Research Article
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Silicon in Hollow Carbon Nanospheres Assembled
Microspheres Cross-linked with N-doped Carbon Fibers
toward a Binder Free, High Performance, and Flexible
Anode for Lithium-Ion Batteries
Ruiyu Zhu, Zehua Wang, Xuejiao Hu, Xiaojie Liu,* and Hui Wang*
Silicon (Si), as the most promising anode material, has drawn tremendous
attention to substitute commercially used graphite for lithium-ion batteries
(LIBs). However, recently, the insufficiently high structural stabilities and elec-
tron/ion conductivities of silicon-based composites have become the main
concerns, hindering the further progress of silicon as the anode material for
LIBs. Herein, to cope with these concerns, a binder-free and free-standing
type anode electrode paper is fabricated from self-assembled microspheres
and intertwined fabrics, in which a 3D interconnected nitrogen/carbon net-
work connects hollow carbon nanospheres with uniformly distributed silicon
nanodots (SHCM/NCF). The as-prepared SHCM/NCF paper maintains a
reversible capacity of 1442 mAh g−1 at 1 A g−1 for 800 cycles in lithium half-cell,
and 450 mAh g−1 at 0.5 A g−1 for 200 cycles in lithium full-cell, respectively.
The excellent battery performances are mainly attributed to the free-standing
paper electrode suppressing side reactions, nitrogen/carbon networks main-
taining electrical contact, and silicon nanodots alleviating the harm caused
by volume expansion. Furthermore, this excellent performance combined
with the simplicity of the synthesis method and the saving of excess polymer
binder, current collector and conducting additives, make the designed paper
exhibit great potential in practical applications.
1. Introduction
Silicon (Si) has been considered as the most promising anode
material to replace commercially used graphite for lithium-
ion batteries (LIBs), which is due to the ultrahigh theoretical
capacity (Li22Si5, 4200 mAh g−1), natural abundance and suitable
delithiation voltage (0.4 V vs Li/Li+) of silicon.[1,2] However, sil-
icon suffers from extreme volume expansion and shrinkage (up
to 300%) during (de)lithiation processes as well as low lithium
Dr. R. Zhu, Z. Wang, Dr. X. Hu, Prof. X. Liu, Prof. H. Wang
Key Laboratory of Synthetic and Natural Functional Molecule
of the Ministry of Education
Shaanxi Joint Lab of Graphene (NWU)
College of Chemistry & Materials science
Northwest University
Xi’an 710127, P. R. China
E-mail: xiaojie.liu@nwu.edu.cn; huiwang@nwu.edu.cn
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/adfm.202101487.
DOI: 10.1002/adfm.202101487
Adv. Funct. Mater. 2021, 31, 2101487 2101487  (1 of 12)
diffusion coefficient (10−14–10−13 cm2 s−1),
eventually causing the significant cracking
and low conductivity of silicon.[3] What
is important, the structural cracking and
even pulverization of silicon, ascribed to
the enormous volume expansion/contrac-
tion during cycling, could further result in
the repetitive formation of solid electrolyte
interphase (SEI) layers on the exposed sur-
faces of broken silicon, ultimately giving
rise to a degraded electrochemical stability
of silicon material and a serious safety con-
cern of LIBs.[4] Obviously, these unwanted
intrinsic characteristics of silicon have
become huge obstacles, restricting its uti-
lization and advancement in LIBs greatly.
To address the above-mentioned issues,
a variety of strategies, including nano-
fabrication, hybridization with carbo-
naceous and structure and morphology
building, has been adopted to carefully
design and synthesize novel silicon-based
multifunctional composite, aiming to
improve markedly the ion/electron con-
ductivity, alleviate the damage caused by
silicon volume change and strengthen
greatly the structural stability.[5–7] As is well known, nanostruc-
tured silicon materials such as nanowires and nanospheres have
obstruction to pulverization during cycling process and own the
enhanced ion/electron conductivity because the nano-silicon
can not only curtail lithium-ion transport paths effectively
but also enable the electrolyte contact well with the materials,
yielding outstanding battery capability.[8] Nevertheless, the high
surface area and poor conductivity of most nano-Si types lead
to the unwanted consumption reaction of lithium and excess
formation of solid electrolyte interphase (SEI) layers, giving
birth to low energy density and low initial coulombic efficiency
(ICE). On that account, seeking an advantageous route to solve
nano-Si defects is critical for its practical application. Until now,
the valid route of building silicon-carbon composites has been
demonstrated to be effective, mainly consisting of the introduc-
tion of the carbonaceous materials to improve ion/electron con-
ductivity and the establishment of the additional buffer space
(such as hollow structure) to adapt to the structural changes
of the entire material, so as to ameliorate electrode stability
and LIBs battery performance.[9–11] For example, Yang et  al.
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prepared Si nanodots within carbon framework structure,
exhibiting 647 mAh g−1 at 1 A g−1 over 1500 cycles.[12] Meanwhile,
our group also reported a silicon-carbon composite of double
shelled hollow carbon nanospheres encapsulated with silicon
nanodots that exhibited 750  mA h g−1 capacity at 1 A g−1 after
2000 cycles.[13] Clearly, it is proved that carbonaceous materials
are able to provide a buffer layer for the volume change of elec-
trode, elevate charge transfer, and avoid redundant SEI layer
formation in the designed carbon/silicon composites. Addition-
ally, the hollow structure carbon, as additional space buffer, can
accommodate a large amount of active nanodots and supply a
confined room for lithium intercalation and de-intercalation,
further enhancing the battery performance. Although the com-
bination of silicon nanoparticles and carbon has displayed a
successful approach to modify the lithium storage behaviors of
silicon-based composites, their structural stabilities and elec-
tron/ion conductivities, as the most crucial parameters deciding
whether the LIBs can be further progressed for large scale use
of electric vehicles, have still drawn considerable attention
rather than the lithiation/de-lithiation mechanism of silicon. As
well, considerable attention has also been paid to the electrode
preparation method in order to reduce the cost of fabrication,
simplify the fabrication process and increase the electrode life
performance.
Until now, heteroatoms such as nitrogen (N), phosphorus
(P), and sulfur (S) have been commonly introduced into car-
bonaceous materials for acquiring their unique chemical
and physical properties.[14,15] Among these heteroatoms,
nitrogen doping has been currently the most widely studied
because nitrogen acts as an electron donor implying higher
electronegativity for doped area, which attracts plenty of
positive ions and further enhance charge transfer. More-
over, nitrogen doping not only improves battery capacity by
enhancing pseudocapacitors, but also provides additional
active sites and increase material conductivity by reducing
the semiconductor gap.[16] Regarding the structural stability
of electrode, to assemble nanomaterials into aggregates
has been proved to be an effective route because a rational
design of the agglomerates could avoid the shortcomings of
low tap density and agglomeration for single nanoparticles.
The rationally designed aggregation can weaken the specific
surface area to avoid the side reaction with the electrolyte
and overcome undirected agglomeration to reduce the con-
tact area between the electrode and electrolyte, resulting in
high coulomb efficiency.[17,18] Besides, the assembled micro-
structure promotes great physical contact between nanopar-
ticles by manufacturing suitable agglomerates, and limits
the size of the agglomerates to ensure rapid propagation in
the Li+ insertion/extraction cycling, which will elevate the
charge transfer and transport through the interconnected
carbon matrix to a certain degree.[19,20] For example, Li et  al.
designed carbon-nanotube@ silicon@ carbon hierarchical
microspheres structures via in-situ thermite reduction of
CNT@SiO2, delivering excellent stability.[21] Furthermore,
regarding the electrode preparation method, the exploita-
tion of wearable and bendable electronic devices requires
more foldable and flexible electrode materials, thus a free-
standing material electrode allows all materials to participate
in charge storage, thereby increasing power density and volu-
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metric energy. The advanced free-standing electrode paper
materials can supply plenty of space inside like a sponge to
absorb the expansion of silicon to prevent breaking even pul-
verizing, and large amount of pores intersect each other to
offer a good mechanical stability and conductivity.[22] Electro-
spinning, as a convenient method, has many advantages to
prepare free-standing paper, which can not only freely adjust
the thickness and size of paper according to time period and
distance of electrospinning, but also change obtained paper
structure via the voltage and speed conditions, proving that it
is an extremely diverse and flexible technique for numerous
applications.[23] Compared with traditional material prepa-
ration technology, its equipment is easier to build, simpler
to operate, and more excellent to fine-tune the morphology,
mass production, diversified ingredients and uniform distri-
bution, which surely have gained great attention in the fields
of batteries, catalysis and supercapacitors.
Herein, motivated by the above appealing structural merits,
for the first time as far as we known, we elaborately developed
three dimensional assembled microspheres cross-linked with
N-doped carbon fibers (NCF), in which the microspheres are
assembled by hollow carbon nanospheres impregnated uni-
formly with silicon nanodots (SHC), toward a binder free, high
performance and flexible anode for LIBs. The as-obtained mate-
rial is denoted as SHCM/NCF. Note that, the polyacrylonitrile
(PAN)/polyvinyl pyrrolidone (PVP)-derived carbon can not only
impregnate magnesiothermic reduction-derived SHC nano-
spheres within the micro spherical skeleton, but also can be
electrospun into special fabrics structure intertwined with SHC
microspheres, which favors for forming the highly electron/
ion conduction network for a higher electrochemical property
and self-standing structure for binder-free electrode. The as-
developed 3D interconnected architecture can mainly deliver
these following benefits: a) the nitrogen/carbon networks are in
favor of rapid ion/electron conduction, which can elevate ther-
modynamic stability and provide buffer layer to adapt to struc-
tural changes of the entire material during cycling. b) a rational
design of microspheres could not only avoid the shortcomings
of low tap density and agglomeration for single nanoparticles,
but also could weaken the specific surface area to avoid the side
reaction with the electrolyte and overcome undirected agglom-
eration to reduce the contact area between the electrode and
electrolyte. c) PVP and PAN are green polymer products, which
are conducive to the bending performance of the synthesized
paper, and could also provide quantitative existence of N-doping
to improve the conductivity of the paper. d) the binder free,
free-standing and flexible paper from designed fabric inter-
twined with microsphere structure can eliminate effect of
insulating polymer binder and excrescent conducting additives
during preparing electrode, avoid side effects and minimize
the cost, which can be prepared in large quantities and useful
in practice. Consequently, combining these advantages, the
SHCM/NCF paper electrode displays significantly improved
cyclic and rate performance for lithium half/full battery. As
expected, the prepared SHCM/NCF paper demonstrates good
reversible capacity of 1442 mAh g−1 after 800 cycles at 1 A g−1 for
Li half battery, even at 3.2 A g−1, the capacity still maintains at
800 mAh g−1 and 450 mAh g−1 after 200 cycles at 0.5 A g−1 for
Li full cell.
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Figure 1.  Schematic illustrated for formation procedure of the SHCM/NCF paper.

2. Results and Discussion freestanding SHCM/NCF paper is quite flexible, which can be
bent to 90° or even 180° without fracture (Figure 2b).
The formation procedure of 3D interconnected SHCM/NCF The obtained SHCM/NCF paper was then cut into self-
paper mainly involves two steps, magnesiothermic reduction supporting electrode with great adaptability, which was directly
and electrospinning, as shown in Figure  1. Initially, according used as anode electrode. Also, the PVP/PAN carbonized under-
to previous report, SiO2 nanospheres, synthesized as core by takes the conductive channels for electron transfer. In addition,
Stöber method, were coated one layer of SiO2/RF as shell by to investigate the properties of papers, Figure 2c and Figure S2g
continuously hydrolyzed of tetraethyl orthosilicate (TEOS) (Supporting Information) illustrates the surface wet ability of
and poly-condensation of resorcinol (R)/formaldehyde (F). a LiPF6 droplet on the SHCM/NCF and SHC. It is clear that
Then, after RF carbonization under Ar protection to form SHC show the larger contact angle of 32.8° at the LiPF6/SHC
SiO2@SiO2/C, the SHC were further obtained by magnesio-
thermic reduction of SiO2 from SiO2@SiO2/C nanospheres:
2Mg(g)+SiO2(s) = Si(s)+2MgO(s). It is well known that HCl can
removed unreacted Mg and by-product MgO, while HF could
etch unreacted SiO2. Figure S1 (Supporting Information) dis-
cusses the XRD and SEM images before and after etching. It
is obvious that the impurity peaks disappear after etching and
the morphology of SHC nanospheres before etching, after HCl
and HF washing has not too much change. On the one hand,
silicon nanodots were uniformly dispersed in both cavity and
skeleton of the carbon shell, thus exhibiting special conduc-
tivity and electrochemical stability. On the other hand, obtained
silicon became smaller in size compared with traditional bulk
silicon and the etched SiO2 will leave vacancies for buffer space
to volume expansion of Si.
At last, SHC, polyvinyl pyrrolidone (PVP), polyacrylonitrile
(PAN) were dissolved in N,N-Dimethylformamide (DMF) and
then electrospun into yellowish-brown paper. The carboniza-
tion process was completed after stabilization at 250 °C under
air and heat treatment at 700 °C under Ar atmosphere. During
the calcination, PAN/PVP carbonized was wrapped around
SHC and self-assembled into intertwined microspheres and
then cross-linked with N-doped carbon fibers to form the 3D
interconnected paper. The photographs of the paper before and Figure 2.  Photographs of a) pyrolysis process change, b) bending per-
after pyrolysis are shown in Figure 2a, exhibiting they all have formance of SHCM/NCF paper; c) surface wet ability of a LiPF6 droplet
excellent bending properties. Furthermore, the as-prepared on the SHCM/NCF.

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interface compared with LiPF6/SHCM/NCF interface (20.8°).
After 8 s, the LiPF6 droplet spread on the surface of SHCM/
NCF and contact angle at the LiPF6/SHC interface only slightly
decreases (23.0°), which means that the SHCM/NCF paper has
better contact with nonpolar LiPF6 electrolyte, yielding good
battery performance.
As exhibited in Figure S2 (Supporting Information),
SiO2@SiO2/RF as the initial material has the 292 ± 25  nm
spherical shape with high uniformity. After RF carboniza-
tion, since RF shrinks to amorphous carbon during pyrol-
ysis, SiO2@SiO2/C has 280 ± 28  nm spherical shapes.
Eventually, the SHC nanospheres with 279 ± 26  nm was
obtained after the magnesiothermic reduction of SiO2,
conveying that there is maintain nanosphere shape and
distributed uniformly in all processes. After electrospin-
ning, the diameter of the SHC/PVP/PAN precursor micro-
spheres assembled by SHC is about 3.5–6µm  with distinct
3D interconnected 70–100 nm  diameter fibers (Figure S3a,b,
Supporting Information). The microstructure and morphology
of obtained SHCM/NCF paper after pyrolyzed are characterized
by the scanning electron microscopy (SEM) and transmission
electron microscopy (TEM) images as given in Figure 3.
After pyrolysis, there is no significant change in diameter
and morphology of SHCM/NCF (Figure 3a). The magnification
SEM view of one SHCM/NCF microsphere visually illustrates
Figure 3.  Morphology/composition characterization of SHCM/NCF paper: a–c) SEM, inset of b,c) TEM; d) SAED; e) HRTEM; f) element distributions
in different regions; g) element mapping; h) EDX scan line.
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that the microsphere is formed by the reasonably aggregation
through numerous SHC nanospheres, and each SHC is con-
nected and surrounded by PVP/PAN carbonized (Figure  3b),
while Figure  3c demonstrates the enlarged fibers. To ulterior
discuss the detailed interior structure of SHCM/NCF paper,
transmission electron microscopy is measured, which further
proved its aggregation architecture from many SHC nano-
spheres for one microsphere, and internal fiber structure
(Figure S3c,d, Supporting Information and inset of Figure 3b,c).
Furthermore, the selected area electron diffraction (SAED)
image of SHCM/NCF in Figure  3d displays three noticeable
diffraction rings that can be assigned to (311), (220), and (111)
planes of crystal silicon, conforming the existence of crystalline
silicon nanodots.[24] The high resolution (HR) TEM of SHCM/
NCF in Figure 3e reveals many irregularly shaped silicon nan-
odots (indicated by yellow squares). In addition, clear lattice
fringes can be seen in the inset Figure (the magnification of
the yellow areas), with an interplanar spacing of 0.31  nm, cor-
respond to the (111) plane of Si, which is consistent with the
SAED consequence.[25] Besides, Energy-dispersive X-ray (EDX)
element mapping of SHCM/NCF (Figure  3g) was performed
to determine the distribution of C, N, and Si elements, which
obviously display the aggregated carbon hollow shell struc-
ture (red), evenly distributed Si (yellow) and N (green), which
intuitively illustrate the homogeneously exist of C, N, and Si,
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matching with the EDX line scanning (Figure  3h). This 3D
interconnected skeleton structure can enhance the charge
transfer as an ion/electron conductor, provide buffer space for
the volume expansion of silicon to avoid cracking and improve
the structural stability of the entire material, yielding excellent
battery performance. Meanwhile, the energy-dispersive X-ray
(EDX) outcomes about areas 1, 2, 3, and 4 (highlighted by yellow
squares in Figure 3f) illustrate the atomic ratios of C, N, and Si
in area 1 and 2 hardly changed, indicating the uniformity of the
SHCM/NCF paper. Besides, the element contents in area 3 and 4
mean that the content of C are relatively affluent, which can serve
as an ion transport channel. Identically, as a comparison, the
hollow carbon nanospheres brimmed with silicon nanodots with
diameter of 276 nm are observed in Figure S4 (Supporting Infor-
mation), which can be consistent with SEM results. Figure S4a,b
(Supporting Information) clearly indicated the single shelled
hollow carbon structure of SHC with around 13 nm carbon shell,
and plenty of active silicon nanodots uniformly encapsulated in
the carbon shell cavity and surface (Figure S4c,d, element map-
ping and line scan, Supporting Information).
The X-ray diffraction (XRD) patterns of SHCM/NCF and
SHC in Figure  4a demonstrated that all characteristic diffrac-
tion peaks at 28.3°, 47.3°, and 56.2° were well matched with
(111), (220), (311) planes of crystalline Si (JCPDS Card No.
27-1402).[26] Additionally, the broad peaks appeared on the left
of (111) plane at ≈25° can be assigned to amorphous carbon,
which is originated from RF/PVP/PAN carbonization. Based on
the Scherrer equation, the grain sizes of crystalline silicon in
SHCM/NCF paper can be calculated as 19, 20, and 19 nm corre-
sponding to (111), (220), and (311) planes respectively, while the
grain sizes of SHC are 18, 20, 15 nm. The average grain size of
SHCM/NCF and SHC is 19 and 17 nm, separately. The similar
value also indicates that SHCM/NCF are assembled from SHC
and could matched with HRTEM images.
In addition, the Raman spectra of SHCM/NCF and SHC in
Figure  4b illustrate the D band at ≈1330 cm−1 and G band at
≈1580 cm−1 attributing to the existing of carbon. Commonly
speaking, D band is representative of the disordered/defective
carbon origin by the graphitic sp3-hybridization, while the G
band can be corresponding to the E2g vibratory mode presenting

Figure 4.  a) XRD pattern of SHCM/NCF and SHC; b) Raman spectra of SHCM/NCF and SHC; c) Nitrogen adsorption/desorption isotherms and BJH
pore size distribution of SHCM/NCF; d) electronic conductivities of SHCM/NCF and SHC; e) TGA of Si, C, SHCM/NCF and SHC; f) XPS full spectra
of SHCM/NCF and SHC; g-h) high-resolution XPS spectra of SHCM/NCF.

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in the sp2 bond of the crystalline graphite basal plane.[27] The
deviated Si peak and D band of SHCM/NCF paper (10.3 and
13.2 cm−1, respectively) with regard to strong electron interac-
tion.[28] The intensity ratio of D/G band of SHCM/NCF and
SHC are 1.49 and 1.37, separately. The increased ID/IG value
in SHCM/NCF meaning disorders and defects strengthened,
or sp2 domains of carbon decreased. Figure 4c and Figure S4e
(Supporting Information) presents the N2 adsorption–
desorption isotherms of SHCM/NCF and SHC and the
homologous pore size distribution curves obtained by the
Barrett–Joyner–Halenda (BJH) model (inset in Figure) to
investigate the surface area and porosity of the materials. The
hysteresis loop, which can be observed on N2 adsorption–
desorption isotherms, exhibiting mesopores structure for this
sample. The specific surface area of SHCM/NCF and SHC are
167.5 and 360.5 m2 g−1 according to the Brunauer–Emmett–
Teller (BET) method. In addition, pore size distribution curves
display ranges from 2 to 10 nm of SHCM/NCF and SHC, illus-
trating hierarchical porous structure.
As illustrated in Figure  4d, measured by powder resis-
tivity test (four probe method), the electronic conductivities of
SHCM/NCF are always greater than that of SHC at different
pressure. Electronic conductivity greatly affects battery perfor-
mance, especially rate performance. Therefore, SHCM/NCF
with advanced conductivity is more advantageous to the Li ion
battery performance. Additionally, the Si content of SHCM/
NCF and SHC are determined by thermogra-vimetric analysis
(TGA). The initial weight loss of each curve is due to the evapo-
ration of water in the sample. The continuous weight elevation
of Si represents the oxidation of silicon to SiO2 when the tem-
perature higher than 200  °C. For SHCM/NCF and SHC, the
weight loss between 430 and 600 °C is ascribed to oxidation of
carbon in air. The calculation of Si content based on the equa-
tion: WSi × XSi + (−WC) × (1 − XSi) = WSi/C, in which WSi, WC,
and WSi/C mean the residual weight percentage of Si, C, and
SHCM/NCF or SHC, while XSi represent the required content
of silicon.[29] The calculation results are listed in Table S1 in
the Supporting Information, indicating the Si concentrations
in the SHCM/NCF and SHC are 55 wt.% and 76 wt.%, respec-
tively. Furthermore, the surface chemistry of these materials
is researched by X-ray photoelectron spectroscopy (XPS). The
full spectra in Figure 4f all demonstrate the similar O 1s, C 1s,
Si 2s, and Si 2p peaks, which means that the surface composi-
tion of SHCM/NCF and SHC materials are identical basically,
displaying that SHCM/NCF is assembled by SHC. The exclu-
sive N 1s is identified for SHCM/NCF compared with SHC,
indicating the surface contains PVP/PAN-derived carbon, con-
sistent with element mapping, in which the N content in the
as-prepared SHCM/NCF paper was around 4.5 wt% according
to the EDX. The high-resolution C 1s spectrum of SHCM/NCF
denotes three sub peaks, where the 284.6, 285.2 and 288.9  eV
were assigned to C-C, C = N and C = O bonds, respectively,
which examine the doping of N in the carbon (Figure 4g). The
high-resolution N 1s spectra can be differentiated into three
sub peaks corresponding to pyridinic N (398.3  eV), pyrrolic N
(399.9  eV), and oxidic N (402.9  eV) (Figure  4h). Among them,
pyridinic N can produce good electron donor/acceptor proper-
ties and faraday pseudo-capacitance, while pyrrolic N has fast
charge diffusion properties to promote electron transfer reac-
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tion. In addition, high-resolution Si 2s spectra express peaks
assigned to Si0 and Si4+ at 99.3 and 101.2  eV, respectively
(Figure  4i).[30,31] Considering these above analyses, the-
developed 3D interconnected SHCM/NCF paper are favorably
composed, which can synergize the advantages of high-capacity
Si, microspheres and N-doping fiber at the same time for
lithium storage. Notably, this kind of nitrogen/carbon confor-
mation can be used as an ion channel in the paper to improve
electrochemical performance.
3. Electrochemical Characterization for LIBs
In order to evaluate electrochemical features of as-prepared
SHCM/NCF, SHCM/NCF paper was directly utilized as free-
standing electrode in the CR 2025 type coin cell. Figure  5a
reveals the first three circles charge -discharge curves of
SHCM/NCF, which were consistent with the silicon electrode
voltage platform.
The initial charge/discharge capacities of SHCM/NCF and
compared SHC were 2224/2583 mAh g−1 and 1219/1978 mAh g−1
with initial coulombic efficiency (ICE) of 86% and 60%, respec-
tively. The irreversible capacity loss in the first circle is due
to the construction of solid electrolyte interface (SEI) film on
electrode material surface, which is due to the electrode mate-
rial react with electrolyte on the solid-liquid interface to form
passivation layer of solid electrolyte properties. Figure S5a
(Supporting Information) illustrates cyclic voltammetry (CV)
behavior of SHCM/NCF electrode for the first three cycles at
0.2 mV s−1. A broad peak around 0.5V in the primary cathodic
scan loop (lithiation process) can be attributed to the growth
of the SEI layer, which disappeared in the subsequent cycles.
In the anodic curve, a pair of oxidation peaks appeared at 0.3
and 0.5V was attributed to Li dealloying process of Li-Si alloy.[32]
Notably, the excellent reversibility was proved because the peaks
in the next subsequent two cycles almost coincide.
The rate capabilities of SHCM/NCF paper and SHC can
be illustrated in Figure  5b at current densities from 0.1 to
3.2 A g−1. The SHCM/NCF paper electrode had an advanced
rate capability with higher capacities of 1960, 1500, 1220, 990,
800 mAh g−1 at 0.2, 0.4, 0.8, 1.6, and 3.2 A g−1 than SHC electrode,
respectively. The capacity still has hardly changed when the cur-
rent density returns to 0.2 A g−1 and has 1900 mAh g−1 after
300 cycles. In addition, after three activation cycles at 0.3 A g−1,
a significant reversible capacity of 2200 mAh g−1 was obtained
for the SHCM/NCF paper electrode after 530 cycles at 0.5 A g−1.
Compared to it, SHC anodes maintained lower capacity of
550 mAh g−1 at 0.5 A g−1 (Figure  5c). As the current density
increased to 1 A g−1, the reversible capacity of SHCM/NCF
deliver 1442 mAh g−1 after 800 cycles with 86% capacity reten-
tion, while SHC is 266 mAh g−1, and all the materials have
coulombic efficiency of above 98%. The capacity drop is due
to the formation of stable SEI layer, which is the common
problem in most materials. In addition, the phenomenon that
the capacity shows significant increases was attributed to the
electrochemical activation process and reversible growth of gel-
liked polymer film during the degradation of activated electro-
lyte.[33,34] Obviously, Although SHC can provide nanosilicon to
avoid crush caused by volume effect of silicon, and the hollow
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Figure 5.  a) first three charge/discharge curves of SHCM/NCF; b) rate performance; c,d) cycling property; e) fitting Z′ and ω−1/2 of fresh SHCM/NCF
and SHC electrode; f) GITT curves; g) EIS pattern of fresh and postcycling; h) electrochemical performances comparison.
carbon coating can stabilize the SEI film, but the structural
stability and electrical conductivity are still insufficient. The
better performances are attributed to interconnected nitrogen/
carbon skeletons inside the SHCM/NCF paper, which can
not only serve as electron/ion transmission channels but also
avoid structure collapse of electrode. Meanwhile, heteroatom N
doping leads to unbalanced charge distribution near the doping
point and expands the effective range of electric field, thereby
enhancing charge transfer, providing additional active sites and
increasing material conductivity. In addition, the comparison
of electrochemical performance about SHCM/NCF paper and
reported previously Si-based composite materials are listed in
Table S2 (Supporting Information) and Figure  5h. Obviously,
the SHCM/NCF has good cycle stability and ICE.
The electrochemical impedance spectroscopy (EIS) meas-
urement of fresh and post cycling batteries for SHCM/NCF
and SHC are conducted in Figure  5g, while Figure S6d (Sup-
porting Information) reveals equivalent electrical circuit
model in accordance with the EIS curves and data were enu-
merated in Table S3 (Supporting Information). The intercept
of high-frequency region on Z′ axis represents the resistance
of separator and electrolyte (Rs), while the semicircle at high-
and middle- frequency regions can be attributed to the resist-
ance of SEI layer (Rf ) and the charge transfer resistance of the
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electrode–electrolyte interface (Rct), respectively. Obviously, the
fresh SHCM/NCF electrode delivers lower Rct value (charge
transfer resistance, 52.2 Ohm) than fresh SHC (106.7 Ohm) at
high frequency area, suggesting the improved electrical con-
ductivity. Besides, Warburg impedance about lithium-ion dif-
fusion of SHCM/NCF also was much lower than SHC at low
frequency. After 100 cycles, the value of Rct has slight increase
to 36.1  Ohm, clarifying that the 3D interconnected nitrogen/
carbon networks adequately restrain increased charge-transfer
resistance and yielding excellent stability of SHCM/NCF paper.
These consequences indicate that 3D interconnected skeleton
could not only boost electrical conduction, but also obtain
express Li+ diffusion kinetics. Furthermore, to deeply conclude
the Li+ diffusion process, fitting Z′ and ω−1/2 using the fol-
lowing equation[35]
R2T2
D= (1)
2A n 4 F4 C2σ 2
2
Z′ = R e + R ct + σω −1/2 (2)
in which R means gas constant, T is absolute temperature,
A represents electrode surface area, n stand for transfer elec-
trons number per molecule, F means Faraday constant, C is
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lithium-ions concentration, σ and ω stand for the Warburg
factor and angular frequency. Apparently, the Li+ diffusion
coefficient (DLi+) is inversely proportional to σ, which can
acquire from linear fit between Z′ and the reciprocal square
root of angular frequency ω. Figure  5e and Figure S6h (Sup-
porting Information) illustrate σ value of fresh and postcycling
for SHCM/NCF and SHC electrode are 110 and 37.8, 155 and
47.6, respectively, from which the DLi+ value of fresh SHCM/
NCF and SHC electrode can calculated to be 1.4 × 10−10 and
7.2 × 10−13 cm2 s−1. Furthermore, DLi+ value of postcycling
SHCM/NCF and SHC electrode are calculated to be 1.2 × 10−9
and 7.6 × 10−12 cm2 s−1. It exhibits the larger DLi+ value for fresh
and postcycling SHCM/NCF compared with SHC, implying
more rapid and stabilizing interface kinetics of SHCM/NCF
electrode.
In addition, galvanostatic intermittent titration technique
(GITT) method was conducted to investigate reaction kinetics
of SHCM/NCF and SHC electrode (Figure  5f; Figure S5f–i,
Supporting Information). The electrode was exposed to con-
tinuous charge–discharge at 100 mA g−1 for 5 min with left as
an open circuit for 5 min. The GITT results can be quantified
according to the following equation[36]
2 2
4  m B VM   ∆ES 
D+Li =     (3)
τπ  MBS   ∆Eτ 
while mB/MB and τ are active/molar mass and pulse time, VM
and S stand for molar volume and electrode active surface area
of anode, ΔES and ΔEτ reveal voltage change between steps and
voltage vary between two pulse times. The inset of Figure 5f was
partial enlarged view of the GITT curve. The Li-ion diffusion
coefficient of SHCM/NCF was calculated to 1.9 × 10−9 cm2 s−1,
which was higher than SHC electrode (8.3 × 10−12). Conse-
quently, the 3D interconnected nitrogen/carbon skeleton
structure is beneficial to Li+ diffusion rate and then expedited
dynamic redox reaction of SHCM/NCF paper electrode.
According to previous reports, the pseudocapacitive
behavior is generally favorable for high current density
for charge Li storage. To further illustrate the quantitative
analysis and kinetics of SHCM/NCF and SHC electrode in
detail, a sequence of CV measurements with different sweep
speeds (range from 0.2 to 2.0  mV s−1) were carried out.
Obvious, these curves all exhibit similar shapes when scan
rate increases, including two reduction peaks and one oxida-
tion peak (Figure  6f; Figure S5c, Supporting Information).
The relationship between peak current (i) and scan rate (v)
follows equation[37]
i = av b (4)
log ( i ) = b × log ( v ) + log (a ) (5)
in which a and b are two adjustable parameters. In evidence,
the b value can be acquired from slope of log(v)-log(i) curve.
Particularly, when b equals to 0.5, the storage type of Li+ is dif-
fusion-controlled behavior while b value of 1 indicates surface
capacitive process. The b values of the two electrodes for oxida-
tion and reduction peaks are shown in Figure 6g and Figure S5d
(Supporting Information), representing that Li+ storage
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dynamics of these electrodes simultaneously includes diffusion
mechanism and pseudocapacitance control. More accurately,
the specific percentage of diffusion control and capacitance
mechanism can be quantified by equation
i ( V ) = k 1 v 1/2 + k 2 v (6)
i ( V ) / v 1/2 = k 1 + k 2 v 1/2 (7)
where k1v1/2 and k2v represent diffusion control and pseudoca-
pacitance behavior, respectively. The k1 and k2 can be obtained
from Equation (7). As revealed in Figure S5b (Supporting Infor-
mation), the proportion of capacitive contribution in SHCM/
NCF anode at 0.2 mV s−1 is 52.2% (shaded region). With sweep
rate increasing, the proportion of capacitive contribution either
gradually increase in Figure 6h (52.2% at 0.2 mV s−1, 61.5% at
0.4  mV s−1, 68.3% at 0.6  mV s−1, 74.4% at 0.8  mV s−1, 79.6%
at 1  mV s−1 and 88.1% at 2  mV s−1 for SHCM/NCF). In addi-
tion, the capacitive contribution values at different sweep rate
for SHCM/NCF electrode all exhibit higher percentages com-
pared with SHC electrode, because the unique 3D intercon-
nected nitrogen/carbon structure of SHCM/NCF facilitates
rapid ion insertion, N doping increases conductivity, and the
microsphere structure avoids side reactions with the electro-
lyte. Consequently, the larger pseudocapacitance contribution
for SHCM/NCF anode is conducive to fast Li+ storage kinetics,
yielding remarkable rate performance.
Besides, the phase change and electrochemical reaction
mechanism of SHCM/NCF anode can be further explicated
according to ex situ XRD, EIS and XPS results in different
voltage stages during reaction process for LIB, as presented in
Figure 6. Connected with the voltage curves, Figure 6a,b proves
ex situ XRD curves and contour plots with corresponding dis-
charge voltages at open voltage (I), 0.26 V (II), 0.03 V (III), and
0.005  V (IV) and charge voltages at 0.44  V (V) and 3.0  V (VI).
When partially discharged to 0.26 V (stage II), it is obvious that
the silicon diffraction peaks become weaker compared with
stage I, certificating the partial lithiation about silicon. Con-
tinuing discharge to stage III and IV, the characteristic peaks
of silicon are fully disappearing, indicating that crystal Si react
with Li and amorphous lithiated silicon are generated during
continuous lithiation obey following reaction
 x x
Si + xLi → 1 − −  Si + a − Li y Si (8)
 y y
During the delithiation process at stage V and fully charged
to stage VI, crystalline silicon peaks cannot be reformed and
amorphous silicon peaks still existed, in conformity to previous
papers.[38] Additionally, ex situ EIS exhibited in Figure S6g
(Supporting Information) illustrate homologous patterns at
diverse (de)lithiation states with the similar shape, implying
there are no significant form changes in impedance resistances
at different stages. The ex situ high resolution XPS character-
istic spectra for C 1s, Si 2p and Li 1s elements are revealed in
Figure  6c–e. For fresh SHCM/NCF, as discussed above, C 1s
spectrum contains C–C, C = O and C = N peaks while Si 2p
consists of Si0 and Si4+ and without Li 1s peak exists. Upon dif-
ferent (de) lithiation stages, the electrolyte may decompose on
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Figure 6.  a) Ex situ XRD, b) contour plots, c–e) ex situ XPS for different discharge voltages; f) different scan rates CV curves; g) log i versus log v plots
of SHCM/NCF; h) percent of capacitance control bar chart exhibiting.
the SHCM/NCF paper surface to constitute species such as
Li2CO3 lithium carbonate, and/or ROCO2Li, which lead to the
C = O peak is increased. As for Si 2p characteristic spectrum,
the peaks centered at 97.8 ev and 102.1 ev correspond to LixSi and
LixSiOy at discharge voltages at 0.03  V (stage III), respectively,
which are existed during discharge voltages at 0.005V (stage IV)
and charge voltages at 0.44 V (V) and 3.0 V (VI), corresponding
to the previous ex situ XRD results. Furthermore, Li 1s charac-
teristic peak centered at 54.6 eV proves the existence of LixSiOy
after (de)lithiation states, which make the conclusion of the Si
2p peaks more persuasive.[39,40] Besides, after dis-assembling
the post cycling coin battery, the SHCM/NCF has no surface
cracks and the SEM image reveal morphology of the SHCM/
NCF paper electrode remains intact, while SHC electrode has
obvious cracks even peeling, proving superior cycling stability
of SHCM/NCF paper (Figure  7a–c; Figure S6a–c, Supporting
Information).
Adv. Funct. Mater. 2021, 31, 2101487
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In order to verify practicability and feasibility of free-standing
SHCM/NCF paper anode material, full cell LIBs can be assem-
bled by using SHCM/NCF and SHC as the anode with com-
mercial LiCoO2 electrode material as cathode. Figure S6e,f
(Supporting Information) illustrates LiCoO2 discharge curve
(LiCoO2 half battery while lithium foil as counter electrode)
combined with SHCM/NCF charge curve and LiCoO2 charge
curve combined with SHCM/NCF discharge curve. Obvious,
the SHCM/NCF || LiCoO2 full battery reveals discharging
platforms at 3.60, 3.25, and 2.62  V when charging platforms
at 3.56  V and 3.90  V, which demonstrate voltage platform of
SHCM/NCF || LiCoO2 full cell is 2.6–3.9 V.
The initial three cycles galvanostatic discharge/charge curves
of SHCM/NCF || LiCoO2 in Figure  7d show initial charge/dis-
charge capacity is 1780.6 and 890.6  mA h g−1 with 50% initial
coulombic efficiency (ICE). The second and third curves are
mainly coinciding, indicating great stability for the binder-free
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Figure 7.  a–c) Dis-assembling the post cycling SHCM/NCF electrode; d) initial three cycles galvanostatic discharge/charge curves and Photograph of
open-circuit voltage (inset); e) cycling capacity; f) rate performance; g–i) photograph of powering LED.

3D interconnected paper. Moreover, long-term cycling patterns
of SHCM/NCF and SHC full cell are illustrated in Figure  7e
reveal the specific capacities at 0.5 A g−1 after 200 cycles are
450 and 170 mA h g−1, respectively. It is clear that SHCM/NCF
|| LiCoO2 full cell has higher capacity and more stable perfor-
mance. Meanwhile, rate capability of SHCM/NCF full cell is
superior and more stable than that of SHC in Figure 7f, which
further demonstrates the superiority and practicality of SHCM/
NCF paper. Besides, open-circuit potential (OCP) at 3.128  V is
measured for SHCM/NCF full cell (inset of Figure  7d). The
charged flexible SHCM/NCF soft packing lithium battery is
capable for powering light emitting diode (LED) not only flat
but also bent states. After bending, the brightness of the LED
lamp does not change when return to flat stage. (Figure 7g–i),
indicating excellent flexibility of the SHCM/NCF electrode.
including 3D interconnection network to accelerate ion/elec-
tron conduction, N-doped carbon to improve conductivity, sil-
icon nanodot alleviate damages caused by volume effect and
binder-free electrode to reduce cost, making it is suitable for the
practical application. The SHCM/NCF electrodes exhibit high
specific capacity of 1442 mAh g−1 and distinguished cycling
stability at 1 A g−1 for 800 cycles with high-capacity retention
rate of 86% as lithium half cell and good cycle stability at
0.5 A g−1 for 200 cycles as lithium full cell. Besides, this strategy
opens up a convenient new path to design 3D interconnected
micro-nano architecture with flexible and free-standing paper
property, which has important implication for practical applica-
tion and can be extended to preparation of other interconnected
structure materials.

4. Conclusion
In summary, the designed microsphere self-assembled by
hollow carbon nanosphere uniformly distributed with sil-
icon nanodots, interconnecting with carbon/nitrogen fibers
(SHCM/NCF), which will competently possess plenty of merits,
5. Experimental Section
Synthesis of SiO2@SiO2/C Nanospheres: All reagents have not
undergone further processing before use. First, DI water (20  mL),
ethanol (60  mL) and ammonia aqueous solution (1.5  mL, 25  wt
%) were mixed uniformly under rapid stirring. Then, tetraethyl
orthosilicate (TEOS, 4.5 mL) was lentamente added to above solution.
After stirring 30  min, formaldehyde solution (1  mL) and resorcinol

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(0.6 g) were added into dispersion, following under room temperature
for stirring 36 hours. The reddish precipitate was centrifugal collected.
Finally, the reddish precipitate was annealed at 800 °C for 6 h under Ar
atmosphere.
Synthesis of SHC Nanospheres: Typically, the SiO2@SiO2/C was mixed
with magnesium powder at a weight ratio of 1:1 evenly in the mortar and
magnesiothermic reduction occurs at 650 °C for 6 h, and the resulting
product was purified through 20 wt% HCl and 5 wt% HF to remove the
unreacted Mg and SiO2, and by-product MgO.
Synthesis of SHCM/NCF: 25 wt% polyvinyl pyrrolidone (PVP,
Mw  = 130000), 25 wt% polyacrylonitrile (PAN, Mw  = 150000), and
50 wt% SHC were dissolved in N,N-Dimethylformamide (DMF, 99.8%).
During electrospinning process, the applied voltage and feed rate were
maintained at ≈15 kV and 0.9 mL h−1, respectively. After, the sample were
stabilized at 250 °C for 2 h in air and then carbonized at 700 °C for 2 h
under an Ar atmosphere.
Materials Characterization: The phase characterization of
the materials was measured by X-ray diffraction (XRD, Bruker
D8 ADVANCE) between 10° and 80° with Cu Kα radiation
(λ = 0.15 418 nm). The morphologies and crystal structure of materials
were analyzed by scanning electron microscopy (SEM, Hitachi
SU8010, accelerating voltage: 30  kV) and transmission electron
microscopy (TEM, Talos F200X). Raman spectra were characterized
with 633  nm excitation wavelength. The surface areas and porosities
were characterized by Brunauer-Emmett-Teller (BET) method using
ASAP 2020 Plus 1.03. The chemistry states were recorded using
X-ray photoelectron spectroscopy (XPS, PHI5000 VersaProbeIII).
Thermogravimetric analysis (TGA) was employed in a flow of air from
room temperature to 800 °C at a heating rate of 10 °C min−1.
Electrochemical Measurements: CR2025 coin-type cells were
assembled in an argon-filled glove box. The electrochemical
characteristics were conducted with free-standing SHCM/NCF
paper as the working electrode as well as lithium foil as the counter
electrode. The mass loading of anode ranged from 1.0 to 1.8  mg cm−2.
Contrast material SHC electrode was prepared using 70 wt% of
SHC, 20 wt% of acetylene black and 10 wt% carboxymethylcellulose
sodium (CMC) dissolved in ethanol and deionized water, the
slurry was applied directly to the 12  mm diameter nickel foam,
followed by drying under vacuum (loading mass: 1.0  mg cm−2).
The polypropylene membrane was used as the separator, while
electrolyte was 1 m LiPF6 dissolved in 1:1:1 v/v/v dimethyl carbonate/
diethyl carbonate/ethylene carbonate. In addition, lithium full batteries,
using SHCM/NCF or SHC as anode and LiCoO2 as cathode, were
assembled. The galvanostatically discharged and charged performances
were employed at a LAND battery test system in the voltage range
between 0.005 and 3V. The cyclic voltammetry (CV) was measured with
0.2 mV s−1 sweep rate and electrochemical impedance spectra (EIS) was
examined with frequency ranges from 0.01  Hz–100  kHz on CHI 660D
electrochemical workstation.
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
This work was supported by the National Natural Science Foundation
of China (No. 52072299), Industrial Innovation Chain of Key Research
and Development Project of Shaanxi Province (No. 2018ZDCXLGY08-04,
2019ZDLGY16-07), the Key Science and Technology Innovation Team
Project of Natural Science Foundation of Shaanxi Province (No. 2017KCT-
01), Major Project of Shaanxi Coal Joint Fund of Shaanxi Provincial
Science and Technology Department(2019JLZ-07), Northwest University
Cross-discipline Fund for Postgraduate Students (No.YZZ17106).
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Conflict of Interest
The authors declare no conflict of interest.
Data Availability Statement
The data that support the findings of this study are available from the
corresponding author upon reasonable request.
Keywords
3D interconnected paper, electrospinning, lithium storage, N-doped
carbon, silicon
Received: February 10, 2021
Revised: March 16, 2021
Published online: June 17, 2021
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