Electrochimica Acta 328 (2019) 135116

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Controlling the oxygen deficiency for improving the insertion

performance of the layered LiNi0.6Co0.2Mn0.2O2
Yanbin Zhu, Xiaohui Tian, Xuan Zhou, Pengfei Zhang, Natarajan Angulakshmi,
Yingke Zhou*
The State Key Laboratory of Refractories and Metallurgy, Institute of Advanced Materials and Nanotechnology, College of Materials and Metallurgy, Wuhan
University of Science and Technology, Wuhan, 430081, PR China

a r t i c l e i n f o a b s t r a c t

Article history: Spherical Ni0$6Co0$2Mn0$2(OH)2 precursor was synthesized by a co-precipitation method, and then
Received 11 August 2019 uniformly mixed with Li salts and calcined to obtain the layered Ni-rich LiNi0$6Co0$2Mn0$2O2 materials.
Received in revised form The obtained layered product was further treated at 600
C for 2 h in four different atmospheres (oxygen,
16 October 2019
air, argon, argon/hydrogen (95/5)), to explore the effect of oxygen deficiency on the lithium-insertion and
Accepted 19 October 2019
Available online 21 October 2019
storage performance. X-ray diffraction, scanning electron spectroscopy and X-ray photoelectron spec-
troscopy were used to characterize the phase composition and structure, and the electrochemical per-
formances were evaluated. A well developed layered crystal structure is obtained and the cations arrange
Keywords:
LiNi0$6Co0$2Mn0$2O2
more regularly under a high oxygen partial pressure, which leading to the remarkable electrochemical
Oxygen deficiency performance of higher discharge specific capacity (176 mAh g1 at 0.1 C), excellent rate performance and
Layered structure structural stability (67.17% in capacity retention after 300 cycles at 1.0 C). These results demonstrate the
Lithium-ion batteries positive effects and the underlying mechanisms of the oxygen deficiency regulated lithium-insertion
properties in the layered materials.
© 2019 Elsevier Ltd. All rights reserved.

1. Introduction lead to degradation in rate performance, cyclic stability and safety

Rechargeable lithium-ion batteries are used widely in various
electronic devices and energy storage facilities for their advantages
of high working voltage, high discharge capacity, excellent safety
performance and long cycle life [1]. The cost and performance of
the lithium-ion batteries are largely depended on the cathode
materials, which are mainly composed of the lithium transition
metal oxides (LiCoO2, LiNiO2, LiMn2O4, etc) and the olivine struc-
tural polyanion LiFePO4 [2e4]. Recently, the mixed metal oxides of
LiNi1-x-yCoxMnyO2 (0  x, y  1, x þ y  1) with a layered hexagonal
a-NaFeO2 structure have attracted intense attention for the com-
bined effects of NieCoeMn, namely, they simultaneously possess
the merits of high specific capacity of lithium nickelate, good cycle
performance of lithium cobaltate, stable structure and low cost of
lithium manganite [5e8]. When the Ni content increases, the ca-
pacity of LiNi1-x-yCoxMnyO2 increases, however, excessive nickel
will aggravate the Liþ/Ni2þ cation mixing in the layered crystal and
* Corresponding author.
E-mail address: zhouyk@wust.edu.cn (Y. Zhou).
[9,10]. Therefore, enhancement of the rate capability and cycle
performance of the Ni-rich layered electrode materials is the key to
promote their wide application, and various doping and surface
coating strategies have been developed to effectively increase the
electrode performances [11e13].
Recent studies have shown that the oxygen non-stoichiometry
or vacancy can affect the phase formation, crystal structure and
stability. In addition, the oxygen vacancy type (Schottky defect and
Frenkel defect) and concentration have a direct influence on the cell
structure evolution and lattice parameter. Yuan et al. compared the
difference of properties and internal structure of
LiNi0$6Co0$2Mn0$2O2 with different sintering atmospheres (oxygen
and air), and found that the electrode material treated in oxygen
displayed lower cation mixing degree, more matured hexagonal
structure and less surface residual alkali [14]. Wang et al. also
prepared the LiNi0$8Co0$1Mn0$1O2 materials with oxygen non-
stoichiometry by changing the oxygen partial pressure (N2, O2 ra-
tio of 95:5, 79:21, 50:50, 0:1, v/v), and found that the oxygen
deficiency could accelerate the Li/Ni mixed degree and increase the
decomposition of surface layer, led to the performance deteriora-
tion of electrode material due to the related structural relaxation

https://doi.org/10.1016/j.electacta.2019.135116
0013-4686/© 2019 Elsevier Ltd. All rights reserved.
2 Y. Zhu et al. / Electrochimica Acta 328 (2019) 135116
and polarization [15]. Moreover, Idris et al. prepared the
LiNi0$8Co0$1Mn0$1O2-d positive materials with oxygen non-
stoichiometry using a rotary vaporization technique combined
with a high-temperature calcination, and found that the content
and interlayer ion ordering have a strong impact on the electrode
performance [16]. Though the oxygen deficiency effects on the
layered structured electrode performance have been investigated
and verified by different groups, the underlying mechanisms of the
corresponding effects still remain unclear.
In this work, we prepared the layered LiNi0$6Co0$2Mn0$2O2
cathode material using the chemical co-precipitation and following
calcination processes, and which was further heated respectively in
an atmosphere of oxygen, air, argon and argon/hydrogen (95/5) at
600
C for 2 h, to systematically modulate and investigate the ef-
fects of the oxygen deficiency/oxygen non-stoichiometry. By careful
analyses of the morphology, structure and their relationship with
the electrochemical performance, we found that the oxygen defi-
ciency/oxygen non-stoichiometry of the layered materials aroused
distinct changes of the degree of Liþ/Ni2þ mixing, the ratio of Ni2þ/
Ni3þ and Co2þ/Co3þ, and the relative proportion of the lattice ox-
ygen and surface oxygen absorption, which further greatly affected
the LiNixCoyMnzO2 electrode performance. These results and find-
ings have significant implications for further designing high-
performance layered electrode materials of lithium-ion power
batteries.
2. Experimental
2.1. Synthesis of materials
The Ni0$6Co0$2Mn0$2(OH)2 precursor was prepared using a
chemical co-precipitation technique. 1.5 mol L1 mixture solution
of sulfates of nickel, cobalt and manganese was added into a
continuously stirred tank of 1 L with a flow rate of 2 rpm under
argon atmosphere, and the ratio of Ni2þ, Co2þ and Mn2þ is 6:2:2.
Simultaneously, a 4.0 mol L1 NaOH solution as a precipitating
agent and a certain amount of solution of NH3$H2O as a chelation
agent were respectively pumped into the reactor. The stirring
speed, temperature and pH of the reaction are 400 rpm, 55
C and
11.2 ± 0.5, respectively. After reaction of 25 h, the solution collected
from the tank was filtered, and then washed with deionized water
þ
several times to remove impurity ions such as SO2 4 and Na , before
during for 24 h at 80
C in an oven to obtain the precursor. The
precursor was then mixed thoroughly with LiOH (molar ratio of Li
and precursor was 1.05:1), pre-heated in air for 4 h at 550
C, and
then calcined in a flowing oxygen atmosphere for 12 h at 820
C, to
obtain the LiNi0$6Co0$2Mn0$2O2 material (NCM622).
To understand how the oxygen deficiency affects the lithium-
insertion performance of the electrode materials, the obtained
NCM622 materials were further heat-treated respectively in at-
mospheres of oxygen, air, argon, and argon-hydrogen (volume ratio
of H2:Ar ¼ 5/95) at 600
C for 2 h. When treated in an argon
hydrogen atmosphere, the temperature was first raised to 600
C in
an argon atmosphere, then switched to an argon-hydrogen atmo-
sphere and kept for 15 min to generate the layered NCM622 with a
higher concentration of oxygen defects for the comparative anal-
ysis, and then switched back to the argon atmosphere for further
processing. The obtained samples are named as NCM, O2-NCM, Air-
NCM, Ar-NCM and AH-NCM, respectively.
2.2. Morphology and structure characterization
An Xpert Pro MPD diffractometer with Cu Ka radiation
(Ka ¼ 0.15418 nm) was used to characterize the crystalline struc-
ture of the samples and the XRD data were acquired between 10

and 80
. To further explore the difference of crystal structure
caused by the oxygen deficiency, the Rietveld refinement program
was used to calculate the XRD data as well. Scanning electron mi-
croscopy equipped with EDXS (SEM, PHILIPS XL30 TMP) at an ac-
celeration voltage of 18 kV was used to characterize the
morphological features and particle sizes of the samples. X-ray
photoelectron spectroscopy (XPS, Escalab 250Xi, Thermo) was used
to analyze the chemical state information of the nickel, cobalt,
manganese and oxygen elements of the electrode material.
2.3. Electrochemical measurements
The 2032-type coin cells are assembled in a glove box with a
lithium metal negative electrode, a Celgard 2400 separator, and an
electrolyte solution of 1 mol L1 LiPF6 in ethylene carbonate (EC)-
dimethyl carbonate (DMC)-diethyl carbonate (DEC) (1:1:1). To
prepare the working electrode, the active material, polyvinylidene
difluoride binder (PVDF) and Super-P conductive carbon black were
mixed at a mass ratio of 8:1:1 in N-methyl-2-pyrrolidone to get a
slurry, and then uniformly coated on the current collector (Al foil)
before drying for 15 h at 100
C and cutting into disks. The
charging-discharging tests were performed between 2.80 and
4.25 V at various current densities at 25
C with a computer-
controlled battery test system (Neware BTS, 5V50mA). Cyclic vol-
tammograms (CV) were measured using a BioLogic VMP3 electro-
chemical work station within the voltage window of 2.8 and
4.25 V at 0.1 mV s1, and electrochemical impedance spectroscopy
(EIS) from 100 kHz to 10 mHz was acquired with a 10 mV
amplitude.
3. Results and discussion
3.1. Material characterization
The XRD patterns of NCM and the samples processed in four
different atmospheres are shown in Fig. 1a. All of the samples are
indexable to a well-defined hexagonal a-NaFeO2 layered structure
with a space group of R-3m. There is neither any impurity phase nor
distinct difference of the X-ray diffraction patterns between the
processed samples and the original sample, implying that the heat
treatment does not change the crystalline structure greatly. The
cation mixing of Ni2þ and Liþ is indirectly determined by the in-
tensity ratio (R) of the (003)/(104) peaks, and R > 1.2 indicates the
cation mixing is effectively restrained [17e19]. As displayed in
Fig. 1b, the R values are respectively 1.66, 1.73, 1.68, 1.58 and 1.50 for
NCM, O2-NCM, Air-NCM, Ar-NCM and AH-NCM. All samples display
a restrained cation mixing, and as the heat treatment atmosphere
shifts from an oxidation to a reduction one, the R value decreases.
Compared to NCM, the larger R values and smaller cation mixings of
O2-NCM and Air-NCM are ascribed to the partial Ni2þ to Ni3þ
oxidation in the layered materials, which significantly reduces the
mixing with Liþ [20e22]. When calcined in an inert atmosphere
(Ar-NCM) and a reduction atmosphere (AH-NCM), the oxygen
deficiency is formed due to the insufficient oxygen partial pressure,
leading to the partial reduction of Ni3þ and a more severe mixing of
Liþ and Ni2þ [19]. The enlargement of the (003) diffraction peak
between 17
and 20
is shown in Fig. 1c. The clear shift to low
angles for the samples reprocessed in the four different atmo-
spheres indicates an increase of the interplanar spacing d and the
lattice constant a and c, according to the Bragg equation (Formula
(1)) and the plane spacing formula of hexagonal crystal (Formula
(2)) [23]:
 Y. Zhu et al. / Electrochimica Acta 328 (2019) 135116 3

Fig. 1. (a) XRD patterns of the five samples; (b) The varied intensity ratio of the (003) and (104) diffraction peaks; (c) The enlarged view of the (003) peak in (a); (d) XRD Rietveld
refinement patterns of O2-NCM.

represents the formation of a layered structure, and the larger this

2dsin q ¼ nl (1) value, the better the layered structure [24]. Compared with NCM
material, the c/a value and layered structure of O2-NCM and Air-


2 2 2 NCM are improved, while those of the Ar-NCM and AH-NCM ma-
1 4 h þ hk þ k l2
¼ þ 2 (2) terials are decreased, indicating that the layered structure may be
d2 3a2 c damaged in the reductive atmosphere.
Fig. 2 presents the EDS elemental mapping images of O2-NCM,
where d is the interplanar spacing, l is the X-ray wavelength, q is
and the homogeneously distributed elements of Ni, Co and Mn are
the Bragg angle, n is the Reflection series, h, k, l are the crystal
observed. Fig. S2 shows the SEM images of NCM (a, f), O2-NCM (b,
surface index, a and c are the lattice constant.
g), Air-NCM (c, h), Ar-NCM (d, i) and AH-NCM (e, j). The spherical
Rietveld refinements were further used to analyze the diffrac-
NCM powders present a good dispersibility and the average particle
tion results of all the samples to explore the differences of crystal
size is around 8e15 mm. In addition, these spherical particles are
structures. The XRD refinement patterns of O2-NCM and other
consisted of primary grains of 300e500 nm. After the re-heating
samples are displayed in Fig. 1d and Fig. S1 (a-d), and the obtained
treatment, the morphology and size of the other four samples
results are displayed in Table 1. After the second heat treatment, the
have not significantly changed.
lattice constants (a and c) and the unit cell volumes (V) of the other
XPS technology was used to characterize the chemical valence
four samples increase compared to NCM, and the smaller the ox-
states of the nickel, cobalt, manganese and oxygen elements after
ygen partial pressure, the larger the lattice constant and the cell
the introduction of oxygen deficiency in the layered structural
volume. For O2-NCM and Air-NCM, the increase of the unit cell
electrode materials. The binding energies for all spectra were cali-
parameters is due to the more perfect development of the unit cell.
brated with the XPS peak of C 1s. The XPS spectra and its corre-
For Ar-NCM and AH-NCM, the severe Liþ/Ni2þ disordering may
sponding fitting curves for O2-NCM and other samples are shown in
cause the increase of the unit cell parameters [21]. The value of c/a
Fig. 3 and Figs. S3eS6, respectively. As displayed in Fig. 3a, the Ni
spectra of O2-NCM is similarly composed of the Ni 2p3/2 and Ni 2p1/
Table 1 2 peaks and their corresponding satellite peaks. The main and
Rietveld refinement results of the five samples. satellite peaks of Ni 2p3/2 respectively locate at 855.2 and 861.6 eV,
Samples a(Å) c(Å) c/a V(Å3) Rwp Rp while the main and satellite peaks of Ni 2p1/2 are observed at
around 872.9 and 879.6 eV [14,25]. The peaks at 854.9 and 856.0 eV
NCM 2.865878 14.203478 4.956065 101.030 6.24% 3.27%
O2-NCM 2.866151 14.208679 4.957408 101.080 7.68% 4.55%
in the Ni 2p3/2 main region correspond to the Ni2þ and Ni3þ ions,
Air-NCM 2.866378 14.207463 4.956591 101.090 7.72% 4.67% respectively [15]. The Ni 2p spectra of NCM, Air-NCM, Ar-NCM and
Ar-NCM 2.866753 14.205817 4.955365 101.110 7.79% 4.73% AH-NCM are demonstrated in Fig. S3. The peak position, including
AH-NCM 2.867119 14.206386 4.954934 101.140 7.92% 5.03% the main peak and the satellite peak, are consistent with the O2-
4 Y. Zhu et al. / Electrochimica Acta 328 (2019) 135116
Fig. 2. (a) SEM image of O2-NCM, and EDS elemental mappings of (b) Ni, (c) Co and (d) Mn.
NCM sample. As shown in Fig. 4a, the relative proportion of the Ni2þ
ions for NCM, O2-NCM, Air-NCM, Ar-NCM and AH-NCM is estimated
to be respectively 54.77%, 39.58%, 51.98%, 54.79% and 54.87%.
Compared with NCM, reprocessing in an oxidation atmosphere
significantly decreases the percentage of Ni2þ ions, which can
reduce the Liþ/Ni2þ mixing and the cell volume, while reprocessing
in a reductive atmosphere results in a slightly increased Ni2þ,
consistent with the previous XRD results. Fig. 3b and Fig. S4 illus-
trate the Co 2p spectra of all the samples, where the Co 2p3/2 peak is
located at around 780.4 eV, the satellite peak is at 790.1 eV, and the
peak of Co 2p1/2 appears at 795.8 eV [26,27]. The fitting results
show that the heat treatment atmosphere has a significant effect on
the valence of Co, Co3þ is dominant when the samples are pro-
cessed in a relatively high oxygen partial pressure, while Co2þ is
present when a reductive atmosphere is applied. The Mn 2p spectra
are displayed in Fig. 3c and Fig. S5, consisting of the peaks of Mn
2p3/2 (642.6 eV) and Mn 2p1/2 (654.0 eV) [28]. An auger peak at
approximately 637.8 eV and a satellite peak at around 645.1 eV of
Mn 2p3/2 appear for all of the five samples, ascribed to the creation
of electron holes with a relatively long lifetime at the core levels.
Comparing the fitting results of the transition metal elements in
Fig. 4a, the change trend of valence state of Co and Ni is consistent,
and the influence of the oxygen partial pressure on Co is more
obvious, while there is no obvious valence change of the Mn
element for the samples processed in different atmospheres.
The O 1s spectra of O2-NCM are shown in Fig. 3d, and that of the
other four samples are shown in Fig. S6. The low binding energy
peak at 529.3 eV is originated from the lattice oxygen (O2lattice),
while the high binding energy peak at around 531.5 eV is related to
the absorbed oxygen (O2active) due to the surface absorbed H2O
and CO2 from the environment and the generated LiOH and LiCO3
[15,29]. The formation of LiOH and LiCO3 can be illustrated by the
following equations:
. .
O2 2
active þ CO2 H2 O/CO3 2OH (3)
. .
2Liþ þ CO2
3 2OH /Li2 CO3 LiOH (4)
The relative contents of O2lattice and O2active are demonstrated
in Fig. 4b. When heat treatment atmosphere converts from oxida-
tive to reductive, the content of O2lattice gradually increases, and
the O2active gradually decreases. Namely, the relative content of
the lattice oxygen decreases when the partial pressure of oxygen
decreases. Compared to NCM sample, the percentage of lattice
oxygen is increased and the formation of LiOH and LiCO3 is deterred
when processed in the oxidation atmosphere, and O2-NCM displays
the highest lattice oxygen content of 38.68% among all the samples.
More lattice oxygen surrounding the transition metal elements of
NCM may result in stronger metal-oxygen bonding, promoting the
formation of a more stable layered structure. At the same time, less
absorbed oxygen may reduce the side reaction on the nickel-cobalt-
manganese electrode material surface and then decrease the
possible dissolution of transition metal elements during the elec-
trochemical reaction [30,31].
3.2. Electrochemical performances
The charge and discharge curves between 2.80 and 4.25 V at
0.1 C for the five samples are demonstrated in Fig. 5a. The initial
discharge specific capacities of NCM, O2-NCM, Air-NCM, Ar-NCM
and AH-NCM at 0.1 C are respectively 170, 176, 173, 169 and
168 mA h g1. The discharge specific capacities increase after the re-
processing in oxygen and air, and decrease in argon and argon/
 Y. Zhu et al. / Electrochimica Acta 328 (2019) 135116 5

Fig. 3. XPS spectra of (a) Ni 2p, (b) Co 2p, (c) Mn 2p and (d) O 1s of O2-NCM.

Fig. 4. (a) Comparison of contents of nickel, cobalt and manganese in the five samples; (b) Comparison of lattice oxygen and absorbed oxygen content in the five samples.

hydrogen compared to the NCM sample. The discharge specific
capacities do not change much in contrast to NCM at 0.1 C. Simul-
taneously, the charge/discharge curves of O2-NCM and other four
samples at different rates are shown in Fig. 5b and Fig. S7. The
capacitance difference of the samples becomes more pronounced
with the increase of current density. For instance, at 10.0 C, the
discharge specific capacities of the electrode materials treated in
the oxidative atmosphere (O2-NCM and Air-NCM, 109 and 103 mA h
g1, respectively) are greatly increased compared to NCM
(103 mA h g1), the materials treated in an inert atmosphere (Ar-
NCM, 47 mA h g1) and in the reductive atmosphere (AH-NCM,
38 mA h g1). This also demonstrates that the greater the concen-
tration of oxygen deficiency in the layered material, the more se-
vere the decay of specific capacity at high rate. As analyzed in the
previous XRD and XPS results, the heat treatment atmosphere is
crucial for the valence of the transition metal, the degree of the
crystalization, and the arrangement of the atoms in the electrode
materials [15,32]. The relationship between the discharge specific
capacity of the five samples at 2.0 C and the percentage of Co3þ and
lattice oxygen is plotted and shown in Fig. 5c and d, respectively.
Apparently, the specific discharge capacity is positively correlated
with the Co3þ content and the lattice oxygen content. Among the
6 Y. Zhu et al. / Electrochimica Acta 328 (2019) 135116

Fig. 5. (a) Comparison of the charge/discharge curves of the five samples at the rate of 0.1 C; (b) The charge-discharge curves of O2-NCM at different rates; The relationship between
the discharge specific capacity at 2.0 C and the content of (c) Co3þ, (d) Olattice; (e) Rate capability of the five samples; (f) Cycling performance of the five samples at the rate of 1.0 C.

five samples, the O2-NCM sample with the highest content of Co3þ
and lattice oxygen exhibits the highest discharge specific capacity,
opposite to that of the AH-NCM sample. Under the oxidative at-
mosphere, the layered crystal structure is more completely devel-
oped and the oxygen deficiency concentration is lower, which is
beneficial to improve the reaction kinetics and reversibility of the
Li-ion insertion and de-insertion processes.
The differences of the rate capabilities and the cycling perfor-
mance of NCM and the samples processed in different atmospheres
were further evaluated. Fig. 5e displays the rate capability curves at
various rates. For all samples, the higher the current density, the
lower the specific discharge capacity. The O2-NCM sample prepared
under oxygen atmosphere displays higher discharge specific ca-
pacity than the other four samples at each current density. From
0.1 C to 10.0 C, the capacitance retention of NCM, O2-NCM, Air-NCM,
Ar-NCM and AH-NCM is 60.3%, 61.9%, 59.6%, 27.7% and 22.8%,
respectively. When the rate is gradually increased, the decay of Ar-
NCM and AH-NCM with higher oxygen deficiency concentration is
more serious than that of NCM sample and the O2-NCM and Air-
NCM samples treated in an oxidative atmosphere. This phenome-
non indicates that the higher the rate, the more obvious the impact
of oxygen deficiency on the capacity of active material. The
improvement of the rate performance of O2-NCM may be correla-
tive to the decrease occupy of Ni2þ in the Liþ sites, which is more
advantageous for Liþ to insertion and extraction in the lattice
compared to the other four samples. The cyclic performance of the
materials is illustrated in Fig. 5f. After cycling for 300 times at 1.0 C,
the capacity retentions of NCM, O2-NCM, Air-NCM, Ar-NCM and
AH-NCM are 60.15%, 67.17%, 63.62%, 56.69% and 53.17%, respec-
tively. Moreover, the specific capacities of the O2-NCM and Air-NCM
samples are comparable to those reported in the literature under
similar conditions, and the rate capability and cycle performance of
the prepared materials in this work are much superior (Table S1).
The excellent performance of O2-NCM is originated from the
 Y. Zhu et al. / Electrochimica Acta 328 (2019) 135116
Fig. 6. (a) Cyclic voltammetry curves of the five samples at a scan rate of 0.1 mV s1; (b) Electrochemical impedance of the five samples; Effects of oxygen defect concentration on
the structure and Li-insertion of (c) O2-NCM622, and (d) AH-NCM622.
effectively reduced cation mixing and well developed layered
structure after reprocessing in an oxidative atmosphere [33,34].
To further investigate the correlation of the Liþ concentration
with the oxygen defect concentrations of the layered NCM mate-
rials, XPS measurements were performed on the electrodes in the
fully charged and discharged states. The button cells were first
galvanostatically charged/discharged to the fully charged and dis-
charged states, then the cells were disassembled in a glove box, and
the electrodes were washed several times with DMC solvent to
remove the residue electrolyte and dried in a vacuum oven before
the measurements. The obtained spectra were fitted to obtain the
relative proportions of the transition metal and oxygen elements
(Fig. S8). Fig. S8a shows the change of transition metal elements of
O2-NCM and AH-NCM in the fully charged and discharged states.
Compared to Fig. 4a of the as-prepared materials, the Ni3þ content
is significantly increased under the fully charged state (78.25% vs.
60.42% for O2-NCM and 57.23% vs. 45.13% for AH-NCM), but roughly
unchanged under the fully discharged state (60.62% vs. 60.42% for
O2-NCM and 45.49% vs. 45.13% for AH-NCM). Compared to the as-
prepared materials, the valence of the Mn element keeps almost
unchanged for both O2-NCM and AH-NCM in the fully charged and
discharged states, while the ratio of the Co3þ is increased for AH-
Table 2
EIS parameters of the assembled cells for the five samples.
Samples Rs(U cm2) Rf(U cm2)
NCM 1.219 166.4
O2-NCM 1.095 126.6
Air-NCM 1.132 144.8
Ar-NCM 1.238 171.7
AH-NCM 1.885 192.0
7
NCM in the fully charged state. These phenomena might be due
to the oxidation of transition metal elements during the delithia-
tion processes towards the fully charged state [35,36]. The variation
of oxygen element of O2-NCM and AH-NCM in the fully charged and
discharged states is shown in Fig. S8b. The lattice oxygen content in
the fully charged state is higher than the fully discharged state for
both O2-NCM and AH-NCM, consistent with Liþ intercalation/de-
intercalation processes. Compared to Fig. 4b, the percentage of
lattice oxygen is reduced in the fully charged/discharged states for
both materials, probably attributed to delithiation/lithiation of the
layered structure and the electrolyte decomposition and deposition
of the oxygen-containing products on the electrode surface after
charging/discharging [37e40].
The cyclic voltammograms (CV) of NCM, O2-NCM, Air-NCM, Ar-
NCM and AH-NCM are shown in Fig. 6a. There is only one pair of
redox peaks, indicating that there are no phase conversion re-
actions between hexagonal and monoclinic within the voltage
range during charging and discharging. The voltage gap of the
oxidation and reduction peaks of the O2-NCM sample (89 mV) is
smaller than that of NCM (94 mV), Air-NCM (94 mV), Ar-NCM
(138 mV) and AH-NCM (158 mV), revealing that the polarization
of the layered material is reduced upon the decrease of the oxygen
Rct(U cm2) CPE1(  e6 F cm2) CPE2(  e3 F cm2)
46.19 30.49 2.496
37.49 26.35 2.77
38.97 44.38 2.998
46.71 59.47 3.287
78.27 33.88 1.43
8 Y. Zhu et al. / Electrochimica Acta 328 (2019) 135116
deficiency. The charge transfer ability of all samples were further
evaluated by AC impedance test (EIS). The electrochemical
impedance spectra shown in Fig. 6b are composed of three parts,
the surface film resistance (Rf, the first semicircle) in the high-
frequency region, the charge transfer resistance (Rct, the second
semicircle) in the mid-frequency region, and the Warburg imped-
ance (Zw, the straight line) in the low-frequency region [41e43].
The impedance spectra are fitted according to the equivalent circuit
given in the inset of Fig. 6b and the obtained fitting parameters are
listed in Table 2. Comparing the fitting data, the solution imped-
ances of the materials are roughly the same, while the Rf and Rct of
the samples treated in the reductive conditions are much larger
than the samples obtained under higher oxygen partial pressure,
implying the great effects of the oxygen deficiency concentration
on the surface film formation and the charge transfer kinetics.
Increasing oxygen content in the calcination atmosphere can
effectively reduce the oxygen deficiency concentration in the pro-
duced nickel-cobalt-manganese electrode material, inhibit the
cation mixing, and also decrease side reactions on the surface of
active materials surface through suppressing the formation of
lithium carbonate and lithium hydroxide, to improve the specific
capacity and cyclic performance [15,22].
From the above results and analyses, it can be confirmed that
the oxygen defect concentration is closely correlated to the specific
capacity and cycling stability of the layered nickel-cobalt-
manganese cathode. As described in the model in Fig. 6c and d,
the mechanisms behind the observed electrochemical performance
variations can be proposed as following. The oxygen deficiency
mainly affects discharge specific capacity of the nickel-cobalt-
manganese oxide by impacting the valence state of nickel and co-
balt, content of lattice oxygen, cation mixing degree and lattice
parameters. The lower the oxygen defect concentration, the smaller
the probability that Ni2þ will occupy the Liþ position, which en-
sures that the extracted lithium ions can insert again in their
original lattice position. The content of lattice oxygen has the most
outstanding effect on the discharge specific capacity and cycle
stability, as the lattice oxygen content directly affects the number of
electrons outside the core of nickel and cobalt, which determine the
strength of the MeO bonds.
4. Conclusions
Layered LiNi0$6Co0$2Mn0$2O2 electrode materials were synthe-
sized using a co-precipitation reaction and a subsequent heat
treatment process. The obtained materials have been re-calcined in
different atmospheres, to investigate the relationship of the oxygen
deficiency concentration (oxygen partial pressure) with
morphology, crystal structure, elemental valence and Li-insertion
performance. It’s found that there is a close relationship between
the specific capacity and the contents of Co3þ and lattice oxygen in
the layered materials, and the layered material re-heated in oxygen
also exhibits remarkable high rate performance and cyclic stability.
The significant performance improvement of the layered materials
re-heated in oxygen is attributed to the better developed layered
structure (increased lattice oxygen content), the more regular
cation arrangement (partial oxidation of Ni2þ to Ni3þ), the less
Li2CO3 and LiOH formation on material surface, and the greatly
increased Liþ insertion kinetics and reversibility. Therefore, the
oxygen deficiency has an important effect on the layered electrode
materials, and rational control of the oxygen deficiency may lead to
significantly improved overall electrochemical performance.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (No. 51372178) and the Natural Science
Foundation of Hubei Province of China (No. 2013CFA021,
2018CFA022).
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.electacta.2019.135116.
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