Room temperature single phase Li insertion/extraction

in nanoscale “LixFePO4”

Pierre Gibot1, Montse Casas-Cabanas1, Lydia Laffont1, Stephane Levasseur2, Philippe Carlach2, Stéphane Hamelet1, Jean-Marie Tarascon1 & Christian Masquelier1,#

SUPPLEMENTARY INFORMATION

XRD Rietveld refinement details for sample S40 Table 1. Lattice constants and Rietveld refinement results for sample S40

Wavelength (Å) 1.78919 1.79321 Space group (No.) Pnma (62) a (Å) 10.3007(7) b (Å) 5.9673(3) c (Å) 4.7038(1) V (Å3) 289.13(1) Z 4 Rp(%) 9.86 Rwp(%) 7.81 Rexp(%) 4.59 χ2 2.891 RBragg (%) 2.74 Rf (%) 2.36

The reliability factors have been calculated with all non-excluded points. Table 2. Atomic coordinates of sample S40 Atom Wyck. x/a y/b z/c Biso S.O.F. Li 4a 0 0 0 0 0.79 Fe 4a 0 0 0 0 0.064(4) Fe 4c 0.2806(3) 0.25 0.9750(4) 0.9(1) 0.905(4) P 4c 0.0975(6) 0.25 0.426(1) 1.1(2) 1 O(1) 4c 0.0956(1) 0.25 0.736(2) 0.6(4) 1 O(2) 4c 0.446(2) 0.25 0.209(2) 0.0(3) 1 O(3) 8d 0.164(1) 0.051(1) 0.286(1) 0.0(2) 2 Anisotropic displacement parameters Atom Wyck. B11 B22 B33 B12 B13 B23 Li 4a 0.003(8) 0.03(1) 0.025(3) 0 0 -0.005(2) Fe 4a 0.003(8) 0.03(1) 0.025(3) 0 0 -0.005(2)

The site occupation factors (S.O.F.) are given in number of atoms per formula unit. Isotropic (Biso) and anisotropic displacement parameters are given in Å2. Table 3. Microstructural parameters of sample S40

h00 0k0 00l Size (nm) 13 41 35 Strains (ε*10-4) 37 21 6

Strains are defined as ε=∆d*/d*.

Fig 1. Experimental X-ray powder diffraction pattern (dotted curve) compared to the Rietveld-refined profile (continuous line) and difference curve corresponding to the formula [□0.18Li0.82]M1[Fe]M2PO4.

Fig 2. Experimental X-ray powder diffraction pattern (dotted curve) compared to the Rietveld-refined profile (continuous line) and difference curve corresponding to the formula (�0.21Li0.79)M1(�0.04Fe0.964)M2PO4.

NPD Rietveld refinement details for sample S70 Table 3. Lattice constants and Rietveld refinement results for sample S70

Wavelength (Å) 1.911 Space group (No.) Pnma (62) a (Å) 10.3237(4) b (Å) 5.9824(2) c (Å) 4.6989(1) V (Å3) 290.21(2) Z 4 Rp(%) 13.0 Rwp(%) 11.4 Rexp(%) 8.53 χ2 1.79 RBragg (%) 5.29 Rf (%) 2.98

The reliability factors have been calculated with all non-excluded points. Table 4. Atomic coordinates of sample S70 Atom Wyck. x/a y/b z/c Biso S.O.F. Li 4a 0 0 0 0 0.89(4) Fe 4a 0 0 0 0 0.039(9) Fe 4c 0.2816(6) 0.25 0.976(2) 0.2(1) 0.921(9) P 4c 0.097(1 ) 0.25 0.415(2) 0.5(2) 1 O(1) 4c 0.101(1) 0.25 0.743(2) 0.8(2) 1 O(2) 4c 0.456(1) 0.25 0.208(2) 0.8(2) 1 O(3) 8d 0.166(1) 0.043(1) 0.282(1) 0.8(1) 2 Anisotropic displacement parameters Atom Wyck. B11 B22 B33 B12 B13 B23 Li 4a 0.0070(1) 0.0050(3) 0.020(6) -0.001(3) 0.00(1) Fe 4a 0.0070(1) 0.0050(3) 0.020(6) -0.001(3) 0.00(1)

The site occupation factors (S.O.F.) are given in number of atoms per formula unit. Isotropic (Biso) and anisotropic displacement parameters are given in Å2. Table 5. Microstructural parameters of sample S70

h00 0k0 00l Size (nm) 15 29 31 Strains (ε*10-4) 2 8 2

Strains are defined as ε=∆d*/d*.

2 θ (º)

Inten

sity(

arb.

unis)

M1

M2

c

ab

c

ab

0 .1 .2 .3 .4 .5 .6 .7 .8 .9 10.1.2.3.4.5.6.7.8.91

x/a

y/b 15 nm

0 .1 .2 .3 .4 .5 .6 .7 .8 .9 10.1.2.3.4.5.6.7.8.91

x/a

y/b 15 nm

0 .1 .2 .3 .4 .5 .6 .7 .8 .9 10.1.2.3.4.5.6.7.8.91

y/b

z/c 29 nm 31 nm

0 .1 .2 .3 .4 .5 .6 .7 .8 .9 10.1.2.3.4.5.6.7.8.91

y/b

z/c 29 nm 31 nm

Fig 3. Experimental neutron powder diffraction pattern (dotted curve) compared to the final Rietveld-refined profile (continuous line) and difference curve of sample S70 corresponding to the formula ((□0.07Li0.89Fe0.04)M1(□0.08Fe0.92)M2PO4). The insets correspond to the refined unit cell, in which M1 and M2 sites are indicated, and to the average apparent size and shape of the diffraction domains along the directions specified.