metals

Article
Electrochemical Performance of Iron Oxide
Nanoflakes on Carbon Cloth under an
External Magnetic Field
Lei Geng 1, *, Zenglai Gao 1 and Qibo Deng 2
1 Tianjin Key Laboratory of Optoelectronic Detection Technology and Systems, School of Electronics and
Information Engineering, Tianjin Polytechnic University, No. 399 Binshui West Street Xiqing District,
Tianjin 300387, China; 15922161767@163.com
2 Tianjin Key Laboratory of Advanced Functional Porous Materials, Institute for New Energy Materials &
Low-Carbon Technologies, School of Materials Science and Engineering, Tianjin University of Technology,
No. 391 Binshui West Street Xiqing District, Tianjin 300384, China; qibodeng@tjut.edu.cn
* Correspondence: genglei@tjpu.edu.cn; Tel.: +86-022-8395-5164




Received: 22 October 2018; Accepted: 11 November 2018; Published: 13 November 2018


Abstract: In this work, the iron oxide (Fe2 O3 ) nanoflakes on carbon cloth (Fe2 O3 @CC) were
triumphantly prepared and served as the electrode of supercapacitors. By applying an external
magnetic field, we first find that the magnetic field could suppress the polarization phenomenon
of electrochemical performance. Then, the influences of the mono-/bi-valent cations on the
electrochemical properties of the Fe2 O3 @CC were investigated under a large external magnetic
field (1 T) in this work. The chemical valences of the cations in the aqueous electrolytes (LiNO3 and
Ca(NO3 )2 ) have almost no influences on the specific capacitance at different scan rates. As one of
important parameters to describe the electrochemical properties, the working potential window
of the Fe2 O3 @CC electrode was also investigated in this work. The broad potential window in
room-temperature molten salt (LiTFSI + LiBETI (LiN(SO2 CF3 )2 + LiN(SO2 C2 F5 )2 )) has been obtained
and reached 1.2 V, which is higher than that of the traditional aqueous electrolyte (~0.9 V).

Keywords: Fe2 O3 nanoflakes; magnetic field; molten salt; wide working windows; electrochemical
capacitors

1. Introduction
Electrochemical capacitors have been considered as a reliable supplement in power sources
aspect, which is due to their fast charging/discharging processing, good cycling properties and
high power density [1–3]. Nevertheless, their low energy density becomes a stumbling block
to the rapid development of supercapacitors. In order to get higher energy density several
strategies have been explored to design and fabricate electrode materials with various porous and
hierarchical nanostructures, which are conducive to enhance specific capacitances and modify the
rate performances [4–8]. Iron oxides (such as Fe2 O3 and Fe3 O4 ) have been brought into focus
as electrode candidates for supercapacitors in a variety of materials [9–12]. Specifically, α-Fe2 O3
materials have been synthesized and reported elsewhere because of their high theoretical capacitance,
low cost, and abundant chemical valences. Currently, various α-Fe2 O3 nanostructures, for instance
nanoparticles, nanotubes, nanosheets, and nanospheres with high super-paramagnetic behaviors,
porous structure, and high surface area have been researched and exhibited excellent electrochemical
properties [13–17]. However, the weak electrical conductivity of α-Fe2 O3 materials (10−4 Ω−1 ·m−1
for bulk and 2.5 × 10−3 Ω−1 ·m−1 for nanostructures) still makes it difficult to completely use the
active material, giving rise to finite enhancement of the specific capacitance [18–20]. There is literature

Metals 2018, 8, 939; doi:10.3390/met8110939 www.mdpi.com/journal/metals

Metals 2018, 8, 939 2 of 9

reporting that very small external magnetic fields (mT) have induced capacitance enhancement of
the Fe2 O3 -graphene nanocomposites [21]. This could explain why the external magnetic field is
deemed to facilitate the electrons/ions transmission between the electrolyte and the electrode during
charging/discharging procedure. However, one wonders if the very large magnetic field has an effect
on the capacitance. More recently, a finer morphology of nanoporous magnetic material has been
prepared by applying an external magnetic field (~0.5 T) which modulates different dealloying stages
of the nanoporous structure formation. We have reported the effect of an external magnetic field on
the dealloying process of the Ni-Al alloy in alkaline solution [22].
Munichandraiah et al. found that the aqueous electrolytes with bivalent cations (Ca2+ or
2+
Mg ) contributed to modify the MnO2 electrochemical utilization and, thus, improved the specific
capacitance [23,24]. However, the common aqueous electrolytes cannot overcome the thermodynamic
limitation of water splitting, ~1.23 V [25,26], and the non-aqueous electrolytes (e.g., organic electrolytes)
are generally combustible and expensive. Over the years, the inventive “water-in-salt” hybrids and
room-temperature molten salts have been proven to broad the working voltage window (much larger
than 1.23 V) [27–29]. Herein, this work investigates the influences of the mono-/bi-valent cations on
the electrochemical properties of the Fe2 O3 @carbon cloth (Fe2 O3 @CC) under an external magnetic field
(1 T). The electrochemical performances of the Fe2 O3 @CC electrode in a room-temperature molten salt
electrolyte have been also studied for the broad working potential window.

2. Materials and Methods

The carbon cloth (WOS 1002 PHYCHEMi Co., Ltd., Wuhan, China) in the work was conducted
the hydrophilic treatment. The detailed process is following: the carbon cloth was washed
with concentrated H2 SO4 and H2 O2 mixed solution, and deionized water under sonication for
2 h. The treated carbon cloth (CC) served as the substrate for the growth of Fe2 O3 nanoflakes.
Electrochemical deposition was performed at 1.5 V for 5 min in a conventional three-electrode system:
the treated CC, the Pt, and an Ag/AgCl as the working, counter and reference electrodes, respectively.
The working electrolyte was 0.05 M FeCl2 aqueous solution for iron deposition. Then the working
electrode was washed with deionized water and ethanol, and dried for a night. Lastly, the dried
precursors were calcinated at 650 ◦ C for 2 h in an inert atmosphere.
The structural information, constitute and morphology features of the Fe2 O3 @CC composites were
determined by X-ray diffraction (XRD, Rigaku D/Max-2500, Japan) with native Standard Measurement
software, and field emission scanning electron microscopy (FESEM, FEI Verios 460 L, Eindhoven,
The Netherlands). The electrochemical measurements were carried out in a three-electrode system:
the Fe2 O3 @CC (5 × 5 mm), the Pt (50 × 50 mm) and Ag/AgCl were used as working electrode, counter
electrode, and reference electrode, respectively. All electrochemical measurements were carried out
under an external magnetic field (EMP-5, East Changing, Beijing, China). The magnetic field was
controlled through adjusting the magnitude of the current and the magnetic flux density was then
measured by a Digital Gauss Meter (PF-045B, Mianyang, China). The direction of magnetic field
was perpendicular to the surface of working electrode. Cyclic voltammetry (CV) and electrochemical
impedance spectroscopy (EIS) of the Fe2 O3 @CC electrode were performed using electrochemical
workstation (CHI 760E, Shanghai, China) in different aqueous electrolytes of 1 M LiNO3 , 1 M Li2 SO4 ,
1 M KNO3 , 1 M Ca(NO3 )2 , and 1 M LiTFSI + LiBETI.

3. Results and Discussion

The phase and constitute of the composites were characterized by XRD analysis and the
corresponding result is shown in Figure 1. The distinct diffraction peak located at around 25◦ can
be ascribed to the carbon cloth substrate. Although the intensity of the remaining peaks is very
weak, the peak positions can be matched well with the Fe2 O3 (JCPDS No. 04-755), demonstrating the
triumphant preparation of the Fe2 O3 @CC composite. The crystallite size of the Fe2 O3 phase from XRD
pattern was 3.7 nm estimated by using the Scherrer equation.
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Figure 1. XRD pattern of the Fe2O3@CC composite.

Figure 1. XRD pattern of the Fe2 O3 @CC composite.
Figure 1. XRD pattern of the Fe2O3@CC composite.
Figure
Figure 22 shows
shows thethe microstructure
microstructure of of the
the Fe
Fe2OO3@CC composite electrode. After electrochemical
2 3 @CC composite electrode. After electrochemical
deposition,
Figure the
2 whole
shows the braided structure
microstructure of
deposition, the whole braided structure of the carbon of
thethe
Fe carbon
2O cloth
3@CC composite
cloth is is successfully
electrode.
successfully maintained
After
maintained and the
electrochemical
and the diameter
diameter of carbon fiber is approximately unchanged. Comparing to
of the carbon fiber is approximately unchanged. Comparing to the smooth surface of theand
deposition, the whole braided structure of the carbon cloth is the
successfully smooth surface
maintained of the
carbon
carbon
diameter
cloth, thecloth,
of the
Fe the Fe2O3fiber
carbon @CC iscomposite exhibits
approximately a rough Comparing
unchanged. surface, which indicates
to the smooththe successful
surface of the
2 O3 @CC composite exhibits a rough surface, which indicates the successful deposition of
deposition
carbon of
cloth, Fe
the2OFe
3. 2In
O Figure
3@CC 2b, the
composite flimsy
exhibits Fe O
2a nanoflakes
3rough with
surface, around
which 20 nm
indicates
Fe2 O3 . In Figure 2b, the flimsy Fe2 O3 nanoflakes with around 20 nm thickness are interconnecting and thickness
the are
successful
interconnectingof Feand
depositiondecorate
uniformly 2O3.uniformly
theIncarbon decorate
2b, the the
Figurefiber. flimsycarbon
Fe2O fiber.
3nanoflakes with around 20 nm thickness are

interconnecting and uniformly decorate the carbon fiber.

Figure 2.
Figure Low-resolution SEM
2. Low-resolution SEM image
image (a)
(a) and
and high-resolution
high-resolution SEM
SEM image
image (b)
(b) of
of the
the Fe
Fe22O
O33@CC
@CC
composite.
composite.
Figure 2. Low-resolution SEM image (a) and high-resolution SEM image (b) of the Fe2O3@CC
composite.
To verify the external magnetic field effect on the electrochemical performances of the Fe O @CC
To verify the external magnetic field effect on the electrochemical performances of the Fe22O33@CC
electrode, the CVs were carried out in different electrolytes with or without applying an external
electrode, the the
To verify CVsexternal
were carried
magneticoutfield
in different
effect onelectrolytes with or performances
the electrochemical without applying of theanFeexternal
2O3@CC
magnetic field and the results are shown in Figure 3. In Figure 3a, it is seen that the contribution
magnetic
electrode,field and the
the CVs results
were are out
carried shown in Figureelectrolytes
in different 3. In Figure with
3a, it isorseen that the
without contribution
applying from
an external
from the CC substrate can be negligible and the specific capacitance of the Fe2 O3 @CC electrode
the CC substrate
magnetic field and can
theberesults
negligible and the
are shown specific3.capacitance
in Figure In Figure 3a, ofitthe Fe2Othat
is seen 3@CC theelectrode
contributionis mainly
from
is mainly from the contribution of Fe2 O3 . In terms of CV shape, the specific capacitance of the
from
the CC the contribution
substrate can beofnegligible
Fe2O3. Inand termsthe of CV shape,
specific the specific
capacitance of the capacitance of the Fe
Fe2O3@CC electrode is2O 3@CC
mainly
Fe2 O3 @CC electrode is the combination of the double layer and pseudo-capacitive characteristic [30–32].
electrode
from the is the combination
contribution of Fe2Oof3.the
In double
terms oflayerCV and
shape,pseudo-capacitive characteristic
the specific capacitance of the[30–32].
Fe2O3@CC The
The specific capacitances of the Fe2 O3 @CC electrode are almost the same by integrating the enclosed
specific
electrode capacitances of the Fe2of
is the combination O3the
@CCdouble
electrode areand
layer almost the same by integrating
pseudo-capacitive the enclosed
characteristic [30–32]. areaThe
area with or without the external magnetic field. But their shapes of the CV curves have some
with or without
specific the external
capacitances of the Fe magnetic field. But are
2O3@CC electrode their shapes
almost ofsame
the the CV bycurves have the
integrating some differences
enclosed area
differences to a certain extent. Concretely, the polarization phenomenon of the CV plot is obtaining
to a certain
with or withoutextent.
the Concretely, the polarization
external magnetic phenomenon
field. But their shapes of the of theCVCV plothave
curves is obtaining efficient
some differences
efficient control when adding the external magnetic field. That is to say, the splitting of water in the
control whenextent.
to a certain addingConcretely,
the externalthe magnetic field. That
polarization is to say, the
phenomenon of splitting
the CV plotof water in the electrolyte
is obtaining efficient
electrolyte is suppressed by the external magnetic field. Therefore, the following electrochemical tests
is suppressed
control by thethe
when adding external
externalmagnetic
magnetic field. Therefore,
field. That thethefollowing
is to say, splitting ofelectrochemical tests in
water in the electrolyte
in different aqueous electrolytes are conducted under the external magnetic field. Figure 3 depicts CV
different aqueous
is suppressed by electrolytes
the externalaremagnetic
conducted under
field. the external
Therefore, the magnetic
followingfield. Figure 3 depicts
electrochemical testsCVin
plots of the Fe2 O3 @CC electrode in various aqueous electrolytes of 1 M Li2 SO4 , 1 MLiNO3 , 1 MKNO3 ,
plots of the
different Fe2O3@CC
aqueous electrode
electrolytes areinconducted
various aqueous
under electrolytes
the externalof 1 M Li2SO
magnetic 4, 1 MLiNO
field. Figure 33,depicts
1 MKNO CV3,
and 1 MCa(NO3 )2 , for exploring the better specific capacitance.The measurements were performed at
and
plots1 of
MCa(NO
the Fe2O 3)23,@CC
for exploring
electrode the better specific
in various aqueous capacitance.The
electrolytes of measurements
1 M Li2SO4, 1 MLiNO were performed
3, 1 MKNO at3,
the magnetic flux density (1 T). Among the CV in monovalent cationic electrolytes, the one in LiNO3
the
andmagnetic
1 MCa(NO flux
3)2,density (1 T). Among
for exploring the better thespecific
CV in monovalent
capacitance.The cationic electrolytes,were
measurements the one in LiNOat3
performed
solution presents the largestenclosed area. The CV plot shapes are nearly the same for the bivalent case,
solution presents
the magnetic flux the largestenclosed
density (1 T). Among area.
the The
CV inCV plot shapescationic
monovalent are nearly the samethe
electrolytes, forone
thein bivalent
LiNO3
solution presents the largestenclosed area. The CV plot shapes are nearly the same for the bivalent
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suggesting
case, the same
suggesting the electrochemical procedure.
same electrochemical Moreover,
procedure. the enclosed
Moreover, areas inareas
the enclosed CV for
in the
CVbivalent
for the
casepossess larger enclosed area than that in LiNO solution.
bivalent casepossess larger enclosed area than that 3in LiNO3 solution.

Figure 3.
Figure CV curves
3. CV curves ofof the
the Fe
Fe22OO33@CC
@CCandandCCCCelectrodes
electrodes with
with or
or without
without magnetic
magnetic field
field in
in various
various
aqueous electrolyte: (a) LiNO , (b) Li SO , (c) KNO , and (d) Ca(NO
aqueous electrolyte: (a) LiNO33, (b) Li22SO4,4 (c) KNO3,3and (d) Ca(NO3)32. 2) .

The variation
The variation of of the
the corresponding
corresponding specificspecific capacitance
capacitance with with the
the scan
scan rates
rates of of the
the Fe
Fe22O @CC
O33@CC
electrode in
electrode indifferent
differentelectrolytes
electrolyteshas hasexhibited
exhibitedinin Figure
Figure 4. 4.
TheThe calculated
calculated specific
specific capacitance
capacitance of the of
the Fe O @CC electrode measured in 1 M Li SO electrolyte are 52, 40, 29, 26, 23, and 19 mF cm −2
2 3 2 4
Fe2O3@CC electrode measured in 1 M Li2SO4 electrolyte are 52, 40, 29, 26, 23, and 19 mF cm at 1, 2, −2
at 8,
5, 1, 10,
2, 5,and
8, 10,
20 and
mV 20 s−1,mV s−1 , respectively.
respectively. As reported
As reported in the literature,
in the literature, the specific
the specific capacitancescapacitances
reduce
reduce with increase in the scan rate in any electrolytes [33–36]. The
with increase in the scan rate in any electrolytes [33–36]. The situation could be seen in other situation could be seen in other
electrolytes. The values of specific capacitance obtained in 1 M LiNO solution
electrolytes. The values of specific capacitance obtained in 1 M LiNO33solution are 53, 44, 28, 24, 24, are 53, 44, 28, 24, 24,
and 18 mF · cm −2 , respectively. However, these values obtained in 1 M KNO solution decrease to
and 18 mF·cm−2, respectively. However, these values obtained in 1 M KNO3 solution 3 decrease to 30,
30, 24, 20, 17, 15, and 9 mF · cm −2 , respectively. The slightly higherspecific capacitance of Fe O @CC
24, 20, 17, 15, and 9 mF·cm , respectively. The slightly higherspecific capacitance of Fe22O33@CC
−2
electrodeobtained in
electrodeobtained inlithium
lithiumions ions electrolyte could
electrolyte be ascribed
could be ascribedto more effortless
to more migration
effortless for lithium
migration for
ions. It possesses the applicable crystal size (0.69 Å for Li + , 1.38 Å for K + , and 0.99 Å for Ca 2+ ) [37].
lithium ions. It possesses the applicable crystal size (0.69 Å for Li , 1.38 Å for K , and 0.99 Å for Ca2+)
+ +
Simultaneously,
[37]. Simultaneously, the lower saturated
the lower concentration
saturated concentration of theofKNO solution
the 3KNO (only 3.1 M, about 10 M for
3 solution (only 3.1 M, about 10
LiNO ) results in its lowest specific capacitances at all scan rates.
M for3LiNO3) results in its lowest specific capacitances at all scan rates. Interestingly, Interestingly, the specific the capacitance,
specific
variation trend and retention are practically consistent in both LiNO
capacitance, variation trend and retention are practically consistent in both LiNO3 and Ca(NO 3 and Ca(NO 3 ) 2 solutions. Thus,
3) 2
the different valence of the cations in the electrolytes has no effects on
solutions. Thus, the different valence of the cations in the electrolytes has no effects on the the electrochemical performances
of the Fe2 O3 @CC
electrochemical electrode. of the Fe2O3@CC electrode.
performances
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Figure 4. The corresponding variation of the specific capacitances with the scan rate of the Fe2O3@CC
Figure4.4. The
Figure
electrode The
in corresponding
corresponding
different variation
variationof
electrolytes. ofthe
thespecific
specificcapacitances
capacitanceswith
withthe
thescan
scanrate
rateofofthe
theFeFe
2O 3 3@CC
2O @CC
electrode in different electrolytes.
electrode in different electrolytes.
EIS measurements were carried out to get more information about the impact of the cations
EIS measurements were carried out to get more information about the impact of the cations
EISon
valency measurements were carried
the electrochemical propertiesoutoftothe
getFemore
2O3@CC information
electrode. about the impact
Using Zview of the
software cations
(V2.0.1.6,
valency on the electrochemical properties of the Fe2 O3 @CC electrode. Using Zview software (V2.0.1.6,
valency on
Southern the electrochemical
Pines, NC, USA), the properties
equivalentof the Feand
circuit 2O3@CC electrode.
the best fitting Using Zviewplots
of Nyquist software (V2.0.1.6,
in LiNO 3 and
Southern Pines, NC, USA), the equivalent circuit and the best fitting of Nyquist plots in LiNO3 and
Southern
Ca(NO Pines, NC,are
3)2 solutions USA), the equivalent
exhibited in Figure circuit
5. The and
bestthe bestgives
fitting fittingthe
of RNyquist
s valuesplots in LiNO
for the Fe2O3@CC 3 and
Ca(NO3 )2 solutions are exhibited in Figure 5. The best fitting gives the Rs values for the Fe2 O3 @CC
Ca(NO ) solutions are exhibited in Figure 5. The best fitting gives the
electrode in LiNO3 and Ca(NO3)2 solutionas2.32 and 2.34 Ω, respectively, which are almost the same.
3 2 R s values for the Fe 2O 3 @CC
electrode in LiNO3 and Ca(NO3 )2 solutionas2.32 and 2.34 Ω, respectively, which are almost the same.
electrode
The Rct valuesin LiNO 3 and
for the FeCa(NO
2O3@CC 3)2electrode
solutionas2.32
in LiNO and 2.34Ca(NO
3 and Ω, respectively,
3)2 solution which are almost
are 287.12 the same.
and 289.35 Ω,
The Rct values for the Fe2 O3 @CC electrode in LiNO3 and Ca(NO3 )2 solution are 287.12 and 289.35 Ω,
The Rct valuesThereis
respectively. for thenot
Fe2O 3@CC electrode
strictly parallel toin each
LiNOother
3 and inCa(NO 3)2 solution are 287.12
the low-frequencies, and 289.35
indicating similarΩ,
respectively. Thereis not strictly parallel to each other in the low-frequencies, indicating similar
respectively.
Warburg Thereis not
impedance. strictly to
According parallel to each other
the literatures, the R inct the
valuelow-frequencies,
could be usually indicating
linked similar
to the
Warburg impedance. According to the literatures, the Rct value could be usually linked to the diffusive
Warburgresistance
diffusive impedance. andAccording
the distributedto the literatures,
resistance of thethe Rct value
electrode could which
material, be usually linked
hints the to the
negligible
resistance and the distributed resistance of the electrode material, which hints the negligible influences
diffusive resistance and the distributed resistance of the electrode material,
influences by the nature of electrolyte [25]. Therefore, there is no distinct differences on the EIS which hints the negligible
by the nature of electrolyte [25]. Therefore, there is no distinct differences on the EIS between LiNO3
influences
between LiNO by 3the
andnature
Ca(NOof3)2electrolyte
solution. [25]. Therefore, there is no distinct differences on the EIS
and Ca(NO3 )2 solution.
between LiNO3 and Ca(NO3)2 solution.

Figure 5. Nyquist plots of the Fe O3 @CC electrode in aqueous LiNO3 and Ca(NO3 )2 electrolytes.
Figure 5. Nyquist plots of the Fe2O23@CC electrode in aqueous LiNO3 and Ca(NO3)2 electrolytes. The
The circuit for fitting is inserted in the figure.
Figurefor
circuit 5. Nyquist
fitting is plots of the
inserted Fe2O
in the 3@CC electrode in aqueous LiNO3 and Ca(NO3)2 electrolytes. The
figure.
circuit for fitting is inserted in the figure.
Lately, Yamada et al. explored a room-temperature hydrate melt of Li salts (LiTFSI + LiBETI)
Lately, Yamada et al. explored a room-temperature hydrate melt of Li salts (LiTFSI + LiBETI)
served as aqueous electrolyte, which expanded the stable working voltage window [28]. In this work,
servedLately, Yamada
as aqueous et al. explored
electrolyte, a room-temperature
which expanded hydratevoltage
the stable working melt ofwindow
Li salts [28].
(LiTFSI + LiBETI)
In this work,
1 M LiTFSI + LiBETI aqueous solution was configured, and used as the electrolyte to investigate
1served as aqueous
M LiTFSI + LiBETIelectrolyte, which expanded
aqueous solution the stable
was configured, andworking
used asvoltage window to
the electrolyte [28]. In this work,
investigate the
the electrochemical performances compared with 1 M LiNO3 aqueous solution. Firstly, Figure 6a
1 M LiTFSI + LiBETI
electrochemical aqueous compared
performances solution was configured,
with 1 M LiNOand used as
3 aqueous the electrolyte
solution. to investigate
Firstly, Figure the
6a depicts
depicts CV curves of the Fe2 O3 @CC electrode with different working voltage window in 1 M LiTFSI +
electrochemical
CV curves of the performances compared
Fe2O3@CC electrode withwith 1 M LiNO
different 3 aqueous
working solution.
voltage windowFirstly,
in 1 MFigure
LiTFSI6a depicts
+ LiBETI
CV curves of the Fe2O3@CC electrode with different working voltage window in 1 M LiTFSI + LiBETI
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Metals 2018, 8, 939 6 of 9

electrolyte. Through expanding the negative voltage from −0.9 to −1.4 V, we investigate the stable
working voltage window
LiBETI electrolyte. Throughof the LiTFSI
expanding the +negative
LiBETI voltage
electrolyte.
from The−0.9CVto −shape always
1.4 V, we maintains
investigate the
rectangular-like
stable when expanding
working voltage window ofthe thenegative
LiTFSI + voltage
LiBETI from −0.9 toThe
electrolyte. −1.2CVV. shape
With further
always expanding
maintains
the negative voltage,
rectangular-like the response
when expanding current increases
the negative voltage fromrapidly,
−0.9 to hinting
−1.2 V.the Withsplitting
furtherofexpanding
water in
electrolyte.
the negativeThus, thethe
voltage, stable working
response voltage
current window
increases is −1.2
rapidly, to 0 V,the
hinting while it is −0.9
splitting to 0 Vininelectrolyte.
of water the above
aqueous
Thus, the electrolyte. Then
stable working the stability
voltage windowofis the
−1.2Feto
2O03@CC
V, whileelectrode in to
it is −0.9 1 0MVLiTFSI + LiBETI
in the above is in
aqueous
comparison with that in 1 M LiNO solution (Figure 6b). The primary rectangular-like
electrolyte. Then the stability of the Fe2 O3 @CC electrode in 1 M LiTFSI + LiBETI is in comparison
3 shapes are
similar,
with thatwhile
in 1 Ma LiNO
severe3 polarizationoccurred
solution (Figure 6b). Thein 1primary
M LiNOrectangular-like
3 solution due to the easier
shapes ions migration
are similar, while a
than 1 M LiTFSI + LiBETI with relatively high viscosity. This finding is in accordance
severe polarizationoccurred in 1 M LiNO3 solution due to the easier ions migration than 1 M LiTFSI with the
+
expanded working voltage window obtained for the room-temperature hydrate
LiBETI with relatively high viscosity. This finding is in accordance with the expanded working voltage melt of Li salts
electrolyte.
window obtained for the room-temperature hydrate melt of Li salts electrolyte.

Figure 6. CV curves of the Fe2 O3 @CC electrode: by increasing the negative potential limit from −0.9
Figure
to −1.4 6.
V CV
in 1 curves of the
M LiTFSI Fe2O3@CC
+ LiBETI electrode:
(a), from by increasing
−1.2 and 0 V in LiNOthe negative potential limit from −0.9 to
3 and LiTFSI + LiBETI (b), variation of
the specific capacitance with the scan rates (c), the Nyquist plots ofLiTFSI
−1.4 V in 1 M LiTFSI + LiBETI (a), from −1.2 and 0 V in LiNO 3 and the Fe2+OLiBETI (b), variation of the
3 @CC electrode in LiNO3
specific
and capacitance
LiTFSI with the scan rates (c), the Nyquist plots of the Fe2O3@CC electrode in LiNO3 and
+ LiBETI(d).
LiTFSI + LiBETI(d).
The variations of the specific capacitances in these two different electrolytes with the scan rates
The variations
are exhibited in Figureof the
6c tospecific capacitances
illustrate the electrolytesin these two different
effects. electrolytes
Not surprisingly, the with the scan
variation trendsrates
of
are exhibited in Figure 6c to illustrate the electrolytes effects. Not surprisingly,
the specific capacitances are similar, and the specific capacitances decrease with increasing the scan the variation trends
of the Moreover,
rates. specific capacitances
the specific are similar, andin
capacitances the1 specific
M LiNOcapacitances decrease
3 at all scan rates with increasing
are higher than thatthein scan
1M
rates. Moreover,
LiTFSI the specific
+ LiBETI, which is due capacitances in 1 M
to the lower ionic LiNO3 at all
conductivity, scan rates
slower are higher than
ions transportation andthat in 1 M
diffusion
LiTFSI + LiBETI,
limitation between which is due to the
the electrode andlower ionic conductivity,slower
electrolyte. However, the capacitance ions transportation
retention in and
1 M diffusion
LiTFSI +
limitation
LiBETI between
is higher thanthe electrode
that and electrolyte.
in 1 M LiNO 3 , that is to However,
say, the the capacitance
capacitance retention
attenuation in in 1 M
traditionalLiTFSI
Li-salt+
LiBETI iselectrolytes
aqueous higher thanis that
moreinsignificant.
1 M LiNO3, that is to say, the capacitance attenuation in traditional Li-
salt aqueous
Likewise,electrolytes
the EIS (afteris more significant.
fitting) of the Fe2 O3 @CC electrode in 1 M LiTFSI + LiBETI electrolyte
Likewise,
has been the EIS
measured to (after
contrastfitting)
withofthat
the inFe21OM 3@CCLiNOelectrode
3 . The in 1 M LiTFSI
whole shapes+areLiBETI electrolyte
similar, has
which are
been measured to contrast with that in 1 M LiNO
constituted by a semi-circle and a straight line. By best fitting with the some equivalent circuitare
3 . The whole shapes are similar, which in
constituted by a semi-circle and a straight line. By best fitting with the some equivalent circuit in
Metals 2018, 8, 939 7 of 9

Figure 5, the Rs values for the Fe2 O3 @CC electrode in LiNO3 and LiTFSI + LiBETI solution are 2.32
and 3.72 Ω, respectively, which are approximatelyequal. The Rct values in LiNO3 and LiTFSI + LiBETI
solution are 287.12 and 379.28 Ω, respectively. The higher charge transfer resistance may be attributed
to the high viscosity and the low ionic conductivity. Thus the straight line in 1 M LiTFSI + LiBETI is
more inclined, suggesting larger Warburg impedance. [38] And above all, the EIS plot in 1 M LiTFSI +
LiBETI indicates a higher resistance and more difficult ions diffusion than that in 1 M LiNO3 .

4. Conclusions
In summary, the electrochemical properties of the prepared Fe2 O3 @CC electrode have been
investigated in various aqueous electrolytes with or without external magnetic field. There is no
distinct influence of the larger external magnetic field (1 T) on the specific capacitance, while the
external magnetic field suppresses the water splitting. In addition, the specific capacitances at all scan
rates of the Fe2 O3 @CC electrode in usual aqueous electrolytes have been virtually unaffected by the
chemical valences of the cations. Finally, the Fe2 O3 @CC electrode in 1 M LiTFSI + LiBETI electrolyte
exhibits a broad working voltage window (1.2 V), but shows slightly low specific capacitances at
all scan rates. This may be due to the high viscosity and low conductivity of the room-temperature
molten salts.

Author Contributions: L.G. and Q.D. designed the experiments. L.G. and Z.G. performed the experiments.
All authors discussed the results and commented on the manuscript.
Funding: This research was funded by the Program for Innovative Research Team in University of Tianjin
(no. TD13-5034), the Plan Program of Tianjin Educational Science and Research (no. 2017KJ087), the National
Natural Science Foundation of China (no. 61771340), and Tianjin Natural Science Foundation (17JCQNJC01400).
Acknowledgments: L.G. and Q.D. acknowledge Cuihua An for great helpful discussion.
Conflicts of Interest: The authors declare no competing financial interest.

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