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Modified Coprecipitation Synthesis of Nickel-Rich NMC

(Li1.0Ni0.6Mn0.2Co0.2O2) for Lithium-Ion Batteries: A Simple, Cost-
Effective, Environmentally Friendly Method
Thao Le Thi, Truong Phan Van, Bo Nguyen Van, Nguyen To Van,* Tuan Nguyen Van,
Tien Phat Doan, Thi Lan Ngo, Ngoc Hung Vu, Tien-Thanh Nguyen, Huyen Nam Nguyen,
Nguyen Vo Anh Duy, and Minh Triet Dang*
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ABSTRACT: Lithium-ion batteries lay the foundation for

satisfying the fast-growing demand of portable electronics and
electric vehicles. However, due to the complexity of material
syntheses, high fabrication temperature condition, and toxic gas
emission, high volume manufacturing of lithium-ion batteries is still
challenging. Here, we propose a modified coprecipitation method
to synthesize Li1.0Ni0.6Mn0.2Co0.2O2 (NMC622-MCP) as a cathode
material in a simple, cost-effective, and environmentally friendly
approach. We demonstrate that the proposed method can be
operated in a lower temperature environment, with respect to the requirement of conventional synthesis methods. Furthermore, only
CO2 gas is emitted during synthesis. We also employed first-principles simulations to evaluate the crystallinity of the synthesized
materials via X-ray diffractometer patterns. During charge/discharge processes, the obtained cathode materials induce outstanding
electrochemical performance with a maximum specific capacity of up to 206.9 mAh g−1 at 0.05 C and a retention capacity of 83.22%
after 100 cycles. Thus, the simple, cost-effective, environmentally friendly, and highly electrochemical performance of the newly
acquired material envisages the modified coprecipitation method as a promising tool to manufacture cathode materials for lithium-
ion batteries.

1. INTRODUCTION
Recently, strong consumer demand for electric vehicles
requires significant development of energy storage devices
with high reversible capacity, reasonable long-term cycling life,
and environmentally friendly manufacturing. Currently, one of
the most effective commercialized energy storage devices is
lithium-ion batteries (LIBs). Identical to other energy storage
devices, LIBs consist of an anode electrode, a separator, and all
immersed electrolyte solution. Among these standardized
components, the cathode electrode material plays an important
role in determining the electrochemical properties of LIBs;1
thus, to enhance the performance of LIBs on electric vehicles,
it is crucial to improve the electrochemical performance of
cathode materials.1,2
Several exciting commercial types of cathode electrode
materials for LIBs are LiCoO2 (LCO),3,4 LiMnO2 (LMO),5,6
LiFePO4 (LPO),7,8 and Li[NixMnyCoz]O2 (NMC).9,10 For
electric vehicles, among these cathode materials, nickel-rich
NMC-layered cathodes can be considered as an excellent
candidate to reconcile the requirement of high specific
discharge capacity, reasonable durability and working voltages,
and affordable production cost.11 NMC materials share almost
the same specific energy density as LCO but possess a better
© XXXX The Authors. Published by
American Chemical Society
A ACS Omega XXXX, XXX, XXX−XXX
discharge rate and lower cost, while their durability is as high
as that of LFO. 12 Some typical NMC materials are
LiNi 1/3 Mn 1/3 Co 1/3 O 2 (NMC111), LiNi 0.6 Mn 0.2 Co 0.2 O 2
(NMC622), and LiNi0.8Mn0.1Co0.1O2 (NMC811). NMC111
materials, synthesized by a coprecipitation method combined
with calcination at 930 °C, deliver a discharge specific capacity
of 183.9 mAh g−1 at 0.1 C and a retention of 79.66% after 120
cycles.13 Furthermore, NMC11 materials, synthesized by the
solid-state method at 900 °C in the presence of citric acid and
polyvinylpyrrolidone, show an initial specific capacity of 173
mAh g−1 at 0.1 C and a retention of 83.2% after 100 cycles at
0.5 C.14 NMC622 materials, synthesized by the modified sol−
gel method, exhibit an initial discharge capacity of 223.7 mAh
g−1 at 0.1 C, but their durability is limited (a retention of 80%
capacity after 50 cycles at 1 C).15 NMC811 materials,
synthesized by the sol−gel method combined with calcination
Received: July 2, 2023
Revised: November 7, 2023
Accepted: November 10, 2023
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at 750 °C, deliver a specific capacity up to 200 mAh g−1 at 0.1
C with a capacity retention of 75.8% after 100 cycles at 0.5
C.16 The above examples highlight the essential role of the
Ni:Mn:Co molar ratio to control LIBs’ electrochemical
properties: Ni-rich layered cathodes successfully increased
the specific capacity; however, they resulted in poor
durability.17 Thus, the application of Ni-rich NMC materials
is still limited. To improve the electrochemical performance of
Ni-rich NMC cathodes and to facilitate the feasibility
requirements in practice, it is essential to find the optimal
procedure and conditions to synthesize material electro-
des.14,16 Each synthesis method has its own advantages and
disadvantages. For instance, the sol−gel method is the best
method in terms of electrochemical efficiency, but it requires
sophisticated manufacturing procedures and releases toxic NOx
gases during synthesis.16 Solid-state reaction methods over-
come the limitation of the sol−gel method, but the obtained
materials have low homogeneity and lower electrochemical
efficiency. In addition to those drawbacks, this method is
slightly more expensive in terms of energy consumption during
fabrication as the working temperature environment is above
900 °C.18 The coprecipitation method can take advantage of
the above two methods, but the fabrication process is more
complicated than that of the solid-state reaction method, and
the electrochemical efficiency is not as high as that of the sol−
gel method. Therefore, it is essential to explore novel
approaches to overcome the disadvantages of each method
described above and to increase the future applications of LIBs.
Here, we propose a modified coprecipitation method to
synthesize Li1.0Ni0.6Mn0.2Co0.2O2 materials (NMC622-MCP),
which overcomes the limitations of traditional material
synthesis methods. Specifically, carbonate salts have been
used as precursors to provide metal ions. The precursor oxalic
acid provides C2O42− radicals for the coprecipitation process
and decomposes the carbonate radical. Thanks to this simple
approach, a solid mixture of lithium−nickel−manganese−
cobalt oxalates (LiNiMnCo-ox) and an excess of oxalic acid
was produced and calcined at a lower working temperature
than that of the traditional conventional synthesis approach to
achieve the desired material. We demonstrate that this method
allows us to obtain a high synthesis efficiency (an efficiency of
forming the cathode material from raw materials), easily
control the ratio of atoms, and generate nontoxic gases during
the synthesis process. More essentially, the obtained NMC622-
MCP material still has outstanding electrochemical perform-
ance with a maximum specific capacity of 206.9 mAh g−1 at a
rate of 0.05 C and a retention of 83.22% capacity after 100
cycles. To demonstrate the outperformance of the modified
coprecipitation method relative to the traditional synthesis
approach, we also performed the solid phase reaction method
to synthesize Li1.0Ni0.6Mn0.2Co0.2O2 under the same calcination
conditions (NMC622-SS). At identical experimental con-
ditions with the NMC622-MCP sample, the NMC622-SS
sample cannot reach the desired phase structure and shows a
very poor electrochemical performance (a specific capacity of
126.2 mAh g−1 and a retention of 63% initial capacity after 50
cycles at 0.05 C). In addition, the quantitative agreement
between experimental X-ray diffractometer patterns and those
obtained from density functional theory (DFT) simulations of
the pristine and active materials at various Li dissolutions
consolidates the impact of the proposed synthesis approach on
structural stability. Our results promise a greener way to
synthesize cathode materials for LIBs with reasonable electro-
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Article
chemical properties but with less energy consumption during
fabrication.
2. METHODS
Chemicals for Experimentation. All chemicals for
experimentation were supplied by the Sigma-Aldrich chemical
company. They include lithium carbonate (Li2CO3), nickel
carbonate (NiCO3), manganese carbonate (MnCO3), cobalt
carbonate (CoCO3), oxalic acid dihydrate (H2C2O4·2H2O),
lithium foil (Li), lithium perchlorate (LiClO4), carbon black
(Supper P), polyvinylidene fluoride (PVDF), N-methyl-2-
pyrrolidone (NMP), ethylene carbonate (EC), and diethyl
carbonate (DC).
Material Preparation. Our modified coprecipitation
synthesis method for Li1.0Ni0.6Mn0.2Co0.2O2 material consists
of four essential steps. Step 1: A mixture of Li2CO3 (10.5
mmol), NiCO3 (12 mmol), MnCO3 (4 mmol), and CoCO3 (4
mmol) is ground and mixed by ball-milling ata speed of 300
rpm for 30 min to obtain a homogeneous solid mixture. Step 2:
40 mmol of H2C2O4·2H2O is dissolved in 80 mL of H2O by
magnetic stirrers at 500 rpm for 30 min. Step 3: The solid
mixture obtained from “step 1” is slowly dropped into the
solution prepared by “step 2”. The magnetic stirrers are
continuously rotated at a speed of 500 rpm. At this state, a
solution of oxalic acid provides H+ ions to decompose the
carbonate radical of the precursor salt and releases a large
amount of CO2 gas. The transition metal ions (Ni, Mn, and
Co) combine with C2O42− radicals to form precipitates, while
lithium ions still exist in a solvated state and are in charge
balance with C2O42− ions.19−21 After perfectly mixing, the
sample is heated at 100 °C until all water evaporates to form a
solid mixture of lithium−nickel−manganese−cobalt oxalates
(LiNiMnCo-ox) and an excess of oxalic acid. Step 4: The solid
mixture obtained from “step 3” is calcinated at 850 °C for 10 h
under an oxygen stream flowing in at a rate of 1 L min−1.
Finally, the Li1.0Ni0.6Mn0.2Co0.2O2 material is formed and
denoted as NMC622-MCP. To demonstrate the outperform-
ance of our proposed synthesis approach with respect to the
standard solid-state reaction method, we also prepared a
Li1.0Ni0.6Mn0.2Co0.2O2 sample from a mixture of Li2CO3 (10.5
mmol), NiCO3 (12 mmol), MnCO3 (4 mmol), and CoCO3 (4
mmol). This mixture is ground and mixed by ball-milling at a
speed of 300 rpm for 30 min to obtain a homogeneous solid
mixture and then calcined under similar conditions as
NMC622-MCP (850 °C for 10 h under an oxygen stream
flowing in at a rate of 1 L min−1). We denote this sample as
NMC622-SS.
Characterization. The structural, microstructural, and
elemental composition characterizations are measured by the
X-ray diffractometer (XRD) from Siemens D5005 in a Bragg−
Brentano geometry of θ−2θ configuration (Cu Kα1 radiation)
at a scanning rate of 0.03°/s, from 2θ ranging between 10° and
70° and by field emission scanning electron microscopy (SEM,
Hitachi S-4800) equipped with energy dispersive spectroscopy
(EDS) of a Horiba EMAX analyzer. High resolution and more
accurate characterization for structural, microstructural, and
compositional properties are carried on inductively coupled
plasma-optical emission spectrometry (ICP-OES, Agilent) and
transmission electron microscopy (TEM, JEM 2100) at a
working accelerated voltage of 200 kV and at TEM, HR-TEM,
and STEM-EDS modes. The oxidation states of elements of
both synthesized materials are determined by X-ray photo-
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electron spectroscopy (XPS) on the Shimadzu Kratos AXIS-

ULTRA DLD high-performance XPS system.
The electrochemical performance of synthesized materials is
evaluated on a coin-cell CR2032 (half-cell) through the
measurement of cyclic voltammetry (CV), galvanostatic
charge−discharge (GCD), and electrochemical impedance
spectroscopy (EIS). The CV is performed on the device
Metrohm Autolab PGSTAT 302N at different scan rates (0.1,
0.2, 0.5, and 1 mV s−1) with a potential range from 2.5 to 4.5
V. The GCD is conducted on the device NEWARE battery
tester at different current densities (10, 20, 50, 100, and 200
mA g−1) with a potential range from 2.5 to 4.5 V. The EIS is
performed on the device Metrohm Autolab PGSTAT 302N in
the frequency range of 10−1 − 105 Hz with a voltage applied of
2.5 V. The coin-cell CR2032 is assembled from the anode Figure 1. SEM images of NMC622-SS (a, b) and NMC622-MCP
electrode (Li foil), cathode electrode (prepared from samples (c, d).
synthesized materials), 1 M LiClO4 solution in the mixture
of ethylene carbonate/diethylene carbonate (EC/DEC,
volume ratio of 1:1), and polypropylene (PP) membrane as and deintercalation of lithium ions face many disadvantages.30
the separator. Note that the assembly process of coin-cell In contrast, the NMC622-MCP particles, synthesized by our
CR2032 is carried out in a glovebox with an oxygen and modified coprecipitation method, exhibit homogeneous
moisture level below 0.1 ppm. The cathode electrode is distribution with their size of about 500 nm as shown in
prepared from a mixture of synthesized materials, black carbon, Figure 1c,d. These particles, obtained from a mixed metal
and PVDF with a mass percentage ratio of 80:10:10. The oxalates precipitated simultaneously in solution, as reported in
electrode fabrication process was carried out as presented in ref. 29, form perfect grain boundary networks. Such grain
ref. 22. The thickness and mass of the active material layer on boundary structures allow lithium ions to diffuse faster along
each cathode electrode plate are about 15 μm and 8−10 mg, the grain boundary, thus enhancing the electrochemical
respectively. performance of the synthesized cathode materials.31,32 These
Computational Methods. We performed DFT simu- observations illustrate the advanced surface modification
lations to uncover the structural origin of the experimental X- achieved from our proposed modified coprecipitation method,
ray diffraction peaks of the synthesized NMC622-MCP which promises a high electrochemical efficiency of the
samples. All DFT simulations are performed using the NMC622-MCP samples.
Projector Augmented Wave (PAW) method implemented in To evaluate the atomic composition of these samples, we
the Vienna Ab initio Simulation Package (VASP).23−25 We measured the EDS of NMC622-SS and NMC622-MCP
used the generalized gradient approximation of the Perdew− samples. The molar ratios of Ni, Mn, Co, and O elements in
Burke−Ernzerhof (PBE) functional26 as exchange-correlation both NMC622-SS and NMC622-MCP samples are quite
functionals. To consider the self-interaction error of 3d orbitals identical (Ni:Mn:Co:O = 0.6:0.21:0.22:2.04 for NMC622-MCP
of transition metals, we also apply Hubbard U corrections (6.7, and 0.6:0.21:0.21:1.85 for NMC622-SS) (Figures 2a,b). The
4.91, and 4.64 eV for Ni, Co, and Mn 3d orbitals, respectively,
as suggested in ref. 27). For geometrical optimization, the
integration in the Brillouin zone was employed using the
Monkhorst−Pack scheme28 (2 × 3 × 1) with an energy cutoff
of 450 eV. The convergence threshold for the self-consistent
field calculations was set to 10−5 eV per cell, and the
geometrical structures were fully optimized until the
Hellmann−Feynman forces acting on atoms were less than
0.035 eV Å−1.27

3. RESULTS AND DISCUSSION

3.1. Structural, Morphological, and Chemical Char-
acterization. The morphology and surface stability of cathode
materials are crucial for their electrochemical performance and
structural integrity. In Figure 1, we show the SEM images of
NMC622-SS and NMC622-MCP samples. The NMC622-SS
particles are smaller in size (about 200−500 nm), but they can
aggregate to form superstructures in a larger scale of 3−5 μm
(in Figure 1a,b). In contrast, the NMC622-MCP particles,
synthesized by our modified coprecipitation method, exhibit
homogeneous distribution with their size of about 500 nm as
shown in Figure 1c,d. These particles result from a mix of
metal oxalate precipitated simultaneously in solution, as Figure 2. EDS results of NMC622-SS (a) and NMC622-MCP (b),
reported in ref. 29. Such large sized particles prevent the SEM images and the corresponding SEM-EDS elemental mapping of
redox centers to reach the electrolyte; thus, the intercalation NMC622-MCP (c−g).

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Figure 3. XPS spectrum of Ni 2p (a), Mn 2p (b), Co 2p (c), and O 1s (d) in the NMC622-MCP.
ICP-MS measurement is performed to determine the atomic
ratios of all elements in the sample. These atomic ratios of
Li:Ni:Mn:Co in NMC622-MCP and NMC622-SS are about
1.0:0.61:0.21:0.19 and 1.0:0.59:0.21:0.20, respectively. We did
not observe any additional elements from all SEM-EDS and
ICP-MS analyses, indicating the level of purity of our
synthesized materials. The element mapping on the surface
of NMC622-MCP is shown in Figure 2c−g. These SEM-EDS
elemental mapping images show the presence of Ni, Mn, Co,
and O elements, as well as their distribution over the surface of
the NMC622-MCP particles, which agrees well with the
observations on the EDS spectrum (Figure 2a) and the ICP-
MS results.
We also perform XPS to determine the changes in
composition and redox states of atoms of the NMC622-
MCP sample in Figures 3 and S1. In Figure S1, the XPS
spectrum (red line) of pristine NMC622-MCP shows the
presence of Li 1s, Ni 2p, Mn 2p, Co 2p, and O 1s, which well
matches the element composition of Li1.0Ni0.6Mn0.2Co0.2O2
formula. The presence of C 1s at a bending energy of 284.6 eV
in the XPS spectrum is caused by the carbon atoms on the
sample holder, which is also used as a standard measure to
calibrate the XPS spectrum of all other elements. The high-
resolution XPS spectra of Ni 2p, Mn 2p, Co 2p, and O 1s
(Figure 3) show that, while metal elements exist in two
oxidation states (+2, +3 for Ni 2p; +3, +4 for Mn 2p and Co
2p), the oxygen atom appears in two types (oxygen in the
metal at 529.5 eV and defective oxygen at 531.6 eV) in
excellent agreement with other reports.33−35 The peaks
observed on the XPS spectra of Ni 2p, Mn 2p, and Co 2p at
855.01/872.27, 856.22/873.72, 642.44/653.61, 642.84/
654.84, 780.20/795.20, and 782.01/795.98 eV correspond to
the spin−orbit doublets of Ni2+, Ni3+, Mn3+, Mn4+, Co3+, and
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Co4+, respectively.33,36 In addition, the shakeup satellite peaks
of Ni and Co are observed at 861.46/879.24 eV and 789.61/
804.39 eV in the high-resolution XPS of Ni 2p and Co 2p,
respectively, further demonstrating the presence of Ni2+
cations36 and Co3+ cations.36,37
To characterize the lattice structure of the synthesized
materials, we simultaneously measured the XRD patterns, HR-
TEM, and SAED of NMC622-MCP and directly compared the
experimental XRD patterns with those obtained from DFT
simulations in Figure 4. Using the Rietveld refinement, we
associate the experimental XRD peaks of NMC622-MCP with
the hexagonal lattice structure of LiNiO2 (R3̅m space group)
(PDF-00-0963).38,39 The observed peaks are assigned to
(003), (101), (006), (102), (104), (105), (107), (108), (110),
and (113) planes in agreement with previous reports.1,39,40
Comparing the XRD patterns of NMC622-MCP and
NMC622-SS (Figure S2), besides the LiNiO2 phase, we also
detected the secondary phase transition in the NMC622-SS
sample, illustrating that to reach the R3̅m space group using
the solid phase reaction method, the sample should be
performed at temperatures above 900 °C, as reported in refs. 41
and 42
. The ratio between the diffraction intensity (003) and
(104) peaks (I(003)/I(104)) reflects the degree of structural order
of the NMC layers and the mixing of Li+ and Ni2+ ions. As
suggested in ref.43, when this ratio is greater than 1.2, the
synthesized material has a good order and small mixing cation.
As illustrated in Figure 4a, our calculated I(003)/I(104) ratio of
NMC622-MCP is 1.88, indicating a highly ordered layer
structure with minimal cation mixing between Li+ and Ni2+. In
addition to the high ratio of I(003)/I(104) peaks, we observe
double peaks at (006)/(102) and (108)/(110), which is also
an excellent indication of the high order of crystallinity of
NMC622-MCP crystal structures.1 These observations dem-
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Figure 4. Experimental and DFT structural characterizations of NMC622-MCP samples: XRD pattern and Rietveld refinement results (a) and the
Williamson−Hall plot (b) of NMC622-MCP. The optimized configuration of NMC lattice with the R3̅m space group (c) and XRD reconstruction
from the theoretical prediction (d). The gray, purple, blue, green, and red spheres represent Ni, Mn, Co, Li, and O atoms, respectively. HR-TEM
image (e) and SAED (f) of NMC622-MCP.

onstrate that at a relatively low temperature environment, the
NMC622-MCP crystalline structures underwent lower internal
stress and less lattice distortion, resulting in a better structural
orientation than that obtained from the standard synthesized
technique. To quantify the local distortion of our NMC622-
MCP sample, we plotted Williamson−Hall (W−H) diagram in
Figure 4b using the following equation:
K×
hkl
× cos = +4× sin
D (1)
where βhkl is the full width half-maximum (fwhm), θ the Bragg
angle, K a constant value of 0.9, λ the wavelength of the
radiation (1.54056 Å), D the mean crystallite size, and ε the
micro strain. By fitting the experimental values of βhkl × cos θ,
we obtained the D and ε values of 114.03 nm and 4.68 × 10−4,
respectively. The small value of the fitted ε parameter indicates
that the microstrain of our NMC622-MCP is smaller than
those reported for NMC811 (ε = 8.6 × 10 −4 ), 44
Li1.2Ni0.2Mn0.6O2 (ε = 2.45 × 10−2),45
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Li1.2Ni0.13Co1.13Mn0.54O2 (ε = 2.45 × 10−2),46 which also
emphasizes the high order of crystallinity of our NMC622-
MCP sample.
We further compare the atomic lattice of experimental
NMC622-MCP with the optimized equilibrium structures of
LiNi0.6Co0.6Mn0.6O2 (NMC622-DFT) via DFT simulations
with Hubbard U corrections. Our stable bulk structure is a 5 ×
2 × 1 supercell containing 30 Li, 18 Ni, 6 Mn, 6 Co, and 60 O
atoms. Table S1 demonstrates an excellent agreement between
the optimized lattice parameters and those measured
experimentally. The transition metal (TM) Ni/Mn/Co slabs
are sandwiched in between Li slabs, and the TM−O bond
length is around 2.0 Å for almost all cases (Figures 4c and S3).
To further characterize the symmetrical order of the
synthesized samples using the proposed coprecipitation
method with our DFT results, we normalized and super-
imposed the experimental XRD pattern onto our DFT one in
Figure 4d. We also calculated the relative difference between
these XRD peaks obtained from both methods, which is the
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Figure 5. GCD profiles of NMC622-SS (a) and NMC622-MCP (b). The CV curves at different scanning rates (c) and Randles−Sevcik plots (d)
of NMC622-MCP.
ratio between the experimental and DFT peak difference
versus the experimental peak value. Figure 4d and Table S1
demonstrate a quantitative agreement between our exper-
imental and DFT XRD peaks, with an average relative
difference of ∼0.15%. This excellent agreement between the
experimental observations and our theoretical prediction
highlights the advantage of our proposed modified coprecipi-
tation method to reduce the energy cost for synthesizing
NMC622-MCP materials in high-volume manufacturing.
In addition, we also resolved the lattice fringes of the
synthesized materials via HR-TEM images (Figure 4e). The
lattice spacing between two adjacent fingers on HR-TEM
images is 0.47 nm corresponding to the (003) plane and 0.24
nm corresponding to the (102) plane. The selected area
electron diffraction (SAED) was also performed to clarify the
phase structure of NMC622-MCP samples. The sharp
diffraction dots, indexed by the (102), (104), and (110)
planes, on concentric rings of SAED image (Figure 4f) suggest
that the synthesized materials have high crystallinity and
polycrystalline nature,47 which are all consistent with the
previously reported XRD, HR-TEM, and DFT results.
The XRD, SEM, SEM-EDS, HR-TEM, SAED, XPS, and
ICP-MS results combined with theoretical calculations strongly
emphasize the success of our synthesized nickel-rich NMC
(Li1.0Ni0.6Mn0.2Co0.2O2). The homogeneous and single-phase
NMC622-MCP promises an outstanding electrochemical
performance with respect to the NMC622-SS and other
similar materials.
3.2. Electrochemical Characteristics. Figure 5a,b
presents a three-initial GCD curve of the synthesized materials
at 0.05 C in the potential ranging from 2.5 to 4.5 V. The
voltage plateaus on the GCD curves might be attributed to the
redox process taking place during the charging and discharging
procedure. In addition, we observe the largest difference in the
GCD curves of the two synthesized samples in the charging
process of the first cycle. In the NMC622-SS sample, while two
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voltage plateaus reside at about 3.8−4.0 and 4.2−4.5 V (Figure
5a), there is only a broadened voltage plateau at 3.75−4.5 V in
the NMC622-MCP sample (Figure 5b). This variation might
be caused by the distinction in the phase/atomic structure
between the two samples (as evidenced in the XRD analysis).
It is noteworthy that the disappearance of the voltage plateau
at 4.2−4.5 V on the charging lines in the next cycles (Figure
5a), this feature, suggests a poorly reversible characteristic of
the NMC622-SS material. In other words, the NMC622-MCP
exhibits much better symmetric properties during the charging
and discharging lines in each single cycle. The relatively
smooth GCD curve indicates a more stable behavior of the
electrodes during the charging/discharging process.
Figure S4a,b demonstrates the doublet peaks occurring on
the first derivative curves of the GCD profiles of both
NMC622-SS and NMC622-MCP materials. Note that the first
derivative curve of the NMC622-SS (Figure S4a) was
calculated from the second cycle of the GCD profile. Thus,
the peak at a higher voltage of 4 V is not observed in this
derivative. Moreover, the first derivative curve of NMC622-
MCP shown in Figure S4b reveals good symmetries in terms of
both the peak position and peak intensity, which is completely
different from the first derivative from the NMC622-SS. This
result suggests that the electrode polarization of NMC622-
MCP during charge/discharge is much smaller than that of
NMC622-SS.48−50 The presented analysis indicates the single-
phase NMC622-MCP revealing superior reversibility com-
pared to the multiphase NMC622-SS, which will be discussed
in detail in the next paragraphs. As described in Figure 5a,b,
the initial charging/discharging specific capacities of the
NMC622-SS and NMC622-MCP are about 209.1/126.2 and
257.5/206.9 mAh g−1, respectively. These values correspond to
0.77/0.46 and 0.93/0.75 mol of Li+ ions extracted/inserted
from/into the structure. This observation suggests that almost
all of the lithium ions in the pristine material were extracted
from the material structure in the first charging process.
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Figure 6. Rate capacity and cycle performance of NMC622-SS (a,b) and NMC622-MCP (c,d).
However, the amount of lithium ions inserted into the cathode
electrodes during discharging of the NMC622-SS is about
49.4%, which inhibits the use of the NMC622-SS in the high
electrochemical efficiency material. In fact, the favorable
temperature to achieve Li1.0NixMnyCozO2 (x + y + z = 1,
NMC) material by the solid state reaction method is above
900 °C.13,51 The obtained NMC622-MCP allows 75% of the
Li+ ions to insert into the electrode during the discharging
process. The recent report demonstrates that, in the first
charging/discharging curves, the reversibility of Li+ ions
extracting/inserting process is relatively low (<90%).52 It is
fascinating to note that the charging and discharging lines of
the NMC622-MCP in the next cycles are almost overlapped,
which exhibits a good reversible characteristic of the developed
materials. The variation in the phase structure during the
charging/discharging process will be discussed later.
The CV analysis was performed to better comprehend the
electrochemical behaviors during the charging/discharging
process. Figure S4c displays the CV curves at a scanning rate
of 0.1 mV s−1 in the potential range from 2.5 to 4.5 V. The
curves depict a strong reduction peak at around 3.89 V and
another strong oxidation peak at 3.62 V, which can be
attributed to the redox reaction of the Ni2+/Ni3+/Ni4+ and
Co3+/Co4+ during the extracting/inserting process of Li+
ions.48,53 Furthermore, at high potential (4−4.5 V), a very
weak peak at 4.25/4.1 V has been noted, which corresponds to
the redox reactions of Mn3+/Mn4+. These characteristics are
consistent with those of the typical CV curves of NMC
electrodes found in the previous reports.48,53,54 Figure 5c
interprets the CV curves of the NMC622-MCP electrode at
different scanning rates (0.1, 0.2, 0.5, and 1 mV s−1). The
redox pairs are clearly observed on all CV curves, and the
potential difference between the oxidation and reduction peaks
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Article
grows as the scanning rate increases. This phenomenon might
be due to the Li+ ion diffusion rate not responding to the
increase of the scanning rate,54 which results in a decrease in
the electrochemical reaction efficiency as (i) the scanning rate
increases for the CV analysis, and (ii) the current density
increases for the GCD analysis. However, the current at redox
peaks grows dramatically as the scan rate increases, revealing
the rapid extraction/inserting process of Li+ ions. The Li+ ion
diffusion rate is estimated through the Randles−Sevcik
equation as follows:
Ip = 2.69 × 105 × n3/2 × A × D1/2 × C × v1/2 (2)
where n, A, D, C, ν, and Ip are the number of electrons
transferred in redox reaction (n = 1), the electrode area (1.13
cm2), the diffusion coefficient (cm2 s−1), the concentration (C
= 0.001 mol cm−3), the scanning rate (V s−1), and the peak
current (A), respectively. The dependence of the current at the
redox peak (Ip) on the square root of the scanning rate (v1/2) is
shown in Figure 5d. Linear relationships among Ipa, Ipc, and v1/2
are validated, suggesting a good reversibility in the electro-
chemical reaction of the NMC622-MCP electrode. Exploiting
the slope of the linear fits (k = 2.69 × 105 × n3/2 × A × D1/2 ×
C), the lithium diffusion coefficients in the charging/
discharging process were calculated. The coefficients are
about 2.5 × 10−7/2.1 × 10−7 cm2 s−1 for the charging/
discharging process. This result indicates that the Li+ ion
diffusion coefficient in the extracting process is higher
compared to that of the counterpart of the inserting process.
The achieved values of Li+ ion diffusion coefficients have been
also reported in the other studies,54,55 and they suggest that the
lithium-ions extracting process requires less activation energy.
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Table 1. Summary of the Electrochemical Performance of NMC622-MCP and Some Other Similar Materials
electrode materials synthesized methods electrochemical performance references
NMC622 carbonate coprecipitation 180 mAh g−1 at 0.2 C; maintain 83% after 30 cycles at 0.2 C 57
NMC622 hydroxide coprecipitation 172.8 mAh g−1 at 30 mA g−1; maintain 71.8% after 50 cycles at 30 mA g−1 58
LiNi0.6Mn0.35Co0.05O2 hydroxide coprecipitation 156.6 mAh g−1 at 30 mA g−1; maintain 98.5% after 50 cycles at 30 mA g−1 58
NMC622 solid-state reaction 171 mAh g−1 at 0.2 C; maintain 89.6% after 100 cycles at different densities 59
NMC622 combustion 170 mAh g−1 at 20 mA g−1; maintain 98.2% after 30 cycles at 0.3 C 60
NMC811 Sol−gel 200 mAh g−1 at 0.1 C; maintain 75.8% after 100 cycles at 0.5 C 16
NMC811 hydroxide coprecipitation 195.7 mAh g−1 at 0.1 C; maintain 73.8% after 100 cycles at 0.5 C 16
NMC622 Sol−gel 174 mAh g−1 at 0.1 C; maintain 89% after 100 cycles at 0.1 C 61
NMC622-MCP modified coprecipitation 206.9 mAh g−1 at 0.05 C; maintain 83.22% after 100 cycles at 0.05 C this study

Figure 7. Ex situ XRD patterns of the NMC622-MCP material during the charge/discharge process.

The rate capacity and cycling performance of the NMC622-
SS and NMC622-MCP samples are depicted in Figure 6. Poor
values of the rate performance, the Coulombic efficiency, and
the cycling performance of the NMC622-SS are observed in
Figure 6a,b. While the NMC622-SS only delivers (i) a specific
capacity less than 20 mAh g−1 at a high current density of 2 C
(Figure 6a, with a retention of about 18% of capacity at a
current density of 0.05 C) and (ii) a specific capacity of 78
mAh g−1 at a constant current density of 0.05 C, corresponding
to 63% initial capacity after 50 cycles, the Coulombic efficiency
is fluctuated around 90% (Figure 6b). The discharging specific
capacity of NMC622-MCP decreases from 206 mAh g−1 to 80
mAh g−1 as the current density increases from 0.05 to 2 C
(Figure 6c), which validates a good rate capacity in the
NMC622-MCP. It is noteworthy that the discharging specific
capacity of the NMC622-MCP at 2 C reported in this work is
the value obtained after 20 cycles at different densities (0.05,
0.1, 0.5, and 1 C). The cycling performance of NMC622-MCP
at 0.05 C in the current density illustrates the discharging
specific capacity decreasing rapidly in the first 10 cycles and
then decreasing more slowly, which is in contrast with the
gradual increase of the Coulombic performance in the next
cycles. After 100 cycles, the NMC622-MCP can maintain a
discharging specific capacity up to 172.2 mAh g−1 and the
Coulombic performance up to 95.6% (Figure 6d). The low
electrochemical properties of NMC622-SS with respect to
those of NMC622-MCP result from their physical and
H https://doi.org/10.1021/acsomega.3c04717
structural characteristics of the synthesized materials. First, as
shown in Figure 1, the NMC622-MCP sample has a uniform
size of about 500 nm and clear grain boundaries, while the
NMC622-SS sample has agglomeration that forms large
particles with sizes up to 5 μm, hence the electrolyte ions
reach the redox centers of NMC622-MCP electrode easier
than in the case of NMC622-SS electrode. Thus, these redox
centers of NMC622-MCP lead to a better electrochemical
performance than in the case of NMC622-SS.30 Second, the
low electrochemical performance is also related to the phase
structure of the synthesized materials. The XRD patterns of
NMC622-SS (Figure S2) show that the ratio of (I(003)/I(104))
peak intensity is low, and the separation of double peaks
(006)/(102) and (108)/(110) is not observed, while in the
case of NMC622-MCP, the ratio of (I(003)/I(104)) peak
intensity is up to 1.88, and we observe a clear separation of
(006)/(102) and (108)/(110) double peaks. This provides
excellent evidence that the NMC622-MCP sample has a better
crystallinity and layer structure order with minimal cation
mixing between Li+ and Ni2+, which are crucial for developing
high-quality type-layer structure cathode materials for lithium-
ion batteries. The last important physical property that
contributes to the electrochemical performance of the
synthesized cathode material is the phase composition. Figure
S2 demonstrates that there are a few additional diffraction
peaks rather than the inherent hexagonal lattice structures of
LiNiO2 with R3̅m space group on the XRD pattern of
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Figure 8. XPS spectra of NMC622-MCP of Ni 2p (a), Mn 2p (b), Co 2p (c), and O 1s (d) measured at the pristine state, after the first cycle and
after 100 cycles.
NMC622-SS, which is revealed that the phase formation
process of LiNiO2 was not completed. The electrochemical
performance of the NMC622-MCP is comparably equivalent
to most related materials such as NMC622,1,56 La-doped
NMC622, 56 SiO 2 -coated NMC622, 1 NMC811, 11 and
NMC333.53 The electrochemical properties of some typical
synthesized materials are compiled in Table 1.
The rapid decrease in specific capacity of the synthesized
materials is mainly caused by the formation of solid electrolyte
interphase (SEI) formed on the anode electrode and like-SEI
layer on the cathode electrode62,63 during the first few cycles at
high potentials. These layers increase the surface resistance of
the electrode and decrease of the active centers of Ni, Mn, and
Co.46,47 However, the formation of these SEI and like-SEI
layers is essential for the long-term performance of LIBs
because it prevents decomposition reactions with salts and
solvents.63 If these layers are formed in a proper route, they
have almost no conductivity, high electrolyte diffusion
resistance, and good lithium-ion selectivity and permeability.
Therefore, such layers can protect the electrode and prevent
the decomposition reaction of the electrolyte on the electrode
surface. Figure 6b−d presents the specific capacity loss
occurring mainly in the first 10 cycles, and this capacity loss
further declines in the coming cycles for both NMC622-SS and
NMC622-MCP, suggesting that the SEI or like-SEI layers
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Article
formed on the electrodes of the coin-cell from the NMC622-
SS and NMC622-MCP are at good electrode protection.
To evaluate simultaneously the electrochemical performance
and structural evolution upon the charge and discharge
process, we measured ex-situ XRD patterns of the NMC622-
MCP sample during cycles and compared these experimental
XRD patterns with those of the NMC622-DFT one. In Figure
7, due to the presence of an Al foil, the experimental pristine
XRD pattern has an additional peak at 2θ = 65° with respect to
the one presented in Figure 4a. All other expected peaks in the
2θ window remain almost the same except for the two distinct
(003) and (104) peak evolutions during the charge/discharge
process. During the charge process, the experimental (003)
peak shifts to a lower angle, while the (104) peak shifts to a
higher angle, and these changes are reversible upon discharge.
Specifically, the peak position deviations of the (003) and
(104) peaks at the pristine and fully charged states are about
0.35 and 0.17, respectively. These values are equivalent to
those of NMC622 reported in refs. 39 and 40 but slightly smaller
than those of NMC811 reported in ref. 64, suggesting that the
NMC622-MCP electrode has higher structural stability during
charge. Moreover, upon charge, as Li atoms are extracted from
the pristine NMC622-MCP structure, the c lattice parameter
expands while the a lattice parameter reduces. The expansion
in the c-axis is due to the increase in repulsive force acting on
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Figure 9. Nyquist plot, fit line, and circuit diagram (a,b); the plot between Z’ and the reciprocal root square of the lower angular (c,d) of the
NMC622-MCP electrode before and after charge−discharge.
the two neighboring oxygen layers. Analogous to refs. 39 and 65,
when the NMC622-MCP cathode is charged to 3.8 V, a
second phase of H2 (hexagonal) NMC622-MCP appears. This
new H2 phase has the same R3̅m space group as the H1 phase,
and these phases coexist up to 4.5 V. Upon the discharge
process, the H2 phase disappear at 3.5 V, and the (003) and
(104) peaks are shifted back to their original positions,
indicating that these changes are highly reversible.
The Rietveld refinement was performed on the NMC622-
MCP electrode before, during (cutoff of charging at 4.2 V),
and after the first cycle to provide a more complete insight of
the structural change and stability of the NMC622-MCP
material in the charging/discharging process. As shown in
Figure S5a,b, the two representative samples of the pristine
electrode and electrode at the end of the first cycle match well
with the hexagonal lattice structure (R3̅m space group) of
LiNiO2. In these patterns, we do not observe the presence of
the secondary phase in these samples. Meanwhile, the Rietveld
refinement results for the NMC622-MCP electrode with the
cutoff of charging at 4.2 V exhibited a two-phase coexistence
(H1 and H2), and the H2 phase is more dominant (Figure
S6a), which are reported in refs. 39 and 40. The goodness of the
fit (Rwp‑i, Rexp2, and Chi squared) are 2.8%, 0.0004, and 1.93 for
the pristine NMC622-MCP electrode; 4.4%, 0.0005, and 3.49
for the NMC622-MCP electrode with cutoff of charging at 4.2
V; and 3.1%, 0.0005, and 1.85 for the NMC622-MCP
electrode at the end the first cycle, demonstrating the excellent
agreement between experimental and refinement results. Such
quantitative agreement guarantees the reliability of the
extracted a, c, and V parameters shown in Table S2. In
addition, the slight change of crystallite sizes (D) and the
micro strains (ε) of the active material on the electrode before,
during, and after charging/discharging are calculated from the
Williamson−Hall method (Figures S5c,d and S6b), which
highlight the reversibility of the crystal structure when
removing or inserting lithium ions on the pristine NMC622-
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MCP material. As listed in Table S2, the stages of electrode
preparation (crushing, solvent, and drying) have a small impact
on the NMC622-MCP structure. Namely, the crystallite size
increases and the bias decreases while the lattice parameters
are kept almost constants. However, the I(003)/I(104) ratio of
1.76 remained high, and the doublet peaks (006)/(102),
(108)/(110) clearly separated, which illustrate that the active
NMC622-MCP material on the electrode retains its small
mixing cation and good atomic order properties.1,53 The
crystallographic structure parameters of the NMC622-MCP
material vary strongly during the charging process, especially
the appearance of the H2 phase with predominant intensity at
the charging voltage 4.2 V. While the a lattices of the H1 and
H2 phases decrease sharply compared to that of the H1 phase
in the active material on pristine electrodes, the c lattices
increase, thus resulting in a depletion of the unit cell volume
(V). These results are in good agreement with previous
reports.39,40 For instance, the structural deviation increased
sharply from 4.45 × 10−4 to 10.34 × 10−4 for the H1 phase and
4.45 × 10−4 to 11.30 × 10−4 for the H2 phase. More
interestingly, the lattice parameters of the active NMC622-
MCP material transformed and returned to almost the pristine
material, showing good reversibility and agreeing well with the
previous analysis based on XRD investigation.
To capture this phase transition upon charging, we also
performed DFT simulations at various Li dissolutions (x = 1,
0.83, 0.67, and 0) (see Figures S7−S9 for more simulation
details). In Figures 7 and S9, the generic trend of XRD peak
evolution during charge remains the same for both DFT
simulations and experimental observations. More interestingly,
as shown in Figure S9, besides the main H1 phase of (003) and
(104) peaks at around 2θ = 44.50°, we also observe an increase
in peak intensity of the H2 phase from x = 0.83 to x = 0.67,
demonstrating the significant contribution of the H2 phase of
the NMC622-MCP sample during charge.
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Table 2. Summary of the Equivalent Circuit Element Values of NMC622-MCP and Some Other Similar Materials
NMC622-MCP
contributors/activities parameters before GCD
electrode material Rs (Ω) 4.78
Faradaic capacitance Rsf (Ω)
CPE1−T (F)
CPE1−P
electrode/electrolyte interphase Rct (Ω) 183
W−R (Ω) 2803
W−T (F) 14.04
W−P 0.79
CPE2−T (F) 8.7 × 10−6
CPE2−P 0.75
We also evaluate the oxidation state variation of atoms in the
NMC622-MCP sample at the pristine state after the first cycle
and after 100 cycles via XPS measurements (Figures S1 and 8).
As shown in Figure S1 of the XPS spectra measured after the
first cycle and 100 cycles (blue and green lines, respectively),
there are additional peaks of Cl 2p corresponding to the peak
of Cl atom in the electrolyte (LiClO4) and of F 1s
corresponding to the peak of F atom in the binder (PVDF).
The high-resolution spectra of Ni 2p, Mn 2p, and Co 2p in
Figure 8a−c show that the oxidation states of Ni, Mn, and Co
of the NMC622-MCP electrode after the first cycle and 100
cycles remain almost unchanged compared to those of the
pristine NMC622-MCP. This again confirms the structural
stability of the NMC622-MCP electrode during the charge/
discharge process. In contrast, the defective oxygen increases
sharply right after the end of the first cycle, as illustrated by the
increase of the peak area ratio between defective oxygen and
oxygen in M−O bonding from 0.64 to 1.66 (Figure 8d). This
is caused by the change in phase structure during the charging/
discharging process. After 100 cycles, this ratio only increases
to 1.98, suggesting that the development of defective oxygen
mainly occurs in the first few cycles. Furthermore, the peaks at
an energy of 532 eV correspond to oxygen in the C�O/CO3
bonding (semicarbonate) and of 533 eV correspond to oxygen
in the C−O bonding (esters or polyether), which can be
attributed to the electrolyte decomposition.66,67
The electrochemical impedance spectroscopy measurement
(EIS) was carried out to provide additional comprehension
into the electrochemical behaviors of the electrode in the
frequency range of 0.1−105 Hz, with a voltage applied of 2.5 V
(as illustrated in Figure 9 and Table 2). The Nyquist plot of
the NMC622-MCP electrode prior to the cycle performance
test is presented in Figure 9a, at which a semicircle in the high
to medium frequency regions and a steady growth at low
frequency have been noticed. In the high-frequency regime, the
intersection between the Nyquist plot and the real axis is
assigned to the intrinsic resistance of CR2032 cell (denoted as
Rs), including the electrode material resistance, contact
resistance (Rct) (between the active material and the current
collector), and electrolyte resistance,53 at which (i) the Rct
parameter is attributed to the charge transfer resistance at the
electrode surface; and (ii) the constant phase element (CPE)
and Warburg diffusion (W) correspond to the nonideal
capacitance and the solid-state diffusion of Li+ ions into the
bulk electrode, respectively.68 Similar implications are also
applied to the Nyquist plot of the NMC622-MCP electrode
after 100 GCD cycles (Figure 9b). However, the characterized
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Article
samples
after 100 cycles NMC33353 NMC6221 NCA70
24 4.54−6.54 6.28 8.28
339.9 5.49−6.39 6.88 327.01
2.7 × 10−5
0.606
127.5 6.15−13.02 149.4 200.20
1761
22.12
0.70
6.4 × 10−6
0.58
semicircle is completely different from that of the initial
NMC622-MCP electrode. This might be induced by the
appearance of the SEI and the like-SEI layers on the electrodes
in the lithium-ion extracting/inserting process. In addition, the
equivalent circuit of the Nyquist plots could be obtained
thanks to the Zview software. The parameters of the equivalent
circuit and the elemental values were compiled in Figure 9a,b,
inset, and Table 2. The Rs/Rct values of the NMC622-MCP
electrode before and after cycle performance test are 4.78/183
and 24/127.5 Ω, respectively. The resistance of the initial
NMC622-MCP electrode is small, which is comparable to
those of several other similar materials (Table 2). The
relationship between the SEI and the like-SEI after the cycle
test corresponding to the Rsf//CPEsf component in the
equivalent circuit is demonstrated in Figure 9b, insert. The
obtained Rsf values are somewhat high up to 339.9 Ω,
indicating good electrode protection.63,69 As indicated
previously, the appearance between the SEI and like-SEI
layer leads to the presence of contact resistance, resulting in an
increase in the electrode resistance from 4.78 to 24 Ω. In
contrast, the Rct values of both NMC622-MCP electrodes
before and after cycle performance test are smaller compared
to the NCA material70 but higher compared to the NMC
materials. The high Rct value might be correlated to the high
value of the applied voltage during the measurement (2.5 V),
by which the extracting/inserting process for the Li+ ion does
not take place.
Figure 9c,d describes the relation between Z’ and the
reciprocal root square of the lower angular. A linear
relationship followed the equation: Z’ = Re + Rct +
σω−0.543,45 has been observed, where Re, Rct, and σ are the
electrode resistance (Ω), the charge transfer resistance (Ω),
and the Warburg coefficient, respectively. The Warburg
coefficients of the NMC622-MCP electrode before and after
the cycle performance test are about 131.01 and 108.85,
respectively. The lithium-ion diffusion coefficient into the bulk
electrode is estimated thanks to the following equation:
R2 × T 2
D=
2 × A2 × n4 × F 4 × C 2 × 2 (3)
where R is the universal gas constant (8.314 J mol−1 K−1), T is
the absolute temperature (298 K), F is the Faraday constant
(96,500 C mol−1), A is the surface area of the electrode (0.785
cm2), n is the number of electrons transferred in redox
reaction, and C is the molar concentration of Li+ ion in the
Li1.0Ni0.6Mn0.2Co0.2O2 (4.905 × 10−2 mol cm−3). At room
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temperature of 25 °C, the lithium-ion diffusion coefficients of
the NMC622-MCP electrode before and after the cycle
performance test are 6.7 × 10−16 cm2 s−1 and 9.7 × 10−16 cm2
s−1, respectively. However, the initial NMC622-MCP electrode
with good atomic arrangement results in difficulty in lithium-
ion transfer in the very first cycles. The lithium-ion transfer is
significantly improved after a few cycles, in which the process
becomes smoother, agreeing well with the increase in the
lithium-ion diffusion coefficient after the cycle test. In this case,
the lithium-ion diffusion coefficient obtained in this work is
smaller than the other reported values in NMC materials.71,72
This difference is ascribed to the EIS measurement being
conducted at the coin-cell initial voltage after fabricating.
Moreover, it is demonstrated that the lithium-ion diffusion
coefficient highly depends on the applied voltage and the
electrode states of either charging or discharging process.73,74
The achieved electrochemical properties of the NMC622-
MCP material suggest that this work provides a simple but
effective approach to fabricating high-quality materials for
lithium-ion batteries.
4. CONCLUSIONS
In summary, we successfully synthesized Li1.0Ni0.6Mn0.2Co0.2O2
using a novel, cost-effective, and environmentally friendly
modified coprecipitation method (NMC622-MCP). As
characterized by both structural and electrochemical measure-
ments, we demonstrate that the NMC622-MCP material is a
well-defined layered crystal structure with respect to the
standard solid-state synthesis approach. More interestingly, the
outstanding electrochemical performance, with a maximum
discharge specific capacity of 206.9 mAh g−1 at 0.05 C and a
retention of 83.22% of initial discharge specific capacity after
100 cycles, provides a promising pathway toward cost-effective
and green synthesis for high quality Li1.0NixMnyCozO2 (x + y +
z = 1, NMC) materials. This work paves the way for
developing low-temperature Ni-rich NMC batteries for
cathode materials.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsomega.3c04717.
XPS survey of NMC622-MCP, XRD patterns of
NMC622-SS, optimized configuration of NMC622-
DFT simulations and atomic bond lengths of transition
metal-oxide atoms, the first derivative of the GCD
profiles of NMC622-SS and NMC622-MCP, the CV
curves of NMC622-MCP at 0.1 mV s−1, Rietveld
refinement results and Williamson−Hall plot of
NMC622-MCP electrode before, during, and after the
first cycle, optimized configuration of NMC622-DFT
simulations and projected density of states of NMC-622
bulk with different lithium dissolutions, XRD patterns
with H1−H2 phase separation of NMC622-DFT
simulations, summary table of average relative differ-
ences between experimental and DFT XRD peaks, and
summary table of crystal structure parameter changes of
the pristine material and pristine electrode and at the
end of the first cycle for NMC622-MCP (PDF)
L https://doi.org/10.1021/acsomega.3c04717
Article
■ AUTHOR INFORMATION
Corresponding Authors
Nguyen To Van − Faculty of Chemico-Physical Engineering,
Le Quy Don Technical University, Ha Noi 100000,
Vietnam; orcid.org/0000-0002-0288-5071;
Email: tptnhv@gmail.com
Minh Triet Dang − School of Education, Can Tho University,
Can Tho City 900000, Vietnam; Email: dmtriet@
ctu.edu.vn
Authors
Thao Le Thi − Institute of Tropical Durability, Vietnam
Russia Tropical Science and Technology Research Center, Ha
Noi 100000, Vietnam
Truong Phan Van − Institute of Tropical Durability, Vietnam
Russia Tropical Science and Technology Research Center, Ha
Noi 100000, Vietnam
Bo Nguyen Van − Institute of Tropical Durability, Vietnam
Russia Tropical Science and Technology Research Center, Ha
Noi 100000, Vietnam
Tuan Nguyen Van − Faculty of Chemico-Physical Engineering,
Le Quy Don Technical University, Ha Noi 100000, Vietnam
Tien Phat Doan − Faculty of Chemico-Physical Engineering,
Le Quy Don Technical University, Ha Noi 100000, Vietnam
Thi Lan Ngo − Faculty of Chemico-Physical Engineering, Le
Quy Don Technical University, Ha Noi 100000, Vietnam
Ngoc Hung Vu − Faculty of Biotechnology, Chemistry and
Environmental Engineering, Phenikaa University, Hanoi
10000, Vietnam
Tien-Thanh Nguyen − Institute of Materials Science, Vietnam
Academy of Science and Technology, Ha Noi 100000,
Vietnam
Huyen Nam Nguyen − School of Materials Science, Japan
Advanced Institute of Science and Technology, Nomi,
Ishikawa 923-1292, Japan
Nguyen Vo Anh Duy − FPT University, Can Tho campus,
Can Tho, Ninh Kieu 900000, Vietnam; orcid.org/0000-
0002-2546-9003
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsomega.3c04717
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This research is funded by Vietnam Russia Tropical Science
and Technology Research Center. This research is also funded
by Vietnam National Foundation for Science and Technology
Development (NAFOSTED) under grant number: 15/2022/
TN.
■ REFERENCES
(1) Lu, X.; Zhang, N.; Jahn, M.; Pfleging, W.; Seifert, H. J. Improved
Capacity Retention of SiO2-Coated LiNi0.6Mn0.2Co0.2O2 Cathode
Material for Lithium-Ion Batteries. Appl. Sci. 2019, 9, 3671.
(2) Ding, Y.; Cano, Z. P.; Yu, A.; Lu, J.; Chen, Z. Automotive Li-Ion
Batteries: Current Status and Future Perspectives. Electrochem. Energy
Rev. 2019, 2 (1), 1−28.
(3) Ozawa, K. Lithium-ion rechargeable batteries with LiCoO2 and
carbon electrodes: the LiCoO2/C system. Solid State Ionics 1994, 69
(3), 212−221.
(4) Lyu, Y.; Wu, X.; Wang, K.; Feng, Z.; Cheng, T.; Liu, Y.; Wang,
M.; Chen, R.; Xu, L.; Zhou, J.; et al. An Overview on the Advances of
ACS Omega XXXX, XXX, XXX−XXX
ACS Omega http://pubs.acs.org/journal/acsodf
LiCoO2 Cathodes for Lithium-Ion Batteries. Adv. Energy Mater. 2021,
11 (2), 2000982.
(5) Zhu, X.; Meng, F.; Zhang, Q.; Xue, L.; Zhu, H.; Lan, S.; Liu, Q.;
Zhao, J.; Zhuang, Y.; Guo, Q.; et al. LiMnO2 cathode stabilized by
interfacial orbital ordering for sustainable lithium-ion batteries. Nature
Sustainability 2021, 4 (5), 392−401.
(6) Zhao, H.; Liu, S.; Liu, X.; Tan, M.; Wang, Z.; Cai, Y.;
Komarneni, S Orthorhombic LiMnO2 nanorods as cathode materials
for lithium-ion batteries: Synthesis and electrochemical properties.
Ceram. Int. 2016, 42 (7), 9319−9322.
(7) Zhang, Y.; Huo, Q.-y.; Du, P.-p.; Wang, L.-z.; Zhang, A.-q.; Song,
Y.-h.; Lv, Y.; Li, G.-y. Advances in new cathode material LiFePO4 for
lithium-ion batteries. Synth. Met. 2012, 162 (13), 1315−1326.
(8) Chen, S.-P.; Lv, D.; Chen, J.; Zhang, Y.-H.; Shi, F.-N. Review on
Defects and Modification Methods of LiFePO4 Cathode Material for
Lithium-Ion Batteries. Energy Fuels 2022, 36 (3), 1232−1251.
(9) Jung, R.; Metzger, M.; Maglia, F.; Stinner, C.; Gasteiger, H. A.
Chemical versus Electrochemical Electrolyte Oxidation on NMC111,
NMC622, NMC811, LNMO, and Conductive Carbon. J. Phys. Chem.
Lett. 2017, 8 (19), 4820−4825.
(10) Omenya, F.; Chernova, N. A.; Zhou, H.; Siu, C.; Whittingham,
M. S. Comparative Study Nickel Rich Layered Oxides: NMC 622,
NMC 811 and NCA Cathode Materials for Lithium Ion Battery. ECS
Meeting Abstracts 2018, MA2018−01 (3), 531.
(11) Tatara, R.; Yu, Y.; Karayaylali, P.; Chan, A. K.; Zhang, Y.; Jung,
R.; Maglia, F.; Giordano, L.; Shao-Horn, Y. Enhanced Cycling
Performance of Ni-Rich Positive Electrodes (NMC) in Li-Ion
Batteries by Reducing Electrolyte Free-Solvent Activity. ACS Appl.
Mater. Interfaces 2019, 11 (38), 34973−34988.
(12) Malik, M.; Chan, K. H.; Azimi, G. Review on the synthesis of
LiNixMnyCo1‑x‑yO2 (NMC) cathodes for lithium-ion batteries. Mater.
Today Energy 2022, 28, 101066.
(13) Shuai, H.; Li, J.; Hong, W.; Gao, X.; Zou, G.; Hu, J.; Hou, H.;
Ji, X.; Liu, H. Electrochemically Modulated LiNi1/3Mn1/3Co1/3O2
Cathodes for Lithium-Ion Batteries. Small Methods 2019, 3 (5),
1900065.
(14) Jiang, X.; Sha, Y.; Cai, R.; Shao, Z. The solid-state chelation
synthesis of LiNi1/3Mn1/3Co1/3O2 as a cathode material for lithium-
ion batteries. J. Mater. Chem. A 2015, 3 (19), 10536−10544.
(15) Zhu, J.; Xiao, G.; Li, X. Synthesis of Li(Ni0.6Co0.2Mn0.2)O2 by a
modified sol-gel method for lithium-ion batteries. Synth. Met. 2021,
281, 116905.
(16) Lu, H.; Zhou, H.; Svensson, A. M.; Fossdal, A.; Sheridan, E.;
Lu, S.; Vullum-Bruer, F. High capacity Li[Ni0.8Co 0.1Mn0.1]O2
synthesized by sol−gel and co-precipitation methods as cathode
materials for lithium-ion batteries. Solid State Ionics 2013, 249−250,
105−111.
(17) Noh, H.-J.; Youn, S.; Yoon, C. S.; Sun, Y.-K. Comparison of the
structural and electrochemical properties of layered Li[NixCoyMnz]O2
(x = 1/3, 0.5, 0.6, 0.7, 0.8 and 0.85) cathode material for lithium-ion
batteries. J. Power Sources 2013, 233, 121−130.
(18) Pimenta, V.; Sathiya, M.; Batuk, D.; Abakumov, A. M.; Giaume,
D.; Cassaignon, S.; Larcher, D.; Tarascon, J.-M. Synthesis of Li-Rich
NMC: A Comprehensive Study. Chem. Mater. 2017, 29 (23), 9923−
9936.
(19) Yao, X.; Xu, Z.; Yao, Z.; Cheng, W.; Gao, H.; Zhao, Q.; Li, J.;
Zhou, A. Oxalate co-precipitation synthesis of LiNi0.6Co0.2Mn0.2O2 for
low-cost and high-energy lithium-ion batteries. Mater. Today
Commun. 2019, 19, 262−270.
(20) Ghosh, S.; Jana, R.; Ganguli, S.; Inta, H. R.; Tudu, G.;
Koppisetti, H. V.; Datta, A.; Mahalingam, V. Nickel−cobalt oxalate as
an efficient non-precious electrocatalyst for an improved alkaline
oxygen evolution reaction. Nanoscale Adv. 2021, 3 (13), 3770−3779.
(21) Thao, V. D.; Son, L. T.; Lan, N. T.; Huyen, M. N.; Nguyen, T.-
T.; Le, S. D.; Thao, P. M.; Van Nguyen, T. Facile synthesis of mixed
nickel-cobalt oxalates with composition control as high-performance
electrode materials for supercapacitor. J. Energy Storage 2023, 66,
107428.
M https://doi.org/10.1021/acsomega.3c04717
Article
(22) Thi Thu Hoa, N.; Van Ky, N.; Son, L. T.; Dung, D. T.; Van
Nguyen, T.; Lam, V. D.; Van Nghia, N. Facile synthesis of cobalt-
doped sodium lithium manganese oxide with superior rate capability
and excellent cycling performance for sodium-ion battery. J.
Electroanal. Chem. 2023, 929, 117129.
(23) Kresse, G.; Hafner, J. Ab initio molecular-dynamics simulation
of the liquid-metal–amorphous-semiconductor transition in germa-
nium. Phys. Rev. B 1994, 49 (20), 14251−14269.
(24) Kresse, G.; Joubert, D. From ultrasoft pseudopotentials to the
projector augmented-wave method. Phys. Rev. B 1999, 59 (3), 1758−
1775.
(25) Kresse, G.; Furthmüller, J. Efficiency of ab-initio total energy
calculations for metals and semiconductors using a plane-wave basis
set. Comput. Mater. Sci. 1996, 6 (1), 15−50.
(26) Perdew, J. P.; Burke, K.; Ernzerhof, M. Generalized Gradient
Approximation Made Simple. Phys. Rev. Lett. 1996, 77 (18), 3865−
3868.
(27) Cai, C.; Zhang, D.; Zhang, Q.; Chen, K.; Hua, W.; Peng, C.;
Xue, D. Origin of oxygen-redox and transition metals dissolution in
Ni-rich LixNi0.8Co0.1Mn0.1O2 cathode. J. Chem. Phys. 2023, 158
(11), 114703.
(28) Monkhorst, H. J.; Pack, J. D. Special points for Brillouin-zone
integrations. Phys. Rev. B 1976, 13 (12), 5188−5192.
(29) Dong, H.; Koenig, G. M., III A review on synthesis and
engineering of crystal precursors produced via coprecipitation for
multicomponent lithium-ion battery cathode materials. CrystEng-
Comm 2020, 22 (9), 1514−1530.
(30) Hwang, I.; Lee, C. W.; Kim, J. C.; Yoon, S. Particle size effect of
Ni-rich cathode materials on lithium ion battery performance. Mater.
Res. Bull. 2012, 47 (1), 73−78.
(31) Moriwake, H.; Kuwabara, A.; Fisher, C. A. J.; Huang, R.;
Hitosugi, T.; Ikuhara, Y. H.; Oki, H.; Ikuhara, H. First-Principles
Calculations of Lithium-Ion Migration at a Coherent Grain Boundary
in a Cathode Material, LiCoO2. Adv. Mater. 2013, 25 (4), 618−622.
(32) Yang, S.; Yan, B.; Lu, L.; Zeng, K. Grain boundary effects on Li-
ion diffusion in a Li1.2Co0.13Ni0.13Mn0.54O2 thin film cathode studied
by scanning probe microscopy techniques. RSC Adv. 2016, 6 (96),
94000−94009.
(33) Chen, Z.; Wang, J.; Chao, D.; Baikie, T.; Bai, L.; Chen, S.;
Zhao, Y.; Sum, T. C.; Lin, J.; Shen, Z. Hierarchical Porous
LiNi1/3Co1/3Mn1/3O2 Nano-/Micro Spherical Cathode Material:
Minimized Cation Mixing and Improved Li+ Mobility for Enhanced
Electrochemical Performance. Sci. Rep. 2016, 6 (1), 25771.
(34) Bondarchuk, O.; LaGrow, A. P.; Kvasha, A.; Thieu, T.; Ayerbe,
E.; Urdampilleta, I. On the X-ray photoelectron spectroscopy analysis
of LiNixMnyCozO2 material and electrodes. Appl. Surf. Sci. 2021,
535, 147699.
(35) Nguyen, T.; Son, L. T.; Thuy, V. V.; Thao, V. D.; Hatsukano,
M.; Higashimine, K.; Maenosono, S.; Chun, S.; Thu, T. V. Facile
synthesis of Mn-doped NiCo2O4 nanoparticles with enhanced
electrochemical performance for a battery-type supercapacitor
electrode. Dalton Trans. 2020, 49 (20), 6718−6729.
(36) Sun, Q.; Chen, X.; Xie, J.; Xu, X.; Tu, J.; Zhang, P.; Zhao, X.
Nonflammable quasi-solid-state electrolyte for stable lithium-metal
batteries. RSC Adv. 2019, 9 (72), 42183−42193.
(37) Wei, W.; Chen, W.; Ivey, D. G. Rock Salt−Spinel Structural
Transformation in Anodically Electrodeposited Mn−Co−O Nano-
crystals. Chem. Mater. 2008, 20 (5), 1941−1947.
(38) Moshtev, R.; Zlatilova, P.; Manev, V.; Tagawa, K. Synthesis of
LiNiO2 in air atmosphere: X-ray diffraction characterization and
electrochemical investigation. J. Power Sources 1996, 62 (1), 59−66.
(39) Tian, C.; Nordlund, D.; Xin, H. L.; Xu, Y.; Liu, Y.; Sokaras, D.;
Lin, F.; Doeff, M. M. Depth-Dependent Redox Behavior of
LiNi0.6Mn0.2Co0.2O2. J. Electrochem. Soc. 2018, 165 (3), A696.
(40) Quilty, C. D.; Bock, D. C.; Yan, S.; Takeuchi, K. J.; Takeuchi, E.
S.; Marschilok, A. C. Probing Sources of Capacity Fade in
LiNi0.6Mn0.2Co0.2O2 (NMC622): An Operando XRD Study of Li/
NMC622 Batteries during Extended Cycling. J. Phys. Chem. C 2020,
124 (15), 8119−8128.
ACS Omega XXXX, XXX, XXX−XXX
ACS Omega http://pubs.acs.org/journal/acsodf
(41) Tahmasebi, M. H.; Zheng, L.; Hatchard, T. D.; Obrovac, M. N.
Li[Ni0.6Mn0.2Co0.2]O2 Made From Crystalline Rock Salt Oxide
Precursors. J. Electrochem. Soc. 2023, 170 (3), 030531.
(42) Qian, G.; Zhang, Y.; Li, L.; Zhang, R.; Xu, J.; Cheng, Z.; Xie, S.;
Wang, H.; Rao, Q.; He, Y.; et al. Single-crystal nickel-rich layered-
oxide battery cathode materials: Synthesis, electrochemistry, and
intra-granular fracture. Energy Storage Mater. 2020, 27, 140−149.
(43) Zhang, X.; Jiang, W.J.; Mauger, A.; Qilu; Gendron, F.; Julien, C.
M. Minimization of the cation mixing in Li1+x(NMC)1−xO2 as cathode
material. J. Power Sources 2010, 195 (5), 1292−1301.
(44) Li, X.; Chang, K.; Abbas, S. M.; El-Tawil, R. S.; Abdel-Ghany,
A. E.; Hashem, A. M.; Wang, H.; Coughlin, A. L.; Zhang, S.; Mauger,
A.; et al. Silver Nanocoating of LiNi0.8Co0.1Mn0.1O2 Cathode Material
for Lithium-Ion Batteries. Micromachines 2023, 14, 907.
(45) Abdel-Ghany, A.; Hashem, A. M.; Mauger, A.; Julien, C. M.
Lithium-Rich Cobalt-Free Manganese-Based Layered Cathode
Materials for Li-Ion Batteries: Suppressing the Voltage Fading.
Energies 2020, 13, 3487 DOI: 10.3390/en13133487.
(46) Hashem, A. M.; Abdel-Ghany, A. E.; El-Tawil, R. S.; Mauger,
A.; Julien, C. M. Effect of Na Doping on the Electrochemical
Performance of Li1.2Ni0.13Co0.13Mn0.54O2 Cathode for Lithium-Ion
Batteries. Sustainable Chem. 2022, 3, 131−148.
(47) Agrawal, S.. 7 - Spectroscopy techniques for rare-earth-activated
phosphors. In Rare-Earth-Activated Phosphors; Dubey, V.; Dubey, N.;
Domanska, M. M.; Jayasimhadri, M.; Dhoble, S. J., Eds.; Elsevier,
2022, pp 173−201.
(48) Zhu, P.; Seifert, H.J.; Pfleging, W. The Ultrafast Laser Ablation
of Li(Ni0.6Mn0.2Co0.2)O2 Electrodes with High Mass Loading. Appl.
Sci. 2019, 9, 4067.
(49) Kim, T.; Choi, W.; Shin, H.-C.; Choi, J.-Y.; Kim, J. M.; Park,
M.-S.; Yoon, W.-S. Applications of Voltammetry in Lithium Ion
Battery Research. J. Electrochem. Sci. Technol. 2020, 11 (1), 14−25.
(50) Bloom, I.; Jansen, A. M.; Abraham, D. P.; Knuth, J.; Jones, S.
A.; Battaglia, V. S.; Henriksen, G. L. Differential voltage analyses of
high-power, lithium-ion cells: 1. Technique and application. J. Power
Sources 2005, 139 (1), 295−303.
(51) Wang, T.; Ren, K.; He, M.; Dong, W.; Xiao, W.; Pan, H.; Yang,
J.; Yang, Y.; Liu, P.; Cao, Z.; Ma, X.; Wang, H.; et al. Synthesis and
Manipulation of Single-Crystalline Lithium Nickel Manganese Cobalt
Oxide Cathodes: A Review of Growth Mechanism. Front. Chem.
2020, 8, 747 DOI: 10.3389/fchem.2020.00747.
(52) Wang, T.; Luo, H.; Fan, J.; Thapaliya, B. P.; Bai, Y.; Belharouak,
I.; Dai, S. Flux upcycling of spent NMC 111 to nickel-rich NMC
cathodes in reciprocal ternary molten salts. iScience 2022, 25 (2),
103801.
(53) Wang, Y.; Roller, J.; Maric, R. Morphology-Controlled One-
Step Synthesis of Nanostructured LiNi1/3Mn1/3Co1/3O2 Electrodes for
Li-Ion Batteries. ACS Omega 2018, 3 (4), 3966−3973.
(54) Li, X.; Liu, J.; Banis, M. N.; Lushington, A.; Li, R.; Cai, M.; Sun,
X. Atomic layer deposition of solid-state electrolyte coated cathode
materials with superior high-voltage cycling behavior for lithium ion
battery application. Energy Environ. Sci. 2014, 7 (2), 768−778.
(55) Cui, S.; Wei, Y.; Liu, T.; Deng, W.; Hu, Z.; Su, Y.; Li, H.; Li,
M.; Guo, H.; Duan, Y.; Wang, W.; Rao, M.; Zheng, J.; Wang, X.; Pan,
F.; et al. Optimized Temperature Effect of Li-Ion Diffusion with Layer
Distance in Li(NixMnyCoz)O2 Cathode Materials for High Perform-
ance Li-Ion Battery. Adv. Energy Mater. 2016, 6 (4), 1501309.
(56) Zybert, M.; Ronduda, H.; Da̧browska, K.; Ostrowski, A.;
Sobczak, K.; Moszyński, D.; Hamankiewicz, B.; Rogulski, Z.; Raróg-
Pilecka, W.; Wieczorek, W. Suppressing Ni/Li disordering in
LiNi0.6Mn0.2Co0.2O2 cathode material for Li-ion batteries by rare
earth element doping. Energy Rep. 2022, 8, 3995−4005.
(57) Zhang, Y.; Cao, H.; Zhang, J.; Xia, B. Synthesis of
LiNi0.6Co0.2Mn0.2O2 cathode material by a carbonate co-precipitation
method and its electrochemical characterization. Solid State Ionics
2006, 177 (37), 3303−3307.
(58) Li, J.; Wang, L.; Zhang, Q.; He, X. Synthesis and
characterization of LiNi0.6Mn0.4−xCoxO2 as cathode materials for Li-
ion batteries. J. Power Sources 2009, 189 (1), 28−33.
N https://doi.org/10.1021/acsomega.3c04717
Article
(59) Xia, Y.-F.; Nie, M.; Wang, Z.-B.; Yu, F.-D.; Zhang, Y.; Zheng,
L.-L.; Wu, J.; Ke, K. Structural, morphological and electrochemical
investigation of LiNi0.6Co0.2Mn0.2O2 cathode material synthesized in
different sintering conditions. Ceram. Int. 2015, 41 (9, Part B),
11815−11823.
(60) Ahn, W.; Lim, S. N.; Jung, K.-N.; Yeon, S.-H.; Kim, K.B.; Song,
H. S.; Shin, K. H. Combustion-synthesized LiNi0.6Mn0.2Co0.2O2 as
cathode material for lithium ion batteries. J. Alloys Compd. 2014, 609,
143−149.
(61) Lee, S.-W.; Kim, H.; Kim, M.-S.; Youn, H.-C.; Kang, K.; Cho,
B.-W.; Roh, K. C.; Kim, K.-B. Improved electrochemical performance
of LiNi0.6Co0.2Mn0.2O2 cathode material synthesized by citric acid
assisted sol-gel method for lithium ion batteries. J. Power Sources
2016, 315, 261−268.
(62) Bekaert, E.; Buannic, L.; Lassi, U.; Llords, ́ A.; Salminen, J..
Chapter One - Electrolytes for Li- and Na-Ion Batteries: Concepts,
Candidates, and the Role of Nanotechnology. In Emerging Nano-
technologies in Rechargeable Energy Storage Systems; Rodriguez-
Martinez, L. M.; Omar, N. , Eds.; Elsevier: Boston, 2017; pp 1−43.
(63) An, S. J.; Li, J.; Daniel, C.; Mohanty, D.; Nagpure, S.; Wood, D.
L., III The state of understanding of the lithium-ion-battery graphite
solid electrolyte interphase (SEI) and its relationship to formation
cycling. Carbon 2016, 105, 52−76.
(64) Feng, Z.; Rajagopalan, R.; Zhang, S.; Sun, D.; Tang, Y.; Ren, Y.;
Wang, H. A Three in One Strategy to Achieve Zirconium Doping,
Boron Doping, and Interfacial Coating for Stable LiNi0.8Co0.1Mn0.1O2
Cathode. Adv. Sci. (Weinheim, Ger.) 2020, 8 (2), 2001809.
(65) Tallman, K. R.; Wheeler, G. P.; Kern, C. J.; Stavitski, E.; Tong,
X.; Takeuchi, K. J.; Marschilok, A. C.; Bock, D. C.; Takeuchi, E. S.
Nickel-rich Nickel Manganese Cobalt (NMC622) Cathode Lithiation
Mechanism and Extended Cycling Effects Using Operando X-ray
Absorption Spectroscopy. J. Phys. Chem. C 2021, 125 (1), 58−73.
(66) Björklund, E.; Brandell, D.; Hahlin, M.; Edström, K.; Younesi,
R. How the Negative Electrode Influences Interfacial and Electro-
chemical Properties of LiNi1/3Co1/3Mn1/3O2 Cathodes in Li-Ion
Batteries. J. Electrochem. Soc. 2017, 164 (13), No. A3054.
(67) Li, Q.; Wang, Y.; Wang, X.; Sun, X.; Zhang, J.-N.; Yu, X.; Li, H.
Investigations on the Fundamental Process of Cathode Electrolyte
Interphase Formation and Evolution of High-Voltage Cathodes. ACS
Appl. Mater. Interfaces 2020, 12 (2), 2319−2326.
(68) Yao, Y.; Liu, H.; Li, G.; Peng, H.; Chen, K. Synthesis and
electrochemical performance of phosphate-coated porous Li-
Ni1/3Mn1/3Co1/3O2 cathode material for lithium ion batteries.
Electrochim. Acta 2013, 113, 340−345.
(69) Wohlfahrt-Mehrens, M.; Vogler, C.; Garche, J. Aging
mechanisms of lithium cathode materials. J. Power Sources 2004,
127 (1), 58−64.
(70) Song, C.; Wang, W.; Peng, H.; Wang, Y.; Zhao, C.; Zhang, H.;
Tang, Q.; Lv, J.; Du, X.; Dou, Y. Improving the Electrochemical
Performance of LiNi0.80Co0.15Al0.05O2 in Lithium Ion Batteries by
LiAlO2 Surface Modification. Appl. Sci. 2018, 8, 378.
(71) Zhao, X.; Liang, G.; Lin, D. Synthesis and characterization of
Al-substituted LiNi0.5Co0.2Mn0.3O2 cathode materials by a modified
co-precipitation method. RSC Adv. 2017, 7 (60), 37588−37595.
(72) Liu, Q.; Zhu, H.; Liu, J.; Liao, X.; Tang, Z.; Zhou, C.; Yuan, M.;
Duan, J.; Li, L.; Chen, Z. High-Performance Lithium-Rich Layered
Oxide Material: Effects of Preparation Methods on Microstructure
and Electrochemical Properties. Materials 2020, 13, 334.
(73) Charbonneau, V.; Lasia, A.; Brisard, G. Impedance studies of
Li+ diffusion in nickel manganese cobalt oxide (NMC) during charge/
discharge cycles. J. Electroanal. Chem. 2020, 875, 113944.
(74) Zheng, J.; Shi, W.; Gu, M.; Xiao, J.; Zuo, P.; Wang, C.; Zhang,
J.-G. Electrochemical Kinetics and Performance of Layered
Composite Cathode Material Li[Li0.2Ni0.2Mn0.6]O2. J. Electrochem.
Soc. 2013, 160 (11), No. A2212.
ACS Omega XXXX, XXX, XXX−XXX