Post on 22-Nov-2023
transcript
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One step synthesis of Si@C nanoparticles by
laser pyrolysis: high capacity anode material
for lithium ion batteries
Julien Sourice1,2*, Axelle Quinsac
1, Yann Leconte
1, Olivier Sublemontier
1, Willy Porcher
2,
Cedric Haon2, Arnaud Bordes
3, Eric De Vito
3, Adrien Boulineau
2,
Séverine Jouanneau Si Larbi2, Nathalie Herlin-Boime
1*, Cécile Reynaud
1
1CEA, IRAMIS, NIMBE, CNRS UMR 3685, F- 91191, Gif sur Yvette, France
2Univ. Grenoble Alpes, F-38000, Grenoble, France
2CEA, LITEN, 17 rue des Martyrs, F-38054 Grenoble, France
3CEA, MINATEC, 17 rue des Martyrs, F-38054 Grenoble, France
Corresponding authors: Julien Sourice (julien.sourice@cea.fr), Dr. Nathalie Herlin-Boime
(nathalie.herlin@cea.fr)
2
Carbon capacity in Si@C material
The capacity of the carbon was considered negligible based on the following analysis.
Figure S1 shows 10 cyclic voltammetry sweeps of Si@C in the potential windows 5 mV to
250 mV in order to limit the lithiation to the carbon shells and carbon nanoparticles only. The
anodic (0.8 and 0.5 V) and cathodic current peaks (0.11, 0.15 and 0.2 V) are the classical
signature of lithiation and delithiation from carbon species, therefore proving that the
potential window is correctly chosen (according with I. Uchida et al., Electrochemical and
Solid-State Letters, 1 (1) 10-12, 1998). The capacitive current is due to lithium adsorption on
carbonaceous material.
Figure S1: Cyclic voltammetry (20 µV.s-1
) of Si@C material in the potential window 5 mV
to 250 mV
Based on the precedent result, Figure S2 shows the capacity from the galvanostatic
experiment (C/10 charge/discharge rate) on the same Si@C material and in the same potential
window. The capacity related to carbon species in Si@C reaches approximately 100 mAh.g-1
.
Therefore, we chose not to include the masses of carbon compounds into the calculus of
Si@C specific capacity as their impact on the total capacity can be neglected.
S1
0,00 0,05 0,10 0,15 0,20 0,25
-0,04
-0,02
0,00
0,02
0,04
Intensity [mA]
Potential [V]
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Figure S2: Galvanostatic cycling (C/10) of Si@C sample in the potential window 5 mV to
250 mV
Si@C Raman spectra deconvolution
Deconvolution of Raman spectra of Si@C has been conducted with 100% Lorentzian function
based on A. Santamaria work (Raman features between two classes of carbon nanoparticles
generated in ethylene flames, XXXVI Meeting of the Italian Section of the Combustion
Institute). Figure S3 shows the 5 contributions extracted from the 1100 to 1700 cm-1
Raman
signals and Table S1 report their centers, widths and heights.
Center
[cm-1]
Width
[cm-1]
Height
[arb.uni.]
G 1578 83 1655
D1 1350 180 1681
D2 1602 59 852
D3 1483 95 216
D4 1246 215 408
Table S1: Centers, widths and heights of G, D1, D2, D3 and D4 signals deconvoluted from
the Raman signal of Si@C in the 1100 to 1700cm-1
area.
S2
10 20 30 40 50 60 70 80 90 1000
50
100
150
200
250
300
350
400
delithiation
lithiation
Capacity (mAh.g-1)
Cycle
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Figure S3: Raman spectra of Si@C and the 5 contributions G, D1, D2, D3 and D4 obtained
from the fit analysis
EELS spectra
The EELS spectra associated to the mapping of Si@C nanoparticle of Figure 2f is displayed
in Figure S4. The two features at 285 eV and 290 eV are identified as transitions to the π*
molecular orbital and to σ* orbitals respectively.
Figure S4: EELS spectra of Si@C and insert highlighting C K edge π* and σ*
Additional TEM, HRTEM and SEM images
1000 1200 1400 1600 1800-700
0
700
1400
2100
Intensity [a.u.]
Raman shift [cm-1]
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Figure S5: HRTEM, TEM and SEM images of Si@C (a,b,c and d) and Si (e, f, g and h)
samples
Charge discharge curves
Figure S6: First lithiation/delithiation curves of Si sample (C/10)
0 1000 2000 3000 4000 5000
0,0
0,5
1,0
1,5
2,0
2,5
3,0
3,5
Voltage (V)
Capacity (mAh.g-1)
Si