Article

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Silicon Few-Layer Graphene Nanocomposite as High-Capacity and

High-Rate Anode in Lithium-Ion Batteries
Stefano Palumbo,*,†,‡,§ Laura Silvestri,† Alberto Ansaldo,† Rosaria Brescia,∥
Francesco Bonaccorso,*,†,⊥ and Vittorio Pellegrini†,⊥
†
Graphene Laboratories and ∥Electron Microscopy Facility, Istituto Italiano di Tecnologia (IIT), Via Morego 30, 16169 Genova,
Italy
‡
Dipartimento di Elettronica e Telecomunicazioni, Politecnico di Torino, Corso Duca degli Abruzzi 24, 10129 Torino, Italy
§
Metrology for Quality of Life Departimento, Istituto Nazionale di Ricerca Metrologica (INRIM), Strada delle Cacce 91, 10135,
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Torino, Italy
⊥
Bedimensional S.p.A., Via Albisola 121, 16163 Genova, Italy
*
S Supporting Information

ABSTRACT: A silicon-graphene heterostructure provides optimal

electrochemical performance as anode nanomaterial in both half and
full cells with a commercial NMC111 (LiNi1/3Mn1/3Co1/3O2) cathode.
The anode consists of carbon-coated polycrystalline silicon nano-
particles in between a parallel oriented few-layers graphene flakes
(FLG). Electrochemical tests in lithium cells display high capacity
values (∼2300 mAh/g) with a Coulombic efficiency (CE) reaching
99% at current density of 350 mA/g and 1000 mAh/g at current
density values up to 3.5 A/g (CE = 99%). The laminated graphene-based structure yields a protective coating to the silicon
nanoparticles still enabling exposure to lithium ions. The method of production of the laminated silicon-graphene
nanocomposite is scalable and low-cost, offering a practical route to the introduction of high silicon content anodes in lithium-
ion batteries.
KEYWORDS: silicon, graphene, nanostructured composite, large scale production, high capacity anode, lithium-ion batteries

■ INTRODUCTION
The continuous development of lithium-ion battery (LIB)
technology1−4 over the years has led to large improvements in
terms of specific capacity, energy density, and cycle life
stability, enabling the introduction of LIBs into the market of
hybrid and electric vehicles.5 For example, LIBs increased their
efficiency by 5−10% every year for the past 25 years.6 In fact,
while in the 1990s the highest energy density value for LIBs
was ∼90 Wh kg−1,7 currently their value approaches 260 Wh
kg−1.5
Nevertheless, development of LIBs able to satisfy the
growing demand in terms of energy densities and fast charging
times poses new challenges, which cannot be overcome by
exploiting conventional electrode materials, due to their
intrinsic theoretical limitations.6,8,9
Conventional LIBs consist of graphite-based anodes and
lithiated transition metal oxide cathodes, such as LiCoO2.2
These cells typically supply ∼120 Wh kg−1.2 In these
electrochemical systems, the redox process is based on
intercalation/deintercalation of lithium ions between the two
layered materials,10 a mechanism that displays fundamental
limitations preventing further improvements. In fact, consid-
ering the anode, for example, graphite is able to exchange only
1 Li+ every 6C atoms, achieving a theoretical specific capacity
of 372 mA hg−1.11,12 Alternative processes such as alloying13 or
conversion14 are exploited to overcome these limitations,
leading to higher capacity values, which consequently increase
the energy density of the currents LIBs.10,15
Silicon, currently, represents one of the most promising
alloying anode materials to replace graphite-based ano-
des.13,16−18 Silicon can theoretically react in a lithium cell
through an alloying reaction to form Li4.4Si, achieving a specific
capacity of 4200 mA hg−1.19 However, several issues affect
silicon, as well as other alloying materials, hindering its
implementation in commercial batteries.20 In particular, the
main issue of silicon is associated with the significant volume
changes (>300%) during the lithiation/delithiation pro-
cesses.21 The volume change produces cracks and pulverization
of the electrode leading to the loss of electrical contact and the
consequent poor cycling performance.22 The continuous
volume expansion/contraction of silicon during cycling also
negatively affects the electrode−electrolyte interface.23 In fact,
the exposure of fresh electrode surface (due to expansion)
determines a continuous electrolyte reduction during the
subsequent cycles, resulting in an unstable SEI (solid
electrolyte interface) layer formation.23
Received: November 6, 2018
Accepted: February 4, 2019
Published: February 4, 2019

© 2019 American Chemical Society 1793 DOI: 10.1021/acsaem.8b01927

ACS Appl. Energy Mater. 2019, 2, 1793−1802
ACS Applied Energy Materials
To overcome the aforementioned issues several strategies
have been adopted mainly focusing on the design of advanced
electrode structures,24 including, in particular, the exploitation
of silicon nanoparticles25 and their encapsulation into a carbon
matrix.26
Several experimental works25,27,28 have proven the existence
of a relationship between silicon particle size and the
electrochemical performance, demonstrating that the use of
non-agglomerated nanosized silicon can suppress particle
cracking upon lithiation. However, besides controlling the
size of silicon particles, their morphology (i.e., nano-
spheres,29−31 nanowires32 or nanotubes33) also is known to
affect the electrochemical properties.
In addition to the nanostructuring approach,29−33 the
realization of a composite of silicon nanoparticles with a
conductive carbon material represents another established way
to mitigate the volumetric changes, thus improving the
performance of the electrode in terms of both cycle life and
rate, ensuring the electrical contact of the electrode.34−36 This
approach proved to be effective only when a carbon
nanostructure is able to enclose the silicon nanoparticles.34−36
In fact, only minor improvements are observed by simply
mixing silicon nanoparticles with an amorphous carbon or by
carbon coating methods.17,37 In contrast, more complex
strategies, such as the encapsulation of silicon into carbon
nanostructures with empty spaces,38 as well as their infiltration
into a nanoporous matrix, allow silicon nanoparticles to freely
expand and contract, with a positive effect on cyclability.18
Among the explored conductive carbon structures,34−36
graphene39−41 has recently emerged as a promising silicon
partnering material owing to its excellent mechanical proper-
ties42 and electrical conductivity.43 Several approaches have
been proposed over the last years to successfully integrate
graphene and silicon nanoparticles to obtain anodes with long
cycle life.44−56
So far, the most common graphene-based material used in
combination with silicon is reduced graphene oxide
(RGO).57−61 In fact, the presence of an oxygen-containing
functional group makes the RGO flakes hydrophilic, thus
enabling the possibility of using a large variety of solvents, e.g.,
water.41,62 This means that through simple synthetic strategies,
graphene can be functionalized or modified with electroactive
species through covalent or noncovalent bond.63−65 Another
strategy relies on the use of single- or few-layer graphene (SLG
and FLG, respectively), which, on one hand, accommodates
the electroactive material and, on the other hand, provides a
much more effective pathway for electron conductivity.66,67
Further examples to improve the performance of silicon-based
electrodes make use of nitrogen-doped graphene.68 In fact, it
was experimentally demonstrated69−72 that the doping of
graphene flakes with nitrogen atoms modifies the graphene
electronic structure73 and improves the lithium diffusion
kinetics and transfer,74 resulting in a beneficial effect on its
electrochemical performance.75−77
Different methods have been explored to produce silicon-
graphene composites.26,66,67,78−83 Although the simple physical
mixing of silicon nanoparticles and graphene flakes could
represent an easy way to have a low cost and scalable method
for the industrial production of electrodes,80,81 it has not
always been validated by the cell electrochemical perform-
ance.82 Alternative methodologies enabling the in situ growth
of graphene in order to obtain a controlled morphology of the
silicon-graphene composite26,66,67,83,84 as well as the synthesis
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of silicon nanoparticles onto the graphene surface,78,79,85
demonstrated to be more effective in optimizing the perform-
ance in a lithium cell, but with the downside of being hardly
compatible with large scale industrial production.86−88
Here, we present a laminated silicon-FLG composite to be
used as anodic material in a lithium cell that combines a facile
and low-cost method for preparation with high and stable
electrochemical performance.
Pristine materials include commercial silicon nanoparticles
and FLG flakes produced by a wet jet mill (WJM) process,
which enables the scaling-up of the production of high quality
few-layers graphene.89 Electrode preparation exploits a three-
step process. First, by using ultrasonication, FLG flakes and
silicon nanoparticles are dispersed in a common solvent. Then,
the obtained slurry is directly deposited on the copper current
collector. Finally, the electrode is subjected to a thermal
treatment in a reducing atmosphere.90
We show that the as-prepared electrodes are formed by FLG
flakes with a preferential orientation parallel to the electrode
surface, that entrap polycrystalline carbon-coated silicon
nanoparticles with overall silicon content as high as 57%.
The resulting laminated silicon-FLG electrode shows high
specific capacity values (>2000 mAhg−1), being able to sustain
current densities up to 7 A/g, with a Coulombic efficiency
(CE) of 99%. Furthermore, we also demonstrate the use of
silicon-FLG electrode in a full lithium-ion cell using NMC111
(LiNi1/3Mn1/3Co1/3O2) as the positive electrode. Electro-
chemical tests at C/2 show that the cell can exchange 1800
mAhg−1 (referred to silicon mass) reaching a CE of 99%.
These results surpass previous attempts to develop commer-
cially suitable solutions of high silicon content composites for
Li-ion cells.
■ MATERIAL AND METHODS
Materials. Silicon nanoparticles (<100 nm diameter) were
purchased from Alfa-Aesar. Few-layer graphene flakes were prepared
by WJM, following the procedure developed in our laboratories89 (see
next section for details). NMC111 coated on Al foil (16 mg/cm2) was
provided by Varta Micro Innovation gmbH.
Wet-Jet Mill Exfoliation of Graphite. 200 g of graphite flakes
(+100 mesh, Sigma-Aldrich) was mixed with 20 L of N-methyl-2-
pyrrolidone (NMP) (>97%, Sigma-Aldrich) by a mechanical stirrer
(Eurostar digital Ika-Werke).89 A hydraulic mechanism and a piston
supplied a pressure between 180 and 250 MPa to push the as-
prepared mixture into a set of 5 different perforated and
interconnected disks, called processor. Two jet streams were
generated at the second disk, which have two holes with diameters
of 1 mm. Then, the jet streams collided between the second and the
third disk, which consists of a nozzle (i.e., a half-cylinder channel) of a
diameter of 0.3 mm. The shear force generated by the solvent when
the sample passes through such nozzle promotes the graphite
exfoliation.89 The sample was then separated in two jet streams,
recombining in the last disk before leaving the processor. Immediately
after the processor, the sample was cooled down by means of a chiller.
The processed sample was then collected. The wet-jet milling process
was repeated passing the sample through the 0.15 mm nozzle. Finally,
a third exfoliation step was carried out by adjusting the diameter of
the nozzle to 0.10 mm. The dispersion in NMP was then subjected to
rotovapor and freeze-drying to completely remove the solvent.
Electrode Preparation. Silicon-FLG electrodes were prepared by
dispersing equal masses of silicon nanoparticles, FLG flakes and
poly(acrylic acid) (PAA) in ethanol by ultrasonication for 90 min.
The mass loading of the active material was 30 mg/mL.
50 μL of the obtained dispersion (corresponding to a mass of 1.5
mg of active material) was subsequently deposited, by drop casting,
onto a copper disk (15 mm diameter) and then dried in air for 5 min.
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Figure 1. (a−c) Cross section and top view SEM micrographs of the silicon-FLG electrode before and (d−f) after annealing.
Finally, the electrodes were annealed in a tubular furnace under a
controlled atmosphere (vacuum + 5 sccm of H2) for 30 min at 750 °C
with a heating rate of 15 °C/min up to 700 °C slowing down to 5 °C/
min to reach 750 °C. To preserve the samples from an undesired
bending of the copper disk, a steel foil was superimposed during the
process.
Physical-Chemical Characterization. The as-prepared silicon-
FLG electrode was characterized via a set of techniques. Scanning
electron microscopy (SEM) images of the electrodes were acquired by
a JEOL JSM-6490LA instrument. High-resolution transmission
electron microscopy (HRTEM) and energy-filtered TEM (EFTEM)
analyses were carried out on an image-corrected JEOL JEM-2200FS
TEM (Schottky emitter source), operated at 200 kV, equipped with
an in-column image filter (Ω-type) and a Bruker XFlash 5060 SDD
energy-dispersive X-ray spectrometer (EDS). EFTEM maps reported
here were obtained using the three-window method at the C K and O
K ionization edges. To prepare the grid for TEM analysis, the
electrodes were first sonicated in ethanol and then 100 μL of each
dispersion was drop cast onto a holey amorphous carbon-coated
copper grid.
Raman measurements were carried out for silicon-FLG electrodes
before and after the annealing process. The Raman spectra were
acquired by using a Renishaw inVia micro-Raman spectrometer with
the 514.5 nm line of an Ar+ laser. The incident laser was focused by a
50× optical microscope objective with a numerical aperture of 0.95
and then the scattered light was detected in a backscattering geometry
dispersed by a 2400 l/mm holografic grating. All the spectra were
collected by acquiring 3 accumulations of 30 s each. Acquired spectra
were analyzed by OriginLab OriginPro 2016 using Voight curves in
order to deconvolute the main Lorentzian components.
X-ray diffraction (XRD) patterns were recorded on a PANalytical
Empyrean X-ray diffractometer equipped with a 1.8 kW CuKα
ceramic X-ray tube, PIXcel3D 2 × 2 area detector and operating at 45
kV and 40 mA. The diffraction patterns were collected in air at room
temperature using Parallel-Beam (PB) geometry and symmetric
reflection mode. X-ray diffraction data analysis was carried out using
HighScore 4.7 software91 from PANalytical.
X-ray photoelectron spectroscopy (XPS) measurements were
performed on a Kratos Axis UltraDLD spectrometer, using a
monochromatic Al Kα source operated at 15 kV and 20 mA. High-
resolution narrow scans were acquired on Si 2p core levels at constant
pass energy of 10 eV in steps of 0.1 eV. The photoelectrons were
detected at a takeoff angle of Φ = 0° with respect to the surface
normal. The data were processed with Casa XPS software v 2.3.17.
Silicon spectra fitting has been performed by considering Voigt
profiles; for elemental silicon, an intensity ratio of 2:1 between the
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two components of the doublet and a doublet separation of 0.6 eV
have been assumed.92
To evaluate the silicon content in the composite, a thermogravi-
metric analysis (TGA) was performed using a TGA Q500-TA
Instrument. As analytic gas, air with a flux of 50 mL/min was implied.
The method used during the measurements provides an initial
stabilization of the sample at 30 °C for 5 min, and then a heat rump of
5 °C/min up to a final temperature of 800 °C maintained for 1 h.
For electrochemical characterization, coin cells 2032 were
assembled facing the as-prepared silicon-graphene electrode with a
lithium foil. A solution consisted of LP30 (1 M LiPF6 in DMC:EC)
and 10% v/v FEC (fluoro-ethylene carbonate) embedded in a
Whatman borosilicate separator was used as electrolyte. The
assembled lithium cells were tested in a Biologic VMP3 potentiostat
through galvanostatic cycling and potentiodynamic cycling with
galvanostatic acceleration (PCGA) measurements. Galvanostatic
cycling was carried out using the potential range of 0.1−1.0 V at
different current density from 0.35 A/g to 7 A/g. Electrochemical
impedance spectra were acquired upon cycling by applying a potential
signal of 5 mV amplitude in the frequency range 100 kHz to 100
mHz. The PCGA measurements were performed setting a potential
step of 5 mV and a cutoff of C/20 between 0.1 and 1.0 V. Before any
electrochemical test, a formation cycle was performed between 0.01
and 2.0 V and applying a current density of 0.35A/g, corresponding to
a C rate of ∼C/10.
Finally, a complete lithium ion cell was assembled using silicon-
FLG electrode as anode, a commercial NMC111, with a nominal
capacity of 2 mAh/cm2 electrode as cathode and LP30 + 10% v/v of
FEC as electrolyte. The electrochemical behavior of the as-assembled
cell was tested by galvanostatic cycling in the potential range of 2.8−
4.0 V, using a C-rate of C/2.
In order to provide a stable electrode−electrolyte interphase, a
formation procedure was carried out before cycling the Li-ion cell and
consisting of (i) a first charge to 4.0 V at C/10, followed by a
potentiostatic step with a current cutoff corresponding to C/20; (ii)
first discharge at 2.8 V at C/10 followed by a rest time of 3 h; then
(iii) two charge−discharge cycles between 4.0 and 2.8 V at C/2, with
a potentiostatic step at 4.0 V with a current cutoff corresponding to
C/20.
For all the electrochemical tests, specific capacity is referred to the
mass of silicon.
■
RESULTS AND DISCUSSION
Morphological and Structural Characterization of the
Silicon-FLG Electrodes. The structural and morphological
properties of the FLG produced by WJM are reported in ref
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Figure 2. (a) Superposition of the normalized Raman spectra for the Si-FLG anode pre-annealing (red) and post-annealing (blue). (b−c) HRTEM
images and corresponding fast Fourier transforms (FFTs) for regions in the (b) pristine and (c) annealed Si-FLG electrode on top of an
amorphous carbon film. The FFTs indicate a [001]-oriented graphite (ICSD 76767) pattern, due to the FLG flakes, and randomly oriented cubic
silicon (ICSD 51688) nanometer-sized domains.

89. Here we report the morphological characterization of the
as-prepared silicon-FLG electrodes carried out by SEM. Figure
1 reports the comparison of the electrodes before (a−c) and
after (d−f) the annealing process.
Figure 1a,b shows the cross section of the electrode once
deposited onto the copper foil. We can clearly distinguish the
two components, with the isotropic silicon nanoparticles in
between the FLG flakes. Observing the top view of the
electrode in Figure 1c, we can see also on the surface of the
electrode the presence of silicon nanoparticles and the FLG
flakes.
After the annealing process, the electrode morphology is
significantly changed. The electrode cross section in Figure 1d
shows that the graphene flakes are oriented parallel one to each
other, the dimension of the silicon aggregates appear reduced
and they are homogeneously distributed between the FLG
flakes. As evident in Figure 1e, FLG flakes entrap the silicon
nanoparticles creating a well-organized and ordered structure.
Differences between electrodes before and after annealing are
also evident in the surface of the electrode (Figure 1f), where
FLG flakes cover a higher surface compared to the electrode
without annealing.
The aim of the annealing process is twofold: (i) achieve a
higher conductivity of the composite by the formation of a
carbon coating over the Si-NPs and in between, i.e., a better
electrical contact between the Si-NPs and the FLG flakes, and
(ii) increase the anode specific capacitance by removing the
binder. To validate this hypothesis, Raman spectra in the
1100−1900 cm−1 range were acquired.
The spectra were then normalized to the intensity of the
carbon G peak and the peaks were deconvoluted in their
Lorentzian components. In Figure 2a the typical Raman
spectra of pristine and annealed samples are reported.
On the pristine sample spectrum, the typical components of
graphene spectrum in the range acquired (D, G, and D′93) can
be clearly identified. The peaks are well-defined and separated
and the I(G)/I(D) ratio is 0.064. On the contrary, after the
annealing process, the intensity of the D peak was strongly
increased, and the D and G peaks are partially overlapping.
By the deconvolution of the Raman spectrum, five different
components can be identified. Of them, three can be ascribed
to the graphene flakes, i.e., D, G, and D′ peaks, while the other
two reveal the typical features of the amorphous carbon.
1796
An explanation of these features can be linked to the carbon-
content present in the binder that turned into a carbon coating
after the annealing process. This hypothesis was then further
explored by means of HRTEM and EFTEM imaging. A deeper
analysis on the Raman spectra is reported in Figure S3.
The fast Fourier transform (FFT) of the HRTEM image,
shown in Figures 2b,c, clearly show the [001] orientation of
the FLG flakes, while the silicon spots are arranged in rings,
corresponding to polycrystalline silicon.
Further details of the electrodes have been highlighted by
EFTEM elemental mapping and XPS measurements.
Figure 3 shows the EFTEM analysis for the silicon-graphene
electrode pre-annealing (Figure 3a−c) and post-annealing
Figure 3. (a,d) Zero-loss filtered Bright Field TEM (BF-TEM) image
and (b,c, e,f) corresponding EFTEM elemental maps for carbon (red)
and oxygen (blue) on regions of (a−c) pristine and (d−f) annealed
Si-FLG electrode, partly suspended on a hole in the holey carbon
support film.
(Figure 3d−f). By comparing the C maps in Figure 3b and e it
is possible to note an inhomogeneous 3-nm-thick carbon
coverage all over the silicon nanoparticles, in the case of the
annealed sample. On the contrary, in the pristine sample there
is a low amount of carbon. Furthermore, a clear surface
oxidation is observed in the annealed sample (Figure 3f), less
prominent in the pristine sample (Figure 3c). From the EDS
quantification, the annealed sample is clearly much richer in
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carbon and slightly richer in oxygen compared to the pristine
sample (Figure S2).
The electrode surface has been further analyzed by XPS
measurements. Figure 4 reports the spectra obtained for the
Figure 4. XPS spectrum comparison of the silicon particles and of the
silicon-FLG electrode post-annealing.
annealed silicon-FLG electrode in comparison to the non-
annealed one and the pristine silicon sample. Both spectra are
characterized by the presence of a doublet of narrow peaks,
with the most intense one centered at (99.4 ± 0.2) eV, typical
of elemental silicon,92 accompanied by a broad peak centered
at (103.4 ± 0.2) eV, corresponding to SiO2.92 The relative
intensity of the oxide peak increased with the annealing
process, passing from 19.6% to 28.3% of the whole silicon
content, as obtained by the fitting procedure (Figure S1).
Besides, there is no significant difference between the pristine
silicon and the silicon-FLG electrode not subjected to the
annealing process.
The increase of oxygen content might be due to annealing
conditions and by the presence of oxygen atoms in the PAA.
Structural and morphological analyses have demonstrated
that with the combined approach of ultrasonication and
annealing, we obtained a silicon-FLG electrode with a well-
organized structure. The annealing step leads to the formation
of a carbon coating onto the silicon surface, which could be the
main cause of the partial oxidation of the silicon (less than
10%). Thermogravimetric analysis revealed silicon content of
57% (Figure S4). In summary, the as-prepared electrodes
consist of a laminated structure in which small silicon
aggregates are entrapped between FLG flakes.
Electrochemical Characterization. Potentiodynamic cy-
cling with galvanostatic acceleration (PCGA) measurements
were performed to provide insight into the redox processes
related to the as-prepared silicon-FLG electrodes. Figure 5
reports the differential potential profile obtained during the
formation cycles (blue line) and the subsequent cycles (red
line).
In agreement with previous work,94 the formation cycle
shows a completely different feature when compared to the
other cycles. During the discharge, it is possible to observe the
occurrence of multiple processes occurring below 0.13 V,
associated with the contemporary intercalation of lithium into
FLG layers and the complete lithiation of Si. As already
reported,94,95 the lithiation of the crystalline silicon phase
initially form amorphous LixSi alloys, according to Si + xLi+ +
xe− → LixSi (0 ≤ x ≤ 4.4) followed by the formation of Li15Si4
below 0.06 V. In the recharge process, two small peaks,
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Figure 5. PCGA response of the annealed silicon-graphene electrode
in lithium cell. Voltage range used for the formation cycle is 0.01−2 V,
while for the other cycles it is in the 0.1−1 V range.
associated with the redox process of FLG, are observable at 0.1
and 0.15 V, followed by two large peaks at 0.3 and 0.45 V
(labeled C and D, respectively) corresponding to the multistep
delithiation process of amorphous Li−Si alloys.96 In the
second cycle, limiting the potential cut-offs to 0.1−1 V, we also
limited the contribution of FLG flakes into redox process,
while the two-anodic process centered at 0.25 and 0.1 V,
according to a-Si + xLi+ → a-LixSi; a-LixSi + yLi+ → a-
Li(y+x)Si,96 and two cathodic peaks at 0.3 and 0.45 V, related to
silicon delithiation process, are still observable.
Figure 6a shows the cycling performance of the annealed
silicon-FLG electrode, obtained in galvanostatic mode with a
current density of 0.35 A/g. When discharged at 0.01 V, the
silicon-FLG electrode achieves a specific capacity >3500 mAh/
g, almost reaching the theoretical one. The recharge to 2 V
shows a CE of almost 89%. In the other cycles, limiting the
potential range between 0.1 and 1 V, the tested electrode
discharges a capacity of ∼2300 mAh/g with an initial
Coulombic efficiency (ICE) of 95% that reach 99% after 12
cycles. The specific capacity achieved at the second cycle
remains rather stable during cycling (with a fading per cycle of
0.13%), delivering 1800 mAh/g after 90 cycles, which
correspond to ∼78% of the initial value. Figure 6b shows the
potential profiles of some representative cycles. We can
observe that the charge−discharge curves exhibit a similar
shape in every cycle, confirming the reversibility of the process.
Furthermore, we can distinguish the typical sloping curve
associated with the alloying/de-alloying of silicon.93−96 In fact,
in agreement with the PCGA analysis, discharge curves are
characterized by two slopes at 0.20 and 0.1 V, while recharge
processes show an initial plateau at 0.15 V, and two slopes
around 0.3 and 0.4 V. Finally, the formation of SEI has been
evaluated acquiring impedance spectra at different cycles
(Figure S5). The sequence of Nyquist plots in Figure S5a
describes a rather regular evolution of a nonblocking
interphase to a blocking one, compatible with a reactive
interphase which is progressively passivated from electrolyte
decomposition products. Upon cycling, the resistance of the
SEI rises from 13 Ω to 38 Ω after 100 cycles (Figure S5b).
For comparison, in Figure S6 is the behavior of the same
electrode when it is not subjected to the annealing step. This
electrode shows a lower specific capacity, not being able to
sustain prolonged cycling. In fact, in a few cycles, it is possible
to observe a loss of specific capacity of ∼40%. Moreover, after
less than 50 cycles the material starts to degrade, with
irreversible damage after only 100 cycles.
In summary, the electrode after annealing demonstrated
enhanced electrochemical properties compared to the
reference electrode. On one hand, the annealing process
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Figure 6. Electrochemical performance of the annealed silicon-FLG
electrode in lithium cell: (a) cycling performance; (b) potential
profiles obtained at 0.35 A/g; and (c) rate capability measured at
different current density values. For all measurements, before cycling,
a formation cycle (indicated as cycle 0) has been performed between
0.01 and 2 V at 0.35 A/g.
determines the creation of a well-organized structure. The
graphene flakes entrapping silicon particles can buffer the
volumetric expansion/contraction of silicon during cycling,
beneficial for the electrochemical performance. On the other
hand, annealing also causes the pyrolysis of the non-conductive
PAA, creating a carbonaceous network that improve the
conductivity and physically sustain the silicon-graphene
structure.
To evaluate the rate capability, the annealed silicon-FLG
electrode was further cycled increasing the current density
from 0.35 A/g (corresponding to C/10) to 7 A/g (∼2 C). As
reported in Figure 6c, the annealed silicon-FLG electrode
exhibits excellent rate performance. However, we noticed that
the exchanged capacity decreases from 2300 mAh/g at 0.35A/
g to 750 mAh/g at 7 A/g (2 C). In addition, when the current
density returns to the initial value of 0.35 A/g, the specific
capacity raises again to ∼2000 mAh/g, which is the same value
obtained during first cycles.
Since the annealed silicon-FLG electrode demonstrated
cyclability at high current densities, it was decided to perform a
prolonged discharge/recharge test of the anode at 3.5 A/g. The
obtained results are shown in Figure S7a. During the first 50
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discharge−recharge cycles, it is possible to observe an initial
drop of the specific capacity (from 1500 mAh/g to less than
1000 mAh/g), corresponding to a loss of ∼30% of the initial
value. Then, in the subsequent cycles the specific capacity
reaches a stable value of ∼1000 mAh/g. After 250 charge/
discharge cycles the specific capacity reached a final value of
750 mAh/g, with capacity retention of 75%. Discharge/charge
profiles in Figure S7b show the signature of the electro-
chemical lithiation/delithiation of silicon, as evident from the
shapes of the curves, showing behavior similar to the electrode
cycled at lower currents.
Ex-Situ Morphological Analysis. In order to study the
changes occurring in the electrode material upon cycling, an
ex-situ morphological and structural analysis has been
performed by the use of SEM and HRTEM. For the analysis,
the electrodes were first cycled under galvanostatic condition
in lithium cell using a current density of 0.35A/g. Afterward,
the tests were stopped at different cycle numbers (i.e., 1, 10,
50, and 100) and the electrode recovered and washed with
anhydrous DMC to eliminate the residual lithium salt on the
electrode surface. The micrographs obtained for the electrode
after 100 cycles are reported in Figure 7.
Figure 7. (a) HRTEM image and (inset) corresponding FFT, (b)
zero-loss filtered BF-TEM image and corresponding elemental maps
of (c) C and (d) O for Si nanoparticles from the post-mortem
electrode (after 100 cycles), suspended on holes in the carbon
support film.
After the first forming cycle, the composite does not show
any appreciable changes in the structure nor in the
morphology. The latter is similar to that of the post-annealing
electrode (Figure 1a). The graphene flakes and the silicon
nanoparticles are clearly visible (Figure S8a,e). According to
EFTEM mapping (Figure S9a), silicon nanoparticles are still
covered by a carbon coating (Figure S9b) of ∼3 nm thick
together with an oxide-reach shell (Figure S9c). HRTEM
images analysis (Figure S10a,e) shows that silicon nano-
particles are still polycrystalline, as already observed just after
the annealing process.
Since the tenth cycle, silicon undergoes a major structural
change, turning from polycrystalline to amorphous, as pointed
out by the HRTEM analysis (Figure S10b,f). This can explain
DOI: 10.1021/acsaem.8b01927
ACS Appl. Energy Mater. 2019, 2, 1793−1802
ACS Applied Energy Materials
the formation of a small valley in the cycling performance of
Figure 6a. This amorphous structure is preserved also for
higher cycles (Figure 7a).
From SEM imaging (Figure S8 in SI), a gradual evolution of
the Si nanoparticles into a flat, continuous layer is observed.
After 50 cycles, SEM images (Figure S8c,g) show how the
cluster of silicon has almost covered the entire electrode
interface. It is still possible to point the most superficial
individual graphene flakes. Moreover, the morphology of the
silicon nanoparticles becomes more and more porous with the
cycling and can no longer be neglected after 50 cycles (Figure
S9d,e). In the same way, the oxidation of the silicon
nanoparticles seems to increase with the cycling, with the
first appreciable evidence only after 50 cycles (Figure S9i).
For higher cycling, the aggregation and deaggregation of
silicon nanoparticles leads to a new structure, as shown in the
top view by Figure S8d. The silicon nanoparticles now are
aggregated in individual cluster, and it is again possible to
observe graphene flakes on the surface.
By contrast, the graphene flakes are not significantly affected
by the cycling (Figure S10d,h), an expected result which
confirms that the silicon nanoparticles are the active material.
Development of Lithium-Ion Battery. After having
demonstrated the electrochemical activity of the silicon-
graphene electrode in a lithium cell, this electrode was tested
in a complete lithium-ion cell.
To this end, a commercial NMC111 with a nominal capacity
of 2 mAh/cm2 was chosen as the positive electrode, while as
electrolyte the same mixture of LP30 and 10% v/v of FEC used
in half-cell experiments, was adopted. Anode and cathode
masses were balanced considering the anode reversible
capacity (2300 mAh/g) and the reversible capacity of the
cathode (137 mAh/g as reported in Figure S8).
After the formation procedure (Figure S9), the cell achieved
a specific capacity of ∼1800 mAh/g (a value referred to the
silicon mass) with a CE > 99% (see Figure 8). After 20 cycles,
Figure 8. (a) Specific capacity vs cycle number plot and (b) cell
voltage profiles in a silicon-FLG/NMC111 cell.
the cell’s specific capacity is still higher than 1600 mAh/g.
Unfortunately, the specific capacity decreases over prolonged
cycling, and after 200 cycles only 33% of the initial capacity is
retained (Figure S9).
■
CONCLUSION
We designed and developed a nanostructured silicon-few-layer
graphene (FLG) electrode to be exploited as anode for lithium
ion battery. The nanostructured silicon-FLG electrode
comprises horizontally oriented FLG flakes entrapping the
silicon nanoparticles. The realization of such nanostructured
anode materials is rather simple, being directly fabricated onto
the copper current collector, exploiting the use of ultra-
sonication followed by an annealing process in reducing
1799
Article
atmosphere. The latter process allows the pyrolysis of
poliacrylic acid, which increases the electrical conductivity of
the silicon nanoparticles and the bond with the graphene
flakes.
The as-prepared nanostructured electrodes have shown
excellent electrochemical performances, achieving high specific
capacity in lithium cell (>2000 mAh/g), able to sustain high
currents (over 750 mAh/g at 7 A/g) maintaining high
reversibility (Coulombic efficiency −CE− ≈ 99%). These
results are in line with those already reported in the literature
(Table S1).
Finally, we demonstrated the use of silicon-FLG electrode in
a complete lithium-ion battery. Our full cell delivered a first
cycle specific capacity of 1800 mAh/g and a good stability (CE
99%).
We believe that such laminated silicon-FLG graphene
nanocomposite represents a potential hybrid morphology for
high silicon loading Li-ion cells displaying high-rate capabilities
and excellent stability. The developed nanostructured silicon-
FLG anode paved the way for further optimization of the
electrode by, for example, exploring different morphologies of
silicon nanoparticles in combination with FLG.
■ ASSOCIATED CONTENT
* Supporting Information
S
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsaem.8b01927.
Additional XPS spectra and galvanostatic cycling
measurements as well as EDS maps, TGA curves and
tables (PDF)
■
AUTHOR INFORMATION
Corresponding Authors
*E-mail: stefano.palumbo@iit.it.
*E-mail: francesco.bonaccorso@iit.it.
ORCID
Alberto Ansaldo: 0000-0002-3493-4157
Francesco Bonaccorso: 0000-0001-7238-9420
Funding
We acknowledge the European Union’s Horizon 2020 research
and innovation program under grant agreement no. 785219,
GrapheneCore2.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
We thank Sergio Marras and Mirko Prato from the Materials
Characterization Facility at the Fondazione Istituto Italiano di
Tecnologia for help with X-ray Diffraction measurements and
XPS analysis. We thank Simone Lauciello for SEM imaging,
Luca Gagliani and Manuel Crugliano for their contribution to
the production of few-layer graphene flakes, Giammarino
Pugliese for thermal analysis, and Christoph Stangl of Varta
Micro Innovation gmbH for useful discussion.
■
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1802 DOI: 10.1021/acsaem.8b01927

ACS Appl. Energy Mater. 2019, 2, 1793−1802