sodium ion battery synthesized by a soft chemistry route

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1 Supporting Information Title: γ-na 0.96 V 2 O 5 : a new competitive cathode material for sodium ion battery synthesized by a soft chemistry route Nicolas Emery 1,, Rita Baddour-Hadjean 1, Dauren Batyrbekuly 1,2, Barbara Laik 1, Zhumabay Bakenov 2, Jean-Pierre Pereira-Ramos 1 1 Institut de Chimie et des Matériaux Paris Est, ICMPE/GESMAT, UMR 7182 CNRS- Université Paris Est Créteil, CNRS 2 rue Henri Dunant, Thiais, France 2 Institute of Batteries LLC, Nazarbayev University, 53 Kabanbay Batyr Avenue, Astana , Kazakhstan Table of content: Figure S1. Rietveld refinements of α-v 2 O 5 (a), γ-liv 2 O 5 (b) and γ'-v 2 O 5 (c) X-Ray diffraction patterns. Figure S2. Raman spectra of α-v 2 O 5 (a), γ-liv 2 O 5 (b) and γ'-v 2 O 5 (c). Figure S3. Representation of an isolated chain of the α-v 2 O 5 structure. White and grey circles represent the oxygen and vanadium atoms, respectively. Interchain contacts (ladder steps) are shown by dashed lines. Figure S4. Comparison of the first galvanostatic cycle of γ-na 0.96 V 2 O 5 and γ'-v 2 O 5 electrodes. C/5 rate. Electrolyte NaClO 4 1M/PC. Table S1. Atomic positions and thermal motion parameters extracted from the Rietveld refinement of α-v 2 O 5 (y = 0.25 for all positions). Table S2. Atomic positions and thermal motion parameters extracted from the Rietveld refinement of γ-liv 2 O 5 (y = 0.25 for all positions). Table S3. Atomic positions and thermal motion parameters extracted from the Rietveld refinement of γ -V 2 O 5 (y = 0.25 for all positions). Table S4. Structural parameters for γ-na 0.96 V 2 O 5 compared to those previously reported for the γ-na 0.97 V 2 O 5 electroformed phase [47].

2 Figure S1. Rietveld refinements of (a) α-v 2 O 5, (b) γ-liv 2 O 5 and (c) γ'-v 2 O 5 X-ray diffraction patterns.

3 Figure S2. Raman spectra of (a) α-v 2 O 5, (b) γ-liv 2 O 5 and (c) γ'-v 2 O 5. Figure S3. Representation of an isolated chain of the α-v 2 O 5 structure. White and grey circles represent the oxygen and vanadium atoms, respectively. Interchain contacts (ladder steps) are shown by dashed lines.

4 Q / mah g E / V vs. Na + /Na γ' - V 2 O 5 γ - Na 0.96 V 2 O x Figure S4. Comparison of the first galvanostatic cycle of γ-na 0.96 V 2 O 5 and γ'-v 2 O 5 electrodes. C/5 rate. Electrolyte NaClO 4 1M/PC. γ -V 2 O 5 first galvanostatic curve is taken from reference [1] [1] M. Safrany Renard, N. Emery, R. Baddour-Hadjean, J. P. Pereira-Ramos, γ -V 2 O 5 : A new high voltage cathode material for sodium-ion battery, Electrochim. Acta 252C (2017) 4-11.

5 Table S1. Atomic positions and thermal motion parameters extracted from the Rietveld refinement of α-v 2 O 5 (y = 0.25 for all positions). Atom type (label) Wyckof pos. x z U iso (Å 2 ) V (V) 4f (1) (3) 0.010(1) O (O 1 ) 4f (3) (7) 0.026(1) O (O 2 ) 4f (2) (7) 0.026(1) O (O 3 ) 2a (9) 0.026(1) Space group : Pmmn a = (3) Å, b = (1) Å, c = (2) Å α = β = γ = 90 χ² = 1.878, wr p = 5.82%, Rp = 4.61%, Background: Shift Chebyschev 10 parameters. Table S2. Atomic positions and thermal motion parameters extracted from the Rietveld refinement of γ-liv 2 O 5 (y = 0.25 for all positions). Atom type (label) Wyckof pos. x z U iso (Å 2 ) Li 4c 0.163(2) 0.221(2) 0.045(5) V (V a ) 4c (2) (2) 0.013(1) V (V b ) 4c (2) (2) 0.013(1) O (O 1a ) 4c (5) (5) 0.030(1) O (O 1b ) 4c (5) (5) 0.030(1) O (O 2a ) 4c (4) (4) 0.030(1) O (O 2b ) 4c (4) (4) 0.030(1) O (O 3 ) 4c (5) (4) 0.030(1) Space group : Pnma a = (2) Å, b = (1) Å, c = (2) Å α = β = γ = 90 χ² = 1.058, wr p = 4.87%, Rp = 3.78%, Background: Shift Chebyschev 10 parameters.

6 Table S3. Atomic positions and thermal motion parameters extracted from the Rietveld refinement of γ -V 2 O 5 (y = 0.25 for all positions). Atom type (label) Wyckof pos. x z U iso (Å 2 ) V (V a ) 4c (2) (2) 0.012(1) V (V b ) 4c (2) (2) 0.012(1) O (O 1a ) 4c (6) (6) 0.027(1) O (O 1b ) 4c (6) (7) 0.027(1) O (O 2a ) 4c (6) (6) 0.027(1) O (O 2b ) 4c (6) (7) 0.027(1) O (O 3 ) 4c (7) (7) 0.027(1) Space group : Pnma a = (2) Å, b = (1) Å, c = (3) Å α = β = γ = 90 χ² = 1.316, wr p = 5.28%, Rp = 4.09%, Background: Shift Chebyschev 10 parameters.

7 Table S4. Structural parameters for γ-na 0.96 V 2 O 5 compared to those previously reported for the γ- Na 0.97 V 2 O 5 electroformed phase [47]. (Å) γ- Na 0.97 V 2 O 5 [47] γ-na 0.96 V 2 O 5 [this work] a b c (V a )O 5 V a -O 1a V a -O V a -O 2a (x2) (V a -O 2a )LS (V a )O 5 Vol (A 3 ) BVS (V b )O 5 V b -O 1b V b -O V b -O 2b (x2) (V b -O 2b )LS (V b )O 5 Vol (A 3 ) BVS (Na/Li)-O 2b (Na/Li)-O 1b (Na/Li)-O 3 (x2) (Na/Li)-O 1a (x2)