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A self-driven alloying/dealloying approach to nanostructuring micro-silicon
for high-performance lithium-ion battery anodes
Qiang Maa, Zhuqing Zhaoa, Yan Zhaoa, Hongwei Xiea, Pengfei Xinga, Dihua Wangc, and
Huayi Yina,b,*
a Key Laboratory for Ecological Metallurgy of Multimetallic Mineral of Ministry of Education,
School of Metallurgy, Northeastern University, Shenyang 110819, P. R. China.
b Key Laboratory of Data Analytics and Optimization for Smart Industry, Ministry of Education,
Northeastern University, Shenyang 110819, P. R. China.
c School of Resource and Environmental Science, Wuhan University, Wuhan, 430072, P. R. China.
* Corresponding author. Email: [email protected] (Huayi Yin)
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Fig. S1. Optical image of (a) the Mg-Si alloy electrode formed after soaking in molten salt for 1.5 h
(the inset is the treated Mg-Si alloy powders). (b) XRD pattern of the as-soaked alloy negative
product. For reference, the standard powder XRD pattern of Mg2Si was also included.
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Fig. S2. Digital images of the (a) mSi, (b) nSi-2, (c) nSi-1.5, (d) nSi-1, and (e) nSi-0.5.
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Fig. S3. (a) Optical image of the formed Mg-Sn alloy electrode (the inset is the obtained Mg-
Sn alloy blocks). (b) XRD pattern of the as-obtained positive product. For reference, the
standard powder XRD patterns of Mg2Sn and Sn were also included.
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Fig. S4. SEM image of the as-obtained Mg-Sn alloy (a) and corresponding EDS elemental
maps of Mg (b) and Sn (c).
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Fig. S5. XRD pattern of the as-vacuum-distillated sample. For reference, the standard powder
XRD pattern of Sn was also included. The inset shows the optical images of the samples
before and after vacuum distillation.
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Fig. S6. (a) SEM image PCC-nSi-2, corresponding Si (b), C (c), N (d) elemental mapping
images.
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Fig. S7. XRD patterns of mSi, nSi-1.5, nSi-1, and nSi-0.5.
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Fig. S8. FTIR spectra of the melamine-formaldehyde resin (MR).
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Fig. S9. The galvanostatic charge-discharge profiles for the first cycle of mSi and nSi-2
electrodes at 0.6 A g-1.
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Fig. S10. Cycling performance and the corresponding Coulombic efficiency of the pyrolytic
carbon (MR) electrode at 0.6 A g-1.
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Fig. S11. Galvanostatic charge/discharge profiles of PCC-nSi-2 at current density of (a) 1 and
(b) 2 A g-1, respectively.
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Table S1. Si, C, N, and O element content (%) obtained from XPS
SamplesElement content (atom%)
Si C N O
PCC-nSi-2 22.64 55.04 10.09 11.42
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Table S2. Electrochemical performance and synthesis method comparison of Si-based anode
materials in LIBs.
Materialsstructure
Synthesismethod
Cycling performance
Ref.Specificcapacity
Cyclenumber
Current/rate
Porous silicon/CLow temperature Al2O3 catalyzed
method
1024 mAh g-1
600 cycles 1 A g-1 [1]
Si/N-doped carbonAssisted
electrospray method
1031 mAh g-1
100 cycles 0.5 A g-1 [2]
Porous Si@CReduction in molten AlCl3
600mAh g-1
3700 cycles 2 A g-1 [3]
Porous Si@CElectrolysis inAlCl3-ZnCl2
molten salt
~ 2100 mAh g-1
250 cycles 1.2 A g-1 [4]
Si@CMg2Si oxidation,
HCl washing892
mAh g-1350 cycles 3.6 A g-1 [5]
Low-cost Si/C nanofibers
Ball-milled and carbonization
1595 mAh g-1
100 cycles 0.4 A g-1 [6]
Si NPs/C/graphiteAqueous sol-gel
system and carbonization
820mAh g-1
100 cycles 0.1 A g-1 [7]
Si/CFlash heat treatment
1150 mAh g-1
500 cycles 1.2 A g-1 [8]
Si/PDAMolten salt
reduction and carbonization
886.2 mAh g-1
200 cycles 0.5 A g-1 [9]
Si/CMg2Si and CO2
acid washing~1124
mAh g-1100 cycles 0.4 A g-1 [10]
Si NPs/CarbonMR, acid etching and carbonization
~1467 mAh g-1
370 cycles 2.6 A g-1 [11]
PCC-nSi-2self-driven
alloying/dealloying in molten salt
1406.5 mAh g-1
400 cycles 0.6 A g-1
This work
1080.2 mAh g-1
1000 cycles 1 A g-1
912.2 mAh g-1
1000 cycles 2 A g-1
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Table S3. Equivalent series resistance (Re) and charge transfer resistance (Rct) of the mSi, nSi-
2, and PCC-nSi-2.
Samples Re (Ω) Rct (Ω)
mSi 7.4 79.1
nSi-2 5.3 64.8
PCC-nSi-2 3.1 45.6
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References
[1] X. Han, Z. Zhang, S. Chen, Y. Yang, Low temperature growth of graphitic carbon on
porous silicon for high-capacity lithium energy storage, J. Power Sources 463 (2020)
228245-228252.
[2] Y.-C. Zhang, Y. You, S. Xin, Y.-X. Yin, J. Zhang, P. Wang, X.-s. Zheng, F.-F. Cao, Y.-G.
Guo, Rice husk-derived hierarchical silicon/nitrogen-doped carbon/carbon nanotube
spheres as low-cost and high-capacity anodes for lithium-ion batteries, Nano Energy 25
(2016) 120-127.
[3] N. Lin, T. Xu, Y. Han, K. Shen, Y. Zhu, Y. Qian, A molten salt strategy for deriving a
porous Si@C nano-composite from Si-rich biomass for high-performance Li-ion batteries,
RSC Adv. 6 (2016) 79890-79893.
[4] K. Mishra, J. Zheng, R. Patel, L. Estevez, H. Jia, L. Luo, P.Z. El-Khoury, X. Li, X.-D.
Zhou, J.-G. Zhang, High performance porous Si@C anodes synthesized by low
temperature aluminothermic reaction, Electrochim. Acta 269 (2018) 509-516.
[5] Z. Hou, X. Zhang, J. Liang, X. Lia, X. Yan, Y. Zhu, Y. Qian, Synchronously synthesized
Si@C composites through solvothermal oxidation of Mg2Si as lithium ion battery anode,
RSC Adv. 5 (2015) 71355-71359.
[6] C.F. Shen, X. Fang, M.Y. Ge, A.Y. Zhang, Y.H. Liu, Y.Q. Ma, M. Mecklenburg, X. Nie,
C.W. Zhou, Hierarchical Carbon-Coated Ball-Milled Silicon: Synthesis and Applications
in Free-Standing Electrodes and High-Voltage Full Lithium-Ion Batteries, ACS Nano 12
(2018) 6280-6291.
[7] J. Kim, C. Oh, C. Chae, D.-H. Yeom, J. Choi, N. Kim, E.-S. Oh, J.K. Lee, 3D Si/C
particulate nanocomposites internally wired with graphene networks for high energy and
16
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stable batteries, J. Mater. Chem. A 3 (2015) 18684-18695.
[8] F.M. Hassan, V. Chabot, A.R. Elsayed, X. Xiao, Z. Chen, Engineered Si Electrode
Nanoarchitecture: A Scalable Postfabrication Treatment for the Production of Next-
Generation Li-Ion Batteries, Nano Lett. 14 (2014) 277-283.
[9] S. Fang, Z.K. Tong, P. Nie, G. Liu, X.G. Zhang, Raspberry-like Nanostructured Silicon
Composite Anode for High-Performance Lithium-Ion Batteries, ACS Appl. Mater.
Interfaces 9 (2017) 18766-18773.
[10] Y. Zhang, N. Du, Y. Chen, Y. Lin, J. Jiang, Y. He, Y. Lei, D. Yang, Carbon dioxide as a
green carbon source for the synthesis of carbon cages encapsulating porous silicon as
high performance lithium-ion battery anodes, Nanoscale 10 (2018) 5626-5633.
[11] H.P. Jia, J.M. Zheng, J.H. Song, L.L. Luo, R. Yi, L. Estevez, W.G. Zhao, R. Patel, X.L.
Li, J.G. Zhang, A novel approach to synthesize micrometer-sized porous silicon as a high
performance anode for lithium-ion batteries, Nano Energy 50 (2018) 589-597.
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