Supporting Information

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1 Supporting Information Zeolite-Templated Mesoporous Silicon Particles for Advanced Lithium-Ion Battery Anodes Nahyeon Kim, Hyejung Park, Naeun Yoon, and Jung Kyoo Lee * Department of Chemical Engineering, Dong-A University, Busan 49315, Republic of Korea *to whom correspondence should be addressed ( jklee88@dau.ac.kr, Tel: , Fax: ) Table S1. Yield and properties of mpsi samples obtained under various MR conditions Entry no. MR conditions mpsi-y Temp. ( ) Time (h) Reactor NaCl Yield (wt%) Impurity Si size (nm) Open X Open X 95.0 MgF Open X 62.0 MgF Open X 87.2 MgF Closed X 71.7 MgF Open Open Closed Closed Closed mpsi-b Closed mpsi-z Closed Table S2. Textual properties of mpsi and mpsi/c samples obtained from BET measurements Zeolite Y mpsi-y (entry 9) (entry 3) mpsi-b mpsi-z mpsi-y/c-40 BET surface area (m 2 /g) Pores volume (at P/P 0 = 0.99) (cm 3 /g) BJH Desorption average pore diameter (nm)

2 Table S3. Nyquist analysis and lithium diffusion coefficient of samples after 50 cycles Table S4. Comparison of electrochemical performances of mpsi-y/c compared with those of other types of porous silicon structures in the literature First cycle Cycle performance Approach Precursor Active Silicon contents Charge Current Coulombic Current material capacity density efficiency density Cycle Retention number Sample Structure Wt. % mah g -1 ma g -1 % ma g -1 % mpsi-y/c-50 mesoporous Si Zeolite Y Si/C This study mpsi-y/c-40 mesoporous Si Zeolite Y Si/C This study This study mpsi-y/c-40@gr mesoporous Si Zeolite Y Si/C This study mpsi-y/c-30@gr mesoporous Si Zeolite Y Si/C This study Ag psi/gns mesoporous Si MCM-41 Si/C [1] mpsi@void@mpc mesoporous Si mp-si@c porous Si mesoporous Si mesoporous Si SBA-15 Si/C [2] SBA-15 Si/C [3] SBA-15 Si [4] psi MWNT porous Si KIT-6 Si/C [5] C-ISi Si NBs completely reduced silicon nanoparticles rgo Si NaCl PPy@PHSi inverse Si opal silicon nanotube bundles silicon nanoparticles silicon nanoparticles porous silicon hollow spheres inverse opal nanotube Si/C [6] Si [7] Mesoporo us Si [8] Si/C 76 (EDS) [9] Si/C [10] hollow nano Si C hollow Si Si/C [11] Si nanoparticles Si/C [12] porous Si porous Si@C nanorods porous nanocrystalline Si Si [13] porous Si Si/C [14] nano-si Si nanoparticles Rice husks Si/C [15] gsi@c glass derivedsilicon Reed leaves Si/C [16] [1] Du, F. H.; Wang, K. X.; Fu, W.; Gao, P. F.; Wang, J. F.; Yang, J.; Chen, J. S., A Graphene-Wrapped Silver- Porous Silicon Composite With Enhanced Electrochemical Performance for Lithium-Ion Batteries. J. Mater. Chem. A 2013, 1, [2] Ru, Y. C.; Evans, D. G.; Zhu, H.; Yang, W. S., Facile Fabrication of Yolk-Shell Structured Porous Si-C Microspheres as Effective Anode Materials for Li-Ion Batteries. RSC Adv. 2014, 4, [3] Jia, H. P.; Gao, P. F.; Yang, J.; Wang, J. L.; Nuli, Y. N.; Yang, Z., Novel Three-Dimensional Mesoporous Silicon for High Power Lithium-Ion Battery Anode Material. Adv. Energy Mater. 2011, 1, [4] Chen, W.; Fan, Z. L.; Dhanabalan, A.; Chen, C. H.; Wang, C. L., Mesoporous Silicon Anodes Prepared by Magnesiothermic Reduction for Lithium Ion Batteries. J. Electrochem. Soc. 2011, 158, A1055-A1059. Ref.

3 [5] Kim, H.; Han, B.; Choo, J.; Cho, J., Three-Dimensional Porous Silicon Particles for Use in High- Performance Lithium Secondary Batteries. Angew. Chem. Int. Ed. 2008, 47, [6] Jeong, J. H.; Kim, K. H.; Jung, D. W.; Kim, K.; Lee, S. M.; Oh, E. S., High-Performance Characteristics of Silicon Inverse Opal Synthesized by the Simple Magnesium Reduction as Anodes for Lithium-Ion Batteries. J. Power Sources 2015, 300, [7] Chen, J. J.; Liu, M. M.; Sun, J.; Xu, F. F., Templated Magnesiothermic Synthesis of Silicon Nanotube Bundles and Their Electrochemical Performances in Lithium Ion Batteries. RSC Adv. 2014, 4, [8] Kim, K. H.; Lee, D. J.; Cho, K. M.; Kim, S. J.; Park, J. K.; Jung, H. T., Complete Magnesiothermic Reduction Reaction of Vertically Aligned Mesoporous Silica Channels to Form Pure Silicon Nanoparticles. Sci. Rep. 2015, 5, [9] Kannan, A. G.; Kim, S. H.; Yang, H. S.; Kim, D. W., Silicon Nanoparticles Grown On a Reduced Graphene Oxide Surface as High-Performance Anode Materials for Lithium-Ion Batteries. RSC Adv. 2016, 6, [10] Du, F. H.; Li, B.; Fu, W.; Xiong, Y. J.; Wang, K. X.; Chen, J. S., Surface Binding of Polypyrrole on Porous Silicon Hollow Nanospheres for Li-Ion Battery Anodes with High Structure Stability. Adv. Mater. 2014, 26, [11] Xie, J.; Wang, G. Q.; Huo, Y.; Zhang, S. C.; Cao, G. S.; Zhao, X. B., Hollow Nano Silicon Prepared by a Controlled Template Direction and Magnesiothermic Reduction Reaction as Anode for Lithium Ion Batteries. New J. Chem. 2014, 38, [12] Tao, H. C.; Yang, X. L.; Zhang, L. L.; Ni, S. B., Double-Walled Core-Shell Structured Nanocomposite as Anode for Lithium-Ion Batteries. Ionics 2014, 20, [13] Xing, A.; Zhang, J.; Bao, Z.; Mei, Y.; Gordinc, A. S.; Sandhage, K. H., A Magnesiothermic Reaction Process for the Scalable Production of Mesoporous Silicon for Rechargeable Lithium Batteries. Chem. Commun. 2013, 49, [14] Tao, H. C.; Fan, L. Z.; Qu, X. H., Facile Synthesis of Ordered Porous Si@C Nanorods as Anode Materials for Li-Ion Batteries. Electrochim. Acta. 2012, 71, [15] Liu, N. A.; Huo, K. F.; McDowell, M. T.; Zhao, J.; Cui, Y., Rice Husks as a Sustainable Source of Nanostructured Silicon for High Performance Li-Ion Battery Anodes. Sci. Rep. 2013, 3, [16] Li, C.; Liu, C.; Wang, W.; Mutlu, Z.; Bell, J.; Ahmed, K.; Ye, R.; Ozkan, M.; Ozkan, C. S., Silicon Derived from Glass Bottles as Anode Materials for Lithium Ion Full Cell Batteries. Sci. Rep. 2017, 7, 917.

4 Figure S1. XRD patterns of (a) mpsi (entry 6) and (b) mpsi (entry 3); (i) after reduction (in (a): after reduction followed by water washing), (ii) after HCl washing and (iii) after HF etching.

5 Figure S2. (a) N 2 adsorption/desorption isotherms and (b) BJH pore size distributions of mpsi-b, mpsi-z and mpsi-y (entry 3) and (c) TEM image of mpsi-y (entry 3).

6 Figure S3. SEM images of (a) mpsi-b and (b) mpsi-z. Figure S4. TGA profiles of (a) mpsi-y/c-30, mpsi-y/c-40, mpsi-y/c-50 and mpsi-y(entry 3) /C-30 samples and (b) mpsi-b/c-40 and mpsi-z/c-40.

7 Figure S5. (a and b) TEM images of mpsi-y/c-50 and EDS elemental mapping images of (c) Si and (d) C in (b). Figure S6. Rate responses of mpsi-y/c-40 at a fixed charge current of 100 ma g -1.

8 Figure S7. (a and c) Charge/discharge voltage profiles and (b and d) cycling performances of mpsi-y(entry 3)/C-30 and mpsi-y(entry 9)/C-30, respectively. Figure S8. (a) Charge/discharge voltage profiles and (b) cycling performances of mpsi-b/c- 40 and mpsi-z/c-40.

9 Figure S9. Determination of (a) Warburg factor from the relationship between Z and ω-1/2 at a very low frequency region and (b) lithium diffusion coefficient of samples after 50 cycles. Figure S10. SEM images of electrode cross-sections of (a) mpsi-y/c-40, (b) Si/C-40 and (c) mpsi-y/c-40@gr for their pristine and after 50 cycles at 500 ma g-1.

10 Figure S11. (a) Charge/discharge voltage profiles and (b) cycling performances of Graphite. Figure S12. (a) Charge/discharge voltage profiles, (b) rate responses at a fixed charge current of 100 ma g -1 and (c) cycling performances of mpsi-y/c-40@gr. Figure S13. Electrode coating densities and 1 st cycle Coulombic efficiencies of samples.