Sustainable

Energy & Fuels

View Article Online
PAPER View Journal | View Issue

Dual functions of zirconium modification on

Cite this: Sustainable Energy Fuels,
2018, 2, 413
Published on 17 November 2017. Downloaded on 11/11/2021 12:32:14 AM.
improving the electrochemical performance of Ni-
rich LiNi0.8Co0.1Mn0.1O2†
Xing Li, *a Kangjia Zhang,a MingShan Wang,*a Yang Liu,a MeiZhen Qu,b

Wengao Zhaoc and Jianming Zheng *c

Received 21st October 2017
Accepted 17th November 2017
DOI: 10.1039/c7se00513j
rsc.li/sustainable-energy
Trace amounts of zirconium (Zr) have been adopted to modify the crystal structure and surface of the Ni-
rich LiNi0.8Co0.1Mn0.1O2 (NCM811) cathode material. During cycling at 1.0C, the Zr-modified NCM811
shows an improved capacity retention of 92% after 100 cycles, higher than 75% for pristine NMC811. In
addition, the Zr-modified NCM811 is capable of delivering a discharge capacity of 107 mA h g
1 at
a 10.0C rate, much higher than 28 mA h g
1 delivered by pristine materials. These improved
electrochemical performances are ascribed to the dual functions of Zr modification. On one hand, part
of the Zr enters the crystal lattice, which is beneficial for reducing the Li/Ni cation mixing and enhancing
the crystal stability of the cathode. On the other hand, the rest of the Zr forms a 1–2 nm thick coating
layer on the surface of the NCM811 cathode, which effectively prevents direct contact between NCM
and the electrolyte, thus suppressing the detrimental interfacial reactions. Therefore, the Zr-modified
LiNi0.8Co0.1Mn0.1O2 exhibited significantly enhanced cycling stability and charge/discharge rate capability
in comparison with its untreated counterpart.

comparison with the commercial LiCoO2.9 However, there are

Introduction
Lithium ion batteries (LIBs) have been regarded as the most
competitive candidates as the power source for electric vehicles
(EVs) and hybrid electric vehicles (HEVs), because of their
lightweight and high energy density as compared to other
energy storage devices.1–3 With that being said, the development
of long-range EVs poses higher requirements of the energy
density and power density of LIBs. The Ni-rich layered structure
materials are being perceived as the most promising cathode
candidates for constructing high energy density LIBs due to
their high capacity, high operating voltage, and low cost.4–7
Especially, the LiNi0.8Co0.1Mn0.1O2 (NCM811) with a layered
structure of a-NaFeO2, belonging to the hexagonal crystal
system with the R3 m space group, has attracted increasing
attention in current research. The NCM811 cathode material
not only has a reversible discharge specic capacity as high as
200 mA h g
1,8 but is also more environmentally friendly and
cost effective due to the signicant decrease of Co content in
a
The Center of New Energy Materials and Technology, Southwest Petroleum University,
Xindu Road 8, Chengdu 610500, China. E-mail: lixing@swpu.edu.cn;
wangmingshan@swpu.edu.cn; Fax: +86 28 83037409; Tel: +86 28 83037409
b
Chengdu Institute of Organic Chemistry, Chinese Academy of Science, Chengdu
610041, China
c
Energy and Environment Directorate, Pacic Northwest National Laboratory, 902
Battelle Boulevard, Richland, WA 99354, USA. E-mail: jianming.zheng@pnnl.gov
† Electronic supplementary information (ESI) available. See
10.1039/c7se00513j
still two main challenges existing with the NCM811 cathode
material, including the cation mixing owing to the similar ionic
radius of Li+ (0.76 Å) and Ni2+ (0.69 Å) and the detrimental
interfacial reaction with the electrolyte due to the presence of
oxidative Ni4+ at charged states, which seriously affect its elec-
trochemical performances and impede its large-scale practical
application.10,11
To address the shortcomings of NCM811, lattice doping,
surface coating, and electrolyte optimization are usually
employed to suppress the cation mixing and the adverse inter-
facial reaction.12–15 In particular, the heteroatom doping, anion
doping such as F and Cl,16 or cation doping such as Al,17–19
Ga,20,21 Ti,22,23 Mg,24–27 Mo28,29 and Zn,30 has been proved to
reduce the cation mixing and improve the crystal microstruc-
ture stability. However, it is hardly found that one single
approach could solve the issues of Ni-rich NCM, i.e., both the
cation mixing and the interfacial decay issues.
In our previous work, we found that Zr surface modication
could enhance the electrochemical performance of LiNi1/3Co1/
+ 2+
3Mn1/3O2 (NCM333) via suppressing the Li /Ni mixing and
31
stabilizing the electrode/electrolyte interface, which inspired
us that the Zr modication might also improve the electro-
chemical performance of a more problematic Ni-rich NMC811.
In this work, a trace amount of Zr element was employed to
modify the surface of the NCM811 cathode material. It was
DOI:
found that part of the Zr could enter the crystal lattice to reduce
the cation mixing and the rest of Zr remained on the NCM811

This journal is © The Royal Society of Chemistry 2018 Sustainable Energy Fuels, 2018, 2, 413–421 | 413

Sustainable Energy & Fuels
surface forming a coating layer to enhance the interfacial
stability. This demonstrates that the main shortcomings of the
Ni-rich NCM811 could be solved concurrently via a facile Zr
element surface modication approach. In the present study,
the effects of the Zr modication on the structure, morphology,
and electrochemical performances of the NCM811 cathode
material were systematically investigated. A more detailed
understanding about the functioning mechanism of the Zr
modication was illustrated based on the results of X-ray
diffraction (XRD), X-ray photoelectron spectroscopy (XPS),
electrochemical impedance spectroscopy (EIS), etc.
Experimental
Published on 17 November 2017. Downloaded on 11/11/2021 12:32:14 AM.
Materials synthesis
The Zr surface modied LiNi0.8Co0.1Mn0.1
xZrxO2 (x ¼ 0.01)
cathode material was synthesized by a facile wet chemical
approach. All the chemicals used in this work are of A.R. purity.
Firstly, stoichiometric amounts of Ni(CH3COO)2$4H2O,
Co(CH3COO)2$4H2O, Mn(CH3COO)2$4H2O and Zr(NO3)4$5H2O
(Ni : Co : Mn : Zr ¼ 8 : 1 : 0.9 : 0.1, molar ratio) were dissolved
in deionized water to form a stable solution. Then, stoichio-
metric amounts of Li2CO3 with 5 mol% excess Li+ was added to
the above solution to form a suspension mixture, followed by
being dried at 120  C with magnetic stirring. The precursor was
pre-sintered at 500  C for 5 h, and then further calcined at
800  C for 12 h under a pure oxygen atmosphere with a heating
rate of 5  C min
1 to obtain the nal product. For comparison,
the pristine LiNi0.8Co0.1Mn0.1O2 cathode material was also
prepared in the same manner.
Materials characterization
The crystal structure and phase information of the samples were
identied by powder X-ray diffraction (X-Pert PRO MPD PAN-
alytical B.V. Netherlands) using Cu-Ka radiation in the 2q range
from 10 to 80 with a step size of 0.04 and a sampling time of 5 s.
The morphology and elemental distribution of the as-prepared
samples were observed using a scanning electron microscope
(SEM, ZEISS-EVO-MA15 Germany) coupled with an energy
dispersive spectrometer (EDS) and a transmission electron
microscope (TEM Libra200 Carle Zeiss). Analysis of the surface
and bonding mode of the samples was performed using X-ray
photoelectron spectroscopy (XPS, Thermo escalab 250Xi America).
Electrochemical measurements
The cathode electrodes were prepared by coating the slurry
mixture containing 85 wt% active materials, 10 wt% conductive
additive (acetylene black, AB) and 5 wt% binder (polyvinylidene
uoride, PVDF) on the aluminum substrate. Then, they were
punched into circular pieces with a diameter of 1.4 cm and an
active material loading of 3.0 mg followed by drying at 120  C
under vacuum was done prior to assembling the coin cell. The
CR2032 coin-type cells consisting of the cathode, the Celgard
2400 separator, the lithium metal anode, and the electrolyte
(1 M LiPF6 in EC : EMC : DMC ¼ 1 : 1 : 1 in volume) were
assembled in an Ar-lled glovebox with the water and oxygen
414 | Sustainable Energy Fuels, 2018, 2, 413–421
View Article Online
Paper
content less than 0.1 ppm. The electrochemical performance
evaluation of the assembled CR2032 coin cells were carried out
on a BTS-5V20mA cell testing instrument (NEWARE Electronic
Co., Ltd) within the cut-off voltages of 2.8–4.3 V (vs. Li/Li+) based
on different charge/discharge rates at room temperature. A
constant-current (CC) charge followed by a constant-voltage
(CV) charge was used for the charge step, and a galvanostatic
process was used for the discharge step. Cyclic voltammetry
(CV) and electrochemical impedance spectroscopy (EIS) were
performed on a CHI660D electrochemical workstation. CV was
recorded between 2.8 and 4.3 V (vs. Li/Li+) at a scan rate of
0.2 mV s
1. EIS was performed from 100 kHz to 0.01 Hz with
a potential amplitude of 5 mV. All the EIS measurements were
conducted at the charged state of 4.1 V for the pristine and the
Zr-modied samples.
Results and discussion
The XRD patterns of the pristine NCM811 and the Zr-modied
NCM811 cathode materials are shown in Fig. 1. The diffraction
patterns of the two samples are similar, and all the peaks could
be assigned to the hexagonal a-NaFeO2 structure of the R3 m
space group. The distinct splitting of (006)/(102) and (108)/(110)
peaks (Fig. 1b and c) indicates that the two samples both possess
an ordered layered structure. However, a slight peak shi (the
inset in Fig. 1a) can be observed, which implies that the crystal
structure of the NCM811 has been slightly changed via the trace
amount of Zr modication. The crystal lattice parameters as
calculated from the XRD patterns are listed in Table 1. It can be
observed that the lattice parameters of a and c of the Zr-modied
NCM811 are both larger than those of the pristine NCM811. This
demonstrates that some Zr4+ has entered the NCM crystal lattice,
which increases the interlayer distance because of the relatively
large ionic radius of Zr4+ (0.72 Å) as compared to other transition
metal ions (Ni3+ (0.56 Å), Ni2+ (0.69 Å), Co3+ (0.53 Å), and Mn4+
(0.54 Å)).32 Moreover, as shown in Table 1, it can be observed that
the ratio of c/a and the intensity ratio of the (003) to the (104)
peak (I(003)/I(104)) of the Zr-modied NCM811 are also larger than
those of the pristine NCM811. In particular, the intensity ratio of
the (003) to the (104) peak (I(003)/I(104)) in the diffraction pattern
can be used as an indication of the layered characteristics of the
cathode materials.33 The larger c/a and I(003)/I(104) values disclose
Fig. 1 XRD patterns of (a) the pristine NCM811 and the Zr-modified
NCM811, and the enlarged diffraction peaks of (b) the (006)/(102) and
(c) (008)/(110) of the pristine NCM811 and the Zr-modified NCM811.
This journal is © The Royal Society of Chemistry 2018
 View Article Online

Paper Sustainable Energy & Fuels

Table 1 Crystal cell parameters of the pristine NCM811 and the Zr- and Zr-modied NCM811 (Fig. 2b), both of which present
modified NCM811 irregularly shaped secondary particles with a size of about
400 nm. For the Zr-modied NCM811, it can be observed from
Sample a (Å) c (Å) c/a I(003)/I(104)
the EDS mapping (Fig. 3) that the Zr element homogeneously
Pristine 2.863 14.230 4.970 1.357 distributes among the particles. TEM was then used to further
Zr-Modication 2.866 14.268 4.978 1.511 explore the microstructure of Zr-modied NCM811. The TEM
images in Fig. 4 demonstrate there is an additional coating layer
existing on the surface of the Zr-modied NCM811. Fast Fourier
that the Zr-modied NCM811 has a better ordered hexagonal Transformation (FFT) shown in Fig. 4b further proves that the
layered structure with lower cation mixing than the pristine coating layer on the NCM811 is amorphous. These results reveal
one.31 All the above results suggest that the Zr-modication can that part of the Zr could not enter the crystal lattice, remaining
lead to the incorporation of Zr into the crystal lattice of the on the surface of the NCM811 to form a coating layer.
NCM811, which is favorable for reducing the cation mixing and The XPS results of the pristine NCM811 and the trace
enhancing the crystal structural stability. amount Zr-modied NCM811 are presented in Fig. 5. The XPS
Published on 17 November 2017. Downloaded on 11/11/2021 12:32:14 AM.

The SEM images of the pristine NCM811 and Zr-modied data clearly show the presence of Zr4+ (Zr 3d peak) in the Zr-
NCM811 are shown in Fig. 2. No obvious difference in modied NCM811 (Fig. 5a), which is absent in the pristine
morphology is observed between the pristine NCM811 (Fig. 2a) NCM811. The binding energy of Zr 3d and O 1s shown in Fig. 5b

Fig. 2 SEM images of (a) the pristine NCM811 and (b) the Zr-modified NCM811.

Fig. 3 EDS mapping of the Zr-modified NCM811.

This journal is © The Royal Society of Chemistry 2018 Sustainable Energy Fuels, 2018, 2, 413–421 | 415

Sustainable Energy & Fuels
Published on 17 November 2017. Downloaded on 11/11/2021 12:32:14 AM.
Fig. 4 TEM and Fast Fourier Transformation (FFT) of the Zr-modified
NCM811.
Fig. 5 XPS of the (a) wide scan of the pristine NCM811 and the Zr-modified NCM811 (inset is the magnified Zr 3d XPS spectrum) and the narrow
scan focusing on the elements of (b) Zr 3d, (c) O 1s, and (d) Ni 2p of the samples.
416 | Sustainable Energy Fuels, 2018, 2, 413–421
View Article Online
Paper
and c demonstrates that the oxidation states of Zr and O are +4
and
2 in the surface of Zr-modied NCM811, respectively.
According to the previous report,34 the coating layer on the
surface (as shown in the TEM image) of the NCM811 might be
ZrO2 or Li2ZrO3. Considering the 5% mole excess of Li source
during the synthesis of the NCM, the coating layer on the
surface of the NCM811 is supposed to be the amorphous
Li2ZrO3.35 Moreover, the peak positions of Co and Mn are rela-
tively stable (Fig. S1†), while the peak shape and position of Ni
slightly change in the Zr-modied NCM811 as compared with
the pristine NCM811, which demonstrates the surface chemical
environment of Ni has been modied via the Zr-modication
process. Aer peak tting, as presented in Fig. 5d, it is found
that the ratio of the Ni3+ 2p3/2 intensity to the Ni2+ 2p3/2 intensity
in the Zr-modied NCM811 is obviously larger than that in the
pristine NCM811. This means that a higher percentage of the Ni
element is maintained at an oxidation state of +3 in the surface
of the NCM811 via trace amount of Zr modication, which is
favorable for reducing the cation mixing and enhancing the
ordering of the layered crystal structure of the NCM811.36 This
phenomenon could be ascribed to the strong Zr–O bond, which
could alleviate the formation of oxygen non-stoichiometry in
the Ni-rich NCM cathode during higher temperature calcina-
tion, thus reducing the formation of Ni2+ in the material.37,38
Cyclic voltammetry (CV) was adopted to study the electro-
chemical reaction kinetics in the pristine and the Zr-modied
NCM811 electrodes. Fig. 6a and b present the CV curves for
the rst three cycles of the pristine and the Zr-modied
NCM811 at a scan rate of 0.2 mV s
1. The oxidation and
This journal is © The Royal Society of Chemistry 2018
 View Article Online

Paper Sustainable Energy & Fuels

reduction peaks within the voltage range of 2.8 to 4.3 V corre- Table 2 The potential difference of the first three CV scans of the
spond to the delithiation and lithiation process, respectively, pristine NCM811 and the Zr-modified NCM811 at a scan rate of 0.2 mV
s
1
occurring in the cathode electrode.39,40 The potential differences
for the rst three CV scans are compared in Table 2, showing Anodic peak Cathodic peak Potential difference
that the potential difference of the Zr-modied NCM811 is (V) (V) (V)
obviously smaller than that of the pristine NCM811. Higher
scan rates of 0.5, 1.0, 2.0, 5.0 and 10.0 mV s
1 have also been Pristine
1st cycle 3.946 3.699 0.247
employed to further characterize the electrode reaction kinetics 2nd cycle 3.826 3.702 0.124
of the two samples. As compared with Fig. 6c and d, the Zr- 3rd cycle 3.809 3.702 0.107
modied NCM811 exhibits better capability to maintain the
distinct redox reaction peaks than the pristine NCM811 at Zr-Modication
various scan rates, which demonstrates that the Zr modication 1st cycle 3.823 3.713 0.122
2nd cycle 3.808 3.703 0.105
is benecial for reducing the kinetic barrier of electrochemical 3rd cycle 3.792 3.713 0.079
redox reactions and thus improving the electrochemical
Published on 17 November 2017. Downloaded on 11/11/2021 12:32:14 AM.

reversibility.41 Moreover, the chemical diffusion coefficient of

lithium ions in the NCM811 electrodes can be calculated using
the Randles–Sevcik equation (eqn (1)), which correlates the
relationship between the square root of the scan rate (v1/2) and
the peak current (ip).
ip ¼ 0.4463mAF(F/RT)1/2CLiDLi1/26v1/2
where, ip is peak current in amperes, m is the mass of the active
substance, A is the effective area of the electrode in cm2, F is the
Faraday constant, R is the gas constant, T is the absolute
temperature, C is the initial concentration of lithium ions
(1) in mol cm
3, DLi represents the diffusion coefficient of lithium
ions in cm2 s
1, and v is the scan rate in mV s
1.42 As shown in

Fig. 6 Cyclic Voltammogram (CV) curves of the first three cycles of (a) the pristine NCM811 and (b) the Zr-modified NCM811 at a scan rate of
0.2 mV s
1, (c) the pristine NCM811 and the Zr-modified NCM811 at different scan rates of 0.5, 1.0, 2.0, 5.0 and 10.0 mV s
1, and (e) the rela-
tionship between the oxidation peak current density (ip) and the square root of the scan rate (v1/2).

This journal is © The Royal Society of Chemistry 2018 Sustainable Energy Fuels, 2018, 2, 413–421 | 417
 View Article Online

Sustainable Energy & Fuels Paper

Fig. 6e, a linear relationship between the peak current (ip) and
the square root of the scan rate (v1/2) can be obtained. While the
other parameters remain constant, the DLi1/2 is proportional to
the slope of the curve (ip  v1/2). The calculation results show
that the slope of the Zr-modied NCM811 (k ¼ 3.124) is obvi-
ously larger than that of the pristine NCM811 (k ¼ 1.929). This
indicates that the Zr modication could improve the lithium
ion diffusion coefficient, due to the fact that part of the Zr4+
could enter the crystal lattice of the NCM811 which increases
the interlayer spacing and thereby facilitates the fast lithium
ion transportation.31
Fig. 7a and b present the rate capability and cycling perfor-
mance of pristine NCM811 and Zr-modied NCM811. The rate
capability of the two samples was rstly investigated by testing
Published on 17 November 2017. Downloaded on 11/11/2021 12:32:14 AM.
delivering higher discharge capacity and less electrode polari-
zation at increasing C rates. The discharge capacities of the Zr-
modied NCM811 are 201, 187, 179, 167, 156, 144, 128 and
107 mA h g
1, at the charge/discharge rate of 0.1, 0.33, 0.5, 1.0,
2.0, 3.0, 5.0 and 10.0C, respectively. The charge and discharge
curves at different C rates of the pristine and the Zr-modied
NCM811 are compared in detail in Fig. S2.† With respect to
long-term cycling stability, as shown in Fig. 7b, the rst
discharge specic capacity of the pristine NCM811 is only
137 mA h g
1 at the charge/discharge rate of 1.0C, and the
capacity retention is only 75% aer 100 cycles. In contrast, the
rst discharge capacity for the Zr-modied NCM811 is
171 mA h g
1 at a charge/discharge rate of 1.0C, and a high
capacity retention of 92% can be achieved aer 100 cycles.

with the charge C rate equal to the discharge C rate. As shown in
Fig. 7a, the discharge capacities of the pristine NCM811 are 204,
188, 155, 135, 103, 87, 70 and 28 mA h g
1, at 0.1, 0.33, 0.5, 1.0,
2.0, 3.0, 5.0 and 10.0C, respectively. In comparison, the Zr-
modied NCM811 shows greatly improved rate capability,
Moreover, different charge and discharge protocols have
been employed to better understand the difference of the dis-
charging or charging capability of the pristine and the Zr-
modied NCM811. Fig. 7c and d show the rate performance
of the pristine NCM811 and the Zr-modied NCM811 tested at

Fig. 7 (a) Rate capability of the pristine NCM811 and the Zr-modified NCM811 (charge rate equal to the discharge rate). (b) Cycling stability of the
samples at the charge/discharge rate of 1.0C. (c and d) Charge and discharge curves of the samples under the testing protocol of charging at
0.2C followed by discharging from 0.1C to 10.0C of (c) the pristine NCM811 and (d) the Zr-modified NCM811. (e and f) Charge and discharge
curves of the samples under the testing protocol of charging from 3.0C to 10.0C followed by discharging at 0.2C of (e) the pristine NCM811 and
(f) the Zr-modified NCM811.

418 | Sustainable Energy Fuels, 2018, 2, 413–421 This journal is © The Royal Society of Chemistry 2018
 View Article Online

Paper Sustainable Energy & Fuels

the same charge rate of 0.2C but at increasing discharge rates
from 0.1C to 10.0C. Despite the similar discharge capacity at
a low C rate of 0.2C, the Zr-modied NCM811 delivers higher
discharge capacity than the pristine NCM811 at the elevated
discharge C rates ranging from 0.33 to 10.0C. Fig. 7e and f
Table 3 The CC and CV charge capacity of the pristine NCM811 and
the Zr-modified NCM811 under the testing protocol of charging with
increasing C rates followed by discharging with the same 0.2C rate
Constant current Constant voltage Constant current
charge specic charge specic charge percentage
capacity (mA h g
1) capacity (mA h g
1) (%)
Published on 17 November 2017. Downloaded on 11/11/2021 12:32:14 AM.
compare the rate performance of the pristine NCM811 and the
Zr-modied NCM811 evaluated at increasing charging rates but
with the same 0.2C discharge rate. It is found that both the
charge and discharge capacities of the Zr-modied NCM811 are
larger than those of the pristine NCM811. The detailed capac-
ities contributed from constant-current charging and constant-
voltage charging are summarized in Table 3. With the increase
of the charge current density, the specic capacity obtained by
the constant-current charging of the pristine NCM811 is
dramatically reduced, indicating the poor charging capability of
pristine NCM811 due to the higher kinetic barrier for lithium
ion extraction.43 In contrast, even when the charge current
density is up to 10.0C, the capacity obtained by the constant-
current charging is still as high as 72% for the Zr-modied

Pristine NCM811, which means that the Zr-modication has largely

3C/0.2C 115.47 45.5 71.73 enhanced the charging capability. It is worth noting that the
5C/0.2C 80.46 68.92 53.86 discharge capacity of the Zr-modied NCM811 is slightly lower
10C/0.2C 19.50 102.25 16.02
than that of the pristine NCM811 at the low rate of 0.2C, which
Zr-Modied is because the electrochemically inactive Li2ZrO3 coating layer
3C/0.2C 138.01 26.85 83.71 formed on the surface does not contribute to the capacity.34 The
5C/0.2C 121.11 21.33 79.45 above electrochemical data substantiate that the Zr modica-
10C/0.2C 99.53 38.52 72.10 tion could signicantly improve the cycling stability and

Fig. 8 (a) Nyquist plots of the pristine NCM811 and the Zr-modified NCM811 at the charged state of 4.1 V. (b) Relationship between the real
resistance and the frequency, the slope (Warburg impedance coefficient) of which was used to calculate the lithium–ion diffusion coefficient. (c–
f) Nyquist plots of the pristine NCM811 and the Zr-modified NCM811 (c) after 1 cycle and then being charged to 4.1 V, (d) after 10 cycles and then
being charged to 4.1 V, (e) after 50 cycles and then being charged to 4.1 V, and (f) after 100 cycles and then being charged to 4.1 V.

This journal is © The Royal Society of Chemistry 2018 Sustainable Energy Fuels, 2018, 2, 413–421 | 419

Sustainable Energy & Fuels
charging/discharging capability of the NCM811 cathode mate-
rial, owing to the reduced cation mixing, the enhanced lithium
ion transportation, and the stabilized electrode interface.
To get further insight into the improved electrochemical
performances aer Zr-modication, EIS was performed to track
the impedance evolution during cycling. Fig. 8 shows the
impedance spectra of the pristine and the Zr-modied NCM811.
Fig. 8a shows the EIS of the Zr-doped NCM811 and the pristine
NCM811 at the charged state of 4.1 V. Both of the EIS of the
samples present a semicircle in the high-to-medium frequency
region, followed by a slope in the low frequency region. The
former is associated with the interfacial resistance,44 while the
latter is associated with the diffusion of Li+ ions in the solid-
state electrode (Warburg impedance).45 The lithium ion diffu-
Published on 17 November 2017. Downloaded on 11/11/2021 12:32:14 AM.
sion coefficient of the Zr-modied NCM811 and the pristine
NCM811 could be obtained from the Warburg impedance
coefficient (sw) using eqn (2) and (3).38
Zre ¼ (Rsf + Rct + swu
1/2) (2)
DLi ¼ R2T2/(2A2n4F4Csw2) (3)
Where, DLi represents the lithium ion diffusion coefficient, R is
the gas constant, T is the absolute temperature, A is effective
area of the electrode, n is the number of electrons transferred, F
is Faraday constant, and C is the concentration of lithium ions.
The Warburg impedance coefficient sw could be determined
from the slope between Zre and u
1/2 as shown in Fig. 8b. The
lithium ion diffusion coefficient calculated for the Zr-modied
NCM811 is 1.01  10
8 cm2 s
1, which is much higher than
1.31  10
9 cm2 s
1 obtained for the pristine NCM811.
Although the lithium ion diffusion coefficient obtained from
EIS is a little bit different from that obtained from the CV
method, the lithium ion diffusion coefficient of the Zr-modied
NCM811 obtained from two different methods is obviously
higher than that obtained for the pristine NCM811, which could
explain the superior charging and discharging capability of the
Zr-modied NCM811.
Fig. 8c–f show the EIS of the pristine NCM811 and the Zr-
modied NCM811 aer 1, 10, 50 and 100 cycles at the charge/
discharge rate of 1.0C. The impedance spectra show a semi-
circle in the high frequency region representing the surface lm
(so-called CEI layer) impedance (Rsf), a semicircle located in the
high-to-medium frequency region representing the charge
transfer impedance (Rct), and an oblique line located in the low
frequency region representing the Warburg impedance (W).46
The interfacial resistance (Rsf + Rct) for both electrodes increases
with the increase of the cycle number because of the degrada-
tion of the electrode interface.47 Although the two samples
exhibit similar interfacial resistance at early stages of cycling,
the pristine NCM811 electrode experiences a considerable
increase of interfacial resistance during the subsequent cycling,
indicating the poor interfacial stability of Ni-rich NCM without
treatment. A detailed comparison shows that the Zr-modied
NCM811 exhibits much stable interfacial resistance during
cycling as compared to the pristine NCM811. The total interfa-
cial resistance of Zr-modied NCM811 is only about 250 ohm
420 | Sustainable Energy Fuels, 2018, 2, 413–421
View Article Online
Paper
aer 100 cycles, which is less than half of that observed for the
pristine NCM811 electrode (550 ohm). The improved interfa-
cial stability of the Zr-modied NCM811 electrode could be
ascribed to the Li2ZrO3 coating layer formed on the surface of
the NCM811 that could effectively prevent the direct contact of
NCM with the electrolyte and hence suppress the detrimental
interfacial reactions, accounting for the superior long-term
cycling stability.
Conclusion
The effects of Zr surface modication on the structure,
morphology, and electrochemical performances of the Ni-rich
NCM811 cathode material have been systematically investi-
gated in the present study. The results demonstrated that Zr has
dual roles in both enhancing the ordering of the layered
structure and stabilizing the material interface. Part of the Zr4+
could enter the crystal lattice of the NCM811, which could
reduce the cation mixing, enhance the crystal stability and
result in an improved hexagonal layered structure, facilitating
the lithium ion transportation in the layered structure. More-
over, the rest of the Zr remained on the surface of the NCM811,
forming a kind of Li2ZrO3 coating layer. The Li2ZrO3 coating
layer could mitigate the direct contact between the surface of
the NCM811 and the electrolyte, which is favorable for sup-
pressing the unwanted interfacial reactions. As a result, the Zr-
modied NCM811 exhibited signicantly enhanced cycling
stability and rate capability as compared to the pristine
NCM811. The fundamental ndings of this work shed light on
the importance of identifying an effective dopant for developing
high energy density Ni-rich NCM cathodes for lithium ion
batteries.
Conflicts of interest
There are no conicts to declare.
Acknowledgements
This work was carried out with nancial support from the
National Natural Science Foundation of China (grant no.
51474196, 51502250) and the Science and Technology Depart-
ment of Sichuan Province (grant no. 2016RZ0071, 2017JQ0044).
References
1 D. Andre, S. J. Kim, P. Lamp, S. F. Lux, F. Maglia, O. Paschos
and B. Stiaszny, J. Mater. Chem. A, 2015, 3, 6709–6732.
2 W. Liu, P. Oh, X. Liu, M. J. Lee, W. Cho, S. Chae, Y. Kim and
J. Cho, Angew. Chem., Int. Ed., 2015, 54, 4440.
3 Z. He, Z. Wang, Z. Huang, H. Chen, X. Li and H. Guo, J.
Mater. Chem. A, 2015, 3, 16817–16823.
4 M. V. Reddy, G. V. S. Rao and B. V. R. Chowdari, J. Phys.
Chem. C, 2007, 111, 11712–11720.
5 Y. K. Sun, S. T. Myung, B. C. Park, J. Prakash, I. Belharouak
and K. Amine, Nat. Mater., 2009, 8, 320.
This journal is © The Royal Society of Chemistry 2018

Paper
6 L. J. Li, X. H. Li, Z. X. Wang, H. J. Guo, P. Yue, W. Chen and
L. Wu, Powder Technol., 2011, 206, 353–357.
7 J. Zheng, W. H. Kan and A. Manthiram, ACS Appl. Mater.
Interfaces, 2015, 7, 6926.
8 Y. Bi, W. Yang, R. Du, J. Zhou, M. Liu, Y. Liu and D. Wang, J.
Power Sources, 2015, 283, 211–218.
9 J. Eom, G. K. Min and J. Cho, J. Electrochem. Soc., 2008, 155,
A239–A245.
10 C. Fu, G. Li, L. Dong, L. Qi, J. Fan and L. Li, ACS Appl. Mater.
Interfaces, 2014, 6, 15822.
11 X. Xiong, Z. Wang, P. Yue, H. Guo, F. Wu, J. Wang and X. Li, J.
Power Sources, 2013, 222, 318–325.
12 K. M. Kim, N. V. Ly, J. H. Won, Y. G. Lee, W. I. Cho, J. M. Ko
and R. B. Kaner, Electrochim. Acta, 2014, 136, 182–188.
Published on 17 November 2017. Downloaded on 11/11/2021 12:32:14 AM.
13 B. Li, M. Xu, T. Li, W. Li and S. Hu, Electrochem. Commun.,
2012, 17, 92–95.
14 Y. An, P. Zuo, X. Cheng, L. Liao and G. Yin, Electrochim. Acta,
2011, 56, 4841–4848.
15 B. Yao, Z. Ding, J. Zhang, X. Feng and L. Yin, J. Solid State
Chem., 2014, 216, 9–12.
16 L. Zhu, Y. Liu, W. Wu, X. Wu, W. Tang and Y. Wu, J. Mater.
Chem. A, 2015, 3, 15156–15162.
17 M. Guilmard, C. Pouillerie, L. Croguennec and C. Delmas,
Solid State Ionics, 2003, 160, 39–50.
18 K. K. Lee, W. S. Yoon, K. B. Kim, K. Y. Lee and S. T. Hong, J.
Power Sources, 2001, 97–98, 308–312.
19 S. B. Majumder, S. Nieto and R. S. Katiyar, J. Power Sources,
2006, 154, 262–267.
20 J. H. Chang, W. S. Eom, M. L. Sang, W. I. Cho and H. Jang, J.
Power Sources, 2005, 144, 214–219.
21 C. Wang, X. Ma, J. Cheng, L. Zhou, J. Sun and Y. Zhou, Solid
State Ionics, 2006, 177, 1027–1031.
22 B. V. R. Chowdari, G. V. S. Raob and S. Y. Chowa, Solid State
Ionics, 2001, 140, 55–62.
23 H. Liu, J. Li, Z. Zhang, Z. Gong and Y. Yang, Electrochim. Acta,
2004, 49, 1151–1159.
24 J. Xiang, C. Chang, F. Zhang and J. Sun, J. Electrochem. Soc.,
2008, 155, A520–A525.
25 A. R. Naghash and J. Y. Lee, Electrochim. Acta, 2001, 46, 941–
951.
26 S. Madhavi, G. V. S. Rao, B. V. R. Chowdari and S. F. Y. Li,
Solid State Ionics, 2002, 152–153, 199–205.
This journal is © The Royal Society of Chemistry 2018
View Article Online
Sustainable Energy & Fuels
27 B. Zhang, L. Li and J. Zheng, J. Alloys Compd., 2012, 520, 190–
194.
28 L. Q. Wang, L. F. Jiao, H. T. Yuan, J. Guo, M. Zhao, H. X. Li
and Y. M. Wang, J. Power Sources, 2006, 162, 1367–1372.
29 S. Sivaprakash, S. B. Majumder, S. Nieto and R. S. Katiyar, J.
Power Sources, 2007, 170, 433–440.
30 G. T. K. Fey, J. G. Chen, V. Subramanian and T. Osaka, J.
Power Sources, 2002, 112, 384–394.
31 X. Li, H. Peng, M. S. Wang, X. Zhao, P. X. Huang, W. Yang,
J. Xu, Z. Q. Wang, M. Z. Qu and Z. L. Yu,
ChemElectroChem, 2016, 3, 130–137.
32 C. Wang, L. Chen, H. Zhang, Y. Yang and F. Wang,
Electrochim. Acta, 2014, 119, 236–242.
33 X. Bie, F. Du, Y. Wang, K. Zhu, H. Ehrenberg, K. Nikolowski,
C. Wang, G. Chen and Y. Wei, Electrochim. Acta, 2013, 97,
357–363.
34 K. Park, J. H. Park, S. G. Hong, B. Choi, S. W. Seo, J. H. Park
and K. Min, Phys. Chem. Chem. Phys., 2016, 18, 29076.
35 H. Chen, Q. Hu, Z. Huang, Z. He, Z. Wang, H. Guo and X. Li,
Ceram. Int., 2016, 42, 263–269.
36 T. Li, X. Li, Z. Wang and H. Guo, J. Power Sources, 2017, 342,
495–503.
37 B. Lin, Z. Wen, Z. Gu and X. Xu, J. Power Sources, 2007, 174,
544–547.
38 J. Zheng, J. Xiao and J. G. Zhang, Nano Today, 2016, 11, 678–
694.
39 J. Yang and Y. Xia, ACS Appl. Mater. Interfaces, 2016, 8(2),
1297–1308.
40 K. Chang, B. Hallstedt and D. Music, CALPHAD: Comput.
Coupling Phase Diagrams Thermochem., 2012, 37, 100–107.
41 K. Meng, Z. Wang, H. Guo, X. Li and D. Wang, Electrochim.
Acta, 2016, 211, 822–831.
42 K. Wu, G. Hu, K. Du, Z. Peng and Y. Cao, J. Alloys Compd.,
2015, 650, 718–723.
43 X. Cao, Int. J. Electrochem. Sci., 2016, 11, 5267–5278.
44 G. Li, Z. Zhang, R. Wang, Z. Huang, Z. Zuo and H. Zhou,
Electrochim. Acta, 2016, 212, 399–407.
45 T. Yang, N. Zhang, L. Ye and K. Sun, Electrochim. Acta, 2011,
56, 4058–4064.
46 J. Zheng, W. Shi, M. Gu, J. Xiao, P. Zuo, C. Wang and
J. G. Zhang, J. Electrochem. Soc., 2013, 160, A2212–A2219.
47 X. Lu, X. Li, Z. Wang, H. Guo, G. Yan and X. Yin, Appl. Surf.
Sci., 2014, 297, 182–187.
Sustainable Energy Fuels, 2018, 2, 413–421 | 421