Cube-shaped hierarchical LiNi1/3Co1/3Mn1/3O2 with enhanced growth of nanocrystal planes as high-performance cathode materials for lithium-ion batteries

Article abstract of DOI:10.1039/c5ta03225c

Hierarchical cubed LiNi_1/3Co_1/3Mn_1/3O₂ (CH-NCM) with enhanced growth of electrochemically active planes is synthesized using cube structured MnCO₃ as a self-template, which is synthesized by a fast, simple, and surfactant-free co-precipitation method. The CH-NCM cathode has a reversible discharge capacity as high as 220.9, 216.2, 211.4, 189.6, 171.7 and 144.5 mA h g^-1 at 0.1, 0.5, 1, 2, 5, and 10 C, respectively. After 100 cycles, the capacity retention is 83.34% at 0.1 C. The superior electrochemical performance can be ascribed to the special cube-shaped hierarchical structure and enhanced growth of electrochemically active surface planes of CH-NCM. The primary nanoparticles with enhanced growth of electrochemically active surface planes guarantee ultrafast Li⁺ intercalation/deintercalation, while the submicroassemblies promise good structural stability.

Full text of DOI:10.1039/c5ta03225c

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Journal Name
RSCPublishing
ARTICLE
Cube-shaped hierarchical LiNi Co Mn O with
1
/3
1/3
1/3
2
enhanced growth of nanocrystal planes as high-
performance cathode materials for lithium-ion
batteries
Cite this: DOI: 10.1039/x0xx00000x
Received 00th January 2012,
Accepted 00th January 2012
a
a
a
b
a
Yu Wu, Chuanbao Cao,* Youqi Zhu, Jili Li and Lin Wang
DOI: 10.1039/x0xx00000x
Hierarchical cubed LiNi1/3Co1/3Mn1/3O with enhanced growth of electrochemically active planes (CHꢀ
2
www.rsc.org/
NCM) are synthesized using cube structured MnCO as a selfꢀtemplate, which is synthesized by a fast,
3
simple, and surfactantꢀfree coꢀprecipitation method. The CHꢀNCM cathode has a reversible discharge
ꢀ
1
capacity as high as 220.9, 216.2, 211.4, 189.6, 171.7 and 144.5 mA h g at 0.1, 0.5, 1, 2, 5, and 10 C,
respectively. After 100 cycles, the capacity retention is 83.34% at 0.1 C. The superior electrochemical
performance can be ascribed to the special cubeꢀshaped hierarchical structure and enhanced growth of
electrochemically active surface planes of the CHꢀNCM. The primary nanoparticles with enhanced
+
growth of electrochemically active surface planes, guarantee ultrafast Li intercalation/deintercalation,
while the submicroassemblies promise the good structural stability.
and have an open structure with a wide window between the
Introduction
+
11
layers for Li transportation. This structural analysis indicates
+
+
Lithiumꢀion batteries have played an important role in portable
electronics, and are intensively pursued as a power source for
vehicle applications. LiCoO was the first cathode material
used in commercial Lithiumꢀion batteries, but its limited
capacity, high cost and toxicity prohibit its use in vehicle
applications. To overcome the current drawbacks, layered
that Li transport in NCM is twoꢀdimensional parallel to the Li
layers along the a (or b) axis. Therefore, if most nanocrystal
planes are parallel to (010), (110), and (100) planes,
perpendicular to (001) plane, the rate performance of NCM will
be significantly improved. In our previous reported works,
NCM nanoplates with exposed {010} active planes have been
1
,2
2
3
1
1
LiNi Co Mn O (NCM) has been widely investigated by
1/3
1/3
1/3
2
proved to exhibit superior rate performance. Hence, the
hierarchical NCM with enhanced growth of electrochemically
active planes can be expected to achieve enhanced
comprehensive electrochemical performance. Unfortunately,
the {010} active planes have higher surface energy than {001}
planes through calculation. Because the high surface energy
planes grow faster than the low surface energy planes, the high
surface energy planes tend to vanish during growth. Up to now,
it remains a big challenge to synthesize hierarchical NCM
materials with enhanced growth of electrochemically active
planes.
many researchers due to its advantages of highly reversible
capacity, low safety hazard and relatively low cost.
However, layered LiNi Co Mn O exhibits rapid fading
capacity and inferior rate capability, which prevent its use in
vehicle applications.
4
ꢀ19
1
/3
1/3
1/3
2
Recently, hierarchical microꢀ/nanostructures have attracted
considerable interests because the nanometerꢀsized primary
particles can signally shorten the pathways for lithium ion and
electron, and the microꢀ/submicrometerꢀsized secondary
assemblies can ensure the easy manufacture and good
5
,20,21
stability.
Hierarchical electrode materials with high
Although the literature has reported how to synthesize cube
27ꢀ31
reversible capacity and improved cyclability have been widely
structured materials,
most of synthesis technologies are
2
2ꢀ26
reported
. NCM with a hexagonal layer αꢀNaFeO structure ,
2
sophisticated, timeꢀconsuming. In this work, we report a convenient
coꢀprecipitation method, coupled with heat treatment, to synthesize
which is made up of MO oxygen layers perpendicular to the c
2
8
axis, indexed as {001} planes that include the (001) and (001)
cubeꢀshaped hierarchical LiNi1/3Co1/3Mn1/3O (CHꢀNCM) materials
2
planes at the top and bottom, respectively of the hexagonal
crystal. The {001} planes are formed by NiO , CoO and MnO
with enhanced growth of electrochemically active planes {010} for
the first time. This coꢀprecipitation method is fast, simple, and
6
6
6
octahedra, which interconnect to each other by cornerꢀsharing
oxygen atoms, and consist of a closeꢀpacked structure that
surfactantꢀfree chemical route, in which MnCO cubes as both a selfꢀ
3
template and Mn source was firstly formed and then lithiation
reaction was done to develop the CHꢀNCM at high temperature. The
CHꢀNCM are about 400ꢀ600 nm in size, and consist of aggregates of
approximately 100 nm primary nanoparticles. The CHꢀNCM cathode
+
hinders Li insertion along the c axis. The close packed {001}
+
planes are therefore not electrochemically active for Li
transportation. The 6ꢀsided facets of the hexagonal crystal, i.e.
ꢀ
1
(
010), (010), (100), (110), (110) and (100) planes, are denoted
has a reversible discharge capacity as high as 220.9 mA h g , 216.2
ꢀ
1
ꢀ1
ꢀ1
ꢀ1
as {010} planes, which are perpendicular to the {001} planes
mA h g , 211.4 mA h g , 189.6 mA h g , 171.7 mA h g , and 144.5
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ꢀ
1
mA h g at 0.1 C, 0.5 C, 1 C, 2 C, 5 C, and 10 C rates, respectively. cubes (Fig. S1) prepared by the coꢀprecipitation method are
What is more, the capacity retention is also significantly improved. employed as a selfꢀtemplate and Mn source in the synthesis. Firstly,
After 100 chargeꢀdischarge cycles, capacity retention ratios are MnCO cubes are converted into MnO cubes (Fig. S2) by thermal
3
2
o
8
3.34% (0.1 C), 79.33% (1 C), and 73.36% (2 C), respectively.
decomposition at 400 C. Then, the cubeꢀshaped MnO are mixed
2
along with stoichiometric amounts of Ni(NO ) ·6H O,
3
2
2
Co(NO ) ·6H O and LiOH·H O. Lastly, the calcinations process is
necessary to form the CHꢀNCM.
3
2
2
2
Experimental
Preparation of CH-NCM
Firstly, MnCO cubes with sizes of about 400ꢀ600 nm were obtained
3
by the method reported in the previous literature with minor
32
modifications. Typically, 1 mmol MnSO was dissolved in 70 mL
4
deionized water at room temperature. Then 350 mL ethanol was
added to the MnSO4 solution under stirring, after its complete
dispersion, a solution of 10 mmol NH HCO dissolved in 70 mL
4
3
deionized water was added to the solution mentioned above. After
Scheme 1 The preparation of CHꢀNCM
vigorous stirring for 15 min, the MnCO cubes were separated by
3
centrifugation, and washed with deionized water and ethanol to
The XRD patterns of CHꢀNCM are shown in Fig. 1. The
sharp reflections in the XRD patterns reveal that the asꢀ
prepared materials are wellꢀcrystallized. All of the peaks can be
remove impurities. Then, the MnCO cubes were dried and
3
o
decomposed at 400 C to obtain MnO cubes. After that, the MnO
2
2
cubes were dispersed along with stoichiometric amounts of
Ni(NO ) ·6H O, Co(NO ) ·6H O and LiOH·H O in ethanol to form
indexed as a hexagonal αꢀNaFeO structure with a R
3
m space
2
3
2
2
3 2
2
2
group, indicating that the CHꢀNCM without an impure
suspension. The suspension was then evaporated at room
temperature until dryness. Finally, the mixture was ground manually
17,33
phase.
The clear separations of the (006) from the (102) and
the (108) from the (110) peaks suggest the formation of a wellꢀ
ordered hexagonal layered structure. For the XRD patterns of
CHꢀNCM, the intensity ratio of the (003) and (104) peaks
o
for 10 min, heated at 850 C for 12 h in air.
Characterization
(
I(003)/I(104)) is 1.43, which is larger than 1.2 indicating low
5,33
The crystal structures of the prepared products were analyzed cation mixing.
using a PANalytical Xꢀpert diffractometer (PANalytical,
Netherlands) with Cu Ka radiation. Xꢀray photoelectron
spectroscopy (XPS) (PHI Quanteral II, Japan) were conducted
to evaluated the oxidation states of the Ni, Co and Mn in the
prepared samples and the fittings were carried out by the
XPSPEAK41 program. The chemical compositions of the
samples were analyzed by inductively coupled plasma atomic
emission spectrometry (ICPꢀAES, ICAPꢀ6300). Hitachi fieldꢀ
emission scanning electron microscopy (FESEMS, Hitachi Sꢀ
4
800) was used to analyze the structure and morphology of the
samples. Transmission electron microscopy (TEM) (HRTEM,
FEI Tecnai G2 F20, 200 kV) was used to observe the crystal
structure of the samples.
Electrochemical measurements
Electrochemical measurements were carried out in CR2025 coinꢀ
type cells which were assembled in an Arꢀfilled glove box using
Celgard 2400 films as the separator, a solution of 1 M LiPF6
dissolved into ethyl carbonate–dimethyl carbonate (EC–DMC, 1 : 1
v/v) as electrolyte, and lithium foil as the counter and reference
electrodes. The cathode electrodes were prepared by mixing 80 wt%
sample, 10 wt% carbon black, and 10 wt% polyvinylidene fluoride
Fig. 1 XRD patterns of CHꢀNCM.
(
PVDF) binder, dissolved in Nꢀmethylꢀ2ꢀpyrrolidone (NMP) to form
Xꢀray photoelectron spectroscopy (XPS) measurements were
o
a slurry. The slurry was coated on Al foil and dried at 120 C in carried out to confirm the oxidation states of Ni, Co and Mn in CHꢀ
vacuum for 12 hours. Charge–discharge tests were performed at NCM. Assisted by a fitting process, the assignment of the main peak
different current rates between 2.5 and 4.5 V on a CT2001A Land and the satellite is well established. As shown in Fig. 2, the binding
battery testing system. Cyclic voltammetry (CV; 2.5ꢀ4.5 V, 0.1 mV energies of Ni2p3/2, Co2p3/2 and Mn2p3/2 are 853.65 eV, 779.02
ꢀ
1
s ) and electrochemical impedance spectroscopic (EIS) eV and 641.25 eV, respectively. These values agree well with the
2+
3+
4+ 34
measurements were conducted on an IM6e electrochemical oxidation states of Ni , Co and Mn . The exact ratios of Li: Ni:
workstation (Zahner, Germany). EIS measurements were carried out Co: Mn measured by ICPꢀAES is 3.00: 0.97: 1.09: 0.96 for CHꢀ
with a frequency range of 100 kHz to 0.1 Hz and an AC voltage of 5 NCM, which is the same as the designed value.
mV. All tests were performed at room temperature.
The morphology and structure of the MnO precursors and the
2
CHꢀNCM were characterized by FEꢀSEM and TEM. Fig. 3A and B
show the FEꢀSEM images of the MnO precursors at low and high
magnifications, respectively. It is clearly found that the MnO2
2
Results and discussion
Scheme 1 illustrates the formation process of the CHꢀNCM. MnCO3 precursors show relatively uniform sizes of about 400ꢀ600 nm with a
2
| J. Name., 2012, 00, 1-3
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ART25ICLE
DOI: 10.1039/C5TA032 C
corresponding to the (003) planes of the NCM cathode materials.
This implies that the projected image planes of the primary
nanoplates are parallel to the cꢀaxial direction (parallel to (100),
26
(
010), or (110) planes). Such characteristic lattice spacing can be
frequently observed in the investigation of primary nanoplates of the
CHꢀNCM material (Fig. S4). Fig. 4D shows the HRꢀTEM image of
the plane in Fig. 4C and its corresponding Fast Fourier Transform
(FFT) pattern (the inset image). There are three sets of clear fringes.
Two of them have the same interplanar distance of 0.246 nm
assigned to the (010) and (100) planes of NCM, respectively. And
the other one has a interplanar distance of 0.143 nm assigned to
(110) planes of NCM. The FFT pattern reveals these nanoplates are
single crystalline with a hexagonal symmetry in consistence with the
+
hexagonal structure of NCM. As what mentioned before, Li
preferably moves twoꢀdimensionally along the aꢀb planes ((001)
plane) in hexagonal layer NCM materials. Therefore, we can
conclude that the enhanced growth of electrochemically active
+
planes in favor of Li intercalation/deintercalation has been
successfully achieved for the CHꢀNCM cathode material.
Fig. 2 (A) XPS curves of CHꢀNCM; (B), (C), and (D) XPS curves
of the Ni 2p, Co 2p, and Mn 2p core level for CHꢀNCM.
cubeꢀlike morphology. From the high magnifications FEꢀSEM
image of the MnO precursors, we can distinctly observe the edges
2
and faces of the cube. Fig. 3C shows a FEꢀSEM image of the CHꢀ
NCM. It is obvious that the cubeꢀshaped hierarchical architectures
are maintained after the high temperature solid state reaction.
Compared with the cubeꢀshaped MnO precursors, the faces of CHꢀ
2
NCM are rough due to the crystal growth in the high temperature
sintering process. To further prove the cubeꢀshaped hierarchical
structure, magnified FEꢀSEM images and TEM image of the CHꢀ
NCM are shown in Fig. 3D and Fig. S3, revealing CHꢀNCM with
aggregates of approximately 100 nm primary nanoparticles.
Fig. 4 (A) TEM image of the CHꢀNCM. (B) HRTEM image of the
plane shown in (A). (C) TEM image of the CHꢀNCM. (D) HRTEM
image and fast Fourier transform (FFT) pattern of plane shown in
(C).
To evaluate the electrochemical properties of the CHꢀNCM as
cathode materials for lithiumꢀion batteries, standard CR2025 coinꢀ
type half cells are assembled in an Arꢀfilled glove box. Fig. 5A
shows the cycle performances of the asꢀprepared materials at various
ꢀ
1
current rates. The initial discharge capacities are 220.9 mA h g ,
ꢀ
1
ꢀ1
2
11.4 mA h g , and 189.6 mA h g at 0.1 C, 1 C, and 2 C rates,
respectively. After 100 cycles, the discharge capacities of CHꢀNCM
ꢀ
1
ꢀ1
are maintained at 184.1 mA h g (0.1 C), 167.7 mA h g (1 C), and
1
ꢀ
1
39.1 mA h g (2 C), with the capacity retention ratios are 83.34%
(0.1 C), 79.33% (1 C), and 73.36% (2 C), respectively. Comparative
cycling performances of CHꢀNCM and NCMꢀbulk at 2 C as shown
in Fig. S5. The initial discharge capacity of NCMꢀbulk is far less
than that of CHꢀNCM. After 100 chargeꢀdischarge cycles, the CHꢀ
NCM exhibits better cycle life (73.36% of capacity retention) than
NCMꢀbulk cathodes (57.75% of capacity retention). Fig. 5B shows
the coulombic efficiencies of CHꢀNCM at current rate of 0.1 C and 1
C, respectively. The average coulombic efficiencies are 98.98% (0.1
C) and 98.49% (1 C), which indicated that the cell exhibited high
reversible capacity. Besides the high specific capacity and good
Fig. 3 (A) and (B) FEꢀSEM images at different magnifications of
the MnO2 precursors; (C) and (D) FEꢀSEM images at different
magnifications of CHꢀNCM.
Fig. 4A and C show the TEM images of CHꢀNCM. The cubeꢀ
shaped hierarchical structure can be observed clearly, which is
consistent with the above FEꢀSEM images. Fig. 4B depicts lattice
fringes of the plane with spacing of 0.475 nm shown in Fig. 4A,
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ꢀ
1
cycle performance, the rate capability is also a very important capacity was still maintained at 144.5 mA h g even at the highest
property for cathode materials. To evaluate the rate capability, the rate of 10 C. Significantly, the discharge capacity can recovered to
CHꢀNCM was cycled at various charge/discharge rates from 0.5 to nearly its primal value when cycling back to 0.5 C rate. These results
1
0 C during 2.5ꢀ4.5 V with 5 cycles per step. When the indicated that this material has a superior rate capability.
charge/discharge rates were higher than 1 C, a constant voltage
Fig. 6A and B show the galvanostatic chargeꢀdischarge
profiles of CHꢀNCM in the 1st, 2nd, 10th, 30th, 50th, and 100th
cycles at current rate of 0.1 C and 1 C, respectively.
Surprisingly, the smooth charge and discharge profiles with
little voltage drop can be clearly observed, indicating that the
steady CHꢀNCM electrode structural integrity in the test
5
,35
voltage range.
The irreversible capacity loss of CHꢀNCM
during the first cycle may be attributed to the formation of a
3
3
solid electrolyte interlayer. Compared to other NCM cathode
5,6,9ꢀ14
materials,
the CHꢀNCM has superior electrochemical
performances, especially in terms of rate capability (Table S1).
We believe that the obvious improvement of the rate capability
mainly be ascribed to the special hierarchical structured cubes
and enhanced growth of electrochemically active surface planes
of the CHꢀNCM. The primary nanoparticles with enhanced
growth of electrochemically active surface planes, guarantee
+
+
ultrafast Li intercalation/deintercalation as well as Li
diffusion, while the submicroassemblies promise the good
structural stability. The morphologies of the CHꢀNCM after
1
00 chargeꢀdischarge cycles are shown in Fig. S6, which
suggest that the CHꢀNCM cathodes can maintain their initial
morphology at 0.1 C. Besides, electrochemical inactivity of
Fig. 5 (A) Comparative cycling performances of CHꢀNCM at
various current rates; (B) Coulombic efficiencies of CHꢀNCM at
current rate of 0.1 C and 1 C, respectively; (C) Rate capability of
CHꢀNCM.
charge step was used for 30 minutes after the constant current charge
1
1
step to reach the predetermined voltage. Fig. 5C shows the rate
capability of asꢀprepared materials. A initial discharge capacities of Fig. 6 (A) and (B) Galvanostatic chargeꢀdischarge profiles of CHꢀ
ꢀ
1
ꢀ1
NCM in the 1st, 2nd, 10th, 30th, 50th, and 100th cycles at current
rate of 0.1 C and 1 C, respectively.
2
16.2 mA h g and 171.7 mA h g were obtained at 0.5 C and 5 C,
respectively. What is more, it is clearly found that the discharge
4
| J. Name., 2012, 00, 1-3
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tetravalent Mn ions in LiNi Co Mn O can effectively intercalation/deintercalation and good structural stability, yielding
1/3
1/3
1/3
2
superior electrochemical performances, especially in terms of rate
capability. Therefore, CHꢀNCM would be a promising cathode to be
applied in high performance lithiumꢀion batteries, which could play
an important role in vehicle applications.
prevent capacity fading caused by Mn element dissolution and
JahnꢀTeller distortion.
The chargeꢀtransfer kinetics was investigated by CV and EIS as
shown in Fig. 7. Among the three transitionꢀmetal elements of CHꢀ
NCM, Ni and Co with main oxidation states +2 and +3, respectively,
9
are known to be electrochemically active and Mn with +4 oxidation Acknowledgements
state is not active. The first three representative CV curves of CHꢀ
This work was financially supported by the National Natural
NCM between 2.5 and 4.5 V are shown in Fig. 7A. The CV curves
exhibit an oxidation peak at 3.97 V and a corresponding reduction
Science Foundation of China (Grant No. 50972017 and
21371023) and Research Fund for the Doctoral Program of
Higher Education of China (Grant No.20101101110026).
2+
4+
peak at 3.66 V, which corresponds to redox transition of Ni /Ni .
No obvious Co transition redox peaks are observed because
3+
4+
36
Co /Co conversion comes up at a potential higher than 4.6 V.
Notes and references
With the increased cycles, the oxidation peak decreased from 3.97 V
to the lower value and stabilized at 3.93 V; this behavior also
indicated that the material structure and/or the electrode – electrolyte
a
Research Center of Materials Science, Beijing Institute of Technology,
3
7,38
Beijing 100081, China.Fax: +86 10 68912001; Tel: +86 10 68913792; Eꢀ
interface were modified after the initial cycles.
Fig. 7B shows the
EIS profiles of the CHꢀNCM electrode after different chargeꢀ mail: cbcao@bit.edu.cn.
5
b
discharge cycles. As it was described in the previous work, a highꢀ
Department of Material Science and Engineering, Luoyang Institute of Scie
nce and Technology, Luoyang 471023, China
frequency semicircle, an intermediateꢀfrequency semicircle and a
lowꢀfrequency oblique line are observed. The highꢀfrequency
semicircle ascribes to the solid electrolyte interface (SEI) resistance
1
. P. Gibot, M. CasasꢀCabanas, L. Laffont, S. Levasseur, P. Carlach, S.
Hamelet, J. M. Tarascon and C. Masquelier, Nat. Mater., 2008, 7, 741.
. J. M. Tarascon and M. Armand. Nature, 2001, 414, 359.
(
RSEI). The intermediateꢀfrequency semicircle is related to the
lithium ion migration through the interface between the surface layer
of the particles and the electrolyte, the resistance of Rct. The lowꢀ
frequency oblique line is attributed to the diffusion process of
lithium ions in the bulk of the electrode material, the Warburg
resistance of W. The Nyquist plots are fitted by using the equivalent
circuit (as shown in Fig. 7B). During cycling, resistance of Re
occurred in liquid electrolyte, shows increased values, such as 2.43
to 7.33 ohms in CHꢀNCM from the fresh state to 100th cycle. It
might be due to the minor cathode material dissolved into electrolyte
and/or the minor decomposition of electrolyte. The values of Rct
for the CHꢀNCM cathodes gradually increase from 91.5 ohms when
in a fresh state to 351.8 ohms after 100 charge–discharge cycles. The
slow increase in Rct upon cycling indicates a relatively stable
interface between the CHꢀNCM electrode and electrolyte and
therefore good cycle performance of the CHꢀNCM cathode.
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Fig. 7 (A) The cyclic voltammetry (CV) curves of the CHꢀNCM
2
014, 589, 615.
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ꢀ
1
s ; (B) Nyquist plots after different charge–discharge cycles for the
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3
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1
2
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+
of crystal planes in favor of Li intercalation/deintercalation. The
+
special structure endows the material with ultrafast Li
This journal is © The Royal Society of Chemistry 2012
J. Name., 2012, 00, 1-3 | 5

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DOI: 10.1039/C5TA03225C
Table of contents entry
Hierarchical cubed LiNi1/3Co1/3Mn1/3O cathodes with enhanced
2
growth of electrochemical active planes exhibit enhanced
electrochemical performances.