has better

cycling stability than NCM811 even with a higher Ni content.
Based on this, there's a reasonable prospect that the important
factor of the difference in stability of the two materials may be
the different mechanisms of action of Al and Mn in the tran-
sition metal layer.
In order to verify the difference in stability of transition
metal elements in NCA8515 and NCM811 during the cycles, EDS
line scan was performed in the radial direction to analyze the
cross-section of the secondary particles of the two materials
aer cycling. As shown in Fig. 7(a)–(d), it is found that both
NCA8515 and NCM811 materials show an obvious Ni element
dissolution aer 500 cycles. This dissolution phenomenon has
a gradient difference in the radial direction of the secondary
particles. Meanwhile, it can be seen from Fig. 7(b) and (d) that
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NCA8515 shows a lower degree of Ni dissolution even with

a higher Ni content, and EDS in SEM mode cannot distinguish
Mn, Al, and Co accurately. Therefore, transmission electron
microscopy was used to perform EDS analysis along the cross-
sectional radial direction of the material aer cycling in STEM
mode, as shown in Fig. 7(e) and (f). It is found from Fig. 7(g) and
(h) that the primary particles of NCA8515 and NCM811 also
show a very serious Ni dissolution phenomenon from the inside
to the surface aer the cycles, and the Ni content of the material
surface layer relative to the bulk phase is reduced by 47.23% and
67.25%, respectively. The dissolution degree of Ni in NCA8515
Fig. 6 High resolution TEM and selected area electron diffraction aer the cycles is also much smaller than that in NCM811. The
images of NCA8515 (a–e) and NCM811 (f–j) after 500 cycles; (a) low
magnification bright-field STEM image of the secondary particle
section of NCA8515 after cycling; (b) the enlarged bright-field STEM
image of the portion marked with the red line box in (a); (c–e) high-
resolution images of the portions with the 1, 2, and 3 marks in (b) and
the Fourier transform image and SAED image of each specific area; the
high-resolution TEM SAED images of NCM811 (f–j) are the same as
those of NCA8515 (a–e).

Fig. 6(c) and (e). In the same way, it is found that the thickness
of the rock salt phase layer below the surface of the NCM811
material reaches 50–60 nm aer cycles. A wide range of rock salt
phases and spinel phases can be observed at 50 nm or even
deeper without an apparent layered phase boundary layer.
However, the neatly arranged lattice fringe regions without
phase change can be observed in the region below 60 nm.
Obviously, the rock salt phase layer formed on NCM811 is
thicker than that on NCA8515 aer cycling. The rock salt phase
results from transition metal atoms occupying lithium sites,
which is essentially a phenomenon of atom migration caused by
atomic vacancies. Aer the atoms of the transition metal layer
occupy the lithium layer, the Li+ transmission will change from
two-dimensional to one-way one-dimensional transmission.
The lithium-ion transmission efficiency will be reduced seri-
ously, which will cause severe capacity degradation.31 The
difference in performance between the two materials aer the
cycles is related to the stability of their respective structures.
From the perspective of the composition of the two materials, Fig. 7 The SEM-EDS line scan images (a–d) of the secondary particle
section of NCA8515 and NCM811 after 500 cycles and the STEM
the two materials have the same Co content. It is inferred that
images (e and f) of the primary particle section and the line scan energy
Co may not be the factor causing the difference in the structural spectrum (g and h) along the radial direction of each other.

This journal is © The Royal Society of Chemistry 2021 J. Mater. Chem. A, 2021, 9, 13540–13551 | 13545
 View Article Online

Journal of Materials Chemistry A Paper

EDS line scan in SEM and STEM modes shows that NCA8515 Table 2 ICP analysis of transition metal element contents of lithium
has a more stable structure than NCM811 during the cycles. metal anodes corresponding to NCA8515 and NCM811 after 500
cycles
This proves the excellent electrochemical data of the NCA8515
material in the long cycle. In addition, the dissolution degree of Ni/ppm Co/ppm Mn/ppm Al/ppm
the Co element from the inside of the crystal grain to the surface
layer is slight for both materials, which may be related to the NCA8515 183.33 5.04 — 31.82
ultra-high stability of Co under the normal voltage window. NCM811 256.16 6.16 146.13 —
Previous research studies have proved that Co plays a decisive
role in the cycling stability of nickel-rich materials under a high
voltage window above 4.2 V.32 Finally, it is found that the close to 5 times that of Al, which is 146.13 ppm and 31.82 ppm,
stability of Al and Mn in the two materials showed a huge as shown in Table 2.
difference. The dissolution degree of Mn (88.3%) in the In order to further verify the dissolution of transition metal
NCM811 surface layer was almost twice that of Al (40.47%) in elements, ICP was used to analyze the content of transition
the NCA8515 material. So, the better structural stability of metal elements in NCA8515 and NCM811 before and aer the
NCA8515 in long cycles may be because the incorporation of Al cycles. The result shows that the dissolution of Ni in NCM811 is
much more severe than that in NCA8515. Besides, the dissolu-
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can stabilize the transition metal layer more than Mn, particu-
larly to inhibit the migration and dissolution of Ni during the
cycles. The phase change of the surface layer of the high-nickel
ternary layered material is the change in the atomic occupation
of the original structure. In other words, the cations of the
transition metal layer and the lithium layer have reversed
occupation. The essence of this anti-occupying defect is the
migration and dissolution of cations.31
Fig. 8 shows the EDS mapping analysis of transition metal
elements on the lithium metal anodes in the NCA8515 and
NCM811 half-cell systems aer 500 cycles. As shown in Fig. 8(a)
and (b), it is found that both the surfaces of the lithium metal
anodes corresponding to NCA8515 and NCM811 have severe Ni
element deposition aer the cycles, while the deposition of Co
was very slight. In addition, the dissolution of Mn in the
NCM811 material is much more serious than that of Al in
NCA8515. It can be seen from the ICP test results that the
deposition content of the Ni element on the surface of the
lithium metal anode of an NCA8515 half-cell (183.33 ppm) is
lower than that of NCM811 (256.16 ppm) aer the cycles. The
deposited Co element contents in the two materials are basi-
cally the same. In addition, the molar ratio of Mn in the original
NCM811 material is twice that of Al in NCA8515, but the content
of deposited Mn on the lithium metal anode aer cycling is
tion degree of Mn is also more severe than that of Al, as shown
in Table 3. It can be seen that the ICP results are consistent with
the results of the energy spectrum analysis in the dark eld
STEM mode. Hence, the worse cycling stability of NCM811 is
mainly due to the more serious Ni dissolution, and the key
factor causing this difference is that the contribution of Mn to
material stability is inferior to that of Al during the long cycles,
which is reected in the serious Mn element dissolution
phenomenon. Once this vacancy defect occurs when Mn plays
a role in stabilizing the material structure, it will promote more
serious migration and dissolution of Ni.33
Fig. 9 shows the XPS test on the surface of fresh NCA8515
and NCM811 materials and those aer 500 cycles. From the
spectrum of C1s, it can be seen that the carbon components on
the surface of fresh NCA8515 and NCM811 are mainly from
Li2CO3 and hydrocarbons, which are related to the reaction of
the nickel-rich cathode material with CO2 and H2O in ambient
air. The higher Li2CO3 content in fresh NCA8515 is related to its
higher Ni content. But aer 500 cycles, the Li2CO3 content on
the NCM811 surface is signicantly higher than that in
NCA8515 with a molar ratio of 20.18%, as shown in Fig. 9(b).
However, the proportion of Li2CO3 on the NCA8515 surface
tends to decrease aer cycles, as shown in Fig. 9(a). The possible
reason is that more carbon-containing by-products are gener-
ated on the material surface during the cycles.34 From the
spectrum of Ni2p, it can be seen that the surface Ni state of
fresh NCA8515 and NCM811 is mainly Ni3+, and the proportions
of Ni2+ in the two samples are 26.64% and 23.61%, respectively.
Aer 500 cycles, the Ni2+ contents on the surface of NCA8515

Table 3 ICP analysis of the contents of transition metal elements in

the NCA8515 and NCM811 materials before and after cycles; the total
content of all transition metal elements (Ni + Co + Mn/Al) is normal-
ized to 1.0000

Samples Li Ni Co Mn Al

Pristine NCA8515 1.0142 0.8487 0.1013 — 0.0500

Fig. 8 The SEM image and EDS elemental qualitative analysis of the 500-times cycled NCA8515 0.9277 0.7754 0.0936 — 0.0445
lithium metal anode corresponding to NCA8515 (a) and NCM811 (b) Pristine NCM811 1.0189 0.7969 0.1031 0.1000 —
after 500 cycles. 500-times cycled NCM811 0.8732 0.6928 0.0902 0.0712 —

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Fig. 9 XPS spectra of C (a and b), F (c), Ni (e and f), O (g and h), Al (i) and Mn (j) on the surface of fresh NCA8515 and NCM811 materials and those
after 500 cycles.
and NCM811 are 47.34% and 58.16%, respectively, as shown in
Fig. 9(c) and (d). The reason for this result may be that the Ni3+
on the NCM811 surface is reduced more severely than that on
NCA8515 aer 500 cycles, or the more severe Ni2+ dissolution in
the bulk of the material during the cycles, because the reduction
of Ni3+ itself and the dissolution of bulk Ni2+ can both cause the
increase of Ni2+ on the material surface.35,36 However, since the
surface layers of the NCA8515 and NCM811 materials aer
cycles have been transformed into the rock salt phase, the same
reduction degree of Ni3+ is observed on the surface of the two
materials aer the cycles. Hence, the reason for the higher Ni2+
content on the surface of the NCM811 material aer the cycles
may be the dissolution of more bulk Ni2+ during the cycles,
which is consistent with the previous characterization results of
TEM-EDS. From the F1s spectra of the two materials aer
cycling, it can be seen that the NiF2 (684.5 eV) contents on the
NCA8515 and NCM811 surfaces are 36.41% and 41.31% aer
cycling, respectively, as shown in Fig. 9(e) and (f). It can be seen
that NCM811 has more Ni precipitation and dissolution than
NCA8515 aer the cycles. The dissolved Ni reacts with the
electrolyte components to form NiF2, which is consistent with
the results of the EDS analysis in the STEM mode of the
transmission electron microscope. In addition, the organic
uoride and uoride lithium binding energies are close, and it
is difficult to accurately distinguish them in the F1s spectrum.
However, it is obvious that the total amount of uoride on the
NCM811 surface is more than that on the NCA8515 surface aer
the cycles, which indicates that there is a more severe interfacial
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Journal of Materials Chemistry A
reaction on the NCM811surface during the same cycles.37 The
accumulation of side reaction products on the cathode surface
(CEI) during the cycles is a reversible process. The side reaction
components on the lithium metal anode surface (SEI) will
migrate to the cathode surface during the discharge process,
while the CEI components will dissolve and migrate to the
anode during the charging process. This cross-reaction between
the cathode and the anode is also an important factor affecting
the stability of the cathode material.38 Aer cycling, the surface
of the NCM811 material accumulates more uorine-containing
substances than the NCA8515 material, indicating that there is
more serious cross-reaction between the NCM811 material and
lithium metal anode during the cycles. This is the reason for the
poor interface stability of the NCM811 material during the
cycles.
From the O1s spectrum, the products of side reaction with
air containing CO and C]O can be observed on surface of fresh
NCA8515 and NCM811, and O–TM in uncontaminated mate-
rials has also been detected. As shown in Fig. 9(g) and (h), the
binding energies of oxygen and transition metal atoms in
NCA8515 and NCM811 display high energy shis of 0.75 eV and
0.98 eV aer 500 cycles, respectively, which indicates that the
oxygen in the surface structure of the material has lost electrons
aer cycles.39 The oxygen in the layered nickel-rich material is
mainly xed by bonding with the transition metal atom Ni, and
once the O between the transition metal layer and the Li layer
exhibits electron-loss oxidation behavior, oxygen vacancy
defects are easily generated. Then the transition metal atom Ni
J. Mater. Chem. A, 2021, 9, 13540–13551 | 13547

Journal of Materials Chemistry A
will enter the Li layer along the oxygen vacancies and nally
precipitate out of the material in the delithiation process.40 The
electron loss behavior of oxygen is a charge compensation
phenomenon caused by the reduction of high-valence transi-
tion metal atoms during delithiation, mainly the reduction of
Ni3+ and Ni4+, which is determined by its unstable thermody-
namic properties.41 The more severe electron loss behavior on
the NCM811 surface structure indicates that the structural
stability of the transition metal layer aer cycling is far less than
that of NCA8515. Considering that the same content of Co in the
two materials shows almost no dissolution during the entire
cycling, it can be believed that Al and Mn play a decisive role in
causing the difference in structural stability between NCA8515
and NCM811. It can be seen from the Al2p and Mn2p spectra
that there is no chemical shi in the Al2p peak of the NCA8515
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material before and aer the cycles, which indicates that the Al
in NCA8515 aer the cycles maintains the chemical structure
environment. In contrast, the Mn2p peak in NCM811 has
a chemical shi to a low binding energy, indicating that Mn has
undergone a reduction behavior of electrons. Aer tting
calculations, it is found that the contents of Mn4+, Mn3+, and
Mn2+ in the fresh NCM811 are 79.45%, 10.95%, 9.6%, and
become 55.56%, 33.4%, 11.04% aer cycling, respectively. The
instability behavior of Mn observed by XPS is consistent with
the results of the previous sufficient analysis of the energy
Fig. 10 (a) The final optimized LiNiO2 unit supercell structural model;
(b) mechanism diagram of Mn–O oxygen vacancy defects produced
by the Mn doped structure; (c) mechanism diagram of Al–O oxygen
vacancy defects produced by the Al doped structure; (d) the mecha-
nism diagram of the structure after doping Mn and Al to replace the Ni
sites and the differential charge density distribution of O around the
doping atom.
13548 | J. Mater. Chem. A, 2021, 9, 13540–13551
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Paper
spectrum in the STEM mode. Therefore, the structural stability
of NCA8515 is better than that of NCM811 during the high
temperature and long cycling process, and the possible reason
may be that the doping of Al in NCA8515 leads to more struc-
tural stability than the doping of Mn in NCM811.
Mechanism of difference in stability between Al and Mn in the
transition metal layer of nickel-rich layered oxides
Based on the previous electrochemical data and characteriza-
tion results of NCA8515 and NCM811 in the long cycling
process, it is concluded that the stability of Al in nickel-rich
layered oxides is stronger than that of Mn, and this stability is
mainly manifested in the binding of the O adjacent to the
doping element; the previous characterization has shown that
the oxidation behavior of Al-doped NCA8515 aer long cycles is
much slower than that of Mn-doped NCM811. In order to
conrm the difference in the binding ability of Mn and Al to O
in the nickel-rich layered oxide, we analyzed the formation of
vacancy defects in the adjacent O atoms when the nickel-rich
layered oxide is doped with Al and Mn, respectively.42 First-
principles calculations based on density functional theory
were performed. In view of the same Co content in the two
original material systems and the same effect on the materials,
we have approximately constructed a LiNiO2 super unit cell
structure model which is doped with Mn and Al to replace Ni
sites,43 as shown in Fig. 10. VASP simulation soware was used
throughout the calculation process. The GGA + U approach is
adopted to describe the strongly correlated d electrons of the
TM.44 The Hubbard U parameters of 6.5 and 4.5 eV are used with
Ni and Mn ions, respectively. The plane-wave cutoff is set to
500 eV. The gamma centered Monkhorst–Pack scheme of k-
point generation is applied to grids of 4  4  2 for structural
optimization and 8  8  2 for the nal energy calculation.45
Structural optimization is performed for all of the defective
cases until the maximum residual force on all atoms becomes
less than 0.03 eV Å
1 while the cell is allowed to relax. All 144
atoms (Li12M12O24 expanded 3 times) are used in a 3  3  1
supercell structure with the space group R3 m, where M repre-
sents the TMs Ni, Mn/Al (Ni : Mn ¼ 11 : 1, Ni : Al ¼ 22 : 1),46 as
shown in Fig. 10(a). Only substitution doping is considered in
this study, and one atomic percent (equivalent to one atom) is
doped with either Al or Mn. To obtain the delithiated structures,
the Ewald summation method, which is implemented in the
PyMatgen library, is employed.
The formation energies of O vacancies aer replacing Ni
sites with Mn and Al are calculated based on the following
theoretical formulae, as shown in Fig. 10(b) and (c); the
formation energy (DfE(X)), for defect type X, is computed as:
DfE(Vo) ¼ E(pristineVo) + E(O2)/2
E(pristine) (1)
where E(pristineVo), E(O2), and E(pristine) are the energies of the
pristine structure when one oxygen vacancy is formed, an
oxygen molecule, and the pristine structure without a defect,
respectively. Finally, the calculation results of the formation
energies of vacancy defects in the oxygen atoms adjacent to Mn/
This journal is © The Royal Society of Chemistry 2021

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Al in the Mn-doped and Al-doped structures are shown in Tables
4 and 5.
From the above calculation results, it can be seen that the
formation energy of oxygen vacancies in Al-doped nickel-rich
layered materials is greater than that of Mn-doped layered
materials, indicating that oxygen vacancy defects are more likely
to occur in Mn-doped nickel-rich layered materials. It proves
that the modied Ni-rich layered material by doping Al to
replace Ni shows a better performance than that doped with
Mn. In short, Al doping can better stabilize the adjacent O
atoms, thereby more effectively inhibiting the generation of
oxygen vacancies during cycles, so that the probability of Al
migrating to the Li layer along the O vacancies is much less than
that of Mn. According to this mechanism of action, the Mn
atoms in the Mn-doped structure will migrate and dissolve
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more and more severely, resulting in numerous vacancy defects
of Mn and O in the transition metal layer. Finally, Ni in the
material will migrate and dissolve along this kind of vacancy
defect. This may be the possible reason for the structural
deterioration of NCM811 being more serious than that of
NCA8515 during the long cycles. The above calculation results
of the stability of O in the two doping systems are consistent
with the conclusions of the O spectra in part XPS
characterization.
According to the calculation results of the oxygen vacancy
formation energies in the two doping systems, it can be known
that the oxygen atom stability of the nickel-based transition
metal layer aer doping Al is higher than that that aer Mn
doping. In order to explore the actual reason behind this
difference, rst-principles calculations were performed to
calculate the formation energy of oxygen bonds with Al and Mn
doped to replace Ni sites based on the following theoretical
formula, as shown in Fig. 10(d); the formation energy (DfENi,D),
for the D atom replacing a Ni site, is computed as:
DfENi,D ¼ E(pristineNi,D) + m(Ni)
E(pritineP)
m(D) (2)
where E(pristineNi,D), E(pristineP), m(Ni) and m(D) are the energy
of the pristine structure when one D atom replaced a Ni site, the
energy of the pristine structure without a dopant, and the
atomic chemical potentials of Ni atoms and dopants, respec-
tively. The calculation results are shown in Tables 6 and 7.
Table 4 Calculation results of the formation energies of Mn–O
oxygen vacancies in the Mn-doped structure
E(doped Mn) (eV) E(doped MnVo) (eV) E(O2) (eV) DfE(Vo)Mn (eV)

274.8797
267.7216
8.7210 2.7976
Table 5 Calculation results of the formation energies of Al–O oxygen
vacancies in the Al-doped structure
E(doped Al) (eV) E(doped AlVo) (eV) E(O2) (eV) DfE(Vo)Al (eV)

272.4264
265.2305
8.7210 2.8354
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Journal of Materials Chemistry A
Table 6 Calculation results of bond formation energy with O when
doped with Mn to replace Ni sites
E(LiNiONi,Mn
2 ) (eV) E(LiNiOP2) (eV) m(Ni) (eV) m(Mn) (eV) DfENi,Mn (eV)

274.8797
268.5219
9.9327
8.8700
7.4205
Table 7 Calculation results of bond formation energy with O when
doped with Al to replace Ni sites
E(LiNiONi,Al
2 ) (eV) E(LiNiOP2) (eV) m(Ni) (eV) 2m(Al)
1
(eV) DfENi,Al (eV)

272.4264
268.5219
9.9327
1.8732
11.9641
From the calculation results in Tables 6 and 7, it can be seen
that the O bond formation energy in the Al doped material is
much lower than that of the Mn doped material, indicating that
the O bonding stability with Al is stronger than that of O with
Mn in the transition metal layer, which also explains the
previous calculation results listed in Tables 4 and 5. The
structural stability of Al and Mn doped systems depends on the
bonding stability of doping atoms and oxygen atoms. The
stronger the bonding between dopant atoms and oxygen atoms,
the stronger the stability of the doped system structure. Hence,
the essential thermodynamic factors may be the reasons for the
difference in structural stability between NCA8515 and
NCM811. The reason why NCA8515 has better structural
stability than NCM811 is that the bonding stability of Al–O in
the transition metal layer is stronger than that of Mn–O. It
should be noted that although the above conclusions are based
on the half-cell system, they are also applicable to the full-cell
system. What we studied is the internal structure evolution
mechanism of the material in the process of lithium dein-
tercalation. Whether it is a full-cell or a half-cell system, the
thermodynamic evolution mechanism of the positive electrode
material in the process of lithium deintercalation is the same.
Conclusions
Under the fast kinetics process, LiNi0.85Co0.1Al0.05O2 is better
than LiNi0.8Co0.1Mn0.1O2 in terms of capacity retention and
voltage stability in 500 charge–discharge cycles, even if the
former has a higher nickel content. This result is due to the
serious dissolution of Mn in LiNi0.8Co0.1Mn0.1O2 during the
cycles, which will lead to a large-scale dissolution of Ni. The Ni
migration and dissolution will cause serious Li/Ni anti-
occupancy defects and irreversible phase transitions in the
material, which can accelerate the instability of the grain
boundaries and induce crack gaps, even cavities inside the
material particles. Eventually, the hindered transmission of
lithium ions inside and between particles of the material causes
rapid capacity decay. The difference in the stability of Mn and Al
in nickel-rich ternary materials is determined by thermody-
namic properties, reecting in the lower bonding stability of
Mn–O than that of Al–O. This difference is mainly due to the
fact that O atoms adjacent to Mn are more prone to form
vacancy defects than O atoms adjacent to Al, which in turn
J. Mater. Chem. A, 2021, 9, 13540–13551 | 13549

Journal of Materials Chemistry A
causes Mn to be more easily eluted from the transition metal
layer than Al. Inhibiting the dissolution of transition metal
elements is the focus of future research on the modication of
nickel-rich ternary materials. It is mainly based on the modi-
cation technology of stabilizing the surface structure of the
material, including surface coating, surface doping, and
formation of core–shell and concentration gradient structures.
Future research will continue to explore the mechanism of
material structure evolution to nd lower cost and better
stability modication technologies, so that the application of
nickel-rich ternary materials in the eld of lithium-ion batteries
can be further expanded to meet the social development
demands for high-energy density lithium-ion batteries.
Experimental section
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Materials preparation
To synthesize the cathode samples, LiNi0.85Co0.1Al0.05O2 and
LiNi0.8Co0.1Mn0.1O2, [Ni0.89Co0.11](OH)2 and [Ni0.8Co0.1Mn0.1](-
OH)2 precursors were prepared through transition-metal
coprecipitation. During the reaction, an aqueous solution (a
molar ratio of either Ni : Co ¼ 0.89 : 0.11 or Ni : Co : Mn ¼
0.8 : 0.1 : 0.1) composed of NiSO4$6H2O, CoSO4$7H2O, and
MnSO4$H2O was fed into a batch reactor (5 L) lled with an
aqueous solution of NH4OH and NaOH. In the meantime,
a mixed NaOH and NH4OH aqueous solution was pumped into
the batch reactor separately to maintain the pH within the range
of 11–12. In addition, the temperature (55  C) and stirring rate
(700–900 rpm) were controlled during the coprecipitation. The
hydroxide precursors were then isolated through washing,
ltering, and drying at 100  C overnight. Next, the obtained
[Ni0.89Co0.11](OH)2 precursor was homogenously mixed with
LiOH$H2O and aluminum isopropoxide (a molar ratio of
Li : Al : (Ni + Co) ¼ 1.03 : 0.05 : 0.95) and calcined at 750  C for
15 h under owing O2 to obtain the nal product, LiNi0.85-
Co0.1Al0.05O2. For the preparation of LiNi0.8Co0.1Mn0.1O2, the
[Ni0.8Co0.1Mn0.1](OH)2 precursor was mixed with LiOH$H2O
(Li : (Ni + Co + Mn) ¼ 1.03 : 1 molar ratio) and calcined at 750  C
for 15 h in O2.
Materials characterization
Nickel-rich NCM/NCA and lithium metal electrodes were har-
vested from half cells aer 500 cycles and rinsed with dimethyl
carbonate for a series of electrochemical and physicochemical
characterization. EIS analysis with an impedance spectrometer
(CHI660e) was performed on 500-times cycled half cells charged
to 4.3 V and rested for 6 h. In the tests, the frequency varied
from 100 kHz to 10 mHz with a 5 mV potential perturbation
from the cell open-circuit potential at 55  C.
Powder XRD data of the extensively cycled nickel-rich NCM/
NCA cathodes were acquired on a MiniFlex 600 X-ray diffrac-
tometer with Cu Ka (l ¼ 1.54184 Å) radiation at 10.0–80.0 at
a scan rate of 0.5 min
1. Rietveld renements on the diffrac-
tion data were carried out with GSAS soware. SEM images of
electrode slices of the nickel-rich NCA and NCM before and
aer long-term cycling were collected on a Quanta 650 SEM
13550 | J. Mater. Chem. A, 2021, 9, 13540–13551
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eld-emission scanning electron microscope (FEI). Analyses of
the elemental distribution of the cross-section of particles and
the lithium metal anode were performed using SEM based
energy-dispersive X-ray spectrometer (EDS). Particle sections
were prepared by embedding particles in epoxy resin and then
by mechanically polishing. Chemical composition of the
cathode samples before and aer extensive cell operation was
also evaluated using an ICP-OES (Varian 715 ES).
A Leica EM RES102 Multifunctional Ion Milling System
instrument was used to perform li-outs of the nickel-rich
NCM/NCA cathode samples at the regions-of-interest, followed
by milling to fabricate the lamellar shaped TEM specimens.
Then, STEM and EDS studies were conducted with a JEM-F200
TEM/STEM at 200 kV. The phases were identied using high-
resolution STEM and fast Fourier transform (FFT) images with
the aid of the Java version of Electron Microscopy Soware.
XPS data were taken on the extensively cycled electrode
samples through an Axis Ultra DLD spectrometer with an Al Ka
radiation (hn ¼ 1486.6 eV) beam under a base pressure of
around 2  10
9 mbar. Peak deconvolution of all obtained
spectra was performed with XPSPEAK soware using Shirley
background correction and Gaussian–Lorentzian curve
synthesis. For the cathode samples, the energy scale was cali-
brated based on C1s 248.8 eV.
Electrochemical testing
Carbon black, polyvinylidene uoride (PVdF) binder, and lithium
metal chips were purchased from Kelude Corp. Long-term
cyclability was evaluated in half-cells. To make the composite
cathode electrodes, the active material (NCA8515/NCM811),
carbon black, and PVdF (8 : 1 : 1 by weight) were mixed with an
appropriate amount of N-methyl-2-pyrrolidinone. The obtained
slurries were doctor-bladed onto Al foil and roll-pressed. The
active mass loadings of the cathode were around 2.5 mg cm
2.
Each cell contained one lithium tablet and one cathode, infused
with around 40 mL of electrolyte (1 M LiPF6 in ethylene carbonate-
ethyl methyl carbonate (EC : DEC ¼ 1 : 1 by volume)). Basic
electrochemical characterization was also carried out in 2025
coin-type half cells with Li metal as the anode. Battery tests were
recorded on an 8-channel battery cycler (LAND CT2001A). For
half cells, constant current densities of 18 and 90 mAg
1,
respectively, were applied for SEI formation (eight cycles, 0.1C
rate, 25  C) and long-term cell operation (500 cycles, 0.5C rate, 55

C) within the voltage of 2.7–4.3 V versus Li+/Li.
Conflicts of interest
There are no conicts to declare.
Acknowledgements
This work is mainly supported by the National Natural Science
Foundation of China (Grant No. 51962019), the Natural Science
Foundation of Gansu Province (Grant No. 20JR5RA469), and the
Lanzhou University of Technology Hongliu First-Class Disci-
pline Construction Program.
This journal is © The Royal Society of Chemistry 2021

Paper
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