Electrochimica Acta 318 (2019) 14e22

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

A P2/O3 biphasic cathode material with highly reversibility

synthesized by Sn-substitution for Na-ion batteries
Ranran Li, Yanying Liu, Zhen Wang, Jianling Li*
School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing, No. 30 College, Road, Haidian District, Beijing, 100083,
China

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

Article history: Sodium-ion batteries (SIBs) have been considered to be an appealing alternative as alternatives for
Received 22 April 2019 Lithium-ion batteries (LIBs) on account of abundant resources and low prices. Different cathode materials
Received in revised form have been extensively studied, especially layered oxides (P2 or O3). However, it is crucial to design an
4 June 2019
appropriate cathode material for SIBs with excellent comprehensive performance. Herein, a biphasic
Accepted 4 June 2019
Available online 5 June 2019
cathode material with P2 and O3 structures is successfully synthesized by Sn substitution in
Na0.67Ni0.33Mn0.67O2, which is clearly proved by the XRD and HRTEM results. And Fullprof program
refinement is used to determine the optimal phase ratio of P2 and O3. Besides, the XRD tests at different
Keywords:
Na-ion batteries
voltages illustrate that the cathode material has good reversibility and structural stability during charge
Cathode and discharge. Due to the synergistic effect of P2 and O3 phase, when the phase ratio is about 1:1, the
P2/O3 biphasic material P2/O3eNa0.67Ni0.33Mn0.57Sn0.1O2 exhibits the most outstanding electrochemical per-
Layered oxides formance. The P2/O3eNa0.67Ni0.33Mn0.57Sn0.1O2 cathode delivers a high reversible initial capacity of
155.2 mA h g
1 during the voltage range from 2.0V up to 4.3V with an excellent initial Coulombic effi-
ciency of 98.95%, as well as the satisfactory rate performances and cycling performance. GITT testing also
demonstrates the DNaþ of biphasic material is more stable and conducive to the diffusion of sodium ions.
These results will pave a significant way for designing cathode material for SIBs with different structure
by the substitution of transition metal elements.
© 2019 Elsevier Ltd. All rights reserved.

1. Introduction
Energy is the cornerstone of modern society, the energy
exploitation and utilization is critical to the development and
progress of society. However, coal, oil, and gas all belong to primary
energy, which are not renewable and are bound to be gradually
exhausted. Coupled with the increasingly serious environmental
problems, the exploitation of new next-generation energy storage
system is an inevitable trend [1,2]. Lithium-ion batteries (LIBs) have
been widely applied in various fields due to their advantages of
high voltage, high specific capacity, long cycle life as well as the
green and pollution-free [1]. In recent years, the problem of scarcity
of lithium resources has become more prominent with the rapid
development of LIBs. The cost of materials has risen sharply,
particularly since the commercialization of LIBs [3]. Compared with
LIBs, sodium-ion batteries (SIBs) have lower energy density, but
* Corresponding author.
E-mail address: lijianling@ustb.edu.cn (J. Li).
sodium is the fourth most abundant element in the earth crust,
consequently resulting in a low cost. Moreover, sodium and lithium
are the same main group elements and have similar electro-
chemical properties. Therefore, SIBs are considered to be an
appealing alternative as alternatives for LIBs [4e6]. It is a crucial
factor to realize the practical application of SIBs that design an
appropriate cathode material for SIBs. To date, the cathode mate-
rials include oxide, polyanionic compound and Prussian blue ma-
terial, among which the layered oxide was first reported in 1980s
[7]. It has become a widely studied material on account of the
excellent electrochemical performance and simple synthesis
[8e10]. Layered oxides are generally classified into two categories
according to the structure: P2 and O3. In these two structures, so-
dium ions occupy the triangular prism and octahedral sites be-
tween layers, respectively. The numbers (2 and 3) represent the TM
layers in a repeated stacking unit [1,11].
The layered oxide NaxTMO2 (TM ¼ Transition Metal) has
different structures due to the difference x in formula. When
x > 0.8, the material is more likely to form O3 phase, the material is
more easily to form P2 phase within the range of x < 0.8 [12]. The

https://doi.org/10.1016/j.electacta.2019.06.020
0013-4686/© 2019 Elsevier Ltd. All rights reserved.
 R. Li et al. / Electrochimica Acta 318 (2019) 14e22 15

P2-type NieMn based cathode material belongs to the P63/mmc

space group. The P2-type material has a spacious triangular prism
site that facilitates the diffusion of sodium ions, which is beneficial
to the rate performance of the cells [13,14]. However, the P2-type
material will undergo a phase transition from P2 to O2 in the
high voltage region [15,16] (about 4.2 V) due to the slip of the TMO2
layer, which will cause a sharp decline in capacity [17]. The main
methods adopted by the researchers for this problem are to reduce
the cut-off voltage to below 4.2 V to suppress the phase transition
or increase the reversibility of the phase transition by doping with
elements (Ti [18], Fe [19], Zn [20], Al [21], Mg [22], etc.). The O3-
type NieMn based material belongs to the R-3m space group.
Due to the high initial content of Na, the capacity of O3 phase
material is usually higher than P2-type material [23], but it has
complicated phase transition during charge and discharge (such as
O3eO30 eP3eP30 eP3〞 of O3eNaNi0.5Mn0.5O2) [24]. Note that the
O3 phase material is very sensitive to moisture in the air, which
result in structural changes, so the high conditions for storage are
required [23]. A composite phase material that combines the ad-
vantages of P2 and O3 has attracted broad attention of researchers Fig. 1. XRD patterns of synthesized Na0.67Ni0.33Mn0.67-xSnxO2(x ¼ 0, 0.05, 0.1, 0.2).
in order to meet the comprehensive performance requirements of Inset: Partially enlarged detail of diffraction peaks.
the cells [25e27]. For example, Zhou and Wang synthesized P2/P3
mixed phase materials with good cycling performance [28]. Lee and
Qi synthesized P2/O3 mixed phase materials by incorporation of Li 2.2. Material characterizations
into O3eNaNi0.5Mn0.5O2 material or tuning the sodium contents in
NaxNi0.2Fex-0.4Mn1.2-xO2 with good rate performances and cycling The crystal structures of Na0.67Ni0.33Mn0.67-xSnxO2 (x ¼ 0, 0.05,
performance [25,26], but the cutoff voltage is 4V which results in 0.1, 0.2) were acquired by X-ray diffraction (XRD) with Cu Ka ra-
low initial capacity of about 86 mA h g
1 and 125 mA h g
1. diation in the scan range of 10e70 with a speed of 2 min
1 and a
In this context, we have recently synthesized a new biphasic step size of 0.02 . The XRD patterns were refined using Fullprof
material Na0.67Ni0.33Mn0.67-xSnxO2 (x ¼ 0.05, 0.1, 0.2) by replacing program. The morphologies of the materials were investigated by
part of Mn with Sn, which introduce the O3 structure into the P2 field emission scanning electron microscopy coupled with energy-
phase material. From the stoichiometric ratio of sodium ions (less dispersive X-ray spectroscopy (EDS). Detail local structure was ac-
than 0.8), it should belong to the P2 phase material, but the pres- quired by transmission electron microscopy (TEM; JEOL JEM-2100).
ence of O3 phase in the material may be due to the same ionic The element valence was determined by X-ray photoelectron
radius of Ni2þ (0.69 Å) and Sn4þ (0.69 Å) resulting in cationic dis- spectroscopy (XPS) on a PHI Quantera II SXM system (Japan/Ulvac-
ordering [29]. The ratio of P2 and O3 phases in the material was PHI, Inc.) equipped with Al Ka radiation with the energy step size of
adjusted by changing the content of Sn to obtain a composite phase 0.05 eV.
material with superior electrochemical performance. Moreover, the
structural of biphasic material are refined using Fullprof program
and the structural transformation process is explored by XRD
tests on materials at different voltages. Then the electrochemical
testing is performed between 2.0 and 4.3V, which shows a
high reversible capacity and initial Coulombic efficiency, as well
as the cycling performance and rate performance of the P2/
O3eNa0.67Ni0.33Mn0.57Sn0.05O2, P2/O3eNa0.67Ni0.33Mn0.57Sn0.1O2
and P2/O3eNa0.67Ni0.33Mn0.47Sn0.2O2 are better than pure phase
material P2e Na0.67Ni0.33Mn0.67O2.

2. Experimental section

2.1. Material synthesis

The Na0.67Ni0.33Mn0.67-xSnxO2(x ¼ 0, 0.05, 0.1, 0.2) were syn-

thesized by a solid-state reaction method. The stoichiometric
amounts of manganese oxide (MnO2, Aladdin), nickel oxide (NiO,
Aladdin), tin oxide (SnO2, Aladdin) and sodium carbonate (Na2CO3,
Sinopharm) were mixed. It was worth mentioning that in order to
compensate for the sodium loss at high temperature, Na2CO3
should be excessive 5%. Then sufficiently ground for 3 h with a
mortar. The mixture was heated in air at 1000  C for 15 h (heating
rate was 5  C/min) and cooled down to room temperature to obtain
a brown-black powder material. These materials were used for
characterization and using in coin cells. Fig. 2. Schematic diagram of crystal structure of the P2 and O3 phase.
16 R. Li et al. / Electrochimica Acta 318 (2019) 14e22
2.3. Electrochemical characterizations
The electrochemical tests were carried out by using CR2025 coin
cells. The cathode electrodes consisted of active material (75 wt%),
carbon black (15 wt%) and polyvinylidene fluoride (10 wt%). The
slurry was coated on the aluminum foil then dried at 120  C for 12 h
in a vacuum oven. We used NaClO4 organic solution as electrolyte,
Na metal as an anode and a glass fiber paper was used as the
separator. The assembly of the coin cells was completed in the glove
box, which filled with argon. The galvanostatic charge/discharge
testing was performed between 2.0 and 4.3 V with a Land battery
test system (LANHE CT2001A) at room temperature. Cyclic vol-
tammetry (CV) tests were carried out at a scan rate of 0.1 mV s
1
between 2.0 and 4.3 V (vs. Naþ/Na). The galvanostatic intermittent
titration technique (GITT) was adopted to analyze the evolution of
the sodium ion diffusion coefficient during Naþ insertion/extrac-
tion, which was carried out on a Land battery test system. For the
GITT experiments, the cell was charged at 15 mA g
1 for 10 min,
then rest for 60 min.
3. Results and discussions
All materials Na0.67Ni0.33Mn0.67-xSnxO2(x ¼ 0, 0.05, 0.1, 0.2) were
prepared by a simple solid-state reaction method. Fig. 1 shows the
structural changes of Na0.67Ni0.33Mn0.67-xSnxO2 at different Sn
content, and labeled NMSx. It can be seen from the figure that the
diffraction peaks of NM correspond well to the P63/mmc space
Fig. 3. (a) Rietveld refinement of XRD pattern for P2-NM. (b) Rietveld refinement of XRD pattern for P2/O3-NMS0.05. (c) Rietveld refinement of XRD pattern for P2/O3-NMS0.1. (d)
Rietveld refinement of XRD pattern for P2/O3-NMS0.2. Inset: SEM images of P2-NM, P2/O3-NMS0.05, P2/O3-NMS0.1 and P2/O3-NMS0.2.
group. However, there are some new diffraction peaks appearing
for the Sn-substituted samples, which correspond to the R-3m
space group, indicating the appearance of the O3 phase. Then the
NMSx is transformed from pure P2 phase structure to P2/O3
biphasic structure, and the characteristic peaks of the O3 phase are
gradually enhanced with the content of Sn increasing. This makes
the content of P2 and O3 phase has changed, and the proportion of
the two phases is shown by the subsequent XRD Rietveld refine-
ment results. It is noteworthy that the peaks move to a lower angle
(inset of Fig. 1) with the increasing of Sn content from x ¼ 0 to
x ¼ 0.2 in Na0.67Ni0.33Mn0.67-xSnxO2, indicating that the smaller
Mn4þ (0.53 Å) is replaced by Sn4þ (0.69 Å) with larger ionic radius,
so that the cell volume has increased. Fig. 2 is the schematic dia-
gram of crystal structure of the P2 and O3 phase materials, which
build a layered structure by the sodium layer and the transition
metal layer alternately stacking. In P2 phase material, the oxygen
stacking mode is ABBA, and the sodium ion occupies the trigonal
prismatic site between the oxygen layers. Sodium ions have two
different sites in this coordination environment, sharing faces and
edges with two TMO6 octahedrons. By contrast, the oxygen atom
stacking pattern of O3 phase material is ABCABC, and the sodium
ion occupies the octahedral site between the oxygen layers [11].
There is only one occupancy site for sodium ion, sharing edges with
TMO6 octahedrons. By controlling the ratio of the P2 and O3 phases
in cathode material may obtain the better electrochemical
properties.
In order to further determine the existence of the biphasic and
 R. Li et al. / Electrochimica Acta 318 (2019) 14e22
the ratio of the P2 and O3 phases in NMSx, Rietveld XRD re-
finements of NMS0.05, NMS0.1 and NMS0.2 are carried out, and the
refinement results are shown in Fig. 3. The refinement results
further indicate that the P2 and O3 phases consist in the material,
corresponding to the P63-mmc and R-3m space groups. The mixed
phase materials are referred to as P2/O3-NMS0.05, P2/O3-NMS0.1
and P2/O3-NMS0.2. The specific refinement data is in Tables Se1,
Tables Se2 and Tables Se3. The ratios of P2 and O3 phase in P2/O3-
NMS0.05 materials are 69.74% and 30.26%, respectively. The cell
parameters of P2 phase are a ¼ b ¼ 2.894999 Å, c ¼ 11.193593 Å,
and the cell parameters of O3 phase are a ¼ b ¼ 3.078996 Å,
c ¼ 16.302988 Å. The ratios of P2 and O3 phase in P2/O3-NMS0.1
materials are 49.14% and 50.86%, respectively. The cell parameters
of P2 phase are a ¼ b ¼ 2.893607 Å, c ¼ 11.194968 Å, and the cell
parameters of O3 phase are a ¼ b ¼ 3.073287 Å, c ¼ 16.389244 Å.
The percent of P2 and O3 in P2/O3-NMS0.2 is 30.91% and 69.09%.
The lattice parameters of P2 are a ¼ b ¼ 2.895605 Å,
c ¼ 11.220144 Å, and the O3 phase are a ¼ b ¼ 3.066196 Å,
c ¼ 16.522137 Å. Compared with the lattice parameters of P2-NM
(a ¼ b ¼ 2.8846 Å, c ¼ 11.1705 Å), the lattice parameters (a, c) of
P2/O3-NMS0.05, P2/O3-NMS0.1 and P2/O3-NMS0.2 are gradually
increased as the Sn content increases and the cell volumes of P2/
O3-NMS0.05, P2/O3-NMS0.1 and P2/O3-NMS0.2 are larger than P2-
NM (Rietveld refinement of XRD pattern shown in Fig. 3a), which
is caused by the difference in ionic radius between Sn4þ (0.69 Å)
and Mn4þ (0.53 Å).
The material Na0.67Ni0.33Mn0.67-xSnxO2 (x ¼ 0, 0.05, 0.1, 0.2) is
measured by scanning electron microscopy, as illustrated in Fig. 4. It
can be seen from Fig. S2 that NM is composed of an irregular
polyhedron with the size of 2e4 mm, and the surface is smooth and
clean, indicating that the material has good crystallinity. When the
Fig. 4. (a) SEM image of P2-NMS0.05, (b) SEM image of P2/O3-NMS0.1, (c) SEM image of P2/O3-NMS0.2, (d)-(i) EDX mapping of P2/O3-NMS0.1.
17
Sn is used instead of Mn, it can be apparent from Fig. 4a, b and c that
the particle size exhibits an uneven distribution, but it becomes
smaller as the Sn content increases. EDX mapping analysis of
NMS0.1 was shown in Fig. 4eei. The uniform distribution of O, Na,
Mn, Ni and Sn on the surface of NMS0.1 can be clearly seen.
Fig. 5 shows the TEM and HRTEM images of P2-NM (a and b) and
P2/O3-NMS0.1 (c and d). It can be seen from HRTEM (Fig. 5b) that
the pure phase material P2-NM has uniform lattice fringes inside,
and the inset image of the right area corresponds to the diffraction
spots of P2 phase with the (100) lattice planes, corresponding the
spacing between crystal planes of 0.25 nm. The HRTEM image of
the intergrowth cathode material P2/O3-NMS0.1 is shown in Fig. 5b.
It can be clearly seen that there are two different lattice fringes, and
the lattice spacing is 0.26 nm and 0.53 nm, respectively corre-
sponding to (100) crystal plane of P2 phase and (003) crystal plane
of O3 phase. The diffraction spots of P2 phase with (100) and O3
phase with (003) crystal plane are shown in the inset image. The
crystal spacing of the P2 phase in the biphasic material increases
slightly, which may related to the replacement of a part of the
smaller radius Mn by Sn with a larger radius. It corresponds well to
the peaks of XRD moves to the small-angle region. The energy
spectrum of P2/O3-NMS0.1 is as shown in Fig. S1.
The electrochemical behavior of various Na0.67Ni0.33Mn0.67-
xSnxO2 cathodes was examined using Na metal as an anode.
Fig. 6a shows the initial charge and discharge curves for
Na0.67Ni0.33Mn0.67-xSnxO2(x ¼ 0, 0.05, 0.1, 0.2) at a current density
of 15 mA/g within a cut-off voltage window of 2.0e4.3 V vs. Na/Naþ.
The first charge curves of all electrodes consist of three platform
regions corresponding to 3.3 V, 3.6 V and 4.2 V. It's worth noting
that the Sn substitution in material extended the platform at 4.2 V,
which is considered to be beneficial for capacity increase. It can be
18 R. Li et al. / Electrochimica Acta 318 (2019) 14e22
clearly seen that the charge and discharge capacities of the P2/O3-
NMS0.05, P2/O3-NMS0.1 and P2/O3-NMS0.2 are larger than the P2-
NM. The charge and discharge capacities of the P2-NM are
131.9 mA h g-1 and116 mA h g
1 at 15 mA/g, while the Sn substi-
tution in P2-NM shows a higher initial discharge capacity of
136.4 mA h g
1, 155.2 mA h g
1 and 141 mA h g
1 for P2/O3-
NMS0.05, P2/O3-NMS0.1 and P2/O3-NMS0.2. The enhancement is
may attributed to the formation of biphasic (P2 and O3). It's worth
noting that the initial Coulombic efficiency of P2/O3-NMS0.05
(93.82%), P2/O3-NMS0.1 (98.95%) and P2/O3-NMS0.2 (98.41%) are
close to 100%, which are greatly improved compared with the P2-
NM (87.92%). A quite high initial Coulombic efficiency is achieved.
It is considered that the Sn substitution may be beneficial to the
reversibility of the phase transition. Fig. 6b exhibits the rate per-
formances profiles of the Na0.67Ni0.33Mn0.67-xSnxO2(x ¼ 0, 0.05, 0.1,
0.2). Cathode materials containing Sn exhibit higher discharge ca-
pacity than the P2-NM at various current densities from 15 mA g
1
to 150 mA g
1. The P2/O3-NMS0.1 especially shows a higher
discharge capacity of 99.7 mA h g
1 at 150 mA g
1, while the P2-
NM displays a lower capacity of 79.9 mA h g
1. In addition, P2/O3-
NMS0.1 shows a better performance than P2-NM, P2/O3-NMS0.05
and P2/O3-NMS0.2 when recharged with a low current of 15 mA/g,
suggesting preferable stability of P2/O3-NMS0.1. Such improvement
may be attributed to the fact that the P2/O3 intergrowth cathode
facilitates the diffusion of sodium ions and the stabilization of
layered structures. Cycle performance of three electrodes between
2 and 4.3 V is presented in Fig. 6d. The hybrid structure exhibits a
better cycling performance at 30 mA g
1 compared with the P2-
NM. Fig. 6c exhibits the CV curves of three electrodes in the first
Fig. 5. (a) TEM and (b) HRTEM images of P2-NM, (c) TEM and (d) HRTEM images of P2/O3-NMS0.1.
cycle at a scan rate of 0.1 mV s
1between 2 and 4.3 V. The CV curves
show that oxidation/reduction peaks are reversible, which repre-
sent the oxidation of Ni2þ to Ni3þ and Ni3þ to Ni4þ as well as the
phase transition of P2 and O3, respectively. It can be seen from the
figure that the CV curves of all the electrodes have the same overall
profile, and the redox peaks of Sn substitution electrode become
sharper compared with the P2-NM, which is consistent with the
variable length of the platform in high-voltage zone of the charge-
discharge curve. As expected, all the redox peaks of CV curves
coincide with the all the charge and discharge plateaus. Base on the
above analysis, we found that P2/O3-NMS0.1 has the best electro-
chemical comprehensive performance. This may be associated with
the Sn substitution in materials to produce different phase ratios.
According to the results of XRD refinement mentioned above, it
could be proposed that when the phase ratio of P2 to O3 is 1:1, the
electrochemical performance of hybrid phase materials are the
best.
In order to investigate the oxidation states of Ni, Mn and Sn, X-
ray photoelectron spectroscopy (XPS) measurement is employed.
Fig. 7 displays XPS spectra of Ni2p, Mn2p and Sn2p. As can be seen
from the Fig .7a that there are four peaks in the Ni 2p spectra
corresponding to Ni 2p3/2(854.1 eV), Ni 2p1/2(871.8 eV), and satellite
peaks. It demonstrates the existence of Ni ion at þ2 state. From the
XPS spectra of Mn 2p (Fig .7b), it can be seen that the main peak at
about 642.2 eV and 653.9 eV assigned to the binding energy of
Mn4þ. The XPS spectra of Sn 3d are shown in Fig. 7c, the two
characteristic peaks are at 485.9 eV and 494.6 eV, matching well
with Sn4þ. By the way, Fig. 7a and b show that the positions of the
characteristic peaks in the XPS spectra of Ni and Mn are consistent
 R. Li et al. / Electrochimica Acta 318 (2019) 14e22 19

Fig. 6. The electrochemical performance of coin cells: (a) The initial charge and discharge profiles of Na0.67Ni0.33Mn0.67-xSnxO2(x ¼ 0, 0.05, 0.1, 0.2) between 2.0 and 4.3V at 15 mA/g,
(b) The rate performances profiles of the Na0.67Ni0.33Mn0.67-xSnxO2(x ¼ 0, 0.05, 0.1, 0.2), (c) The CV curves of Na0.67Ni0.33Mn0.67-xSnxO2(x ¼ 0, 0.05, 0.1, 0.2) at a scan rate of 0.1 mV s
1
between 2.0 and 4.3 V, (d) The cycling performance of Na0.67Ni0.33Mn0.67-xSnxO2(x ¼ 0, 0.05, 0.1, 0.2) between 2 and 4.3 V.

in the both P2-NM and P2/O3-NMS0.1 materials. This indicates that
the valence states of the elements have not changed after Sn re-
places partial Mn. This may be attributed to the substitution of the
same valence state. Fig. 7d and e show the binding energies for Ni
2p and Mn 2p of pristine and fully-charged electrodes. As shown in
Fig .7d, the characteristic peaks of Mn 2p are both at 642.2 eV and
653.9 eV, which are no significant shift in position. This indicates
that Mn remains tetravalent in the process of Naþ extraction, which
is beneficial to stabilized structure. However, the XPS spectra of Ni
2p shows obviously differences when the Naþ extract from the
electrode. It can be concluded that Ni exhibits an electrochemically
activity in this process. Fig. 7 f shows the valence state of the nickel

Fig. 7. The XPS spectra of P2/O3-NMS0.1: (a) Ni and (b) Mn for the P2-NM and P2/O3-NMS0.1, (c) Sn for the P2/O3-NMS0.1, (d) Mn and (e) Ni for the pristine and the fully-charged P2/
O3-NMS0.1 electrode, (f) Ni for the fully-charged electrode.
20 R. Li et al. / Electrochimica Acta 318 (2019) 14e22
element under full charged. The main peak is at about 855.7 eV,
which proves the existence of tetravalent nickel. In summary, it
proves the redox reaction of Ni2þ to Ni3þ and Ni3þ to Ni4þduring the
charging process, corresponding to the oxidation/reduction peaks
of CV curves.
In order to explore the structural transformation process of P2/
O3-NMS0.1 electrode during the charge and discharge, we employ
XRD tests on materials at different voltages, which are shown in
Fig. 8a. When the coin cell is charged to 4.2 V (red line), new peaks
appear in the XRD pattern compared to the pristine material (black
line), which belong to the P3 phase. When the voltage is further
increased to 4.3 V, a new peak appears at about 20.2 , which is
considered to be a characteristic peak of the O2 phase according to
the previous reports [19]. It can prove that P2/O3-NMS0.1 has two
phase transition processes during the charging process, including
the phase transition from O3 to P3 and then the phase transition
from P2 to O2. When the material is discharged to 2.0 V, it can be
clearly seen that the XRD pattern is consistent with the spectrum of
the pristine material, and all the peaks coincide with the
Fig. 8. (a) XRD patterns of P2/O3-NMS0.1 at different voltages, (b) Partially enlarged detail of the (002) and (003), (c) The schematic diagram of charging and discharging process.
characteristic peaks of P2 and O3 phase. Therefore, the material is
returned to the P2/O3 structure and we can conclude that the
substitution of Sn is beneficial to the reversibility of phase transi-
tion. However, when the electrode is discharged to 2.0 V, the peaks
of (002) and (003) are shifted to a high angle compared with the
initial material (Fig. 8b), which is indicated that the unit cell
parameter c is reduced and the unit cell volume is decreased.
Through the above analysis, the schematic diagram of charging and
discharging process is shown in Fig. 8c. During the charging pro-
cess, sodium ions are extracted from the interlayer by two different
diffusion paths. In the P2 phase, sodium ions pass through a rect-
angular face of the triangular prism directly entering the next
triangular prism [30]. In the O3 phase, the sodium ions first enter
the tetrahedral hole through a triangular face of the octahedron,
and then through the triangular face of the tetrahedron enter the
adjacent octahedron. When a large amount of sodium ions are
extracted in the high voltage, the structure of the biphasic material
has changed on account of TMO2 layer gliding, which is the phase
transition from O3 to P3 and P2 to O2, respectively.
 R. Li et al. / Electrochimica Acta 318 (2019) 14e22 21

The sodium ion diffusion coefficient (Dþ Na) of composite phase P2/O3-NMS0.1 is in the range of 9.1210
10-1.21109 cm2/s.
material P2/O3-NMS0.1 is investigated by galvanostatic intermittent Compared with the pure phase material P2-NM (3.4310
11-
titration technique (GITT), as shown in Fig. 9. In this experiment, a 1.3910
9 cm2/s), shown in Fig. S3, the DþNa of P2/O3-NMS0.1 is less
galvanostatic current pulse of 15 mA/g was applied for 10 min, fluctuate and more stable. When the voltage is higher than 4.1V, the
followed by a 60 min relaxation. Fig. 9a shows a typical GITT profile sodium ion diffusion coefficient of sodium ions decreases
of the P2/O3-NMS0.1 electrode during the same voltage window of sharply and reaches a minimum value of 2.5571610
13 cm2/s
2.0e4.3 V. Fig. 9b is the profile for a single titration unit. The sodium around 4.2 V, which is lightly higher than the minimum value of
ion diffusion coefficient can be obtained by the following formula: 2.4457510
13 cm2/s of P2-NM. The voltage interval in which the
diffusion coefficient exhibits a sharp decrease corresponds to the
2 32 voltage value at the phase transition. The diffusion coefficient of
2

 .  sodium ions during discharge is shown in Fig. S4. From 4.2 to 4.0 V,
6
4 mBVm 6 DEs 7 7
DNa þ ¼ 4
5 t < < L2 D the sodium ion diffusion coefficient of P2/O3-NMS0.1 decreased from
p MBS
t dE
pffi 6.2148510
10 cm2/s to 1.9658810
13 cm2/s while the P2-NM
d t
decreased from 1.0729710
11 cm2/s to 1.7046310
13 cm2/s. It is
worth mentioning that there are two phase transitions (P2 to O2
where S is the geometric surface of the electrode, mB is the mass of
and O3 to P3) in the biphasic material P2/O3-NMS0.1 in the high-
active material, MB and Vm are the molar mass and molar volume of
voltage zone, while only the phase transition of P2 to O2 occurs in
active material, and t is the time for an applied galvanostatic cur-
the pure phase material P2-NM. It can be seen that P2/O3-NMS0.1 is
rent, respectively. When the voltage is linearly related to t1/2 in the
more favorable for the diffusion of sodium ions in this voltage range,
current pulse interval, the above equation can be simplified as:
which may be related to the presence of multiple phases in the high

2
2 voltage region. While between 4.0 and 2.0 V, the sodium ion diffu-
DEs  . 
4 mBVm sion coefficients of both materials are between 10
10.0 and 10
9, but
DNa þ ¼ t < < L2 D
pt MBS DEt the P2/O3-NMS0.1 is more stable than P2-NM. In brief, the biphasic
material is more conducive to the diffusion of sodium ions.
It can be clearly seen from Fig. 9c that E and t1/2 are linearly
related. Therefore, the DNaþ can be calculated by the above formula.
Where DEs and DEt represent the balanced voltage change value 4. Conclusions
and the voltage change during the current pulse, respectively. Fig. 9d
presents the sodium ion diffusion coefficient of P2/O3-NMS0.1 in In summary, a range of materials Na0.67Ni0.33Mn0.67-
the first charge process. It can be seen that between 2.7 and 3.9 V, xSnxO2(x ¼ 0,0.05, 0.1, 0.2) has been successfully synthesized by a
the diffusion coefficient of sodium ion in the mixed phase material simple solid-state reaction method. The Sn substitution for Mn

Fig. 9. (a) GITT profiles for charge of the P2/O3-NMS0.1 electrode during the voltage window of 2.0e4.3 V, (b) A single titration unit in GITT, (c) Linear fit of the voltage vs.t1/2, (d)
Diffusion coefficient of Naþ.
22 R. Li et al. / Electrochimica Acta 318 (2019) 14e22
results in the generation of composite phase materials and the ratio
of P2 and O3 phases varies with changes of the Sn content. More-
over, the XRD and HRTEM results support the existence of P2 and
O3 phase, and Rietveld XRD refinement provides the ratio of the P2
and O3 phase. Our results indicate the cell electrochemical per-
formance is the most outstanding when the ratio of P2 and O3
phase is about 1:1(P2/O3eNa0.67Ni0.33Mn0.57Sn0.1O2), which de-
livers a high initial capacity of 155.2 mA h g
1 at 15 mA/g during the
voltage range of 2.0e4.3 V. And P2/O3eNa0.67Ni0.33Mn0.57Sn0.1O2
exhibits an excellent initial Coulombic efficiency of 98.95%. The rate
performances and cycling performance is also desirable. These
improvements in electrochemical performance may be due to the
production of composite phases, which has a synergistic effect.
Then the XRD tests at different voltages illustrate the structural
changes of P2 to O2 and O3 to P3 during charge and discharge. This
work shows that the biphasic structure synthesized by the substi-
tution of transition metal elements is a significant guideline for
sodium ion cathode material.
Acknowledgments
This work is financially supported by the National Natural Sci-
ence Foundation of China (Grant 51572024) and the National Nat-
ural Science Foundation of China (Grant 51772025).
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.electacta.2019.06.020.
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