Supporting Information: Multifunctional Mesoporous Ionic Gels and Scaffolds Derived from Polyhedral Oligomeric Silsesquioxanes

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1 Supporting Information: Multifunctional Mesoporous Ionic Gels and Scaffolds Derived from Polyhedral Oligomeric Silsesquioxanes Jin Hong Lee,,, Albert S. Lee,, Jong-Chan Lee, Soon Man Hong,, # Seung Sang Hwang,, # and Chong Min Koo, #, * These authors contributed equally. Materials Architecturing Research Center, Korea Institute of Science and Technology, Seoul (Republic of Korea) Department of Chemical and Biological Engineering, and Institute of Chemical Process, Seoul National University, Seoul (Republic of Korea) # Nanomaterials Science and Engineering, University of Science and Technology, Daejeon 34113, (Republic of Korea) *Corresponding author: C.M. Koo, koo@kist.re.kr Figure S1. (A) 1 H NMR, (B) 13 C NMR, (C) 29 Si NMR, and (D) FTIR spectra for T8- Chloropropyl POSS, I-POSS-VIm, I-POSS-TAmCl, I-POSS-VImTFSI, and I-POSS- TAmTFSI with spectral assignments. Note: the cube represents the [SiO 1.5 ] 8 POSS core. S-1

2 Figure S2. FTIR spectra of I-POSS-G1b 5 wt % (A) before and (B) after thermal curing with inset photograph showing the complete solidification of the neat ionic liquid. S-2

3 Figure S3. Rheological properties of (A) I-POSS-G1b and (B) I-POSS-G2b series as a function of I-POSS concentration (C) ionogels fabricated with MMA-POSS. S-3

4 Figure S4. Chemical structure of MMA POSS. S-4

5 Figure S5. Chronoamperometric curve of Li/I-POSS-G1b/Li cell after a 10 mv dc pulse and impedance response (inset) of the same cell before and after dc polarization. S-5

6 Table S1. Table of ionic conductivity and t values for I-POSS-G2b and other state-of the- Li+ art ionogels. (σ, ms cm -1 ) 20 o C t Li+ MMA POSS I-POSS-G2b Py 14 -Si [1] < PYR 14 TFSI/MC/4mer- (LiTFSI) 4 [2] 0.6 (60 o C) 0.19 GPE/SBA-15 [3] P(EO) 20 LiTFSI/ (40 o C) 0.15 BMPyTFSI [4] ILPEs [5] ~ S-6

7 Figure S6. Linear sweep voltammetry of the neat ionic liquid, 1 M LiTFSI BMPTFSI and I- POSS-G1b. S-7

8 Figure S7. TGA thermograms of (A) EMITFSI with corresponding I-POSS-G1b gels and (B) BMPTFSI with corresponding I-POSS-G2b gels. S-8

9 Figure S8. Charge-discharge profiles at selected cycle number S-9

10 Figure S9. (A) BET absorption-desorption isotherms and (B) Pore-size distribution of I- POSS-S2b. S-10

11 References [1] Wetjen, M.; Navarra, M. A.; Panero, S.; Passerini, S.; Scrosati, B.; Hassoun, J., Composite Poly(ethylene oxide) Electrolytes Plasticized by N-Alkyl-N-butylpyrrolidinium Bis(trifluoromethanesulfonyl)imide for Lithium Batteries. ChemSusChem 2013, 6, [2] Chinnam, P. R.; Chatare, V.; Chereddy, S.; Mantravadi, R.; Gau, M.; Schwab, J.; Wunder, S. L., Multi-ionic Lithium Salts Increase Lithium Ion Transference Numbers in Ionic Liquid Gel Separators. J. Mater. Chem. A 2016, 4, [3] Ferrari, S.; Quartarone, E.; Mustarelli, P.; Magistris, A.; Fagnoni, M.; Protti, S.; Gerbaldi, C.; Spinella, A., Lithium Ion Conducting PVdF-HFP Composite Gel Electrolytes based on N-methoxyethyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)-imide Ionic Liquid. J. Power Sources 2010, 195, [4] Cheng, H.; Zhu, C.; Huang, B.; Lu, M.; Yang, Y., Synthesis and Electrochemical Characterization of PEO-based Polymer Electrolytes with Room Temperature Ionic Liquids. Electrochim. Acta 2007, 52, [5] Kim, J.-K.; Niedzicki, L.; Scheers, J.; Shin, C.-R.; Lim, D.-H.; Wieczorek, W.; Johansson, P.; Ahn, J.-H.; Matic, A.; Jacobsson, P., Characterization of N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide-based Polymer Electrolytes for High Safety Lithium Batteries. J. Power Sources 2013, 224, S-11