Energy Storage Materials 41 (2021) 581–587

Contents lists available at ScienceDirect

Energy Storage Materials

journal homepage: www.elsevier.com/locate/ensm

Tuning oxygen redox chemistry of P2-type manganese-based oxide cathode

via dual Cu and Co substitution for sodium-ion batteries
Quanqing Zhao a, Faheem K. Butt b, Min Yang a, Zefeng Guo c, Xiuyun Yao a,
Maximiliano Jesus Moreno Zapata d, Youqi Zhu a,∗, Xilan Ma a, Chuanbao Cao a,∗
a
Research Center of Materials Science, Beijing Key Laboratory of Construction Tailorable Advanced Functional Materials and Green Applications, Beijing Institute of
Technology, Beijing 100081, China
b
Department of Physics, Division of Science and Technology, University of Education Lahore, Pakistan
c
Datong Coal Mine Group Shuozhou Coal Co. Ltd., Huairen, Shanxi 038300, China
d
Departamento de Física, Laboratório de Cristalografia, Universidade Federal de Minas Gerais, Av. Antônio Carlos 6627, Belo Horizonte, MG 31270-901, Brazil

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

Keywords: High-voltage layered Mn-based oxide is promising high-capacity cathode via exploiting the oxygen redox chem-
Dual substitution istry. But such redox often suffer from irreversible oxygen loss, leading to severe voltage hysteresis, particle
Complementary effect cracking and capacity decay. Hence, the complementary strategy of dual Cu and Co substitution is revealed to
Oxide cathode
stabilizing the anion redox chemistry of P2-Na2/3 (Mn-Ni-Cu-Co)O2 cathode under upper cut-off voltage. Dual
Full cell
substitution with Cu for Mn and Co for Ni forms stable Cu-O and Co-O octahedrons, which modulate the lattice
Sodium ion batteries
structure with the shrinkage of TMO2 sheets and expansion of Na layer spacing to enhance the Na+ diffusion
kinetics. Co substitution can raise high voltage region to tune the cut-off voltage up to 4.3 V and activate oxy-
gen redox to weaken irreversible O2 loss. And Cu substitution can inhibit the O2 loss and suppress the voltage
decay via the interaction between Cu 3d and O 2p orbitals. The P2-type Na0.67 Mn0.6 Ni0.2 Cu0.1 Co0.1 O2 cathode
induced by the complementary effect can boost long cycling life (82.07% capacity retention after 500 cycles) and
remarkable rate capability under high upper cut-off voltage in half-cell. Furthermore, the full cells also exhibit
outstanding rate capability with a high discharge capacity of 62.6 mAh g–1 at 20 C.

1. Introduction
Sodium-ion batteries (SIBs) open up a great possibility for practical
application to replace current lithium-ion batteries (LIBs) due to their
similar “rocker chair” principle with LIBs, earth-abundant and low-cost
sodium source as well as universal cheap Al collector for both cathode
and anode [1-4]. The layered Mn-based oxide cathode promises great
potential as Na+ host materials because of abundant resource, low cost
and environmental friendliness of Mn species, simple preparation pro-
cess and high specific capacity [2,5-8]. According to sodium ion oc-
cupying sites and O sequence, the layered Mn-based oxide cathode is
commonly divided into two categories: P2- and O3-type oxide cathode
[4,9]. P2-type cathode holds much greater advantages in phase transi-
tion, air stability, ion conductivity and Na+ diffusion kinetics compared
with O3-type one [10,11]. Particularly, like Li-rich cathode in LIBs, P2-
type Mn-based oxide cathode can generally provide high specific ca-
pacity through the anionic redox reaction with the cut-off voltage be-
yond 4.2 V [12-21]. However, along with the reversible anionic redox
processes (O2– /O2 n– ), the irreversible O2 loss is inevitable that could
bring about unstable structure evolution and particle cracking, which
can cause cycling stability deterioration and voltage hysteresis aggrava-
tion [16]. Besides, P2-type Mn-based oxide cathode is also confronted
with Jahn-teller effect, interface instability and phase transition under
high voltage [11,19,22-31].
Heteroatom substitution, such as Li, Mg, Zn, Ti, Al etc., has been
widely employed to resolve the aforementioned issues, which can
bring forward tailorable compositional diversity and complex struc-
tural chemistry to adjust crystal structure, Na+ ion conductivity,
phase transition and the irreversible oxygen redox to ensure tunable
electrochemical performance [25,32-43]. Xiao et al. proposed that
Na2/3 Ni1/6 Mn2/3 Cu1/9 Mg1/18 O2 cathode with the optimal morphology
and structure modulation could display excellent electrochemical per-
formance with tailoring voltage below 4.2 V [38]. Kong et al. reported
that Cu/Mg co-doping in P2-Na0.67 Mn0.75 Ni0.25 O2 can modify the lat-
tice structure and improve the reversibility of anionic redox, but the cy-
cling stability also depends on clipping voltage below 4.2 V [32]. Based
on heteroatom substitution, tailoring voltage does avoid the capacity
fading and voltage decay caused by irreversible oxygen redox, but the

∗
Corresponding authors.
E-mail addresses: yqzhu@bit.edu.cn (Y. Zhu), cbcao@bit.edu.cn (C. Cao).

https://doi.org/10.1016/j.ensm.2021.06.029
Received 15 April 2021; Received in revised form 16 June 2021; Accepted 21 June 2021
Available online 26 June 2021
2405-8297/© 2021 Elsevier B.V. All rights reserved.
Q. Zhao, F.K. Butt, M. Yang et al.
reversible specific capacity is decreased to a greater extent. In addition,
Hou et al. introduced electrochemically active Co substitution towards
P2-Na2/3 [Ni0.3 Co0.1 Mn0.6 ]O2 cathode to suppress P2-O2 phase transi-
tion. Wang et al. showed electroactive Cu substituted high-voltage P2-
Na2/3 Ni1/3 Mn2/3 O2 cathode to suppress P2-O2 phase transition [44].
Obviously, the compositional diversity potentially can promise new av-
enues in functioning material properties. However, there are still great
challenges to build the various composition design with detailed mech-
anism analysis and superior cyclic stability under upper cut-off voltage,
especially with regard to the oxygen redox.
Herein, dual substitution with Cu for Mn and Co for Ni were con-
structed to optimize different TMO2 sheets of lattice structure, resulting
in the shrinkage of TMO2 sheets and expansion of Na layers. Further-
more, the high-voltage P2-Na2/3 [Mn-Ni-Cu-Co]O2 cathode was chose to
probe the complementary effect of electrochemically active Cu and Co
substitution on the oxygen redox chemistry. Dual substitution can in-
hibit the unwanted phase transition and reduce the Na+ migration en-
ergy barrier. Optimal Co substitution can raise high voltage region to
control the cut-off voltage up to 4.3 V and activate oxygen redox to
weaken irreversible O2 loss. Cu substitution can introduce the interac-
tion between Cu 3d and O 2p orbitals to suppress the voltage decay
and O2 loss. The P2-Na0.67 Mn0.6 Ni0.2 Cu0.1 Co0.1 O2 cathode induced by
complementary effect of dual Cu and Co substitution can boost a long
cycling life with 82.07% capacity retention after 500 cycles at 10 C and
remarkable rate capability with the discharge capacity of 61.2 mAh g–1
at 20 C in half-cell. Furthermore, the full cell assembled by the prepared
cathode and hard carbon anode can deliver a discharge capacity of 62.6
mAh g–1 at 20 C as well as specific energy density of ca. 208 Wh Kg–1
at 0.5 C based on the whole mass of cathode and anode.
2. Results and discussion
To determine the precise content of the elements in the P2-Na2/3 [Mn-
Ni-Cu-Co]O2 system, optical emission spectroscopy (ICP-OES) is carried
out and the results are illustrated in table S1. The XRD Rietveld re-
finements of dual Cu and Co substituted Na2/3 [Mn-Ni-Cu-Co]O2 cath-
ode are exhibited in Fig. 1a, b and S1. The XRD patterns of all sam-
ples can be indexed to hexagonal P2-type layered structure (the space
group: P63 /mmc) with slight phase impurity [43]. The schematic dia-
grams of crystal structure for Na0.67 Mn0.6 Ni0.2 Cu0.1 Co0.1 O2 (CuCo-NM)
are displayed in Fig. 1c, which is formed by alternating TMO2 sheets
and Na layers with an ABBA oxygen stacking sequence. The detailed
lattice parameters and the corresponding calculation results are pre-
sented in table S2–6. Regularly, with adjusting the ratios of Cu and Co
substituted amount, the lattice parameter a gradually decrease, while c
and d-spacing of Na layer increase. It also means that both Co and Cu
ions successfully enter the P2-type structure and occupy the octahedral
sites of TMO2 sheets. In addition, the shrinkage of TMO2 sheets and ex-
pansion of Na layers along the C axis are most likely agreement with
the smaller ionic radii of Co3+ (0.545 Å) versus Ni2+ (0.69 Å). In ad-
dition, ccompared with CuCo-NM, the Ni 2p peaks for CuCo3 –NM shift
to higher binding energy because of stronger electro-negativity of Co3+
than Ni2+ in figure S2, further indicating that Co3+ partially substitutes
Ni2+ . The morphologic structure was characterized by SEM in Fig. 1d
and S3. The CuCo-NM material is composed of flake-like primary parti-
cles with sharp edges and multilayer oriented stacking structure. On the
contrary, the Na0.67 Mn0.6 Ni0.4 O2 (NM) material particles are smaller
and rob-like. Distinctly, dual Cu and Co substitution promotes crystal
growth to enhance the structure stability, which is consistent with the
TEM image in Fig. 1e. The SAED pattern further displays clearly diffrac-
tion spots consistent with the hexagonal layered P2-type structure along
the [001] axis in Fig. 1f. The adjacent lattice fringe space is measured
to be around 0.247 nm for HRTEM image in Fig. 1g, which can refer
to the (001) plane of hexagonal layered structure. STEM image and the
corresponding EDX mapping indicate that all elements including Cu and
Co are uniformly distributed in Fig. 3h and 3i.
582
Energy Storage Materials 41 (2021) 581–587
CV curves at the scan of 0.1 mV s–1 and the galvanostatic charge and
discharge voltage curves with a voltage range from 2 to 4.5 V were dis-
played in Fig. 2. The multiple redox couples emerge over the whole volt-
age range, which is consistent with voltage platforms of voltage plots at
0.2C. Among them, the weak voltage platform below 3 V are assigned
by Mn3+ /Mn4+ redox reaction. The voltage platforms between 3 and
4.1 V are mainly related to the redox couples of Cu2+/3+ , Ni2+/4+ and
occurred Na+ /vacancy ordering [28,45]. The anionic oxygen redox re-
action that meets charge compensation mechanism can be responsible
for the long and flat voltage platforms beyond 4.2 V. It can be found
that dual Cu and Co substitution significantly reduce the polarization
of the redox pairs to enhance the electrochemical activity. The volt-
age plots further reveal that dual substitution is beneficial to yielding
the higher initial coulombic efficiency and mitigating the irreversible
capacity loss to a great extent. Remarkably, the redox reaction pairs be-
yond 4.3 V regularly change and shift toward higher voltage region via
adjusting the Co content. In addition, XPS spectrums of the Co 2p and
O 1 s for CuCo3 –NM sample are tested after charging to 4.2 and 4.5 V,
as shown in figure S4. Among them, Co 2p peaks shift to higher binding
energy with charging from 4.2 to 4.5 V, indicating that the Co3+/4+ re-
dox occurs at the high-voltage region; Meanwhile, a pronounced peak
emerges at 530.5 eV for O 1 s spectrums owing to peroxo-like species
(O2 2− ), indicating that the anionic redox also occurs at the high-voltage
region. Thus, it can be seen that for CuCo3 –NM sample not only an-
ion oxygen participates in redox, but also Co3+/4+ redox. As a result,
Co substitution can promote the reversible anionic redox and achieve
tunable high cut-off voltage to limit the irreversible O2 loss during the
desodiation/sodiation.
Electrochemical sodium storage behaviors of P2-Na2/3 (Mn-Ni-Cu-
Co)O2 cathode induced by the dual Cu and Co substitution were eval-
uated via tailoring the cut-off high voltage below 4.5 V. As displayed
in Fig. 3a and S5–7, Even though the redox couple between 4.2 and
4.3 V is partly restrained, the irreversible O2 loss is also limited. CuCo-
NM electrode deliverers the initial discharge capacity of 128 mAh g–1
with the specific energy density of 420 Wh Kg–1 . In Fig. 3b and S8, rate
capability between 0.2 C and 20 C demonstrates that optimal Co substi-
tution leads to the improvement of sodium storage properties with the
discharge capacity of 77.7 mAh g–1 at 20 C for CuCo3 –NM. After 100
cycles, CuCo-NM still can deliver higher capacity. But the correspond-
ing mid-point voltage reveal that CuCo3 –NM electrode appear serious
voltage decay when the current density recovers to 0.2C in figure S9.
In contrast, the optimal Cu substitution can obviously suppress the volt-
age hysteresis. In the long run, equivalent dual-substitution fully inte-
grates the complementary advantages of Co and Cu substitution to bring
superior electrochemical properties. CuCo-NM electrode yields high re-
versible specific capacity of 76.4 mAh g–1 and 61.2 mAh g–1 at 10 and 20
C, respectively. Compared with the Cu3 Co-NM and CuCo3 –NM in figure
S10 and S11, the outstanding capacity retention of 82.07% is obtained
after 500 cycles at 10 C with stable coulombic efficiency for CuCo-NM
electrode in Fig. 3c. These superior electrochemical performance could
be attributed to improved Na+ diffusion kinetics that was obtained by
CV curves under different sweep rates between 0.1 and 1 mV s–1 in
Fig. 3d. Combining the corresponding linear fitting of peak current ver-
sus square root of the scan rate with the Randles-Sevcik equation in
Fig. 3e, the calculated Na+ diffusion coefficient (DNa+ ) for the oxidation
peak and the reduction peak is 6.59 × 10–11 and 4.916 × 10–11 cm2
s–1 , which is higher than the NM materials in figure S12 [46]. In order
to better understand the diffusion dynamics in detail, the Na+ kinetic
diffusion coefficient (DNa+ ) is also obtained by GITT as a reliable char-
acterization technique. The typical GITT curve of CuCo-NM electrode in
the second cycle is dispiced in Fig. 3f. DNa+ can be determined through
4 nm Vm 2 ΔEs 2
the equation: DNa+ = πτ ( A ) ( ΔE ) , Where nm , Vm , A stand for the
τ
number of molar, the molar volume and the area of electrode [47]. Cor-
respondingly, the average DNa+ is around 2.81 × 10–10 cm2 s–1 , which
is basically consistent with the result obtained by CV plots, as shown in
Q. Zhao, F.K. Butt, M. Yang et al.
Fig. 1. The obtained XRD Rietveld refinement of NM (a) and CuCo-NM (b). Schematic diagram of TMO2 sheets and Na layers distance for P2-type structure (c), SEM
image (d), TEM image (e), SAED pattern (f), HRTEM image with an inset of FFT image (g), STEM image (h), EDX mapping images (i) of CuCo-NM.
Fig. 3g. Furthermore, the Na+ diffusion coefficients in the current lit-
eratures are compared in table S7 [30,37,38,48-51]. Finally, taking the
practical application into consideration, the full-cell assembling CuCo-
NM as cathode with hard carbon as anode were performed with the
voltage ranging from 1.9 to 4.2 V. The electrochemical performance of
hard carbon in Na half-cell is shown in figure S13. Schematic diagram
and the voltage plots at 0.2 C with hard carbon and Na metal are given
in Fig. 3h and 3i. The full cell can deliver the high discharge capacity of
104 mAh g–1 with the specific energy density of about 208 Wh Kg–1 at
0.5 C in figure S14. CuCo-NM still yields the outstanding rate capability
tested from 0.5 to 20 C in Fig. 3j. The discharge specific capacity at 20C
is 62.6 mAh g–1 . Remarkably, when current density is switched to 1C
again, the discharge capacity is still as high as 73.3 mAh g–1 after 200
cycles.
XPS was used to study the bonding interaction and valence state
change. Figure S15 displays the survey scans of all samples. In fig-
ure S16, the double peaks of O1s spectrums located at 529.5 and
531.6 eV represent lattice oxygen and surface deposited oxygen as well
as Na2 CO3 , respectively [52-54]. As is displayed in table S8, the ratio of
lattice oxygen for CuCo-NM sample is higher, indicating that the bond
energy between oxygen and transition metals is stronger and the lattice
structure is relatively more stable. In addition, Mn-based oxide cath-
ode generally suffer from undesirable Jahn-Teller effect triggered by
Mn3+ . CuCo-NM material obviously has higher Mn average oxidation
state, which contribute to suppress the Jahn-Teller effect [55,56]. Inter-
estingly, the Ex-situ XPS spectrums of the anion (O1s) and cation (Ni2p
and Mn2p) in different charging and discharging states were performed.
When charged to 4.3 V, a pronounced peak emerges at 530.5 eV for O1s
spectrums of CuCo-NM corresponding to peroxo-like species (O2 2− ) in
583
Energy Storage Materials 41 (2021) 581–587
Fig. 4a, confirming that the anionic redox occurs at the high-voltage
region. Even at the 10th fully charged state, the distinct peroxo-like
species for CuCo-NM material still exist to a certain extent. These results
prove that dual Cu and Co substitution can not only promote the bond-
ing interaction between oxygen and transition metals, but also benefit
to improve the reversibility of anionic oxygen redox at high voltage. In
addition, the Ex-situ XPS spectrums of Ni2p suggest that a small amount
of Ni2+ is oxidized to Ni4+ during desodiation process, the similar result
is also obtained even at the 10th charged state in Fig. 4b. And the ra-
tio of peroxo signal at the 10th charge seems larger than that at the
1st charge, which may be attributed to the incomplete electrochemical
reaction of the material under the first charging to 4.3 V. The average
oxidation state of Mn has a slight change during the charging and dis-
charging process in Fig. 4c, confirming that dual substitution suppresses
the Jahn-Teller effect to a certain extent. In view of these results, the
dual Cu and Co substitution can enhance the structure stability and sup-
press the irreversible oxygen release, resulting in a long cycle life for
high-voltage layered P2-type Mn-based oxide cathode. In particular, Cu
elements for CuCo-NM are electrochemically active for P2-Na2/3 (Mn-
Ni-Cu-Co)O2 cathode in figure S16.
The Ex-situ XRD patterns and corresponding schematic diagram of
crystal structural change during Na+ deintercalation at 0.2C were car-
ried out. In Fig. 4d, as more Na ions are extracted, the (002) and (004)
peaks conversely shift to lower angles with lower crystallinity and grad-
ually disappear as well as accompany with the decrease of peaks inten-
sity, implying the formation of P2’’ phase. Such phase transition is detri-
mental for the structural stability and tends to cause particle cracking.
Expectedly, a notable different phase evolution is observed for CuCo-NM
electrode during Na+ deintercalation in Fig. 4e. Both (002) and (004)
Q. Zhao, F.K. Butt, M. Yang et al. Energy Storage Materials 41 (2021) 581–587

Fig. 2. CV curves at the scan of 0.1 mV s − 1 (a) and the corresponding voltage plots (b) of NM, Na0.67 Mn0.6 Ni0.2 Cu0.15 Co0.05 O2 (Cu3 Co-NM), CuCo-NM,
Na0.67 Mn0.6 Ni0.2 Cu0.05 Co0.15 O2 (CuCo3 –NM) between 2 and 4.5 V at 0.2C.

Fig. 3. The voltage plots at 0.2C of CuCo-NM (a), rate capability at different current density (b), long cycling performance and coulombic efficiency at 10C for
CuCo-NM (c), CV curves and the corresponding linear fitting plots about peak current versus square root of the scan rate of CuCo-NM (d and e), GITT curves and
the calculated Na+ diffusion coefficient of CuCo-NM (f and g), schematic diagram of the full cell (h), the voltage plots (i) at 0.2C, the rate capability and coulombic
efficiency (j).

584
Q. Zhao, F.K. Butt, M. Yang et al.
Fig. 4. Ex-situ XPS spectrums of O 1 s (a), Ni 2p (b) and Mn 2p (c) of CuCo-NM, Ex-XRD patterns and the corresponding voltage plot at 0.2C of NM (d) and CuCo-NM
(e).
peaks show higher crystallinity without detecting diffraction peaks of
the P2’’ phase during the charged to 4.3 V, indicating that the dual Cu
and Co substitution can enhance structural stability and inhibit phase
transition. The Ex-situ Reman spectra of CuCo-NM was used to further
verify structural stability induced by dual Cu and Co substitution in fig-
ure S18. Both the main two peaks located at 600 cm−1 and 480 cm−1
represent A1g and Eg attributed to the asymmetrical TM-O bond and the
bending vibration O-TM-O bond. The chemical shifts recover the pris-
tine state after Na+ insertion. SEM image after 100 cycles in figure S19a
indicates that the dual Cu and Co substitution suppress layer slippage
and particle cracking caused by the volume strain. Besides, the flake-like
primary particles are still maintained. TEM image and SAED pattern of
CuCo-NM also explain that the dual Cu and Co substitution can achieve
excellent structure stability in figure S19b-d.
First principles calculation was carried out to unveil the underly-
ing reaction mechanism of dual Cu and Co substitution. Density func-
tional theory (DFT) in Fig. 5a and S20 indicates that Co and Cu atoms
occupy the sites of NiO6 and MnO6 octahedra, respectively, forming
the stable CoO6 and CuO6 octahedra. Meanwhile, the bond valence
energy landscape (BVEL) method simulates an optimum Na+ migra-
tion pathways from crystallographic Na1 to Na2 sites to evaluate the
Na+ diffusion dynamics in Fig. 5a and S21. As shown in Fig. 5b, the
lower Na+ migration energy barrier of Na0.66 Mn0.6 Ni0.2 Cu0.1 Co0.1 O2
compared with Na0.66 Mn0.6 Ni0.4 O2 prove that the dual Cu and Co sub-
stitution could facilitate Na+ migration and offer facile ionic diffusion
585
Energy Storage Materials 41 (2021) 581–587
channels. This result is further verified by EIS under the charged state
of 4.3 V in figure S22. According to the density of states (DOS) of
Na0.66-x Mn0.6 Ni0.2 Cu0.1 Co0.1 O2 (x = 0.00, 0.60), a substituted energy
level triggered by dual Cu and Co substitution appears near the Fermi
level in Fig. 5c, 5e and S23, resulting in a decrease in band gap and
an increase in electronic conductivity. More impressively, the dual Cu
and Co substitution not only reduces the energy level difference be-
tween Mn3+ and Mn4+ to inhibit the Jahn-Teller effect, but also broad-
ens O 2p orbital to confirm the presence of oxygen redox. These re-
sults are fully consistent with the analysis results obtained by the elec-
trochemical analysis, Ex-situ XPS and Ex-situ XRD. When Na is emi-
grated (x = 0.60), the DOS of O 2p orbital increases near the Fermi
level and oxygen redox reaction is facilitated, resulting in the corre-
sponding higher voltage region. And the interaction between the Cu 3d
orbital and O 2p orbital inhibits oxygen loss to suppress the voltage hys-
teresis during the anionic redox progress. In addition, density of states
of Na0.66 Mn0.6 Ni0.2 Cu0.15 Co0.05 O2 and Na0.66 Mn0.6 Ni0.2 Cu0.05 Co0.15 O2
further are carried out, as shown in figure S24. It can be seen that the
interaction with the 2p orbital of O is more obvious and the band gap
disappears with the Cu concentration increase. Furthermore, Co sub-
stituted energy level appears at the conduction band position, result-
ing in an increase in electronic conductivity. In a nutshell, the dual
Cu and Co substitution is responsible for the prominent rate capabil-
ity and cycling stability of the high-voltage layered Mn-based oxide
cathode.
Q. Zhao, F.K. Butt, M. Yang et al.
Fig. 5. First principles computations: schematic diagram of crystal structure for Na migration path (a), the corresponding migration energy barriers (b), density
of states of Na0.66-x Mn0.6 Ni0.4 O2 and the corresponding band structure of Na0.66 Mn0.6 Ni0.4 O2 (c and d), density of states of Na0.66-x Mn0.6 Ni0.2 Cu0.1 Co0.1 O2 and the
corresponding band structure of Na0.66 Mn0.6 Ni0.2 Cu0.1 Co0.1 O2 (e and f).
Conclusion
In summary, through detailed physical characterizations, electro-
chemical analysis and theoretical calculations, comprehensive analysis
of the electrochemical sodium storage behaviors for P2-Na2/3 (Mn-Ni-
Cu-Co)O2 cathode induced by dual Cu and Co substitution has been
clarified. Dual substitution with Cu for Mn and Co for Ni have mutu-
ally reinforcing functions, which can be summarized as follows: 1) dual
substitution can tune the crystal structure with the shrinkage of TMO2
sheets and expansion of Na layers, resulting in enhancing the Na+ dif-
fusion dynamics; 2) optimate Co substitution improves the high voltage
region to bring the tailoring cut-off voltage up to 4.3 V; 3) dual Cu and
Co substitution suppresses the phase transition and Jahn-Teller effect;
4) DFT results uncover that dual Cu and Co substitution adjust local
electronic structure to reduce the Na+ migration energy barrier; 5) dual
Cu and Co substitution broaden the O 2p orbital to lead to an increase
in the oxygen redox reaction; 6) the interaction of Cu 3d orbital and O
2p orbital enhance the reversibility of anionic redox reaction to inhibit
the voltage hysteresis. The dual Cu and Co substitution strategy bring
forward an avenue for practical application of high-energy-density SIBs.
Credit author statement
Quanqing Zhao: conducting experiments and draft manuscript. Fa-
heem K. Butt: some data analysis. Min Yang and Zefeng Guo: theoretical
simulation. Xiuyun Yao, data measurements. Maximiliano Jesus Moreno
Zapata: some data analysis. Youqi Zhu: revise manuscript. Xilan Ma: re-
vise manuscript. Chuanbao Cao: final manuscript, supervisor
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
586
Energy Storage Materials 41 (2021) 581–587
Data availability
Supporting information.
Acknowledgments
This work was supported by the National Natural Science Foundation
of China (No. 21371023) and Beijing Institute of Technology Research
Fund Program for Young Scholars (3090012221914).
Supplementary materials
Supplementary material associated with this article can be found, in
the online version, at doi:10.1016/j.ensm.2021.06.029.
References
[1] P.K. Nayak, L. Yang, W. Brehm, P. Adelhelm, From lithium-ion to sodium-ion bat-
teries: advantages, challenges, and surprises, Angew. Chem. Int. Ed. 57 (1) (2018)
102–120.
[2] N. Ortiz-Vitoriano, N.E. Drewett, E. Gonzalo, T. Rojo, High performance mangane-
se-based layered oxide cathodes: overcoming the challenges of sodium ion batteries,
Energy Environ. Sci. 10 (5) (2017) 1051–1074.
[3] N. Yabuuchi, K. Kubota, M. Dahbi, S. Komaba, Research development on sodium-ion
batteries, Chem. Rev. 114 (23) (2014) 11636–11682.
[4] Q. Liu, Z. Hu, M. Chen, C. Zou, H. Jin, S. Wang, S.L. Chou, S.X. Dou, Recent progress
of layered transition metal oxide cathodes for sodium-ion batteries, Small 15 (32)
(2019) e1805381.
[5] E. Gonzalo, M. Zarrabeitia, N.E. Drewett, J.M. López del Amo, T. Rojo, Sodium man-
ganese-rich layered oxides: potential candidates as positive electrode for Sodium-ion
batteries, Energy Storage Mater. 34 (2021) 682–707.
[6] Y. Xiao, P.-.F. Wang, Y.-.X. Yin, Y.-.F. Zhu, X. Yang, X.-.D. Zhang, Y. Wang,
X.-.D. Guo, B.-.H. Zhong, Y.-.G. Guo, A layered-tunnel intergrowth structure for high-
-performance sodium-ion oxide cathode, Adv. Energy Mater. 8 (22) (2018).
[7] Q. Zhao, Z. Guo, L. Wang, Y. Wu, F.K. Butt, Y. Zhu, X. Xu, X. Ma, C. Cao, Mo-mod-
ified P2-type manganese oxide nanoplates with an oriented stacking structure and
exposed {010} active facets as a long-life sodium-ion battery cathode, ACS Appl.
Mater. Interfaces 11 (34) (2019) 30819–30827.
Q. Zhao, F.K. Butt, M. Yang et al.
[8] N. Yabuuchi, M. Kajiyama, J. Iwatate, H. Nishikawa, S. Hitomi, R. Okuyama, R. Usui,
Y. Yamada, S. Komaba, P2-type Na(x) [Fe(1/2) Mn(1/2) ]O2 made from earth-abundant
elements for rechargeable Na batteries, Nat. Mater. 11 (6) (2012) 512–517.
[9] S. Guo, P. Liu, H. Yu, Y. Zhu, M. Chen, M. Ishida, H. Zhou, A layered P2- and O3-type
composite as a high-energy cathode for rechargeable sodium-ion batteries, Angew.
Chem. Int. Ed. 54 (20) (2015) 5894–5899.
[10] M.H. Han, E. Gonzalo, G. Singh, T. Rojo, A comprehensive review of sodium layered
oxides: powerful cathodes for Na-ion batteries, Energy Environ. Sci. 8 (1) (2015)
81–102.
[11] K. Zhang, D. Kim, Z. Hu, M. Park, G. Noh, Y. Yang, J. Zhang, V.W. Lau, S.L. Chou,
M. Cho, S.Y. Choi, Y.M. Kang, Manganese based layered oxides with modulated
electronic and thermodynamic properties for sodium ion batteries, Nat. Commun.
10 (1) (2019) 5203.
[12] G. Singh, N. Tapia-Ruiz, J.M. Lopez del Amo, U. Maitra, J.W. Somerville, A.R. Arm-
strong, J. Martinez de Ilarduya, T. Rojo, P.G. Bruce, High voltage Mg-doped
Na0.67 Ni0.3-x Mgx Mn0.7 O2 (x = 0.05, 0.1) Na-ion cathodes with enhanced stability
and rate capability, Chem. Mater. 28 (14) (2016) 5087–5094.
[13] C. Ma, J. Alvarado, J. Xu, R.J. Clement, M. Kodur, W. Tong, C.P. Grey, Y.S. Meng,
Exploring oxygen activity in the high energy P2-type Na0.78 Ni0.23 Mn0.69 O2 cathode
material for Na-ion batteries, J. Am. Chem. Soc. 139 (13) (2017) 4835–4845.
[14] T. Chen, W. Liu, H. Gao, Y. Zhuo, H. Hu, A. Chen, J. Zhang, J. Yan, K. Liu, A P2-type
Na0.44 Mn0.6 Ni0.3 Cu0.1 O2 cathode material with high energy density for sodium-ion
batteries, J. Mater. Chem. A 6 (26) (2018) 12582–12588.
[15] Q. Liu, Z. Hu, M. Chen, C. Zou, H. Jin, S. Wang, Q. Gu, S. Chou, P2-type
Na2/3 Ni1/3 Mn2/3 O2 as a cathode material with high-rate and long-life for sodium
ion storage, J. Mater. Chem. A 7 (15) (2019) 9215–9221.
[16] Y. Zhang, M. Wu, J. Ma, G. Wei, Y. Ling, R. Zhang, Y. Huang, Revisiting the
Na2/3 Ni1/3 Mn2/3 O2 cathode: oxygen redox chemistry and oxygen release suppres-
sion, ACS Cent. Sci. 6 (2) (2020) 232–240.
[17] L. Yang, Z. Liu, S. Liu, M. Han, Q. Zhang, L. Gu, Q. Li, Z. Hu, X. Wang, H.-.J. Lin,
C.-.T. Chen, J.-.M. Chen, S.-.C. Haw, Z. Wang, L. Chen, Superiority of native vacan-
cies in activating anionic redox in P2-type Na2/3 [Mn7/9 Mg1/9□1/9 ]O2 , Nano Energy
78 (2020) 105172.
[18] J. Zhang, F. Cheng, S. Chou, J. Wang, L. Gu, H. Wang, H. Yoshikawa, Y. Lu, J. Chen,
Tuning oxygen redox chemistry in Li-rich Mn-based layered oxide cathodes by mod-
ulating cation arrangement, Adv. Mater. 31 (42) (2019) e1901808.
[19] A. Konarov, H.J. Kim, J.H. Jo, N. Voronina, Y. Lee, Z. Bakenov, J. Kim, S.T. Myung,
High-voltage oxygen-redox-based cathode for rechargeable sodium-ion batteries,
Adv. Energy Mater. 10 (24) (2020) 2001111.
[20] R.A. House, U. Maitra, M.A. Perez-Osorio, J.G. Lozano, L. Jin, J.W. Somerville,
L.C. Duda, A. Nag, A. Walters, K.J. Zhou, M.R. Roberts, P.G. Bruce, Superstructure
control of first-cycle voltage hysteresis in oxygen-redox cathodes, Nature 577 (7791)
(2020) 502–508.
[21] R. Sharpe, R.A. House, M.J. Clarke, D. Forstermann, J.J. Marie, G. Cibin, K.J. Zhou,
H.Y. Playford, P.G. Bruce, M.S. Islam, Redox chemistry and the role of trapped molec-
ular O2 in Li-rich disordered rocksalt oxyfluoride cathodes, J. Am. Chem. Soc. 142
(52) (2020) 21799–21809.
[22] J. Alvarado, C. Ma, S. Wang, K. Nguyen, M. Kodur, Y.S. Meng, Improvement of the
cathode electrolyte interphase on P2-Na2/3 Ni1/3 Mn2/3 O2 by atomic layer deposition,
ACS Appl. Mater. Interfaces 9 (31) (2017) 26518–26530.
[23] J.H. Jo, J.U. Choi, A. Konarov, H. Yashiro, S. Yuan, L. Shi, Y.-.K. Sun, S.-.T. Myung,
Sodium-ion batteries: building effective layered cathode materials with long-term
cycling by modifying the surface via sodium phosphate, Adv. Funct. Mater. 28 (14)
(2018) 1705968.
[24] Q. Zhao, F.K. Butt, Z. Guo, L. Wang, Y. Zhu, X. Xu, X. Ma, C. Cao, High-voltage
P2-type manganese oxide cathode induced by titanium gradient modification for
sodium ion batteries, Chem. Eng. J. 403 (2021) 126308.
[25] P.F. Wang, Y. You, Y.X. Yin, Y.S. Wang, L.J. Wan, L. Gu, Y.G. Guo, Suppressing
the P2-O2 Phase Transition of Na0.67 Mn0.67 Ni0.33 O2 by Magnesium Substitution for
Improved Sodium-Ion Batteries, Angew. Chem. Int. Ed. 55 (26) (2016) 7445–7449.
[26] P. Hou, F. Li, Y. Wang, J. Yin, X. Xu, Mitigating the P2-O2 phase transition of high-
-voltage P2-Na2/3 [Ni1/3 Mn2/3 ]O2 cathodes by cobalt gradient substitution for high-
-rate sodium-ion batteries, J. Mater. Chem. A 7 (9) (2019) 4705–4713.
[27] D. Tie, G. Gao, F. Xia, R. Yue, Q. Wang, R. Qi, B. Wang, Y. Zhao, Modulating the
interlayer spacing and Na(+) /vacancy disordering of P2-Na0.67 MnO2 for fast diffusion
and high-rate sodium storage, ACS Appl. Mater. Interfaces 11 (7) (2019) 6978–6985.
[28] Q. Yang, P.F. Wang, J.Z. Guo, Z.M. Chen, W.L. Pang, K.C. Huang, Y.G. Guo, X.L. Wu,
J.P. Zhang, Advanced P2-Na2/3 Ni1/3 Mn7/12 Fe1/12 O2 cathode material with sup-
pressed P2-O2 phase transition toward high-performance sodium-ion battery, ACS
Appl. Mater. Interfaces 10 (40) (2018) 34272–34282.
[29] K. Jiang, X. Zhang, H. Li, X. Zhang, P. He, S. Guo, H. Zhou, Suppressed the high–
voltage phase transition of P2-type oxide cathode for high-performance sodium-ion
batteries, ACS Appl. Mater. Interfaces 11 (16) (2019) 14848–14853.
[30] Y. Liu, Q. Shen, X. Zhao, J. Zhang, X. Liu, T. Wang, N. Zhang, L. Jiao, J. Chen,
L.Z. Fan, Hierarchical engineering of porous P2-Na2/3 Ni1/3 Mn2/3 O2 nanofibers as-
sembled by nanoparticles enables superior sodium-ion storage cathodes, Adv. Funct.
Mater. 30 (6) (2019) 1907837.
[31] N. Tapia-Ruiz, W.M. Dose, N. Sharma, H. Chen, J. Heath, J.W. Somerville, U. Maitra,
M.S. Islam, P.G. Bruce, High voltage structural evolution and enhanced Na-ion dif-
fusion in P2-Na2/3 Ni1/3-x Mgx Mn2/3 O2 (0≤x≤0.2) cathodes from diffraction, electro-
chemical and ab initio studies, Energy Environ. Sci. 11 (6) (2018) 1470–1479.
[32] W. Kong, R. Gao, Q. Li, W. Yang, J. Yang, L. Sun, X. Liu, Simultaneously tuning
cationic and anionic redox in a P2-Na0.67 Mn0.75 Ni0.25 O2 cathode material through
synergic Cu/Mg co-doping, J. Mater. Chem. A 7 (15) (2019) 9099–9109.
[33] Y. Wen, J. Fan, C. Shi, P. Dai, Y. Hong, R. Wang, L. Wu, Z. Zhou, J. Li, L. Huang,
S.-.G. Sun, Probing into the working mechanism of Mg versus Co in enhancing the
587
Energy Storage Materials 41 (2021) 581–587
electrochemical performance of P2-Type layered composite for sodium-ion batteries,
Nano Energy 60 (2019) 162–170.
[34] M.S. Chae, H.J. Kim, J. Lyoo, R. Attias, Y. Gofer, S.T. Hong, D. Aurbach, Anoma-
lous sodium storage behavior in Al/F dual-doped P2-type sodium manganese oxide
cathode for sodium-ion batteries, Adv. Energy Mater. 10 (43) (2020).
[35] T. Chen, W. Liu, Y. Zhuo, H. Hu, M. Zhu, R. Cai, X. Chen, J. Yan, K. Liu, Single-phase
P2-type layered oxide with Cu-substitution for sodium ion batteries, J. Energy Chem.
43 (2020) 148–154.
[36] Y. Huang, Z. Yan, W. Luo, Z. Hu, G. Liu, L. Zhang, X. Yang, M. Ou, W. Liu,
L. Huang, H. Lin, C.-.T. Chen, J. Luo, S. Li, J. Han, S. Chou, Y. Huang, Vital-
ization of P2–Na2/3 Ni1/3 Mn2/3 O2 at high-voltage cyclability via combined struc-
tural modulation for sodium-ion batteries, Energy Storage Mater. 29 (2020) 182–
189.
[37] K. Liu, S. Tan, J. Moon, C.J. Jafta, C. Li, T. Kobayashi, H. Lyu, C.A. Bridges, S. Men,
W. Guo, Y. Sun, J. Zhang, M.P. Paranthaman, X.G. Sun, S. Dai, Insights into the
enhanced cycle and rate performances of the F-substituted P2-type oxide cathodes
for sodium-ion batteries, Adv. Energy Mater. 10 (19) (2020) 2000135.
[38] Y. Xiao, Y.F. Zhu, H.R. Yao, P.F. Wang, X.D. Zhang, H. Li, X. Yang, L. Gu, Y.C. Li,
T. Wang, Y.X. Yin, X.D. Guo, B.H. Zhong, Y.G. Guo, A stable layered oxide cathode
material for high-performance sodium-ion battery, Adv. Energy Mater. 9 (19) (2019)
1803978.
[39] Q. Wang, K. Jiang, Y. Feng, S. Chu, X. Zhang, P. Wang, S. Guo, H. Zhou, P2-type
layered Na0.75 Ni1/3 Ru1/6 Mn1/2 O2 cathode material with excellent rate performance
for sodium-ion batteries, ACS Appl. Mater. Interfaces 12 (35) (2020) 39056–39062.
[40] D. Pahari, S. Puravankara, On controlling the P2-O2 phase transition by optimal Ti–
substitution on Ni- site in P2-type Na0.67 Ni0.33 Mn0.67 O2 (NNMO) cathode for Na-ion
batteries, J. Power Sources 455 (2020) 227957.
[41] Q.C. Wang, J.K. Meng, X.Y. Yue, Q.Q. Qiu, Y. Song, X.J. Wu, Z.W. Fu, Y.Y. Xia,
Z. Shadike, J. Wu, X.Q. Yang, Y.N. Zhou, Tuning P2-structured cathode material
by Na-site Mg substitution for Na-ion batteries, J. Am. Chem. Soc. 141 (2) (2019)
840–848.
[42] P. Hou, Y. Sun, F. Li, Y. Sun, X. Deng, H. Zhang, X. Xu, L. Zhang, A high energy–
density P2-Na2/3 [Ni0.3 Co0.1 Mn0.6 ]O2 cathode with mitigated P2-O2 transition for
sodium-ion batteries, Nanoscale 11 (6) (2019) 2787–2794.
[43] T. Jin, P.F. Wang, Q.C. Wang, K. Zhu, T. Deng, J. Zhang, W. Zhang, X.Q. Yang,
L. Jiao, C. Wang, Realizing complete solid-solution reaction in high sodium content
P2-type cathode for high-performance sodium-ion batteries, Angew. Chem. Int. Ed.
59 (34) (2020) 14511–14516.
[44] L. Wang, Y.-.G. Sun, L.-.L. Hu, J.-.Y. Piao, J. Guo, A. Manthiram, J. Ma, A.-.M. Cao,
Copper-substituted Na0.67 Ni0.3-x Cux Mn0.7 O2 cathode materials for sodium-ion bat-
teries with suppressed P2-O2 phase transition, J. Mater. Chem. A 5 (18) (2017)
8752–8761.
[45] Z. Yan, L. Tang, Y. Huang, W. Hua, Y. Wang, R. Liu, Q. Gu, S. Indris, S.L. Chou,
Y. Huang, M. Wu, S.X. Dou, A hydrostable cathode material based on the lay-
ered P2@P3 composite that shows redox behavior for copper in high-rate and
long-cycling sodium-ion batteries, Angew. Chem. Int. Ed. 58 (5) (2019) 1412–
1416.
[46] Y. Xiao, P.F. Wang, Y.X. Yin, Y.F. Zhu, Y.B. Niu, X.D. Zhang, J. Zhang, X. Yu,
X.D. Guo, B.H. Zhong, Y.G. Guo, Exposing {010} active facets by multiple-layer ori-
ented stacking nanosheets for high-performance capacitive sodium-ion oxide cath-
ode, Adv. Mater. (2018) e1803765.
[47] Y.F. Zhu, Y. Xiao, W.B. Hua, S. Indris, S.X. Dou, Y.G. Guo, S.L. Chou, Manipulat-
ing layered P2@P3 integrated spinel structure evolution for high-performance sodi-
um-ion batteries, Angew. Chem. Int. Ed. 59 (24) (2020) 9299–9304.
[48] Y. Dong, S. Di, F. Zhang, X. Bian, Y. Wang, J. Xu, L. Wang, F. Cheng, N. Zhang, Non-
aqueous electrolyte with dual-cations for high-voltage and long-life zinc batteries,
J. Mater. Chem. A 8 (6) (2020) 3252–3261.
[49] Y. Liu, X. Liu, F. Bu, X. Zhao, L. Wang, Q. Shen, J. Zhang, N. Zhang, L. Jiao, L.-.Z. Fan,
Boosting fast and durable sodium-ion storage by tailoring well-shaped Na0.44 MnO2
nanowires cathode, Electrochim. Acta 313 (2019) 122–130.
[50] X.H. Zhang, W.L. Pang, F. Wan, J.Z. Guo, H.Y. Lu, J.Y. Li, Y.M. Xing, J.P. Zhang,
X.L. Wu, P2-Na2/3 Ni1/3 Mn5/9 Al1/9 O2 microparticles as superior cathode material for
sodium-ion batteries: enhanced properties and mechanisam via graphene connec-
tion, ACS Appl. Mater. Interfaces 8 (32) (2016) 20650–20659.
[51] Q. Shen, X. Zhao, Y. Liu, Y. Li, J. Zhang, N. Zhang, C. Yang, J. Chen, Dual-strategy of
cation-doping and nanoengineering enables fast and stable sodium-ion storage in a
novel Fe/Mn-based layered oxide cathode, Adv. Sci. (Weinh) 7 (21) (2020) 2002199.
[52] M. Sathiya, G. Rousse, K. Ramesha, C.P. Laisa, H. Vezin, M.T. Sougrati, M.L. Dou-
blet, D. Foix, D. Gonbeau, W. Walker, A.S. Prakash, M. Ben Hassine, L. Dupont,
J.M. Tarascon, Reversible anionic redox chemistry in high-capacity layered-oxide
electrodes, Nat. Mater. 12 (9) (2013) 827–835.
[53] E. McCalla, A.M. Abakumov, M. Saubanère, D. Foix, E.J. Berg, Gwenaelle Rousse,
M.-.L. Doublet, D. Gonbeau, P. Novák, G.V. Tendeloo, R. Dominko, J.-.M. Tarascon,
Visualization of O-O peroxo-like dimers in high-capacity layered oxides for Li-ion
batteries, Science 350 (2015) 6267.
[54] X. Cao, X. Li, Y. Qiao, M. Jia, F. Qiu, Y. He, P. He, H. Zhou, Restraining oxygen
loss and suppressing structural distortion in a newly Ti-substituted layered oxide
P2-Na0.66 Li0.22 Ti0.15 Mn0.63 O2 , ACS Energy Lett. 4 (10) (2019) 2409–2417.
[55] Q. Zhao, Y. Wu, X. Ma, R. Wang, X. Xu, C. Cao, Mn oxidation state controllable
spinel manganese-based intergrown cathode for excellent reversible lithium storage,
J. Power Sources 359 (2017) 295–302.
[56] Q. Zhao, Z. Guo, Y. Wu, L. Wang, Z. Han, X. Ma, Y. Zhu, C. Cao, Hierarchical flow-
er-like spinel manganese-based oxide nano-sheets for high-performance lithium ion
battery, Sci. China Mater. 62 (10) (2019) 1385–1392.