SUPPORTING INFORMATION. Cathode Composites for Li-S Batteries via the Use of Oxygenated Porous Architectures

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1 SUPPORTING INFORMATION Cathode Composites for Li-S Batteries via the Use of Oxygenated Porous Architectures Rezan Demir-Cakan, Mathieu Morcrette, Farid Nouar, Carine Davoisne, Thomas Devic, Danielle Gonbeau, Robert Dominko,ξ Christian Serre, Gérard Férey and Jean-Marie Tarascon * LRCS, UMR CNRS 6007, Université de Picardie Jules Verne, 33 Rue Saint-Leu, Amiens cedex, France Fax: ; Tel: ALISTORE-ERI, 80039, 33 Rue Saint-Leu, Amiens France Institut Lavoisier, UMR CNRS 8180, Université de Versailles Saint-Quentin-en-Yvelines, 45 avenue des Etats-Unis, Versailles cedex, France IPREM-ECP, UMR CNRS 5254, Université de Pau et des Pays de l Adour, 2 avenue P. Angot, Pau, France ξ National Institute of Chemistry, Hajdrihova 19, SI-1000 Ljubljana, Slovenia jean-marie.tarascon@sc.u-picardie.fr Figure S1. Structure of MIL-100(Cr) (a) the primary building unit (trimer of chromium octahedra) and the 1,3,5-benzentricarboxylate ligand, forming the hybrid supertetrahedron; (b,c) the two types of spherical cages and (d) the two types of windows (free apertures given in angstroms); (e) the whole 3-D structure, each node corresponding to a supertetrahedron, both type of cages are highlighted in green (small cage) and red (large cage) (f) size of the resulting particles ranging from 80 to 200 nm. S1

2 Figure S2. a) HAADF STEM image of the sample. The red line corresponds to an EDS profile performed across a grain. b) Evolution of the ratio S/Cr along the red line obtained by EDS. Figure S3. DSC experiment performed under an Ar flow from 25 C up to 200 at 5 C/min for MIL-100(Cr), MIL-100(Cr)/S@RT and MIL-100(Cr)/S@155 S2

3 Figure S4. XPS analysis of the a) primary building unit of MIL- 100(Cr) b) The C1s spectrum shows four main peaks i) the peak at 285.0eV, corresponds to several carbon environments like C-H of the rings, C-COO of the rings and hydrocarbon contamination C-H ii) the peak at 286.4eV is attributed to some C-O contamination iii) the distinct peak at 289.0eV is assigned to the carbon of the -COO group iv) a satellite appears at 290.4eV, characteristic of the presence of aromatic rings. c) The O1s spectrum shows 3 main peaks: i) the peak at 530.2eV corresponds to the Cr 2 O 3 like oxygen atoms. 1-2 ii) the peak at 532.1eV corresponds to the oxygen atoms of the group COO of «btc (1,3,5-benzentricarboxylate)», to the OH of the octahedra around Cr, and also to some surface C-O contamination iii) the peak at 533.8eV can be assigned to H 2 O molecules d) The Cr2p 3/2 peak appears at a binding energy of 577.5eV. According to litterature data, 1-4 this result agrees with the mixed environment O-OH- H 2 O-F proposed in several papers 5-6 for chromium in the MIL-100 structure. S3

4 Figure S5. a) HAADF STEM image of the 50%C sample after second cycle. The geometric whiter particles corresponding to the are enclosed in a network of carbon particles. b) EDS analyses on point 1 (MIL100(Cr)/S@155) and point 2 (Carbon). Figure S6. TEM images of the a) SBA-15 silica and b) mesoporous carbon replicated from the SBA-15 through hard templating procedure S4

5 Figure S7. CV scans measured for each x=0.1 change of composition in Li x S (a) MIL- 100(Cr)/S@155+50%C composite (b) mesoporous carbon/sulfur@155 composite and (c) SBA-15/S@155+50%C composite in 1M LiTFSI in TMS electrolyte S5

6 Table S1. The XPS quantitative results (atomic percentages) of MIL-100(Cr) and MIL- O C Cr S F MIL-100(Cr) MIL-100(Cr)/S@ REFERENCES (1) Paparazzo, E. J. of Electron Spec. and Related Phenomena, 1987, 43, (2) Payne, B.P.; Biesinger, B.P.; McIntyre, N.S. J. of Electron Spec. and Related Phenomena, 184 (2011) (3) Maeda, S.; Yamamoto, M. Progress in Organic Coating, 1998, 33, (4) Biesinger, M.C.; Payne, B.P.; Grosvenor, A.P.; Lau, L.W.M.; Gerson, A.R.; Smart, R.St.C. Applied Surface Science, 2011, 257, (5) Loiseau, T.; Férey, G. J. of Fluorine Chemistry, 2007, 128, (6) Latroche, M.; Surblé, S. ; Serre, C.; Mellot-Draznieks, C.; Llewellyn, P.L.; Lee, J.- H.; Chang, J.-S.; Jhung, S.H.; Férey, G. Angew. Chem. Int. Ed. 2006, 45, S6