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Supplementary material
High Nitrogen Doped Carbon Nanofiber Aerogels for Sodium Ion
Batteries: Synergy of Vacancy Defects to Boost Sodium Ion Storage
Yun Lua,c,, Daohao Lib, Chunxiao Lyub, Hongli Liub, Bo Liua, Shaoyi Lyua,
Thomas Rosenauc*, Dongjiang Yangb,d,*
a Research Institute of Wood Industry, Chinese Academy of Forestry, Beijing 100091, China.
b Collaborative Innovation Center for Marine Biomass Fibers, Materials and Textiles of
Shandong Province, School of Environmental Science and Engineering, Qingdao University,
Qingdao 266071, China.
c Division of Chemistry of Renewables, Department of Chemistry, Natural Resources and Life
Sciences, Vienna, (BOKU), Vienna A-1190, Austria.
d Queensland Micro- and Nanotechnology Centre (QMNC), Griffith University, Nathan,
Brisbane, Queensland 4111, Australia
Corresponding author. E-mail: [email protected] (Y. Lu), [email protected] (D. Yang),
[email protected] (T. Rosenau)
Experimental procedures
Characterization
The morphologies of the samples were characterized by field emission scanning electron
microscopy (FESEM; JSM-7001F, JEOL, Tokyo, Japan), transmission electron microscopy
(TEM), high-resolution TEM (FEI Tecnai G20, USA with an accelerating voltage of 200 kV)
and atomic force microscope (AFM, Veeco Di Multimode SPM, Veeco Instruments Inc.,
Plainview, New York, USA, by using a Nanoscope IIIa multimode scanning probe
microscope under tapping mode). The samples were analyzed by Fourier transform infrared
spectroscopy (FTIR; U-4100, Hitachi Instruments Ltd., Japan) in the wavelength range of
400–4000 cm–1 and Solid-state 13C nuclear magnetic resonance (NMR; Varian Inc., USA)
with cross polarization/magic angle spinning (CP/MAS). The specific surface area was
calculated by the Brunauer-Emmett-Teller (BET) method (AutoChem II 2920, USA) from the
data in a relative pressure (P/P0) range between 0.05 and 0.20. The pore size distribution plots
were derived from the adsorption branch of the isotherms based on the BJH model. The phase
structures were characterized with X-ray diffraction (Bruker D8 Adv, Germany) operating
with Cu Kα radiation (l=1.5418 Å) at a scan rate (2θ) of 1° min−1 with an accelerating voltage
of 40 kV. Thermogravimetric analysis (TGA) measurement was carried out on an EXSTAR
TG/DTA 6300 instrument (Seiko Instruments, Japan) in air. Raman spectroscopies were
obtained on a LabRAM HR, Horiba Yvon Raman spectrometer with the 633 nm irradiation
light excitation line of the He-Ne laser. X-ray photoelectron spectroscopies (XPS) were
performed using the SSX-100 ESCA spectrometer operating with monochromatized Al Kα
X-rays (hν=1486.6 eV). The C 1s binding energy (284.8 eV) of adventitious hydrocarbon was
used as an internal standard in calibration.
Figure S1. The TG and DTG patterns of HN-CFA.
Figure S2. The Coulombic efficiency of first ten cycles of A-HN-CFA.
Figure S3. Comparison of specific capacity and cycle life between A-HN-CFA and recently reported high-performance carbon nanofiber as anodes for NIBs.
Figure S4. Characterization of A-HN-CFA after cycled for 5000 cycles. a) TEM image; b) HRTEM image of a single nanofiber.
Figure S5. (a) XRD patterns, (b) N2 adsorption/ desorption isotherms, and (c) the pore size distribution of A-N-CFA.
Figure S6. Optimized structures of N-doped graphene for (a) NG and (b) N5.
Figure S7. Optimized structures of N-doped graphene for (a) N6-N5-2, (b) N6-N5-3, and (c) N6-N5-4.
Figure S8. Optimized structures of N-doped graphene for (a) N6-NG-1, (b) N6-NG-2, (c) N6-NG-3, (d) N6-NG-4, (e) N6-NG-5, (f) N6-NG-6, (g) N6-NG-7, (h) N6-NG-8, and (i) N6-NG-9.
Figure S9. Optimized structures of N-doped graphene for (a) N5-NG-1, (b) N5-NG-2, and (c) N5-NG-3.
Figure S10. Optimized structures of N-doped graphene for (a) N6-N5-NG-2, (b) N6-N5-NG-3, (c) N6-N5-NG-4, (d) N6-N5-NG-5, (e) N6-N5-NG-6, (f) N6-N5-NG-7, (g) N6-N5-NG-8, (h) N6-N5-NG-9, (i) N6-
N5-NG-10, (j) N6-N5-NG-11, (k) N6-N5-NG-12, (l) N6-N5-NG-13, and (m) N6-N5-NG-14.
Figure S11. Calculated the density of states of N6, N6-N5-1, and N6-N5-NG-1.
Table S1. The percentage content of nitrogen in biomass derived N-doped carbon aerogels from XPS results
Samples N content (at%)
HN-CFA 12.2%
A-HN-
CFA 5.3%
A-N-CFA 7.1%
Table S2. Texture properties of chitin nanofiber aerogels and biomass derived N-doped carbon aerogels.
Samples
BET surface area
(m2 g-1)
Pore width
(nm)
Micropore volume
(cm3 g-1)
Pore volume
(cm3 g-1)
Chtin
nanofiber 5.88 37.06 0.001 0.008
HN-CFA 65.27
2.95, 17.21,
37.06 0.004 0.232
A-HN-CFA 746.16
1.76, 17.21,
34.33 0.111 0.899
A-N-CFA 696.03 0.83, 2.4 0.095 0.532
Table S3. The binding energies of the different sites in the N6-N5 models.
Models Site-1/eV Site-2/eV Site-3/eV Site-4/eV Site-5/eV Site-6/eV
N6-N5-
2
-0.171 -0.177 -0.130 -0.175 -0.175 -0.135
N6-N5-
3
-0.519 -0.510 -0.511 -0.510 -0.522 -0.521
N6-N4-
4
-0.790 -0.772 -0.771 -0.773 -0.783
Table S4. The binding energies of the different sites in the N6-NG models.
Models Site-1/eV Site-2/eV Site-3/eV Site-4/eV Site-5/eV Site-6/eV
N6-NG-2 -0.909 -0.906 -0.911 -0.910 1.364
N6-NG-3 -0.887 -0.885 -0.879 -0.887 1.889
N6-NG-4 -0.818 -0.819 -0.818 1.982 1.447
N6-NG-5 -0.815 -0.797 -0.803 -0.816 -0.798
N6-NG-6 -0.886 -0.884 -0.880 -0.880 -0.881 -0.884
N6-NG-7 -0.826 -0.828 -0.828 2.051 -0.826
N6-NG-8 -0.836 -0.840 -0.837 -0.837 1.904
N6-NG-9 -0.771 -0.772 -0.767 1.941 -0.771
Table S5. The binding energies of the different sites in the N5-NG models.
Models Site-1/eV Site-2/eV Site-3/eV Site-4/eV Site-5/eV Site-6/eV Site-7/eV Site-8/eV Site-9/eV
N5-NG-1 -0.046 1.772 -0.036 -0.046 -0.048 -0.039 -0.040 -0.043
N5-NG-2 -0.038 -0.039 -0.032 -0.033 -0.035 1.231 -0.039 -0.035
N5-NG-3 -0.195 -0.198 -0.199 -0.197 -0.191 -0.198 -0.198 -0.193 -0.196
Table S6. The binding energies of the different sites in N6-N5-NG models.Models Site-1/eV Site-2/eV Site-3/eV Site-4/eV Site-5/eV Site-6/eV
N6-N5-NG-3 -1.311 -1.312 -1.311 -1.306 -1.313 -1.312
N6-N5-NG-4 -1.280 -1.285 -1.278 -1.286 -1.280 -1.282
N6-N5-NG-5 -1.149 -1.142 -1.148 -1.133 -1.144 -1.140
N6-N5-NG-6 -1.052 -1.051 -1.050 -1.050 -1.051 -1.050
N6-N5-NG-7 -1.176 -1.173 -1.173 -1.173 -1.173 -1.173
N6-N5-NG-8 -1.531 -1.530 -1.531 -1.531 -1.531 -1.531
N6-N5-NG-9 -1.312 -1.317 -1.312 -1.312 -1.317 -1.312
N6-N5-NG-10
-1.280 -1.281 -1.281 -1.280 -1.282-1.280
N6-N5-NG-11 -1.172 -1.174 -1.173 -1.172 -1.171 -1.168
N6-N5-NG-12
-1.280 -1.276 -1.277 -1.281 -1.279-1.273
N6-N5-NG-13
-1.316 -1.315 -1.316 -1.314 -1.322-1.311
N6-N5-NG-14
-1.399 -1.424 -1.422 -1.426 -1.413-1.425