Journal of Power Sources 520 (2022) 230866

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Journal of Power Sources

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

Nitrogen-doped graphene fiber electrodes with optimal micro-/meso-/

macro-porosity ratios for high-performance flexible supercapacitors
Feng Han a, c, Weixuan Jing a, *, Qian Wu b, Bian Tian a, Qijing Lin a, Chenying Wang a,
Libo Zhao a, Junshan Liu c, Yu Sun d, Zhuangde Jiang a
a
State Key Laboratory for Mechanical Manufacturing Systems Engineering, Xi’an Jiaotong University, Xi’an, 710049, PR China
b
School of Highway, Chang’an University, Xi’an, 710064, PR China
c
Key Laboratory for Micro/Nano Technology and System of Liaoning Province, Dalian University of Technology, Dalian, 116024, PR China
d
Department of Mechanical and Industrial Engineering, University of Toronto, Toronto, Ontario, Canada

H I G H L I G H T S

• Hierarchically structured nitrogen-doped graphene fibers are fabricated.

• The utilization efficiency of fiber inner interface is improved.
• Nitrogen doping improves wettability, nitrogen content and electrical conductivity.
• The all-solid-state flexible fiber-based supercapacitors have been fabricated.
• Fiber-based supercapacitors exhibit outstanding electrochemical performance.

A R T I C L E I N F O A B S T R A C T

Keywords: The introduction of graphene fiber-based supercapacitors as important power storage components in wearable
Fiber-based supercapacitors electronic products has attracted increasing attention because of their lightweight, good flexibility, high power
Nitrogen-doped graphene fiber density, long lifecycle and excellent charge/discharge capacity. However, their capacitance and energy density
Graphene stacking
are greatly confined as a result of the dense graphene stacking, hydrophobicity and poor electrical conductivity
Utilization efficiency
Electrochemical performance
of graphene fiber electrodes. Here we report a nitrogen-doped graphene fiber electrode with optimal micro-/
meso-/macro-porosity ratios to improve the utilization efficiency of fiber inner interface for accumulated charge
storage and boosted ion transport. Urea is employed as both nitrogen doping source and self-removed template
for graphene fibers to tune the hierarchically porous architecture, wettability, nitrogen content, and electrical
conductivity for improved electrochemical performance. The resulting supercapacitors display superior areal
capacitance of 1,217 mF/cm2 (486.3 F/g) and high energy density of 27 μW h/cm2 (10.8 W h/Kg) in polyvinyl
alcohol/H3PO4 gel electrolyte. These metrics represent the highest values to date among existing all-solid-state
fiber-based supercapacitors based on inorganic electrolyte. Moreover, the fiber-based supercapacitors show good
rate capability and excellent cyclic performance. Our work also provides an understanding of the effect of fiber
structure on electrochemical activity and highlights the importance of full utilization of graphene interior
interface.

1. Introduction
In recent years, flexible and wearable electronics has aroused great
interest owing to their wide applications in sensors, collapsible displays,
and intelligent skins [1–3]. Flexible power supplies are urgently needed
to offer the power for these electronics. Since conventional power
sources are generally flat and rigid, it is hard to satisfy the demand for
wearability [4–6]. Fiber-based supercapacitors (FSCs), as promising
energy storage components, have undergone intensive development for
their outstanding advantages of light weight, good flexibility, high
power density, long lifecycle and excellent charge/discharge capacity
[7–17]. According to the charge storage mechanism, there are two

* Corresponding author.
E-mail address: wxjing@mail.xjtu.edu.cn (W. Jing).

https://doi.org/10.1016/j.jpowsour.2021.230866
Received 26 June 2021; Received in revised form 16 November 2021; Accepted 30 November 2021
Available online 7 December 2021
0378-7753/© 2021 Elsevier B.V. All rights reserved.
F. Han et al.
categories of supercapacitors, namely pseudo-capacitors and electrical
double-layer capacitors (EDLCs). The materials used in
pseudo-capacitors mainly include transitional metal oxides/hydroxide
and conducting polymers, which are vital for the enhancement of
pseudo-capacitance through faradaic redox reactions [18–22].
Compared with pseudo-capacitors, EDLCs based on high specific surface
carbon materials have distinct advantages in superior cycling stability,
better reversibility, higher electrical conductivity, and lower cost [22,
23]. Carbonous FSCs are primarily fabricated with activated charcoal,
reduced graphene oxide (rGO) and carbon nanotubes (CNTs), which are
promising candidates to be extensively applied in generators [24],
sensors [25], actuators [26], and nonvolatile memory [27].
Owing to the remarkable mechanical/electrical properties and ul­
trahigh theoretical specific surface area (SSA) (2,620 m2/g), graphene is
considered as a very promising candidate as an attractive electrode
material for FSCs [28–31]. However, the loosely connected graphene
nanosheets are significantly aggregated and closely packed within gra­
phene fibers during dry process because of the strong interaction of
capillary force between layers [32–34]. The severe graphene stacking
causes limited electrolyte penetration and poor utilization of the high
SSA of graphene [35]. Therefore, a variety of materials have been uti­
lized to mitigate graphene stacking and promote the charge-storage
ability [18–22,35–41]. For instance, 286 mF/cm2 in capacitance and
6.4 μW h/cm2 in energy density were achieved through usage of gra­
phene fiber electrodes that incorporated holey graphene [35]. To further
improve electrochemical performance, conducting polymers (polyani­
line and poly(3,4-ethylenedioxythiophene) and metal oxide (Co3O4 and
MnO2) were incorporated on graphene to provide pseudocapacitance
effect [39,40]. Hence, the capacitance and energy density values were
enhanced to 304.5 mF/cm2 and 6.8 μW h/cm2, respectively [18].
Furthermore, the introduction of nitrogen heteroatom into graphene
fiber for large SSA and high electrochemical activity contributed to the
excellent capacitance of 1,132 mF/cm2 and high energy density of 25.1
μW h/cm2 [41].
In the light of the charge storage mechanism of EDLCs, electrode
materials can achieve the storage and release of energy through the
electrostatic interaction of ions at the electrode/electrolyte interface
[42,43]. Although several schemes have been proposed to boost the
utilization of fiber structures, efforts have been mainly made to apply
outer surfaces [44–46]. One strategy is to construct pores on graphene
fibers to shorten the ion diffusion distance between graphene layers,
thus facilitating ion transport to the whole surface area [44]. Electrolyte
ions can only penetrate several nanometers away from the fiber-shaped
electrode surface, leaving the interior parts merely as carbon substrates
and contributing little to charge storage and electrochemical perfor­
mance. Therefore, it is desired to construct graphene fiber electrodes
with an increased effective interfacial area to further promote the per­
formance of graphene-based FSCs (GFSCs). An efficient method is to
synthesize a hollow RGO/conducting polymer composite fiber with
additional inner interface to produce a higher SSA and present a higher
specific capacitance in the fiber supercapacitor [18]. However, the uti­
lization of fiber electrode inner structure in FSCs remains low. Wu et al.
reported nitrogen-doped graphene fibers (NGFs) with uniform porous
structure and demonstrated the significant influence of SSA on their
electrochemical performance [41]. Nevertheless, the electrochemical
performance of GFSCs is also under the influence of ion-accessible pore
size besides SSA [47,48]. Through taking pore curvature into account,
the heuristic theoretical model can be built and substituted for the EDLC
model that a hierarchically porous structure is essential for the ideal
carbon electrode to promote charge storage with micropores (<2 nm),
enhance ion transport with mesopores (2–50 nm) and act as buffer area
for electrolyte ions with macropores (>50 nm) [49–51]. We hypothe­
sized that improved utilization efficiency of fiber inner interface can be
achieved for enhanced charge storage and shorten ion pathway by
varying the micro-/meso-/macro-porosity ratios in the fiber electrode.
In this work, we report hierarchically porous NGFs with an optimal
2
Journal of Power Sources 520 (2022) 230866
micro-/meso-/macro-porosity ratio, elevated wettability, additional ni­
trogen (N)-active sites, and excellent electrical conductivity. By altering
the surface charge density and porous architecture of graphene layers
through chemical interactions, the nitrogen doping effectively tunes the
local electronic structure of electrodes and improves the fiber structure
utilization, resulting in enhanced ion diffusion and superior charge
storage ability. The supercapacitor assembled from 20%-NGFs shows a
high areal capacitance of 1,217 mF/cm2 at 0.1 mA/cm2 (486.3 F/g at
0.4 A/g), corresponding to an ultrahigh energy density of 27 μW h/cm2
at a power density of 40 mW/cm2 (10.8 W h/Kg at 16.0 W/kg). To our
knowledge, these metrics represent the highest values to date among
existing all-solid-state FSCs based on inorganic electrolyte to. Addi­
tionality, the 20%-NGFs based supercapacitor shows good rate perfor­
mance, excellent cycling stability and flexibility.
2. Experimental section
2.1. Preparation of nitrogen-doped graphene fibers (NGFs)
GO was fabricated according to the Hummer’s method with modi­
fications [52]. Then NGFs were fabricated as described below. Urea was
mixed into an aqueous solution of GO (12 mg/mL). Fibers with different
urea/GO weight ratios of 0:1, 1:9, 1:4 and 2:3 (named as GFs,
10%-NGFs, 20%-NGFs, and 40%-NGFs, respectively) were synthesized
to determine the optimal composition of the hybrid fibers for FSCs. The
mixture solution was treated by ultrasonic processing for 30 min and
subsequently injected into a polytetrafluoroethylene (PTFE) tube of 2
mm in inner diameter using a syringe pump at the current velocity of 10
mL/h, which was then heated at 180 ◦ C for 2 h in an oven after sealing
airtight both ends of the tube. The preformed amino-functionalized
reduced-GO (rGO(-NH2)n) fibers with a 1 mm diameter in the wet
state were released from the tube by N2 flow and dried in the air. The
length of the fibers remained almost unchanged, but the diameter
greatly decreased due to water loss. Finally, the fibers were placed into a
furnace with controlled vacuum and gas flows. Before heating a vacuum
of 0.1 Pa and ultrapure argon flow of 200 sccm were used to take away
O2 and water vapor for 2 h. The samples were then annealed with a rate
of 2.5 C/min under argon protection, maintained constant at 1000 ◦ C
◦
for 2 h, and left in the furnace to cool naturally. Ambient air was finally
allowed to the furnace and the fibers were retrieved. After thermal
annealing, the amino-functionalized rGO fibers were reduced to NGFs.
2.2. Assembly of NGFs-based supercapacitors (NGFSCs)
The preparation of the gel electrolyte was as follows: firstly, 1 g
polyvinyl alcohol (PVA) powder was added into 10 mL DI water, fol­
lowed by 30 min of vigorous stir at 90 ◦ C until it became a clear solution.
Secondly, 1 g H3PO4 was added into the mixture when its temperature
dropped to the environment. All-solid-state NGFSCs was then assembled
with two fibers and the PVA/H3PO4 gel electrolyte. The fiber was
immersed in the electrolyte for 1 h and removed to dry in the air for 8 h.
Two fiber electrodes coated with electrolyte were parallelly put on
flexible PET substrate by recoating some electrolyte to make a solid-state
supercapacitor.
2.3. Materials characterization
The observation of surface morphologies was performed using field
emission scanning electron microscopy (FESEM, Hitachi SU-8010). The
tensile stress-strain properties were measured with a microforce tester
(MTS Tytron250). X-ray diffraction (XRD, Brooke Advanced D8 A25)
was employed to analyze the crystal structures of fibers. The chemical
structures were detected with a Bruker VERTEX70 Fourier transform
infrared (FTIR) spectroscopy. Optical contact angle (OCA) measurement
was conducted on a Dataphysics OCA40Micro measuring instrument to
survey the wettability and contact angles. The surface chemical analyses
F. Han et al.
were characterized using a Thermo Fisher Escalab xi + X-ray photo­
electron spectroscopy (XPS). Keithley 2400 Source Meter was utilized to
measure the electrical conductivities. Nitrogen adsorption–desorption
measurement was carried out with a static volumetric gas adsorption
instrument (Micromeritics ASAP 2020 Plus HD88) and calculated using
Brunauer-Emmett-Teller (BET) technique to characterize surface area
and pore structure.
2.4. Electrochemical measurements
An electrochemical workstation (CHI 660D) was employed to mea­
sure the electrochemical performance, including cyclic voltammetry
(CV), galvanostatic charge/discharge (GCD) and electrochemical
impedance spectra (EIS). The areal capacitance (CA) and mass capaci­
tance (CM) of the single fiber electrode can be quantified by:
CA = 4I × t × U − 1 A− 1
CM = 4I × t × U − 1 M − 1
where I represents charge/discharge current, t stands for the discharge
time, U is equal to the potential range, A represents the surface area of
the overlapping part between two electrodes, and M is the mass of the
two fiber electrodes, respectively.
Then, the energy density (E) and power density (P) of the electrode
materials based on the area/mass of the whole FSCs were determined by:
/ highly aligned along the fiber’s main axis. In addition, the cross-
E = CU 2 8 (3)
P = E × t− 1
For the NGFSCs, the surface area (A), volume (V) and mass (M) of the
two electrodes are calculated by:
A = 2πDL
V = 0.5 πD2 L
M = ρV
where D represents the diameter of the fibers, L is the overlapping length
between two fibers, and ρ is the density of the fiber, respectively.
The coulombic efficiency is derived as:
Fig. 1. Schematic illustration showing the fabrication process of porous NGFs. (a) Doping mechanism of nitrogen in graphene. (b) The nitrogen-doped graphene fiber
was prepared by injecting well-dispersed solutions comprising GO and urea into a PTFE tube, followed by a confined self-assembly step in an oven at 180 ◦ C for 2 h,
release from the tube by a pressurized nitrogen flow, and thermal reduction at 1000 ◦ C for 2 h.
Journal of Power Sources 520 (2022) 230866
td
η= × 100% (8)
tc
where tc and td represent the charge and discharge time, respectively.
3. Results and discussions
The formation mechanism of the NGFs is shown in Fig. 1 and Fig. S1.
Well-mixed GO/urea was injected into a PTFE tube, followed by baking
it at 180 ◦ C for 2 h after sealing up the two ends of the tube. The mixture
was uniformly diffused and evenly self-assembled into a 3D network
structure within the tube, followed by drying in air to form amino-
functionalized rGO fibers (also known as NGFs before annealing). The
fiber was heated at 1000 ◦ C in an inert environment such that rGO
experienced a further reduction, and the amino functionalization was
(1) decomposed and doped nitrogen into the graphene lattice. Accordingly,
the nitrogen-doped graphene fiber with a hierarchically porous network
(2) and excellent electrical conductivity was achieved. For comparison, GFs
were also produced with the same procedure but without urea. Notably,
nitrogen contents in the graphene fibers increased with the increasing
urea loadings in the mixture solution, as quantified by XPS analysis.
The porous fibers were first studied by SEM. Fig. 2a is a presentation
of the cross-sectional images of GF with a diameter of ~126 μm,
demonstrating the rough and wrinkled surface. The zoomed-in view
(Fig. 2b) shows that the graphene sheets in GF were densely stacked and
sectional images of GF (Fig. 2c and d) reveal compactly entangled gra­
phene sheets with micropores, which is proved by further BET analysis.
(4) SEM images of 10%-NGF, 20%-NGF, and 40%-NGF with different urea
loadings are shown in Fig. 2e–h, Fig. 2i-l, and Fig. 2m–p, respectively.
For the NGF with a low urea fraction of 10% (Fig. 2f), more inter­
connected mesoporous surface can be seen compared with that of GF.
(5) The number of mesopores in the fiber (Fig. 2j) increases as the weight
ratio of urea increased to 20%. From the zoomed-in view of the cross
(6) section of 20%-NGF (inset of Fig. 2l), the fiber is well distributed with
hierarchical pores with a size range from a few tenths of a nanometer to
(7) over a hundred nanometers. It is beneficial for such a porous structure of
the fiber to provide plenty of ion-accessible path channels for rapid
charge transfer. As a result, the 3D pillared-vertically aligned nitrogen-
doped graphene sheets are constrained within a 1D fibrous structure,
resulting in that our fibers with both the rich pores and effective ion-
3
F. Han et al. Journal of Power Sources 520 (2022) 230866

Fig. 2. Microstructures of the hybrid fibers. (a–d) The surface and cross-sectional images of GF, respectively. The inset of (d) shows the densely stacked graphene
sheets in GFs at high magnification. (e− h) The surface and cross-sectional images of 10%-NGF, respectively. The inset of (h) shows more interconnected porous
surface in 10%-NGF than that of GF. (i–l) The surface and cross-sectional images of 20%-NGF, respectively. The inset of (l) shows hierarchical pores with sizes in the
range of several nanometers to over a hundred nanometers. (m–p) The surface and cross-sectional images of 40%-NGF, respectively. The inset of (p) indicates a
portion of small pores in the fiber are further enlarged into large pores.

accessible interfacial area are attractive for high-areal-performance
FSCs. When the weight ratio of urea is 40%, a portion of small pores
in the fiber is further enlarged into macropores (Fig. 2p), and graphene
sheets become sparsely stacked (Fig. 2n).
The stress-strain data of GFs and NGFs before and after annealing are
shown in Supplementary Fig. 2. Before annealing the tensile strength
and elongation of 20%-NGF are 152 MPa and 6%, respectively, exhib­
iting an increase in tensile strength (126 MPa) and a slight decline in
elongation (6.7%) compared with that of GF. The tensile strengths are
obviously improved (224 MPa for 20%-NGF and 210 MPa for GF) and
elongations are found to decrease (2% for 20%-NGFs and 2.4% for GFs)
after high temperature treatment. In comparison, the mechanical
integrity of 40%-NGFs after annealing is much poorer because of a
largely reduced elongation (1.1%) and prone to breakage during
handling, and parts of the fiber structure lack continuity.
The fibers were nitrogen doped during the nitridation synthesis with
urea, as further investigated by XRD, FTIR, and XPS (Figs. S3–5). Fig. S3
presents the XRD patterns of the hybrid fibers. GF before annealing has
the (002) diffraction peak located at 2θ = 11.49◦ , corresponding to
calculated interlayer spacing of 7.7 Å. However, the diffraction peak for
GF shifts to 2θ = 25.86◦ with a d-spacing of 3.44 Å after thermal
annealing at 1000 ◦ C. Such a decreased interlayer spacing is probably
because the oxygen heteroatoms within rGO(-NH2)n are largely removed
through high temperature treatment [53,54]. As for NGFs with different
urea contents, the XRD patterns exhibit the peak centered at 2θ =
27.64◦ , which corresponds to the interlayer spacing of 3.22 Å. The lower
d-spacing of NGFs than that of GFs indicates the change of inner struc­
ture within rGO, resulting from the further reduction of rGO and the
replacement of certain carbon atoms by nitrogen atoms in graphene.
To further confirm thermal reduction and nitrogen-doping of the
fibers, the FTIR patterns of GFs before and after annealing, 10%-NGFs,
20%-NGFs, and 40%-NGFs were analyzed (Fig. S4). The GF before
annealing shows the distinct peaks at 2665, 2308, 1787, 1555 and 1061
cm− 1, which originate from CHn bonds, CO2, C– – O, C– – C and C–O,
respectively, revealing that the surface of rGO(-NH2)n are attached with
abundant oxygen-containing groups. The GF after annealing has their
characteristic peaks around 2308 (CO2 bond), 1728 (C– – O), 1546
(C–– C) and 1068 cm− 1 (C–O), while there is no obvious peak relating to
CHn bonds but a new peak relating to sp2 C–C bonds is present, sug­
gesting a large quantity of oxygen groups are partially decomposed and
sp2 carbon regions are restored [55]. For all the NGFs, the peaks around
2004 (C–N), 1625 (C– – C), 1284 (C–– N) and 730 cm− 1 (sp2 C–C) confirm
that the NGFs are both further reduced and doped with nitrogen atoms.
The elemental composition of carbon, oxygen and nitrogen in the
fibers was examined by XPS (Fig. S5). As shown in Fig. S5a, the survey
spectra of the GF before and after annealing reveal the existence of C1s
(284 eV) and O1s (532 eV), while the characteristic peak of N1s is
observed in 20%-NGF, suggesting that 20%-NGF has nitrogen incorpo­
rated into the carbon matrices. The high resolution C1s peak of GF
before annealing (Fig. S5b) can be deconvoluted into one main peak at
284.8 eV (sp2 C–C), and three small peaks including C–O (285.4 eV),
C–– O (286.6 eV) and O–C– – O (288.5 eV) at higher binding energies,
demonstrating the presence of oxygen heteroatoms. After annealing, the
GF (Fig. S5c) has more dominance of sp2 C–C in C1s peak, further
illustrating partially decomposition of oxygen functional groups and
better recovery of π-conjugated structure. For 20%-NGF (Fig. S5d), peak
deconvolution of the C1s spectrum presents three sub-peaks of sp2 C–C,
C–– N & C–O and C–N & C– – O, which locate at 284.8, 285.6 and 287 eV,
respectively [56].
The XPS characterization was used to further confirm the nitrogen

4
F. Han et al.
content and bonding configurations to investigate the relationship be­
tween evolution of nitrogen functionalities during synthesis and
capacitive performance of fibers (Figs. 4e and S6). As seen the high
resolution N1s peak in Fig. S6d, the obtained NGFs have rather complex
structure with four types of nitrogen, which is different from that of urea
with only one nitrogen functionality (N–H). Four components of N1s
spectrum consist of pyridinic N (N-6), pyrrolic N (N-5), quaternary N (N-
G) and oxidized N (N–O), locating at 398.6, 399.9, 401 and 402 eV,
respectively. Among these functionalities, N-6 and N-5 mainly exist on
the edge of the graphene nanosheets, and may provide additional elec­
trochemically active sites to enhance pseudo-capacitance. N-G is doped
within the graphitic basal plane, which can help improve electrical
conductivity of carbon materials and enhance fast charge/discharge [57,
58]. Hence, nitrogen-doping shows great impact on the improvement of
specific capacitance owing to the pseudo-capacitive and electrical
conductive contributions. As presented in Figs. S6a–c, the N-G peak
becomes increasingly apparent with higher urea fractions, resulting
from the transformations of the nitrogen configurations and recon­
struction of the NGFs structure. A greater proportion of N-G during
synthesis under enough urea fractions can be ascribed to the higher
stability than that of N-6 and N-5 [56].
To demonstrate the superiority of fiber electrodes for FSCs, the
electrochemical test was performed through CV and GCD in a symmetric
two-electrode configuration (Fig. 3), where our fiber and 1 M PVA/
H3PO4 gel was used as the electrode and electrolyte, respectively. From
the plots in Fig. 3a, the CV curves of the as-synthesized FSCs are ob­
tained at 2 mV/s with the potential in the range 0–0.8 V. Surprisingly, all
the CV curves exhibit a near rectangle in shape behaving as the typical
EDLCs. The GF presents the smallest closed area by comparing CV
curves, which was smaller than that of 10%-NGFs. The 20%-NGF ex­
hibits the surprisingly largest CV area, suggesting the best charge-
storage ability as a fiber electrode. With the increasing urea content to
40%, the CV area dramatically decreases although it is yet larger than
those of GFs and 10%-NGFs, leading to deteriorated electrochemical
performance.
Fig. 3b reveals the GCD curves for the graphene-based FSCs at a
Fig. 3. Electrochemical characterization of FSCs in H3PO4/PVA electrolyte. (a) CV curves of FSCs at a rate of 2 mV/s (b) GCD curves at a current density of 0.1 mA/
cm2. (c) The areal capacitance calculated from GCD curves under different current densities. (d) The Ragone plots of the NGFSCs. The rate capabilities of the GFSCs,
10%-NGFSCs, 20%-NGFSCs and 40%-NGFSCs are marked on the diagram, respectively.
5
Journal of Power Sources 520 (2022) 230866
current density of 0.1 mA/cm2. As compared to that of GF (20.5 mV), the
smaller IR drop can be observed in 10%-NGFs (16.1 mV), 20%-NGFs
(8.2 mV), and 40%-NGFs (14.8 mV). The results may be ascribed to the
smaller overall resistance and shorter diffusion distance in NGFs than
that in GFs, which are conducive to better capacitance characteristics
[59–61]. The discharge time for GF, 10%-NGF, 20%-NGF, and 40%-NGF
is 759s, 1419s, 2434s, and 1878s, respectively. Among these fibers,
20%-NGF possesses the longest discharge time, and thus contributes to
the highest areal capacitance of all the FSCs. Moreover, the GCD curves
of the GFs, 10%-NGFs, 20%-NGFs, and 40%-NGFs present regular isos­
celes triangles in shape, further verifying the good electrochemical
performance and reversibility [44].
For fiber supercapacitors, the specific capacitance based on area is
more common and useful factor than that based on mass to evaluate the
real application for flexible energy-storage devices. When the current
density is in the range of 0.1–1 mA/cm2, the values of areal capacitance
were calculated based on the GCD curves, the results of which were
summarized in Fig. 3c. The GF presents a good capacitance of 379.5 mF/
cm2 at 0.1 mA/cm2, which can be compared with the values for most
FSCs reported previously [18,60,62]. The areal capacitance of 10%-NGF
increases to 709.5 mF/cm2, and it reaches the best value of 1217
mF/cm2 for 20%-NGF, demonstrating 1.87 times and 3.2 times that of
the GF electrode, respectively. Nevertheless, the capacitance value de­
creases to 938.75 mF/cm2 for 40%-NGF. Similar trends were also
observed for all the FSCs under different current densities (Fig. 3c). With
the increasing current density to 1 mA/cm2, satisfactory CA values of
NGFs electrodes (356 mF/cm2, 659 mF/cm2, 298 mF/cm2 for 10%-NGF,
20%-NGF, and 40%-NGF, respectively) are still preserved, whereas the
GF only maintains 168 mF/cm2. In summary, the 20%-NGF electrode
exhibits a high CA value and excellent rate capability.
The Ragone plots in Fig. 3d compare the energy storage performance
of our FSCs with different nitrogen doping in PVA/H3PO4 gel electrolyte.
The energy density increases to 27 μW h/cm2 for 20%-NGFSCs, which is
higher than GFSCs (8.43 μW h/cm2), 10%-NGFSCs (15.77 μW h/cm2)
and 40%-NGFSCs (20.86 μW h/cm2). In addition, a downward trend of
the energy density is shown in all the FSCs with increase in the power
F. Han et al.
density. It is noteworthy that the E/PA curve of 20%-NGFSCs is
comparatively smooth with the best rate capability of 54.1%, whereas
the GFSCs (44.3%), 10%-NGFSCs (46.4%) and 40%-NGFSCs (49.7%)
show the poorer rate performance.
To establish a comprehensive understanding of the influence of ni­
trogen doping on the capacitive performance enhancement of the
NGFSCs, various key characterizations consisting of N2 adsorption/
desorption, contact angle, electrical conductivity measurements, XPS
spectra and EIS were conducted. N2 adsorption/desorption was first
used to achieve and assess the BET SSA (Fig. 4a) and pore size distri­
bution (PSD, Fig. 4b). From N2 adsorption/desorption isotherm test,
together with SEM images (Fig. 2), it is worth noting that the SSA and
pore structures of NGFs are distinct from that of GFs and they vary with
the urea content. The GF isotherm (Fig. 4a) shows typical type-I curves
with strong N2 adsorption observed at relative atmospheric pressure (P/
P0) <0.1, demonstrating the micropore-rich structures, while the NGFs
present typical type-IV isotherms with abundant mesopores. More
detailed information can be provided by further analysis of the PSD
(Fig. 4b) and pore volume percentages (Fig. 4c). With the increasing
urea fraction from 0 to 40%, the microporosity of the as-prepared fibers
reduces, while at the same time the mesoporosity and macroporosity
increase, suggesting a transition from the micropore-rich structure of
GFs to the mesopore-rich structure of NGFs. Such pore size change is
probably because urea can serve as a self-removed pore former as well as
nitrogen source to realize synergetic pore structure optimization and
nitrogen doping [63,64]. In the fabrication process of NGFs, residual
Fig. 4. Characteristics of the hybrid fiber electrode. (a) Nitrogen adsorption/desorption isotherm. (b) pore size distribution and (c) different pore volume percentages
of GF, 10%-NGF, 20%-NGF, and 40%-NGF. (d) Water contact angle measurement for GFs with different urea contents. (e) The relationship between electrical
conductivities and different nitrogen-active sites. (f) Nyquist plots of the FSCs from GF, 10%-NGF, 20%-NGF, and 40%-NGF.
6
Journal of Power Sources 520 (2022) 230866
urea in the fiber (Fig. S7) can be further removed through high tem­
perature annealing with the release of large amounts of gaseous prod­
ucts such as CO2, water molecules and N-containing gases. These gases
decomposed from urea quickly enter the narrow space and cause a
“bombing” effect, thereby overcoming the van der Waals interaction
between adjacent NGFs nanosheets and forming porous structures. This
loose porous structure, including mesoporous and macroporous struc­
tures, can increase the gap between adjacent NGFs nanosheets, thereby
preventing their stacking.
As shown in Fig. 4a, c, the GF has 78.4% micropores, 19.1% meso­
pores, 2.5% macropores and low SSA (228 m2/g). The low SSA can
reduce the available ion-accessible area in GF. Meanwhile, micropores
can strengthen the ion storage for a prominent capacitive performance,
whereas the ultrahigh micropore volume of GF can increase the resis­
tance of electrolyte ion transporting from fiber-shaped electrode surface
to the interior parts, leading to the low rate performance at high current
density. Notably, the GF shows the hydrophobic property with an initial
contact angle of 103.8◦ (Fig. 4d), suggesting the raised resistance and
hindered ion transport at electrode/electrolyte interface because of the
inferior wettability [65,66]. A large IR drop (Fig. 3b) of 20.5 mV and
equivalent series resistance (ESR, Fig. 4f) of 257.2 Ω are obtained due to
the serious blocking of ion diffusion in GF caused by the low electrical
conductivity (175 S/cm, Fig. 4e). Considering all these factors, the GFSC
presents a low areal capacitance of 379.5 mF/cm2 and rate capability
(44.3%).
In contrast to GFs, nitrogen doping leads to an enhanced areal
F. Han et al.
capacitance and rate capability. For instance, 10%-NGF shows a higher
SSA (305 m2/g) with different 41.6% micropores, 50.6% mesopores and
7.8% macropores. It is worth noting that the areal capacitance of 10%-
NGF is as high as 709.5 mF/cm2. The extraordinary capacitive perfor­
mance can be intensely related to the well-defined mesoporosity and
macroporosity, improved wettability, enhanced electrical conductivity
and introduced N-active sites. Thus, investigating the mechanism of the
impact factors mentioned above is of great importance for improving the
electrochemical performance of 10%-NGF.
For 10%-NGF, the microporosity is reduced to 41.6%, but still shows
a large amount of sub-nanometer size distribution (<1 nm). Before
electrolyte ions access to these sub-nanometer pores, the solvated shell
of ions are removed and the diameter of the bare PO43- ions is ~0.46.
With the size matching of the ultrasmall pores and bare ions, a large
number of electrolyte ions are absorbed and stored in the electrodes,
leading to an enhanced specific capacitance [48,67–69]. Additionally,
the increased mesopores (50.6%) accelerate charge transport with
shortened ion pathways, whereas macropores (7.8%) are utilized to be
buffering zone for electrolyte ions to achieve the shortest transport paths
to inner surface. According to the report by Wang et al., a lot of factors
influence the mechanism of ion transportation in porous graphene-based
materials. Among them, the charge transfer resistance and transport
paths are the most critical factors [60]. Therefore, the restacking of
graphene nanosheets within 10%-NGF is mitigated and the rate per­
formance (46.4%) is higher than that of GF due to the synergetic effect of
the decreased charge transfer resistance in mesopores and the curtailed
transport paths in macropores.
Moreover, when the urea fraction increases from 0 to 10%, the
wettability is enhanced, as evidenced from the decreased contact angle
of the fibers (103.8◦ to 83.5◦ ). The data shown in Fig. 4d suggest a
transition from hydrophobic GF to hydrophilic 10%-NGFs. Although a
small contact angle can lower the interfacial ohmic resistance for facil­
itating ion diffusion at the interface between electrode and electrolyte,
the poor wettability of GFs had not been carefully considered to date.
The well-developed porosity and plenty of hydrophilic groups (intro­
duced polar C–N bonds) were vital for the 10%-NGFs to achieve superior
wettability, owing to the additional amino-containing functional groups
(Fig. S8).
Importantly, the addition of 10 wt% urea into GO solutions can
enhance the electrical conductivity of 10%-NGF to 253 S/cm. The
reason for this enhancement is the highly conductive porous networks
modified by doped nitrogen atoms and the higher reduction degree in
10%-NGF. As observed in Figs. S5d and 4e, the improved (C–C)% con­
tent (83.6%) is considered to increase the reduction degree of 10%-NGF,
and the overall nitrogen contents (2.1%) and N-G contents (0.2%) sug­
gest a promoted ion transport. These factors together lead to an
improved electrical conductivity for 10%-NGF, thereby diminishing IR
drop (16.1 mV, Fig. 3b) and ESR (228.7 Ω, Fig. 4f) in the FSCs. The 10%-
NGF electrode has a comparably larger slope of d(-Z′′ )/dZ’ at low fre­
quency than that of GF electrode (Fig. 4f), revealing a better charge
storage behavior owing to the nitrogen doping.
Finally, the electrochemical performance of the 10%-NGFs in FSC is
affected both by nitrogen contents and nitrogen configurations. Among
these functionalities, N-6 and N-5 can alter the electrochemical activities
of fiber electrode due to their existence on the edge of the graphene
nanosheets [57,58]. We observed that the sum of N-6 and N-5 contents
in the fiber is 1.7% and it can provide additional N-active sites, resulting
in the improvement of specific capacitance (Fig. 4e). The unique porous
electrode architecture with higher mesoporosity, improved wettability,
enhanced electrical conductivity and introduced N-active sites has
synergistic effect in strengthening the areal capacitance and improving
the rate capability of 10%-NGF.
The 20%-NGF shows an increased SSA (416 m2/g) with 29.2% mi­
cropores, 58.2% mesopores, and 12.6% macropores. According to the
higher SSA and improved hierarchically porous structure with the
increased amount of mesopores and macropores, more shortcuts are
7
Journal of Power Sources 520 (2022) 230866
generated within the fiber inner interface and the ion path channels are
obviously shortened, which significantly favors enhanced electrode/
electrolyte contact, faster charge transport and higher rate capability
(54.1%) of the 20%-NGF. The improved porosity and increased hydro­
philic groups from N-active sites further enhance surface wettability of
the electrode with a decreased contact angle of 81.5◦ (Fig. 4d). The
superior wettability provides abundant accessible sites on fiber surface
for the physical adsorption of electrolyte ions on the one hand, and on
the other hand it improves ionic conductivity of 20%-NGF. Considering
the nitrogen configuration modification (the sum of N-6 and N-5 con­
tents (3.0%)), more N-active sites are provided for the 20%-NGF to
enhance electrochemical activities. In addition, the 20%-NGF exhibits
the highest electrical conductivity (328 S/cm) among all the NGFs
electrodes. Similar to the 10%-NGF, the larger (C–C)% content (86.4%),
the increased overall nitrogen contents (4.6%) and nitrogen configura­
tions (N-G contents (1.3%)) further contribute to the higher reduction
level and thus better electrical conductivity, decreased IR drop (8.2 mV)
and small ESR (109.2 Ω) in the 20%-NGF. Meanwhile, the 20%-NGF
exhibits a largest areal capacitance of 1217 mF/cm2, which can be
demonstrated from the Nyquist plot with a maximum oblique slope at
low frequency (Fig. 4f).
Although 40%-NGFs exhibits the highest SSA (509 m2/g), the best
wettability (contact angle of 77.2◦ ), the maximum nitrogen content
(6.7%), there are few detectable micropores (7.9%) and excessive
macropores (28.4%) in hierarchical structures. The small micropore
population of sub-nanometer pores, the size of which is equivalent to the
size of bare ion PO43-, contributes to the reduced specific capacitance.
Moreover, the high macroporosity, especially for pore size >200 nm, is
the primary reason for the decrease of electrical conductivity owing to
the lack of continuity in some interior parts of the fibers. As a result, the
areal capacitance and rate capability decreased to 938.75 mF/cm2 and
49.7%, respectively.
Considering the surface double-layer capacitance mechanism of
graphene-based fiber electrodes, electrolyte ions can only be stored and
separated in the range of several nanometers near the electrode/elec­
trolyte interface, leaving the interior parts merely as substrates and
contributing little to the capacitance performance of FSCs [44–46]. In
order to comprehensively access the charge storage ability of our FSCs
and highlight the importance of full utilization of fiber structure, the
electrochemical performance were compared between our 20%-NGFSCs
and the previously reported graphene-based FSCs (Fig. 5). The areal
capacitance value of the 20%-NGFSC reaches 1217 mF/cm2, repre­
senting the highest areal capacitance value among all the reported
porous graphene materials (Supplementary Table 1). For example, it is
three times that of the SG-CPF@GF fiber (391.2 mF/cm2) [46], six times
that of the rGO coaxial fiber (205 mF/cm2) [70], 33 times that of the
plasma-treated GFs (36.25 mF/cm2) [44]. Furthermore, it is of great
significance to maintain the capacitance of the FSCs at high
charge-discharge current density for practical power sources. It can be
observed from Supplementary Table 1 that the 20%-NGF still preserves
the capacitance of up to 659 mF/cm2 even under the high current
density of 1 mA/cm2, which is 2.3 times that of N-40% HG@GF fiber
(274.5 mF/cm2) [35] and five times that of RGO + CNT@CMC fiber
(132.7 mF/cm2) [14].
The 20%-NGFSC demonstrates an exceptional energy storage per­
formance with the highest energy density of 27 μW h/cm2, surpassing all
existing graphene-based hybrid FSCs (Supplementary Table 1). Notably,
the electrochemical performance of our supercapacitors are superior to
that of previously reported NGFSCs [41] owing to the high utilization
efficiency of hierarchically porous structures via adjusting the micro-/­
meso-/macro-porosity ratios to enhance electrolyte permeation and
speed up the ion diffusion kinetics.
Based on the above analysis of the architecture and capacitive
behavior of NGFs electrode materials, we further investigated the po­
tential mechanism of high-performance FSCs. In order to achieve ideal
electrochemical performance, the hierarchically porous architecture
F. Han et al. Journal of Power Sources 520 (2022) 230866

Fig. 5. Comparison of the electrochemical performance of our 20%-NGFSCs with other previously reported FSCs. The supercapacitors assembled from plasma-
treated GFs (36.25 mF/cm2, 0.2 μW h/cm2) [44], rGO coaxial fiber (205 mF/cm2, 17.5 μW h/cm2) [70], SG-CPF@GF fiber (391.2 mF/cm2, 8.7 μW h/cm2) [46]
and some other fibers are listed in the graph.

with macropores, mesopores, and micropores should be constructed in
fiber electrodes. Although micropores are typically dominant in GFs, the
dense graphene stacking often leads to small ion-accessible SSA, and the
lack of adequate mesopores and macropores hinders the efficient
transport of electrolyte ions because of the wormlike winding routes
between different layers. In comparison, in our work, when an increased
SSA and hierarchically porous structure with optimal micro-/meso-/
macro-porosity ratios are introduced in the GFs by nitrogen doping, the
ion diffusion and storage are significantly facilitated (Fig. 6). This is
because more shortcuts are generated within the hierarchical architec­
ture and ion path channels are greatly shortened by the porous structure.
In addition to producing hierarchically porous structures, nitrogen
doping also modifies the local electronic structure of fiber electrodes,
increases surface charge density, and enhances ion binding interaction.
Benefiting from the hierarchically porous structure with optimal micro-/
meso-/macro-porosity ratio, elevated wettability, improved electrical
conductivity and additional N-active sites of NGFs, the high perfor­
mance of the FSCs can be achieved by means of nitrogen doping.
The FSCs in this work have high flexibility and excellent electro­
chemical performance under various deformations. The CV curves
(Fig. 7a) remain almost unchanged as the bending angles increase from
0◦ to 180◦ , which plays a significant role in wearable electronics. As
observed in Fig. 7b, the NGFSC also exhibits the capacitance retention of
96.5% over 20000 GCD cycles, illustrating its superior cyclic stability.
Moreover, the coulombic efficiency is maintained at 99.2% after 20000
cycles (Fig. 7b). To prove the practicability of the 20%-NGFSCs for
powering wearable electronics, four NGFs-based supercapacitors are
arranged in series, which powers up a lab timer (Fig. 7c). Fig. 7d shows
the light up of 23 LEDs into a logo “XJTU” with four NGFs-based
supercapacitors.
4. Conclusion
In summary, a high-performance FSC assembled by flexible and
freestanding NGFs electrodes has been fabricated via a combination of
the structure and capacitive performance design. Urea serves as self-
removed pore former as well as nitrogen source to realize synergetic
pore structure optimization and nitrogen doping, tuning the hierar­
chically porous architecture, wettability, nitrogen content, and elec­
trical conductivity of NGFs for improved electrochemical performance.
It has been demonstrated that the distinctive layer porous architecture of
the fiber electrodes facilitates the ion storage and transport. The optimal
supercapacitor displays a superior specific capacitance of 1,217 mF/cm2
(486.3 F/g) and a high energy density of 27 μW h/cm2 (10.8 W h/Kg),
which demonstrates the highest value in all-solid-state FSCs based on
inorganic electrolyte to date. Moreover, the FSC assembled from 20%-
NGFs maintains ultrahigh capacitance (659 mF/cm2 at 1 mA/cm2 cur­
rent density), and exhibits excellent cyclic stability (96.5% retention
over 20000 cycles). The NGFSC is a very promising candidate for high-
performance and flexible power sources in future wearable electronics.

Fig. 6. The mechanism for the high-performance of the FSCs. Densely stacked GFs with a large quantity of micropores have wormlike S-shaped route between layers
to block the ion transport. The NGFs with optimal micro-/meso-/macro-porosity ratios create more ion path channels to facilitate ion diffusion and storage.

8
F. Han et al.
Fig. 7. The applications of our FSCs for electronics. (a) CV curves of the NGFSCs under bending. (b) Capacitance retention and coulombic efficiency of the NGFSCs.
The inset shows the charge/discharge curves of the last five cycles for 20%-NGFs. Photographs of four NGFSCs connected to power (c) stopwatch, (d) 23 LEDs,
respectively.
CRediT authorship contribution statement
Feng Han: Conceptualization, Investigation, Writing – original draft,
Writing – review & editing. Weixuan Jing: Supervision, Conceptuali­
zation, Writing – review & editing. Qian Wu: Data preparation, Inves­
tigation. Bian Tian: Data preparation, Investigation. Qijing Lin:
Resources, Writing – review & editing. Chenying Wang: Resources,
Writing – review & editing. Libo Zhao: Resources, Writing – review &
editing. Junshan Liu: Resources. Yu Sun: Conceptualization, Writing –
review & editing. Zhuangde Jiang: Conceptualization, Writing – review
& editing.
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.
Acknowledgments
The authors would like to thank the financial supports by National
Natural Science Foundation of China (51805426 & 51975466), Young
Talent Fund of University Association for Science and Technology in
Shaanxi (No. 20190402) and Open Research Fund of State Key Labo­
ratory of High Performance Complex Manufacturing, Central South
University (Kfkt2020-08). We also appreciate the support from the In­
ternational Joint Laboratory for Micro/Nano Manufacturing and Mea­
surement Technologies.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.jpowsour.2021.230866.
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