nanomaterials

Article
Sodium Pre-Intercalation-Based Na3-δ-MnO2@CC for
High-Performance Aqueous Asymmetric Supercapacitor:
Joint Experimental and DFT Study
Anis Ur Rahman 1 , Nighat Zarshad 2 , Wu Jianghua 3 , Muslim Shah 4 , Sana Ullah 4 , Guigen Li 1,5, *,
Muhammad Tariq 6 and Asad Ali 4, *

1 Institute of Chemistry and BioMedical Sciences, School of Chemistry and Chemical Engineering,
Nanjing University, Nanjing 210023, China
2 Department of Polymer Science, School of Chemistry and Chemical Engineering, Southeast University,
Nanjing 211189, China
3 National Laboratory of Solid State Microstructures, Collaborative Innovation Center of Advanced
Microstructures, College of Engineering and Applied Sciences, Nanjing University, Nanjing 210093, China
4 Department of Chemistry, Faculty of Chemical and Life Sciences, Abdul Wali Khan University,
Mardan 23200, Pakistan
5 Department of Chemistry and Biochemistry, Texas Tech University, Lubbock, TX 79409, USA
6 Department of PCB, Bayazid Rokhan Institute of Higher Studies, Kabul 1002, Afghanistan
* Correspondence: [email protected] (G.L.); [email protected] (A.A.)

Abstract: Electrochemical energy storage devices are ubiquitous for personal electronics, electric
Citation: Rahman, A.U.; Zarshad, N.; vehicles, smart grids, and future clean energy demand. SCs are EES devices with excellent power
Jianghua, W.; Shah, M.; Ullah, S.; Li,
density and superior cycling ability. Herein, we focused on the fabrication and DFT calculations
G.; Tariq, M.; Ali, A. Sodium
of Na3 -δ-MnO2 nanocomposite, which has layered MnO2 redox-active sites, supported on carbon
Pre-Intercalation-Based
cloth. MnO2 has two-dimensional diffusion channels and is not labile to structural changes during
Na3 -δ-MnO2 @CC for
intercalation; therefore, it is considered the best substrate for intercalation. Cation pre-intercalation
High-Performance Aqueous
Asymmetric Supercapacitor: Joint
has proven to be an effective way of increasing inter-layered spacing, optimizing the crystal structure,
Experimental and DFT Study. and improving the relevant electrochemical behavior of asymmetric aqueous supercapacitors. We
Nanomaterials 2022, 12, 2856. successfully established Na+ pre-intercalated δ-MnO2 nanosheets on carbon cloth via one-pot hy-
https://doi.org/10.3390/ drothermal synthesis. As a cathode, our prepared material exhibited an extended potential window
nano12162856 of 0–1.4 V with a remarkable specific capacitance of 546 F g−1 (300 F g−1 at 50 A g−1 ). Moreover,
Academic Editors: Jin An Wang,
when this cathode was accompanied by an N-AC anode in an asymmetric aqueous supercapacitor,
Lifang Chen and Luis it illustrated exceptional performance (64 Wh kg−1 at a power density of 1225 W kg−1 ) and incom-
Enrique Noreña parable potential window of 2.4 V and 83% capacitance retention over 10,000 cycles with a great
Columbic efficiency.
Received: 13 May 2022
Accepted: 25 July 2022
Keywords: manganese oxide; pre-intercalation; specific capacitance; wide potential window; asymmetric
Published: 18 August 2022
aqueous supercapacitor; DFT calculation
Publisher’s Note: MDPI stays neutral
with regard to jurisdictional claims in
published maps and institutional affil-
iations. 1. Introduction
The continuous depletion of non-renewable energy resources as a consequence of
rapid economic development around the globe has forced researchers to seek technological
Copyright: © 2022 by the authors.
evolution for the future to satisfy the demands of efficient and renewable energy. In
Licensee MDPI, Basel, Switzerland. this regard, the supercapacitor stands out as the most promising candidate owing to its
This article is an open access article fast charge/discharge rate, supreme cyclic stability [1], as well as high power density [2].
distributed under the terms and However, the lower energy density of the currently employed supercapacitors is a limiting
conditions of the Creative Commons factor for their practical applicability [3]. Therefore, it is indispensable to boost the energy
Attribution (CC BY) license (https:// density of supercapacitors without impacting their stability and power density. This
creativecommons.org/licenses/by/ can be accomplished by either enhancing the specific capacitance or cell voltage. The
4.0/). construction of an asymmetric supercapacitor is a viable route for achieving high cell

Nanomaterials 2022, 12, 2856. https://doi.org/10.3390/nano12162856 https://www.mdpi.com/journal/nanomaterials

Nanomaterials 2022, 12, 2856 2 of 15

voltage, where the negative electrode is present at a lower potential, while the positive
electrode is present at a higher potential and operates in a different potential window [4,5].
This results in improved cell voltage and energy density of the material. However, the
maximum cell voltage obtained so far lies between 1.4 and 2.0 V, which is still not enough to
practically fulfill the energy demands [6,7]. Therefore, the quest of developing asymmetric
supercapacitors with a voltage range higher than 2.0 V is still an untangled issue [8].
As a cathode material, MnO2 has been a fascinating choice because of its large theo-
retical specific capacitance value (~1370Fg−1 ) and wide potential window (~1.0 V) [9–12].
MnO2 can be found in a variety of crystal structures, such as α, β, γ, δ, and λ MnO2 . The
electrochemical properties of α, β, and γ-MnO2 are associated with their chain/tunnel type
crystal structure facilitating electron transport for achieving high specific capacitance [13].
Moreover, the layered sheet-like structure of δ-MnO2 makes it suitable for the intercalation
of various cations, so as to increase the interlayer spacing, improving the migration rate of
electrons, which increases the specific capacitance [14,15].
Pre-intercalation of MnO2 has acquired much attention in recent years as a viable
strategy to escalate the electrochemical efficiency of MnO2 -based supercapacitors [16].
Pre-intercalated MnO2 has several ions intercalated into the redox channel and the in-
terlayer of MnO2 before electrochemical measurements [17]. Chemical bonding allows
these intercalated ions to interact with the host framework and the incorporated carrier
ions on an electrostatic and physical level, which has a significant impact on the intrinsic
structure of MnO2 and the carrier ion transport kinetics [18,19]. High specific surface area
and optimized channels available for quick and reversible ion injection and extraction
play a key role in achieving excellent specific capacitance, increased energy density, and
extended potential window [20].
To elucidate the availing influence of pre-intercalation, some published works are
mentioned below. It has been proposed [21] that pre-intercalated K+ ions inside 2 × 2
tunnels of MnO2 would improve Li+ diffusivity by increasing electronic conductivity and
interlayer spacing and electrostatic interactions between the inserted Li+ ions and host
anions. On the other hand, they are thought to have a big impact on the activation barrier
for Li+ hopping in the layered lithium transition metal oxides [22–24]. The charge shielding
property of crystal water lowers electrostatic interactions between the carrier ions and
host anions, improving carrier ion diffusion kinetics in MnO2 cathodes, according to the
literature [25,26].
We intended to construct ultra-thin Na+ ions pre-intercalated MnO2 cathode material
on carbon cloth (CC), as shown in Scheme 1, a high-performance supercapacitor with an
extended working potential window of 0–1.4 V, which has a very high reversible capacitance
of 560 F g−1 . The high capacitance is due to the pre-intercalated Na+ ions in the MnO2
nanosheets. Furthermore, an asymmetric aqueous supercapacitor with Na3 -MnO2 positive
and N-AC negative electrode was constructed, demonstrating a wide potential window of
2.4 V with a high energy density of 64 Wh kg−1 at a power density of 1225 W kg−1 and
strong cycling stability of 83% capacitance retention. Our sample has a substantially greater
content of pre-intercalated Na ions, which was prepared using a simple one-pot technique.
Furthermore, the quick and effortless procedure, the low hydrothermal temperature, and
the shorter time spent formulating our samples make the materials and process strong and
significant in comparison to all the MnO2 -based electrodes.
Nanomaterials 2022, 12,
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x FOR PEER REVIEW 33 of
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17

Scheme 1.
Scheme 1. Synthesis of Na-MnO22@CC.
@CC.

2.
2. Materials
Materials and
and Methods
Methods
All
All the chemicalreagents
the chemical reagentswere
wereofof
analytical grade
analytical andand
grade used after
used purchase
after without
purchase any
without
purification. All chemicals were Aladdin reagents and purchased from Shanghai
any purification. All chemicals were Aladdin reagents and purchased from Shanghai Macklin
Biochemical Co., Ltd.,Co.,
Macklin Biochemical Shanghai,
Ltd. China.
The
The crystalline structureswere
crystalline structures werecharacterized
characterizedbybyBruker D8D8
Bruker super speed
super X-ray
speed diffrac-
X-ray dif-
tometer (XRD)
fractometer withwith
(XRD) Cu KαCuradiation. The morphology
Kα radiation. of samples
The morphology was observed
of samples with scan-
was observed with
ning electron
scanning microscopy
electron (SEM)(SEM)
microscopy by (NAVO NanoSEM450
by (NAVO electron
NanoSEM450 microscope
electron FEI, USA),
microscope FEI,
transmission electron microscopy (TEM) by JEOL 2010 transmission electron
USA), transmission electron microscopy (TEM) by JEOL 2010 transmission electron mi- microscope,
and high-resolution transmission electron microscope (HRTEM). Chemical characteriza-
croscope, and high-resolution transmission electron microscope (HRTEM). Chemical
tion was performed by X-ray photoelectron spectroscopy (XPS) with an ESCALAB 250Xi
characterization was performed by X-ray photoelectron spectroscopy (XPS) with an ES-
spectrometer (Thermo Fisher, Loughborough, UK). Energy-dispersive X-ray spectroscopy
CALAB 250Xi spectrometer (Thermo Fisher, Loughborough, UK). Energy-dispersive X-
(EDS) and HRTEM were used for elemental mapping.
ray spectroscopy (EDS) and HRTEM were used for elemental mapping.
2.1. Treatment of Carbon Cloth (CC)
2.1. Treatment of Carbon Cloth (CC)
CC was cut into a 4 cm × 2 cm rectangular strip, soaked, and sonicated in deionized
waterCCforwas cut into
10 min. Thea CC
4 cm × 2then
was cm rectangular strip,
sonicated in soaked,
ethanol and
for 10 sonicated
min. Acetonein deionized
was used
to repeat the process. Water, ethanol, and acetone were used to sonicate threewas
water for 10 min. The CC was then sonicated in ethanol for 10 min. Acetone used
times to
each.
repeat the process. Water, ethanol, and acetone were
◦ used
Finally, the carbon cloth was dried overnight at 60 C in an oven.to sonicate three times each.
Finally, the carbon cloth was dried overnight at 60 °C in an oven.
2.2. Synthesis of Na3 -MnO2
2.2. Synthesis
KMnO (0.5of Nammol,
3-MnO2
0.079 g) and Na SO (21 mmol, 3 g) were dissolved using 50 mL
4 2 4
KMnO4 (0.5mmol,
of deionized water, and0.079 g) and Na
the solution 2SOstirred
was 4 (21 mmol,
for 1 3hg)
atwere
roomdissolved
temperature.usingThe
50 mL of
clear
deionized
solution water,
was andinto
poured the asolution
100 mLwas stirred
PTFE liner for 1 h at room
enclosed temperature. autoclave,
by a stainless-steel The clear solu-
into
tion was
which CCpoured into afterward.
was placed a 100 mL ThePTFEhydrothermal
liner enclosed by a stainless-steel
reaction took place at 120 ◦ C for 1.5
autoclave, into
h.
The
whichsample
CC wasgrown
placedonafterward.
the CC was Therinsed three times
hydrothermal withtook
reaction DI water and,
place at 120finally, with
°C for 1.5 h.
ethanol. Thegrown
mass onloading of was
Na3rinsed
-MnO2three
on the CC with
was 1.2 −2 . Pure MnO was
mg cmand,
The sample the CC times DI water finally, with2 eth-
produced usingloading
anol. The mass the same of technique
Na3-MnO2but without
on the CC wasthe1.2
addition
mg cmof. Pure
−2 Na2 SO
MnO4 . 2 was produced
using the same technique but without the addition of Na2SO4.
3. Results
The Na+ pre-intercalated MnO2 on CC was synthesized by a reasonably simple hy-
3. Results
drothermal
The Natechnique. To ensure
+ pre-intercalated MnOstructural integrity, the CC chosen as a substrate for
2 on CC was synthesized by a reasonably simple hy-
growing
drothermal technique. To ensure structural integrity, additives
samples prevented the addition of conductive and the
the CC chosen aspolymer binder.
a substrate for
CC, with its significant mechanical stability and flexibility, is a strong contender
growing samples prevented the addition of conductive additives and the polymer binder. for binder-
free
CC, electroactive materialmechanical
with its significant development [27,28].and flexibility, is a strong contender for
stability
Figure 1 shows an X-ray diffraction
binder-free electroactive material development (XRD) investigation.
[27,28]. δ-MnO2 (JCPDS card no.80-
1098) can be given from the inset pattern because of the four main representative peaks
Figure 1 shows an X-ray diffraction (XRD) investigation. δ-MnO2 (JCPDS card no.80-
detected at 12.4◦ , 25◦ , 37◦ , and 65.5◦ indexed with (001), (002), (111), and (020) having an
1098) can be given from the inset pattern because of the four main representative peaks
interlayer spacing of 0.7 Å [27,29]. The XRD patterns show the genesis of pure δ-MnO2 , but
detected at 12.4°, 25°, 37°, and 65.5° indexed with (001), (002), (111), and (020) having an
the low intensity and broadness of the peaks indicate the formation of nano-sized crystallites
interlayer spacing of 0.7 Å [27,29]. The XRD patterns show the genesis of pure δ-MnO2,
with poor crystallinity. There is no discernible change in the position of diffraction peaks
but the low intensity and broadness of the peaks indicate the formation of nano-sized crys-
tallites with poor crystallinity. There is no discernible change in the position of diffraction
Nanomaterials 2022,
Nanomaterials2022,
Nanomaterials 12,
2022,12, xxFOR
FORPEER
12,2856 PEERREVIEW
REVIEW 444of
of 17
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peaks
after
peakstheafter the
the addition
addition
after of
of Na
of Na ions,
addition ions,
ions, demonstrating
demonstrating
Na that
that pre-intercalated
demonstrating Na+ ions do
that pre-intercalated
pre-intercalated Na ++ ions do not
Nanot affect
ions do the
not
affect
affect the
crystal crystal
structure
the structure
crystalof MnO2 . of
structure of MnO
MnO22..

Figure 1.
Figure1. XRD
1.XRD patterns
XRDpatterns of
patternsof Na
Na000-MnO
ofNa -MnO222and
andNa
Na333-MnO
-MnO2.
Figure -MnO and Na -MnO22..

Field-emission
Field-emission
Field-emissionscanning scanning electron
scanningelectronelectron microscopy
microscopy
microscopy was
was used
was used to
to observe
to observe
used observe the
the morphology
the morphologymorphology and
and structure
structure of
of all the
and structure all the
Nathe
of all Na
3 -MnO -MnO
Na32-MnO
3 samples.
samples.
2 Figure
FigureFigure
2 samples. 2 shows 2 shows that
that thethat
2 shows the
morphology morphology
the morphology did not diddid not
change not
change
after
change theafter the
pre-intercalation
after of Na+ toof
the pre-intercalation
pre-intercalation Na
ofMnONa++2to MnO
MnO22.. Furthermore,
. Furthermore,
to high-magnification
high-magnification
Furthermore, high-magnification SEM images SEM
SEM
images
imagesrevealed
revealed that thethat
revealed Na3the
that theNa
-MnO Na233-MnO
is made
-MnO 22 is made
isup up
up of
ofultra-thin
of ultra-thin
made uniform
ultra-thin uniform
nanosheets
uniform nanosheets
of about
nanosheets of
ofabout
aabout
few
aa few
nm few nm thicknesses that are uniformly grown on the carbon cloth (Figure 2c).
nm
thicknessesthicknesses
that are that
uniformly are uniformly
grown on grown
the carbon on the
cloth carbon
(Figure cloth
2c). (Figure
Nanosheets of
2c).
Nanosheets
Na -MnO
Nanosheets
0 of Na
(Figure -MnO
2c) are (Figure
thickner 2c)
than are thickner
the than
nanosheets
2 of Na0-MnO2 (Figure 2c) are thickner than the nanosheets
0 2 the
of Na nanosheets
3 -MnO 2 of Na
(Figure -MnO
2f), which
of Na3-MnO2 (Fig-
3 2 (Fig-
is
ure 2f),
thought which
to be is thought
helpful for to
ions be helpful for
insertion/extraction. ions insertion/extraction.
The specific
ure 2f), which is thought to be helpful for ions insertion/extraction. The specific surface surface The
areasspecific
and surface
electron-
areas
ion
areas and
andelectron-ion
transfer distance affect
electron-ion transfer distance
the thickness
transfer distanceof affect
the the
affect thethickness
nanosheet,
thickness of
whichof the has
the nanosheet,
a pronounced
nanosheet, which
which has
hasaa
impact
on the electrochemical
pronounced
pronounced impact
impact on onproperties
the of Nax -MnO
the electrochemical
electrochemical 2 [30]. The
properties
properties of EDS
of Na
Na xx-MnOspectrum
-MnO [30].of
22 [30]. TheNaEDS
The -MnO
3EDS 2 is
spec-
spec-
shown
trum in
of Figure
Na -MnO S1. The
is presence
shown in of the
Figure NaS1. element
The in MnO
presence
trum of Na3-MnO2 is shown in Figure S1. The presence of the Na element in MnO
3 2 2 nanosheets
of the Na can
elementbe seen
in in
MnO the22
elemental
nanosheets mapping
can be of the
seen energy-dispersive
in the elemental X-ray spectroscope
mapping
nanosheets can be seen in the elemental mapping of the energy-dispersive X-ray of the in Figure S2.
energy-dispersive EDS analysis
X-ray
demonstrated
spectroscopethat
spectroscope in only Mn,
in Figure
Figure S2.Na,
S2. EDS
EDS C,analysis
O, and Kdemonstrated
analysis elements were present
demonstrated that
that only in the
only Mn,
Mn,Na 3 -MnO
Na,
Na, C,
C, O,2 . This
O, and
and
analysis proves that Na + ions successfully pre-intercalated and occupied the+interlayer sites
KKelements
elementswere werepresent
presentin inthetheNaNa33-MnO
-MnO22..This
Thisanalysis
analysisproves
provesthat thatNa Na+ionsionssuccess-
success-
of the pre-intercalated
fully
fully layered δ-MnO2 and
pre-intercalated and occupied
occupied the the interlayer
interlayer sites
sites ofof thethe layered
layered δ-MnO δ-MnO22

Figure 2.
Figure2.
Figure SEM
2.SEM images
SEMimages of
imagesof Na
Na000-MnO
ofNa -MnO222(a–c);
-MnO (a–c); Na
Na333-MnO
-MnO222(d–f).
(d–f).
(d–f).

TEM
TEManalysis
analysis was
wasused
usedto toinvestigate
investigatethe
investigate thestructural
structuraldetails
detailsin
ingreater
greaterdepth
depthandandto to
to
assess the impact
impact of
of the
the introduction
introduction ofof
NaNa ions
ions on on
the the morphology
morphology
assess the impact of the introduction of Na ions on the morphology of the Na3-MnOof of
the the
Na 3 Na
-MnO -MnOelec-
3 2 elec-
2 2
electrode.
trode. Figure
trode. Figure
Figure 3 depicts
33 depicts
depicts TEM
TEM TEM representations
representations
representations of of 3Na
of Na
Na 3 -MnO
3-MnO
-MnO 2 and
22 and
and MnO
MnO MnO 2 electrodes
22 electrodes
electrodes withwith
with and
and
and without
without
without Na Na
Na ions.
ions.
ions. TheThe
The uniform
uniform
uniform MnO
MnOMnO nanostructuresare
22 nanostructures
2nanostructures are composed
are composed of
composed of
of ultra-thin
ultra-thin
ultra-thin
nanosheets,
nanosheets, as shown in Figure 3a,c. The pre-intercalated Na ions decrease the grainsize
as shown in Figure 3a,c.
3a,c. The pre-intercalated Na ions decrease the grain size
Nanomaterials 2022, 12, 2856 5 of 15
Nanomaterials 2022, 12, x FOR PEER REVIEW 5 of 17

of MnO nanosheets to a minuscule. Consequently, the active sites for ion adsorption are
of MnO22 nanosheets to a minuscule. Consequently, the active sites for ion adsorption are
increased duetotoexceptional
increased due exceptional electrochemical
electrochemical performance.
performance. The creation
The creation of oxygen
of oxygen vacanciesvacancies
might emphasize the intrusion of electrolytes ions, leading to improved
might emphasize the intrusion of electrolytes ions, leading to improved redox reaction and redox reaction and
boosted conductivity. Figure 3b is the HRTEM image of
boosted conductivity. Figure 3b is the HRTEM image of Na3-MnO2 nanosheets Na 3 -MnO nanosheets
2 verifying the verifying
the
XRD XRD
data,data,
as theas the lattice
lattice space inspace in the
the central central
region region
is 0.7 is 0.7correlates
nm, which nm, which withcorrelates
the crystalwith the
crystal plane
plane (001) (001) of
of δ-MnO δ-MnO
2. The .
high-angle
2 The high-angle
annular annular
dark-field dark-field
(HAADF) imaging(HAADF)
in Figureimaging
3e in
indicates a sustained arrangement of atomic species in the crystal phase of MnO
Figure 3e indicates a sustained arrangement of atomic species in the crystal phase of MnO2 , 2, which also
proves also
which the presence
proves the of pre-intercalated Na ions in the layers
presence of pre-intercalated Na of δ-MnO
ions 2. layers of δ-MnO .
in the 2

Figure 3. (a,c) TEM image of Na3-MnO2; (b,d) HRTEM image of Na3-MnO2; (e) elemental
Figure 3. (a,c) TEM image of Na3 -MnO2 ; (b,d) HRTEM image of Na3 -MnO2 ; (e) elemental mapping
mapping of Na3-MnO2; (f) elemental mapping of MnO2; (g,h) HAADF-STEM images.
of Na3 -MnO2 ; (f) elemental mapping of MnO2 ; (g,h) HAADF-STEM images.
Spherical aberration-corrected
Spherical aberration-corrected electron
electron microscopy
microscopy revealed
revealed the atomic
the atomic resolution resolution
structure of
structure ofthe
theNa
Na3-MnO
3 -MnO2 (Figure 3g,h).
2 (Figure In Figure
3g,h). 3h, the
In Figure 3h,white spots reflect
the white spots the position
reflect the position
of Mn
of Mn atoms
atomsasasseen
seenfrom
fromthethe
<001> zonezone
<001> axis.axis.
The Na 3-MnO2 was analyzed by X-ray photoelectron spectroscopy (XPS). The survey
The Na3 -MnO2 was analyzed by X-ray photoelectron spectroscopy (XPS). The survey
spectrum shown in Figure 4a indicates the presence of C, O, Mn, and Na elements. Figure
spectrum shown in Figure 4a indicates the presence of C, O, Mn, and Na elements. Figure 4b
4b reveals the high-resolution spectrum of Mn 2p. The peaks are pinpointed at binding
reveals the high-resolution spectrum of Mn 2p. The peaks are pinpointed at binding energies
energies of 642.3 eV and 654 eV, which correlate with the binding energies of Mn 2p3/2 and
of 642.3 eV and 654 eV, which correlate with the binding energies of Mn 2p3/2 and
Mn 2p1/2, respectively, with a difference of 11.7 eV. This stipulates that the oxidation state
Mn 2p1/2 ,
respectively,
of Mn in the Na3-MnO2 is +4, which is consistent with the previous literature [31–34]. Fig- in the
with a difference of 11.7 eV. This stipulates that the oxidation state of Mn
Nanomaterials 2022, 12, x FOR PEERNa
ure3 -MnO
REVIEW 2 ishigh-resolution
4c shows +4, which is consistent
XPS spectrawith the1s,previous
of Na which has literature
a binding[31–34].
energy ofFigure
1071.44c 6shows
of 17
high-resolution XPS spectra
eV [35–37]. It authenticates the of Na 1s, which
successful has a of
intercalation binding
the Na+energy
into theof
Na1071.4
3-MnOeV 2. [35–37]. It
authenticates the successful intercalation of the Na+ into the Na3 -MnO2 .

Figure 4. (a) Survey spectrum of Na3-MnO2; (b) high-resolution spectrum of Mn 2p; (c) high-resolu-
Figure 4. (a) Survey spectrum of Na3 -MnO2 ; (b) high-resolution spectrum of Mn 2p; (c) high-
tion spectrum of Na 1s.
resolution spectrum of Na 1s.
To evaluate the electrochemical efficiency of the designed electrodes in a module of
a three-electrode system, the electrochemical measurements were carried out on a VMP3
biologic workstation. This system consists of Na0-MnO2 and Na3-MnO2 as a working elec-
trode and a Hg/HgO as a reference electrode and is completed with platinum foil as a
Nanomaterials 2022, 12, 2856 6 of 15

To evaluate the electrochemical efficiency of the designed electrodes in a module of

a three-electrode system, the electrochemical measurements were carried out on a VMP3
biologic workstation. This system consists of Na0 -MnO2 and Na3 -MnO2 as a working
electrode and a Hg/HgO as a reference electrode and is completed with platinum foil as a
counter electrode. We recorded the galvanostatic charge/discharge (GCD) measurements,
electrochemical impedance spectroscopy (EIS), and cyclic voltammetry (CV) with 1M
Na2 SO4 solution as the electrolyte.
Figure 5a displays the characteristics of CV curves of Na3 -MnO2 at the enlarged
working potential range of 0–1.4 V at different scan rates (2, 5, 10, 20, and 50 mV s−1 ). All
the graphs represent a nearly rectangular shape comprising a noticeable redox peak at
about 0.8 V. The current density increases correspondingly with the increase in scan rate,
which is typical of MnO2 -based electrodes. By examining the CV curves of Na3 -MnO2 at
varying potential ranges (Figure S3a), it is clear that the CV curves at 0–1.0 V potential
range and various scan rates from 2 to 50 mV s−1 have perfectly rectangular shapes at all
scan rates with a small redox peak. Similarly, at 0–1.2 V, all the CV curves are rectangular,
as shown in Figure S3b. However, a prominent pair of redox peaks is observed in the
CV curves
Nanomaterials 2022, 12, x FOR PEER REVIEW at 0–1.3 V (Figure S3d). The rectangular shape of enumerating the7 of continuous
17
and reversible faradaic redox transition with a pair of broad redox peaks at 0.4–0.6 V is
noticeable in all the CV curves at all scan rates.

Figure 5. Electrochemical
5. Electrochemical performanceof
performance ofNa
Na3-MnO 2 electrode at potential range of 0–1.0, 0–1.1, 0–
Figure 3 -MnO2 electrode −1at potential range of 0–1.0, 0–1.1, 0–1.2,
1.2, 0–1.3, and 0–1.4 V (a) CV curves at 2, 5, 10, 20, and 50 mV s scan rate and 0–1.4 V potential
0–1.3,window;
and 0–1.4 V (a) CV curves at 2, 5, 10, 20, and 50 mV s−1 scan rate and 0–1.4 V potential window;
(b) GCD curves at 5, 10, 15, 20, 30, 40, and 50 A g−1 current densities and 0–1.4 V potential
(b) GCD
window;curves at 5,curves
(c) CV 10, 15, 20, 30, 40,atand
comparison 50 A
various g−1 current
potential rangesdensities and 0–1.4
of 0–1.0, 0–1.1, 0–1.2, V potential
0–1.3, and 0– window;
(c) CV1.4curves
V at a comparison
scan rate of 10atmV s ; (d)potential
−1
various GCD curves comparison
ranges at 0–1.1,
of 0–1.0, different potential
0–1.2, 0–1.3,windows
and 0–1.4of 0–
V at a scan
rate of1.0,
100–1.1,
mV s0–1.2, 0–1.3, and 0–1.4 V at 10 A g−1 current density; (e) Specific capacitance comparison
−1 ; (d) GCD curves comparison at different potential windows of 0–1.0, 0–1.1, 0–1.2, 0–1.3,
at various current densities of 5, 10, 15, 20, 30, 40, and 50 A g−1 and 0–1.0, 0–1.1, 0–1.2, 0–1.3, and 0–
and 0–1.4 V at 10 A g −1 current density; (e) Specific capacitance comparison at various current densities
1.4 V potential window.
of 5, 10, 15, 20, 30, 40, and 50 A g−1 and 0–1.0, 0–1.1, 0–1.2, 0–1.3, and 0–1.4 V potential window.
Figure 5c shows the comparison of typical CV curves of the Na3-MnO2 electrode at a
scan rate of 10 mV s−1 in varying potential windows of 0–1.4, 0–1.3 0–1.2, 0–1.1, and 0–1.0
V, respectively. The CV curves of 0–1.0 and 1.1 V have an archetypal rectangular appear-
ance with no redox peaks, which corresponds to the characteristic CV behavior for elec-
trodes based on MnO2 [38,39]. The CV curve developed a very small redox peak by esca-
lating the potential range to 1.2 V. By further increasing the upper cutoff potential to 1.3
Nanomaterials 2022, 12, 2856 7 of 15

Figure 5c shows the comparison of typical CV curves of the Na3 -MnO2 electrode at a
scan rate of 10 mV s−1 in varying potential windows of 0–1.4, 0–1.3 0–1.2, 0–1.1, and 0–1.0 V,
respectively. The CV curves of 0–1.0 and 1.1 V have an archetypal rectangular appearance
with no redox peaks, which corresponds to the characteristic CV behavior for electrodes
based on MnO2 [38,39]. The CV curve developed a very small redox peak by escalating
the potential range to 1.2 V. By further increasing the upper cutoff potential to 1.3 V, we
observed a prominent couple of redox peaks at around ≈0.4 V. Upon further extending the
potential window to 0–1.4 V, two pairs of redox peaks emerged: one at the lower potential
range at about 0.4–0.6 V and the other at the higher potential range of about 0.8–1.2 V.
The first redox peaks are due to the characteristic charge storage mechanism of MnO2 by
the intercalation and deintercalation of electrolytes on the Na3 -MnO2 electrode [40,41].
However, the mechanism of the second redox peak differs from that of the first, as stated by
Nawishta J. et al. [42] and Gang L. et al. [43]. The CV curve area of Na3 -MnO2 at the 0–1.4 V
potential window is much larger than that at 0–1.3 0–1.2, 0–1.1, and 0–1.0 V. A reversible
redox reaction causes the current to rise at around 1.0 V [44].
As one can observe, irrespective of the potential range, the CV graph exhibited a pair of
distinguishing redox peaks at about 0.8 V for the anodic scanning and 1.2 V for the cathodic
scanning at a potential range of 0–1.4 V, which appeared due to fast reversible redox reaction of
the Mn3+ /Mn4+ plus the intercalation/deintercalation of the Na+ . Remarkably, the potential
windows sustain a fine rectangular shape even at a higher scan rate of 50 mV s−1 and 0–1.4 V.
This justifies the fact that due to the insertion of the Na+ , the charging potential window rises
noticeably [35]. It offers the prospect of designing SCs with a much higher energy density [45].
Figure 5b demonstrates the GCD curves at a potential range of 0–1.4 V and varying
current densities (5, 10, 15, 20, 30, 40, and 50 A g−1 ). The fact that all of these curves are
completely triangular confirms the pseudocapacitive existence of the Na3 -MnO2 electrode.
The GCD curves at 0–1.0 V, 0–1.1 V, 0–1.2 V, and 0–1.3 V at current densities of 5, 10, 15, 20,
30, 40, 50, 80, and 100 A g−1 are shown in Figure S4a–d, respectively. Figure 5d shows a
comparison of GCD curves at 5 A g−1 current density at various potential ranges of 0–1.0,
0–1.1, 0–1.2, 0–1.3, and 0–1.4 V. Among these curves, the GCD curves at 0–1.4 V show a
longer charge–discharge time. The charge–discharge time declined as the current density
increased due to the reduced passage of electrolyte ions across the electrode [33]. Still, at
a higher current density of 100 A g−1 , the nanocomposite MnO2 electrode displayed a
linear triangular shape, demonstrating that the pre-intercalation of Na+ leads to superlative
electrochemical performance.
Figure 5e expresses a comparative analysis of specific capacitance of Na3-MnO2 at various
potential windows (0–1.0, 0–1.1, 0–1.2, 0–1.3, and 0–1.4 V) as a function of current density. The
specific capacitance of the Na3-MnO2 electrode at a potential window of 0–1.4 V can reach
546, 535, 490, 450, 390, 350, and 300 F g−1 at 5, 10, 15, 20, 30, 40, and 50 A g−1, respectively,
which surpasses that of 480 F g−1 at the potential window of 0–1.3 V and is far better than
451 F g−1 at the potential window of 0–1.2 V at 5 A g−1 current density. The specific capaci-
tance of the Na3-MnO2 electrode is much higher than the recently published work based on
MnO2 electrodes, such as δ-MnO2 (251.4 F g−1 at current density 1 A g−1) [46], δ-MnO2 NFs@
α-MnO2 NWs (310 F g−1 at current density 1 A g−1) [47], MnO2@SBA-C (219 F g−1 at current
density 1 A g−1) [48], 3D-HPCS@MnO2 (231.5 F g−1 at current density 1 A g−1) [49], δ-MnO2
(194.3 F g−1 at current density 1 A g−1) [50], NSs@MnO2 HNPAs (244.54 F g−1 at current
density 1 A g−1) [51], α-MnO2@δ-MnO2 (206 F g−1 at current density 1 A g−1) [52], and
rGO/CNT/MnO2 (209 F g−1 at current density 1 A g−1) [53]. At the same current density, the
specific capacitance of the Na3-MnO2 electrode at the potential window of 0–1.1 and 0–1.0 V is
420 and 365 F g−1, respectively.
To comprehensively understand the stability of Na3 -MnO2 electrodes in different poten-
tial ranges, the cycle stability of Na3 -MnO2 is analyzed and correlated at a current density
of 10 A g−1 over 6000 cycles and is shown in Figure S11. The Na3 -MnO2 electrode has a
capacitance retention of 95, 93, 94, and 96% in different working potential windows of 0–1.1,
0–1.2, 0–1.3, and 0–1.4, respectively. Noticeably, extending the potential window to 0–1.4 V has
Nanomaterials 2022, 12, 2856 8 of 15

good cycling stability, which could be explained by the pre-intercalated Na+ in the Na3 -MnO2
structure as a result of charge balancing, which acts as pillars to stabilize the nanosheets’ lay-
ered structures. The electrochemical performance of pure MnO2 was recorded to upgrade the
understanding of the pre-intercalation of Na+ into MnO2 and its effect on the electrochemical
behavior of the Na3 -MnO2 electrode. Figure S6 shows the CV of the MnO2 electrode at a scan
rate of 1, 2, 5, 10, 20, 50, and 100 mV s−1 in different working potential windows of 0–1.0
(Figure S6a), 0–1.2 (Figure S6c), and 0–1.4 V (Figure S6e), respectively. It is obvious that no
redox peaks polarization occurred when the potential window exceeded 1 V. The current
density of the CV curve was observed to be increased as the potential window was increased,
without any observable redox peaks for all potential ranges. Furthermore, the CV curve of
MnO2 at a potential range of 0–1.4 showed water decomposition with the evolution of oxygen.
In addition, the area under the CV curve for Na3 -MnO2 is larger than the current density of
MnO2 at all potential windows. Similarly, the GCD analysis of MnO2 electrodes at different
potential windows of 0–1.0 (Figure S6b), 0–1.2 (Figure S6d), and 0–1.4 V (Figure S6f) at various
current densities of 1, 2, 5, 10, 15, 20, 30, 40, 50, 80, and 100 A g−1 showed different results to
Na3 -MnO2 . The most important point is that it did not even reach the potential window of
1.4 V. The GCD curves of Na3 -MnO2 are more symmetric than those of MnO2 , indicating the
better reversibility of Na3 -MnO2 electrode than that of the MnO2 . Moreover, the discharge
time of the Na3 -MnO2 electrode is much longer than the pure MnO2 electrode, indicating
higher capacitance of the Na3 -MnO2 electrode. These results indicate that the pre-intercalation
of Na+ can increase the capacitance performance and extend the stable potential window of
MnO2 [54].
Similarly, Figure S7 compares the specific capacitance of the MnO2 electrode as a
function of current density at various potential ranges of 0–1.0, 0–1.2, and 0–1.4 V. MnO2
has a very low specific capacitance relative to the Na3 -MnO2 electrode at all current
densities. The highest recorded specific capacitance was noted to be 217 F g−1 at a current
density of 1 A g−1 and a potential window of 1.4 V.
To test the applicability of the electrochemical performances of the Na3 -MnO2 elec-
trode in a full device for a wide potential window, an aqueous Na3 -MnO2 //N-AC device
was engineered with a Na3 -MnO2 electrode as the positive electrode (cathode) and com-
mercial N-doped activated carbon (N-AC) electrode as the negative electrode (anode),
completing this device with 1 M Na2 SO4 solution as aqueous electrolyte. Before measuring
the electrochemical performance of the Na3 -MnO2 //N-AC device, the electrochemical
performance of N-AC was analyzed, as shown in Figure S8.
Figure S9a depicts the CV curves for the Na3 -MnO2 electrode and the N-AC in their re-
spective potential windows of 1.4–0 V and 0–1.0 V at a scan rate of 10 mV s−1 . Theoretically,
it is clear from the separate potential window of cathode and anode that the Na3 -MnO2 //N-
AC device could accomplish the working potential window of 0–2.4 V. To experimentally
optimize the highest possible upper cutoff voltage for the Na3 -MnO2 //N-AC device, CV
curves were reported at different potential windows from 1.6 to 2.6 V at a scan rate of
10 mV s−1 , as shown in Figure S9b. As the potential window of the Na3 -MnO2 //N-AC
device extended beyond 0–2.4 V, a distinct current leap began to appear at a potential
window of about 0–2.6 V, indicating the decomposition of the water started here. Notably,
the CV curves of the Na3 -MnO2 //N-AC device could sustain a quasi-rectangular shape
with potential windows ranging from 0 to 2.4 V, confirming the maximum potential win-
dow for the Na3 -MnO2 //N-AC device could reach as high as 2.4 V without any aqueous
electrolyte decomposition.
To adjust the electrochemical performance of the Na3 -MnO2 //N-AC device, the mass
ratio of the cathode to the anode was calculated to be 1.2:3.4, based on the charge balance
theory (Equation (1)), at a current density of 1 A g−1 . The electrochemical performance of
the Na3 -MnO2 //N-AC device is shown in Figure 6.
Nanomaterials
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12, x2856
FOR PEER REVIEW 109 of
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15

Figure
Figure 6.
6. Electrochemical
Electrochemical performance
performance of of Na
Na3-MnO
-MnO2//N-AC
//N-AC device
device(a)
(a)CV
CVcurves
curvesatat5,5,10,
10,20,
20,50,
50,100,
100,
3 2
and 200 mV s−−11 scan rate and 0–2.4 V potential window; (b) GCD curves at 1, 2, 4, 8, 10, 15, 20, 30,
and 200 mV s scan rate and 0–2.4 V potential window; (b) GCD curves at 1, 2, 4, 8, 10, 15, 20, 30, and
and 50 −
A g−1 current densities and 0–2.4 V potential window; (c) Specific capacitance at various current
50 A g 1 current densities and 0–2.4 V potential
densities of 1, 2, 4, 8, 10, 15, 20, and 30 A g−1 currentwindow;
densities(c)
(d)Specific
Ragonecapacitance at various current
plot of the gravimetric energy
densities of 1, 2, 4, 8, 10, 15, 20, and 30 A g−1 current densities (d) Ragone plot of the gravimetric energy
density and power density comparison of this work Na3-MnO2//N-AC device and other previously
density and
reported power
works; density
(e) The comparison
cycling stability of
andthis work Naefficiency
Columbic 3 -MnO2 //N-AC
at 10 A gdevice and other previously
−1; (f) EIS.

reported works; (e) The cycling stability and Columbic efficiency at 10 A g−1 ; (f) EIS.
CV curves of Na3-MnO2//N-AC device at various scan rates (5, 10, 20, 50, 100, and 200
mV sCV−1) incurves
a wideof(0–2.4
Na3 -MnO 2 //N-AC
V) potential device were
window at various scanand
recorded rates (5, 10,in20,
shown 50, 100,
Figure
−1 ) in a wide (0–2.4 V) potential window were recorded and shown in Figure 6a.
6a.and
In-
200 mV s
terestingly, the quasi-rectangular shape of the CV curve was preserved at an even higher
Interestingly,
scan rate of 200 themV
quasi-rectangular
s−−11, exhibiting shape of the CV curve
the exceptional was preserved
electrochemical at an even higher
characteristics of the
Na3-MnO2//N-AC device. GCD measurements were used to further investigate theofelec-
scan rate of 200 mV s , exhibiting the exceptional electrochemical characteristics the
Na3 -MnO2 //N-AC device. GCD measurements were used to further investigate the
trochemical properties of Na3-MnO2//N-AC device at 1, 2, 4, 8, 10, 15, 20, 30, and 50 A g−1
electrochemical properties of Na3 -MnO2 //N-AC device at 1, 2, 4, 8, 10, 15, 20, 30, and
current−densities and 0–2.4 V potential window (Figure 6b). All these GCD curves dis-
50 A g 1 current densities and 0–2.4 V potential window (Figure 6b). All these GCD
played quasi-triangular shape and good symmetry, confirming the ideal super capacitive
curves displayed quasi-triangular shape and good symmetry, confirming the ideal super
behavior of the Na3-MnO2//N-AC device. From these GCD curves, the specific capaci-
capacitive behavior of the Na3 -MnO2 //N-AC device. From these GCD curves, the specific
tances for the Na3-MnO2//N-AC device were calculated and are represented in Figure 6c.
capacitances for the Na3 -MnO2 //N-AC device were calculated and are represented in
Fascinatingly, the Na3-MnO 2//N-AC device has the highest specific capacitance of 80 F g−1
Nanomaterials 2022, 12, 2856 10 of 15

Figure 6c. Fascinatingly, the Na3 -MnO2 //N-AC device has the highest specific capacitance
of 80 F g−1 at a current density of 1 A g−1 and can retain 50% of its capacitance even at a
high current density of 30 A g−1 , indicating the excellent rate capability of the device.
According to Equations (1) and (2), the Na3 -MnO2 //N-AC device demonstrated the
highest energy of 64 Wh kg−1 at the power density of 1225.53 W kg−1 . This device maintained
a higher energy density of 32 Wh kg−1 at a current density of 30 A g−1 even at the highest
power density of 38400 W kg−1 (Figure 6d). These high-energy and power densities outper-
form those of recently published Mn-based devices, such as MnO2 @PCN//PCN (energy
density 31.13 Wh kg−1 , at power density 193.6 W kg−1 ) [55], N/P-HCS@MnO2 -30 (energy
density 32.21 Wh kg−1 , at power density 449.8 W kg−1 ) [43], G/MnO2 (energy density
19.6 Wh kg−1 , at power density 351 W kg−1 ) [56], MnO2 @SnO2 //AC (energy density
18.05 Wh kg−1 , 403.6 W kg−1 ) [57], MnO2 @N-APC//N-APC (energy density 28 Wh kg−1 , at
power density 560 W kg−1 ) [58], AC//MnO2 @NH4 MnF3 (energy density 11.2 Wh kg−1 , at
power density 1000 W kg−1 ) [59], MnO2 /SHAC-3//SHAC (energy density 46.2 Wh kg−1 ,
at power density 98.5 W kg−1 ) [60], Fe-MnO2 //AC (energy density 40 Wh kg−1 , at power
density 250 W kg−1 ) [61], and ov-MnO2 @MnO2 //AC (energy density 40.2 Wh kg−1 , at power
density 891.2 W kg−1 ) [62]. Furthermore, the quick and effortless procedure, low hydrother-
mal temperature, and shorter time spent formulating our samples make the materials and
process strong and significant versus all the MnO2 -based electrodes.
Figure S10 shows the results of the volumetric energy and power density calculations.
The Na3 -MnO2 //N-AC device delivered excellent volumetric energy and power density
(12.8 Wh cm−3 at 245 W cm−3 ). Cycling performance is another very important parameter
used to check the stability of the device. As noticed in Figure 6e, the cycling performance
of the Na3 -MnO2 //N-AC device was recorded under a current density of 10 A g−1 for
10,000 cycles at a 2.4 V potential window. As seen in the graph, the device retained 83% of
capacitance, confirming its outstanding cycling durability. Pre-intercalation could markedly
mitigate these capacity fading concerns caused by structural instabilities during cycling
because of the limited volumetric variability during the intercalation/de-intercalation
phase of the carrier ions.
The EIS results of the Na3 -MnO2 //N-AC device are illustrated in Figure 6f, with a
semicircle at a higher-frequency and a straight line at a lower-frequency region.
The electrochemical performance of Na ions pre-intercalated MnO2 was improved in
this study. The most likely reasons are as follows. A broader interlayer space is particularly
favorable for the intercalation–deintercalation of various ions during the redox process,
which is given by wide interlayers of MnO2 . The lattice space in the central region of the
Na3 -MnO2 nanosheets is 0.7 nm, which matches with the crystal plane (001) of δ-MnO2 , as
revealed by the HRTEM image, which supports the XRD results.. The electrochemically
active sites were increased due to the morphology with very thin nanosheets, which helped
reduce the electron transport channel and the diffusion pathway of the ions of electrolyte,
which optimized the electrochemical performance. Furthermore, the pre-intercalation of
Na ions shrinks the nanosheets and disrupts the lattice alignment, as seen in the SEM
images, resulting in a large turnout of grain borders. These numerous grain boundaries
provide more active sites for redox reactions, as well as a simple diffusion pathway for ions
and electrons, allowing the electrode materials to be used more competently. Furthermore,
greater grain boundaries stimulate the formation of lattice defects, which increase the
number of oxygen vacancies and so refine the electrical conductivity of Na3 -MnO2 .

4. Computational Studies
The present study was performed by implementing the density functional theory (DFT)
using the generalized gradient approximation (GGA) and the Perdew–Burke–Ernzerhof
(PBE)59 functional for the exchange correlation potentials that were accomplished through
the Vienna ab initio simulation package (VASP)60-62. The structure was optimized using
8 × 6 × 4 k-points, and a 520 eV energy cutoff was applied. The electronic properties of
bulk MnO2 were calculated using Dudarev’s PBE+U method [63], with U = 3.9 eV applied
Nanomaterials
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2022,12,
12,x 2856
FOR PEER REVIEW 1211ofof1715

3.9
to eV
theapplied
3d states to of
theeach
3d states of each
Mn atom. TheMn U atom.
= 3.9 eVThe UMn
for = 3.9iseV forreported
also Mn is also reported
in the previous in
the previous literature study [64,65]. Furthermore, the high symmetry
literature study [64,65]. Furthermore, the high symmetry and denser 16 × 12 × 10 k-points and denser 16 × 12
×were
10 k-points
used forwerethe used for the of
calculations calculations of the bandstructure
the bandstructure and density of and density of states.
states.
The
TheMnOMnO 2 was
2 wasmodeled
modeledvia viaa aperiodic
periodiccellcellcontaining
containing1212atoms
atoms(4(4manganese
manganeseand and88
oxygen
oxygenatoms).
atoms).The TheMnOMnO 2 supercell
2 supercell was
was orthorhombic
orthorhombic 2.92
2.92 ××4.58
4.58× ×9.43 Å3
9.43 for
Å3 the
for x,x,y,y,
the
and
andz-directions,
z-directions,with withαα==ββ= =γ γ= =90°,90◦and the
, and theperiodic
periodiccondition
conditionwas wasemployed
employedalongalongthe the
x,x,y,y,and z directions. The total energy was
and z directions. The total energy was converged to converged to an accuracy of 1 × 10 −
−5 5
× 10 eV toeV to
obtain
obtainaccurate
accurateforces,
forces,andandaaforce
force tolerance
tolerance of of −0.02
−0.02eV/Å
eV/Åwas wasapplied
appliedininthethestructure
structure
optimization.
optimization.The Theddorbital
orbitalof ofmanganese,
manganese, p orbital of oxygen,oxygen, andandssorbital
orbitalofofNa
Nahybridize,
hybrid-
ize,
whichwhich results
results in in the
the crowdingofofbands
crowding bandsnear
nearthethe Fermi
Fermi level in in Na-intercalated
Na-intercalatedhybrid hybrid
structures
structuresc candandd,d,exhibiting
exhibitingbandbandgap gapreduction,
reduction,which
whichassists
assistsinincharge
chargetransportation.
transportation.
Figure7c7calso
Figure alsoexhibits
exhibitsthe theaffinity
affinitybetween
betweenNa Naand
andoxygen
oxygenofofmanganese
manganeseoxide, oxide,
therefore concluding that the intercalation of sodium is due to
therefore concluding that the intercalation of sodium is due to strong bonding betweenstrong bonding between
oxygenand
oxygen andsodium
sodiumatoms.atoms.

Theelectronic
Figure7.7.The
Figure electronicband
bandstructure,
structure,the
thespin-polarized
spin-polarizedtotal
totaldensity
densityofofstates
states(TDOS),
(TDOS),andandpartial
partial
densityofofstates
density states(PDOS)
(PDOS)plotted
plottedtogether
togetherwith
withcorresponding
correspondingoptimized
optimizedstructures
structuresofof(a,b)
(a,b)pure
pure
MnO
MnO ; and(c,d)
2;2and (c,d)Na-doped
Na-dopedMnOMnO ; The
2; 2The spin-up
spin-up (↑)(↑and
) and spin-down
spin-down (↓).
(↓).

Toanalyze
To analyzethe
thecharge
chargetransfer
transferand
and charge
charge population,
population, Figure
Figure 8,
8, bader
bader charge
charge calcula-
calcu-
tions were
lations wereperformed
performedaccording
accordingtotothe
thefollowing
followingequation.
equation.
Workfunction
Work function==Vacuum
Vacuumpotential
potential(E(E vac))−
vac − Fermi Level (Eff)) (1)
(1)
The charge density difference (Δρ) was calculated as
The charge density difference (∆ρ) was calculated as
Δρ = ρ δ − MnO2 − ρ Na
∆ρ = ρ δ − MnO2 − ρ Na
where ρ δ-MnO2, ρ Na represents the charge densities of δ-MnO2 and Na-pre-intercalated
where 2.ρ δ-MnO2, ρ Na represents the charge densities of δ-MnO2 and Na-pre-intercalated δ-MnO2.
δ-MnO
 Nanomaterials2022,
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13 15

Figure 8. The charge density difference plot of Na-doped MnO2 . The violet and yellow colors specify
Figure 8. The
electron charge density
accumulation and difference plot of Na-doped
depletion regions, MnOThe
respectively. 2. The violet
red, andand
bluish, yellow colors
green specify
colors balls
electron
representaccumulation andatoms,
O, Mn, and Na depletion regions, The
respectively. respectively. The
iso-surface red,isbluish,
value and green
set to 0.002 −3 .
e Bohrcolors balls
represent O, Mn, and Na atoms, respectively. The iso-surface value is set to 0.002 e Bohr−3.
The zero-point energy, entropy, and enthalpy corrections were added to the adsorbates
to convert electronicenergy,
The zero-point energyentropy,
to free energy. The Gibbs
and enthalpy free energy
corrections (G)added
were at 0 Vto
is the
modified by
adsorb-
Equation (2)
ates to convert electronic energy to free energy. The Gibbs Z free energy (G) at 0 V is modi-
fied by Equation (2) G = EDFT + EZPE − TS + Cp dT (2)
R G = EDFT + EZPE − TS + ∫ CpdT (2)
where EDFT , EZPE , TS, and Cp dT denote the electronic energy obtained from DFT opti-
mization,
where EDFTzero-point vibrational
, EZPE, TS, and energy,the
∫ CpdT denote entropy, and heat
electronic capacity
energy at room
obtained fromtemperature.
DFT optimi-
zation, zero-point vibrational energy, entropy, and heat capacity at roomtransferred
The bader charge calculations prove that 7.40 |e| electrons are temperature.from
manganese
The bader to sodium, which mayprove
charge calculations assist that
in the intercalation/de-intercalation
7.40 |e| electrons are transferredprocess.
from man-
ganese to sodium, which may assist in the intercalation/de-intercalation process.
5. Conclusions
In conclusion, we designed Na+ pre-intercalated MnO2 for high-performance superca-
5. Conclusions
pacitors with a potential
In conclusion, range ofNa
we designed 0–1.4 V. The potentialMnO
+ pre-intercalated window of the Na3 -MnO2 electrode
2 for high-performance super-
can reach up to 1.4 V versus
capacitors with a potential Hg/HgO.
range of As
0–1.4 a result,
V. The the Na -MnO
3 window
potential 2 electrode
of thehas
Na a3-MnO
high specific
2 elec-
capacitance of 546 F g−1 and good rate capability. It demonstrated exceptional cycling stability
trode can reach up to 1.4 V versus Hg/HgO. As a result, the Na3-MnO 2 electrode has a
withspecific
high nearly 95% retentionof
capacitance of546
the F
capacitance
g−1 and goodafter 6000
rate cycles at 10
capability. A g−1 at 1.4 V. Furthermore,
It demonstrated exceptional
the Na -MnO2 //N-AC device with Na3 -MnO2 as positive and N-AC as negative electrodes
cycling 3stability with nearly 95% retention of the capacitance after 6000 cycles at 10 A g−1
demonstrated superior electrochemical performance with a wider potential window (0–2.4 V)
at 1.4 V. Furthermore, the Na3-MnO2//N-AC device with Na3-MnO2 as positive and N-AC
and higher energy and power densities (64 Wh kg−1 at 1225.53 W kg−1 ), as well as excellent
as negative electrodes demonstrated superior electrochemical performance with a wider
long-term cycling stability (83% capacitance retention after 10,000 cycles). This technique aims
potential window (0–2.4 V) and higher energy and power densities (64 Wh kg−1 at 1225.53
to bring new insights into the goal of a simple nanostructure, potentially leading to novel
W kg−1), as well as excellent long-term cycling stability (83% capacitance retention after
supercapacitor designs with longer working potential windows, more energy, and improved
10,000 cycles). This technique aims to bring new insights into the goal of a simple
power density.
nanostructure, potentially leading to novel supercapacitor designs with longer working
potential windows,
Supplementary more energy,
Materials: and improved
The following supportingpower density.
information can be downloaded at: https://
www.mdpi.com/article/10.3390/nano12162856/s1,
Supplementary Materials: The following supporting Figure S1: EDS elemental
information can mapping of Na3 -MnO
be downloaded at:2 ;
Figure S2. EDS mappingFigure
www.mdpi.com/xxx/s1, of NaS1:
3 -MnO
EDS2 ;elemental
Figure S3.mapping
The CV of Na33-MnO22; at a scan
Figure S2.rate
EDS of mapping
1, 2, 5, 10,
of20,
Na and
3-MnO50 mV s−1 inS3.
2; Figure different
The CVworking
of Na3-MnOpotential windows
2 at a scan rate ofof1,(a) 0–1.0
2, 5, V (b)
10, 20, and0–1.1
50 mVV; (c)
s−1 0–1.2 V; and
in different
working
(d) 0–1.3potential
V; Figurewindows
S4. The GCDof (a)of0–1.0 V (b)20–1.1
Na3 -MnO V; (c) current
at various 0–1.2 V;densities
and (d) of 0–1.3 V;15,
5, 10, Figure
20, 30,S4.40,
The50,
GCD
80 and of Na A g−12 in
1003-MnO at various
differentcurrent
working densities
potential of 5, 10, 15, 20,
windows of 30,
(a) 40, 50,V80(b)
0–1.0 and 100V;
0–1.1 A (c)
g−1 0–1.2
in different
V; and
working
(d) 0–1.3potential
V; Figurewindows
S5. Nyquistof plots
(a) 0–1.0 V (b) 0–1.1
recorded at 100V; (c) to
kHz 0–1.2 V; and
10 MHz of (d)
Na30–1.3
-MnO V;2 at
Figure S5. Nyquist
different working
plots
potential windows; Figure S6. Electrochemical performance of the of MnO2 without Na ions;Figure
recorded at 100 kHz to 10 MHz of Na 3-MnO 2 at different working potential windows; CV at
S6. Electrochemical
a scan rate of 1, 2, 5, performance
10, 20, 50 andof the
100ofmVMnO s−12 without Na working
in different ions; CV potential
at a scan rate of 1, 2,(a)
windows 5, 0–1.0
10, 20,V;
50
(c)and 100
0–1.2 V;mV s−1 in V;
(e) 0–1.4 different working
GCD curves at apotential windows
various current (a) 0–1.0
density of 1,V;
2, (c) 0–1.2
5, 10, 15, V;20,(e)
30,0–1.4
40, 50,V;80
GCDand
curves at−a
1 various current density of 1, 2, 5, 10, 15, 20, 30, 40, 50, 80 and 100 A
100 A g in different working potential windows of (b) 0–1.0 V; (d) 0–1.2 V and (f) 0–1.4 V; Figure S7. g −1 in different working

potential
comparison windows of (b)
of specific 0–1.0 V; (d)
capacitance 0–1.2 electrode
of MnO V and (f) at 0–1.4 V; Figure
different S7. comparison
potential window of 0–1.0, of specific
0–1.2, ca-
and
2
pacitance of MnO 2 electrode at different potential window of 0–1.0, 0–1.2, and 0–1.4 V as function of
0–1.4 V as function of current density; Figure S8. the electrochemical performance of AC was recorded
Nanomaterials 2022, 12, 2856 13 of 15

in the three-electrode system; (a) CV of the at a scan rate of 10–200 mV s−1 in 0–1.0 V; (b) GC of the
at a current density of 1–20 A g−1 in 0–1.0 V; (c) specific capacitance as a function of current density;
Figure S9. Comparison of CV curves of Na3 -MnO2 electrode and N-AC in their separate potential
windows of 1.4–0 V and 0–1.0 V respectively at a scan rate of 10 mV s−1 ; (b) CV curves at different
potential windows from 1.6 to 2.6 V were recorded at a scan rate of 10 mV s−1 ; Figure S10. Ragone plots
of Na3 -MnO2 //N-AC device volumetric energy and power density; Figure S11. Cycling performance
comparison at potential window of 0–1.0, 0–1.1, 0–1.2, 0–1.3, and 0–1.4 V.
Author Contributions: A.U.R. and W.J. designed the project. A.U.R. and N.Z. performed the ex-
periments. A.U.R. and N.Z. analyzed the data and wrote the manuscript. A.A. and G.L. critically
reviewed the manuscript. G.L. supervised and rechecked the manuscript. M.T., S.U., and M.S.
performed the DFT. All authors have read and agreed to the published version of the manuscript.
Funding: This research was supported by National Natural Science Foundation of China, award number
91956110, 22071102, 11911530174 and the Robert A. Welch Foundation (D-1361-20210327, USA).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: The data are available on reasonable request from the corresponding author.
Conflicts of Interest: The authors declare no conflict of interest.

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