Supporting Information

Copyright WILEY-VCH Verlag GmbH & Co. KGaA, 69469 Weinheim, Germany, 2017. Supporting Information for Adv. Sci., DI: 10.1002/advs.201600517 Strategies Based on itride Materials Chemistry to Stabilize Li Metal Anode Yizhou Zhu, Xingfeng He, and Yifei Mo*

Supporting Information Strategies Based on itride Materials Chemistry to Stabilize Li Metal Anode Yizhou Zhu 1, Xingfeng He 1, Yifei Mo 1,2 * 1 Department of Materials Science and Engineering, 2 University of Maryland Energy Research Center, University of Maryland, College Park, MD 20742 * Email: yfmo@umd.edu 1

1. List of Compounds. The lithium ternary compounds Li-M-X (X =,, S, F) investigated in Fig. 1 are summarized in Table S1. The structures and energies of most compounds were obtained from the Materials Project (MP) database. We added 26 additional lithium ternary compounds (Table S2), of which 21 were predicted using substitution prediction algorithm and 5 were from Inorganic Crystal Structure Database (ICSD). Table S1. Lithium ternary compounds Li-M-X (X =,, S, F) Cation Ternary Compounds Li-M-X Cation Ternary Compounds Li-M-X Er 3+ LiEr 2, LiErS 2 Tm 3+ LiTm 2 Ho 3+ LiHo 2, LiHoS 2 Y 3+ LiY 2, LiYS 2, LiYF 4 Gd 3+ LiGd 2 Sm 3+ LiSmS 2 Ca 2+ LiCa Be 2+ LiBe, Li 2 BeF 4 Sr 2+ LiSr, Li 4 Sr 2 Mg 2+ LiMg Sc 3+ Li 3 Sc 2, LiSc 2, LiScS 2 Hf 4+ Li 2 Hf 2, Li 2 Hf 3, Li 6 Hf 2 7, Li 2 HfF 6 Zr 4+ Li 2 Zr 2, Li 6 Zr 2 7, Li2Zr 3, Li 2 ZrS 3, Li 4 ZrF 8, Li 2 ZrF 6, Li 3 Zr 4 F 19 a + LiaS K + LiKS Ce 4+ Li 2 Ce 2, Li 2 Ce 3, LiCeF 5 Si 4+ Li 2 Si 2 5, Li 8 Si 6, Li 4 Si 4, Li 8 SiS 6, Li 5 Si 3, Li 2 Si 2, LiSi 2 3 Li 2 Si 3, Li 2 SiS 3, Li 2 SiF 6 Al 3+ Li 3 Al 2, LiAl 5 8, LiAl 2, Li 5 Al 4, LiAlS 2, Li 5 AlS 4, Li 3 AlF 6 Zn 2+ LiZn, Li 10 Zn 4 9, Li 6 Zn 4, Li 2 ZnF 4 Ta 5+ Li 4 Ta 3, Li 7 Ta 4, LiTa 2, LiTa 3 8, Li 5 Ta 5, LiTa 3, Li 3 Ta 4, Li 3 TaS 4, LiTaF 6 Sn 4+ Li 2 Sn 2, Li 8 Sn 6, Li 2 Sn 3, Li 2 SnS 3, Li 2 SnF 6 Ga 3+ Li 3 Ga 2 LiGa 2, Li 5 Ga 4, LiGa 5 8, LiGaS 2, Li 3 GaF 6 b 5+ Li 7 b 4, Lib 2, Lib 3, Lib 3 8, b 4, Li 8 b 2 9 bs 4, LibF 6 Ge 4+ Li 5 Ge 3, Li 2 Ge 2, LiGe 2 3, Li 2 Ge 7 15, Li 4 Ge 4, Li 4 Ge 5 12, Li 2 Ge 3 Li 2 GeS 3, Li 4 GeS 4, Li 2 GeF 6 P 5+ LiP 2, Li 7 P 4, Li 4 P 2 7, LiP 3, Li 3 P 4, Li 3 PS 4, LiPF 6 V 5+ Li 7 V 4, LiV 2, Li 3 V 4, LiV 3, Li 3 VS 4, LiVF 6 Co 4+ Li 8 Co 6 In 3+ LiIn 2, LiInF 4 Ti 4+ Li 2 Ti 2, Li 5 Ti 3, Li 4 Ti 4, Li 2 Ti 3, Li 4 Ti 5 12, Li 2 TiS 3, Li 2 TiF 6 B 3+ Li 3 B 2, Li 2 B 4 7, LiB 2, Li 3 B 3, Li 3 B 7 12, Li 3 BS 3, Li 5 B 7 S 13, LiBF 4 i 2+ Li 2 if 4 Fe 3+ Li 3 Fe 2, LiFe 2, Li 5 Fe 4, Li 3 FeF 6 W 6+ Li 6 W 4, Li 2 W 4, Li 4 W 5 Mo 6+ Li 6 Mo 4, Li 2 Mo 4, Li 4 Mo 5 Mn 4+ LiMn 2 3, Li 2 Mn 2, Li 2 Mn 3, Li 4 Mn 5 12, Li 2 MnF 6 2

Table S2. Additional lithium ternary compounds. Compound Form. E (ev/atom) Spacegroup Structure source LiAlS 2-1.614 P4 1 2 1 2 S- substitution from LiAl 2 (ICSD-23815) Li 5 AlS 4-1.583 Pcab S- substitution from Li 5 Al 4 (ICSD-42697) Li 8 SiS 6-1.496 P6 3 cm S- substitution from Li 8 Si 6 (ICSD-65176) Li 2 SiS 3-1.385 Ccm2 1 S- substitution from Li 2 Si 3 (ICSD-853) Li 2 SiF 6-3.423 P321 ICSD-425923 Li 2 Ge 2-0.609 P-3m1 Ge-Zr substitution from Li 2 Zr 2 (ICSD- 78790) LiGe 2 3-0.516 Cmc2 1 Ge-Si substitution from LiSi 2 3 (ICSD-34118) Li 2 GeS 3-1.218 Ccm2 1 S- substitution from Li 2 Ge 3 (ICSD-100403) Li 2 Sn 2-0.403 P-3m1 Sn-Zr substitution from Li 2 Zr 2 (ICSD-78790) Li 2 SnS 3-1.211 C2/c S- substitution from Li 2 Sn 3 (ICSD-21032) Li 2 SnF 6-3.043 P-31m Sn-Zr substitution from Li 2 ZrF 6 (ICSD-2644) Li 2 Ti 2-1.194 P-3m1 Ti-Zr substitution from Li 2 Zr 2 (ICSD-78790) Li 2 TiS 3-1.668 C2/c S- substitution from Li 2 Ti 3 (ICSD-15150) Li 2 ZrS 3-1.800 C2/c S- substitution from Li 2 Zr 3 (ICSD-94893) Lib 2-1.035 R-3m Li-a, b-ta substitution from ata 2 (ICSD-67347) LibF 6-3.414 R-3 ICSD-165202 LiTa 2-1.233 R-3m Li-a substitution from ata 2 (ICSD- 67347) Li 3 TaS 4-1.526 C2/c S- substitution from Li 3 Ta 4 (ICSD-281301) LiTaF 6-3.598 R-3 ICSD-165205 Li 2 ZnF 4-2.941 Fd-3m Zn-i substitution from Li 2 if 4 (ICSD- 202859) Li 2 HfF 6-3.788 P-31m ICSD-251074 Li 2 Hf 2-1.353 P-3m1 Hf-Zr substitution from Li 2 Zr 2 (ICSD-78790) LiCeF5-3.830 I4 1 /a ICSD-426211 LiV 2-1.024 Pna2 1 Li-Mg, V-Si substitution from MgSi 2 (ICSD- 23501) LiMn 2 3-0.496 Cmc2 1 Mn-Si substitution from LiSi 2 3 (ICSD- 78790) Li 2 Mn 2-0.663 Pbca Mn-Si substitution from Li 2 Si 2 (ICSD- 420126) 3

2. Lithiation/delithiation reaction of materials Table S3. Lithiation and delithiation reactions of typical Al-abiding ternary nitride, oxide, sulfide and fluoride. a) Li 3 Al 2 Potential ϕ (V) μ Li (ev) Δn Li ref. to Li/Li + ref. to Li metal per formula Phase equilibria -0.316 0.316 5.25 Li 9 Al 4, / / 0 Li 3 Al 2 0.789-0.789-2.667 Al, Li 3 1.668-1.668-3 Al, 2 b) LiAl 2 Potential ϕ (V) μ Li (ev) Δn Li ref. to Li/Li + ref. to Li metal per formula Phase equilibria 0.056-0.056 5.25 Li 9 Al 4, Li 2 0.071-0.071 2.625 Li 9 Al 4, Li 5 Al 4 0.167-0.167 2.25 Li 3 Al 2, Li 5 Al 4 / / 0 LiAl 2 3.697-3.697-0.8 LiAl 5 8, 2 4.101-4.101-1 Al 2 3, 2 c) LiAlS 2 Potential ϕ (V) μ Li (ev) Δn Li ref. to Li/Li + ref. to Li metal per formula Phase equilibria 0.071-0.071 5.25 Li 9 Al 4, Li 2 S 0.190-0.190 4.5 Li 3 Al 2, Li 2 S 0.359-0.359 4 LiAl, Li 2 S 0.963-0.963 3 Al, Li 2 S 0.973-0.973 1.5 Li 5 AlS 4, Al / / 0 LiAlS 2 2.812-2.812-1 Al 2 S 3, S d) Li 3 AlF 6 Potential ϕ (V) μ Li (ev) Δn Li ref. to Li/Li + ref. to Li metal per formula Phase equilibria 0.071-0.071 5.25 Li 9 Al 4, LiF 0.190-0.190 4.5 Li 3 Al 2, LiF 0.359-0.359 4 LiAl, LiF 1.057-1.057 3 LiF, Al / / 0 Li 3 AlF 6 6.477-6.477-3 AlF 3, F 2 4

Table S4. Cathodic limits and lithiation reactions for all binary and ternary fluorides, sulfides, oxides and nitrides plotted in Fig. 1. The reaction energy E D normalized to per Li inserted is for the lithiation of selected compound to from the phase equilibria with Li metal. For materials that are stable against Li metal (i.e., with negative cathodic limit), the Phase equilibria at Li column lists the fully lithiated products after lithiation with overpotential. Compound Cathodic limit /V ref. to Li/Li + Phase equilibria at cathodic limit Phase equilibria at Li E D /ev norm. to Li Er -0.699, Er, Er 0.699 ErF 3 0.371 Er, LiF LiF, Er -0.371 Er 2 S 3 0.991 LiErS 2, ErS Er, Li 2 S -0.284 LiErS 2 0.484 Li 2 S, ErS Er, Li 2 S -0.200 Er 2 3-0.239 LiEr 2, Er Er, Li 2 0.288 LiEr 2-0.304 Er, Li 2 Er, Li 2 0.304 Tm -0.728, Tm, Tm 0.728 TmF 3 0.837 Tm, LiF LiF, Tm -0.837 Tm 2 S 3 0.660 TmS, Li 2 S Li 2 S, Tm -0.276 Tm 2 3-0.238 LiTm 2, Tm Tm, Li 2 0.316 LiTm 2-0.342 Li 2, Tm Tm, Li 2 0.342 Ho -0.675, Ho, Ho 0.675 HoF 3 0.378 LiF, Ho LiF, Ho -0.378 Ho 2 S 3 0.997 LiHoS 2, HoS Ho, Li 2 S -0.280 LiHoS 2 0.541 Li 2 S, HoS Ho, Li 2 S -0.204 Ho 2 3-0.237 LiHo 2, Ho Ho, Li 2 0.270 LiHo 2-0.280 Ho, Li 2 Ho, Li 2 0.280 Y -0.639 Y,, Y 0.639 YF 3 0.625 LiYF 4, Y Y, LiF -0.429 LiYF 4 0.364 Y, LiF LiF, Y -0.364 Y 2 S 3 1.167 Y 5 S 7, LiYS 2 Y, Li 2 S -0.278 LiYS 2 0.600 Li 2 S, YS Y, Li 2 S -0.209 Y 2 3-0.204 LiY 2, Y Y, Li 2 0.215 LiY 2-0.219 Y, Li 2 Y, Li 2 0.219 La -0.398, La, La 0.398 LaF 3 0.339 La, LiF LiF, La -0.339 La 2 S 3 0.846 LaS, Li 2 S La, Li 2 S -0.174 La 2 3-0.139 La, Li 2 La, Li 2 0.139 Gd -0.559, Gd, Gd 0.559 GdF 3 0.856 LiF, Gd LiF, Gd -0.856 Gd 2 S 3 0.935 GdS, Li 2 S Li 2 S, Gd -0.281 Gd 2 3-0.132 LiGd 2, Gd Li 2, Gd 0.149 5

LiGd 2-0.154 Gd, Li 2 Li 2, Gd 0.154 Sm -0.500, Sm, Sm 0.500 SmF 3 0.404 LiF, Sm Sm, LiF -0.404 Sm 2 S 3 0.906 LiSmS 2, SmS Sm, Li 2 S -0.283 LiSmS 2 0.858 Li 2 S, SmS Sm, Li 2 S -0.275 Sm 2 3-0.126 Sm, Li 2 Li 2, Sm 0.126 Ca 3 2 0.263 Ca 2, LiCa, Li 2 Ca 0.075 LiCa -0.111, Li 2 Ca Li 2 Ca, 0.111 CaF 2 0.009 LiF, Li 2 Ca Li 2 Ca, LiF -0.009 CaS -0.061 Li 2 Ca, Li 2 S Li 2 S, Li 2 Ca 0.061 Ca -0.096 Li 2 Ca, Li 2 Li 2 Ca, Li 2 0.096 d -0.418, d, d 0.418 df 3 0.441 d, LiF LiF, d -0.441 d 2 S 3 0.900 Li 2 S, ds Li 2 S, d -0.288 d 2 3-0.059 d, Li 2 d, Li 2 0.059 Be 3 2-0.069 LiBe, Be Be, 0.414 LiBe -0.587 Be,, Be 0.587 BeF 2 1.119 Li 2 BeF 4, Be Be, LiF -0.999 Li 2 BeF 4 0.879 Be, LiF Be, LiF -0.879 BeS 0.943 Li 2 S, Be Be, Li 2 S -0.943 Be -0.015 Be, Li 2 Be, Li 2 0.015 SrLi 0.237 SrLi 4 2, Sr 2, Sr 3 Li 2 0.011 SrLi 4 2-0.054 Sr 3 Li 2,, Sr 3 Li 2 0.054 SrF 2-0.013 Sr 3 Li 2, LiF Sr 3 Li 2, LiF 0.013 SrS -0.105 Sr 3 Li 2, Li 2 S Sr 3 Li 2, Li 2 S 0.105 Sr 0.013 Li 2, Sr Li 2, Sr 3 Li 2-0.011 Mg 3 2 0.064 LiMg 2, LiMg, Li 5 Mg 0.022 LiMg -0.047, Li 5 Mg, Li 5 Mg 0.047 MgF 2 0.585 Mg, LiF Li 5 Mg, LiF -0.186 MgS 0.575 Mg, Li 2 S Li 5 Mg, Li 2 S -0.184 Mg 0.065 LiMg 2, Li 2 Li 2, Li 5 Mg -0.030 Sc -0.689 Li 3 Sc 2, Sc Sc, 0.790 Li 3 Sc 2-0.892, Sc, Sc 0.892 ScF 3 0.600 Sc, LiF Sc, LiF -0.600 Sc 2 S 3 1.252 LiScS 2, ScS Sc, Li 2 S -0.410 LiScS 2 0.664 ScS, Li 2 S Sc, Li 2 S -0.312 Sc 2 3 0.148 LiSc 2, Sc Sc, Li 2 0.215 LiSc 2-0.336 Sc, Li 2 Li 2, Sc 0.336 Hf 3 4 0.667 Hf, Li 2 Hf 2, Hf 0.486 Li 2 Hf 2-0.771, Hf, Hf 0.771 HfF 4 1.481 Li 2 HfF 6, Hf LiF, Hf -1.173 Li 2 HfF 6 1.019 Hf, LiF LiF, Hf -1.019 HfS 2 0.942 Li 2 S, Hf 2 S Hf, Li 2 S -0.821 6

Hf 2 0.457 Hf, Li 2 Hf 3 Hf, Li 2-0.077 Li 6 Hf 2 7-0.153 Li 2, Hf Li 2, Hf 0.153 Li 2 Hf 3 0.122 Li 6 Hf 2 7, Hf Li 2, Hf 0.113 Zr 3 4 0.956 Li 2 Zr 2, Zr, Zr 0.374 Li 2 Zr 2-0.603 Zr 2, Zr, 0.651 ZrF 4 1.619 Li 3 Zr 4 F 19, Zr LiF, Zr -1.331 Li 4 ZrF 8 1.209 LiF, Zr LiF, Zr -1.209 Li 2 ZrF 6 1.239 Li 4 ZrF 8, Zr LiF, Zr -1.216 Li 3 Zr 4 F 19 1.510 Li 2 ZrF 6, Zr Zr, LiF -1.277 ZrS 2 1.705 Li(ZrS 2 ) 2 Li 2 S, Zr -0.870 Li 2 ZrS 3 1.227 Li(ZrS 2 ) 2, Li 2 S Zr, Li 2 S -0.810 Zr 2 0.583 Li 2 Zr 3, Zr 3 Zr, Li 2-0.232 Li 6 Zr 2 7 0.048 Li 2, Zr 3 Zr, Li 2-0.041 Li 2 Zr 3 0.339 Li 6 Zr 2 7, Zr 3 Zr, Li 2-0.079 af 0.445 LiF, a a, LiF -0.445 a 2 S 0.417 a, alis a, Li 2 S -0.399 alis 0.381 a, Li 2 S a, Li 2 S -0.381 a 2 0.925 Li 2, a a, Li 2-0.925 KF 0.449 LiF, K LiF, K -0.449 K 2 S 0.488 KLiS, K K, Li 2 S -0.410 KLiS 0.333 Li 2 S, K Li 2 S, K -0.333 K 2 1.209 Li 2, K K, Li 2-1.209 Li 2 Ce 2-0.451 Ce, Ce, 0.495 CeF 4 3.228 LiCeF 5, CeF 3 Ce, LiF -1.257 LiCeF 5 3.158 CeF 3, LiF Ce, LiF -1.248 CeS 2 1.955 Ce 2 S 3, Li 2 S Li 2 S, Ce -0.734 Ce 2 1.225 Ce 11 20, Li 2 Ce 3 Li 2, Ce -0.147 Li 2 Ce 3 1.174 Ce 11 20, Li 2 Ce, Li 2-0.144 Al -0.004 Li 3 Al 2, Li 9 Al 4, Li 9 Al 4 0.160 Li 3 Al 2-0.316, Li 9 Al 4, Li 9 Al 4 0.316 AlF 3 1.289 Li 3 AlF 6, Al Li 9 Al 4, LiF -0.767 Li 3 AlF 6 1.057 Al, LiF Li 9 Al 4, LiF -0.701 Al 2 S 3 1.597 Al, LiAlS 2 Li 9 Al 4, Li 2 S -0.740 LiAlS 2 0.973 Li 5 AlS 4, Al Li 9 Al 4, Li 2 S -0.650 Li 5 AlS 4 0.963 Al, Li 2 S Li 9 Al 4, Li 2 S -0.647 Al 2 3 1.233 LiAl 5 8, Al Li 9 Al 4, Li 2-0.233 LiAl 2 0.167 Li 5 Al 4, Li 3 Al 2 Li 9 Al 4, Li 2-0.105 Li 5 Al 4 0.056 Li 2, Li 9 Al 4 Li 9 Al 4, Li 2-0.056 LiAl 5 8 0.802 LiAl 2, Al Li 9 Al 4, Li 2-0.195 Si 3 4 1.127 LiSi 2 3, Si Li 21 Si 5, -0.067 LiSi 2 3 0.245 Li 2 Si 2, Li 13 Si 4, Li 21 Si 5 0.011 Li 2 Si 2 0.022 Li 5 Si 3, Li 21 Si 5, Li 21 Si 5 0.091 Li 5 Si 3-0.148, Li 21 Si 5, Li 21 Si 5 0.148 7

SiF 4 2.298 Si, Li 2 SiF 6 Li 21 Si 5, LiF -1.112 Li 2 SiF 6 1.839 Si, LiF LiF, Li 21 Si 5-1.038 SiS 2 1.633 Li 2 SiS 3, Si Li 21 Si 5, Li 2 S -0.872 Li 2 SiS 3 1.455 Li 8 SiS 6, Si Li 21 Si 5, Li 2 S -0.840 Li 8 SiS 6 1.411 Si, Li 2 S Li 21 Si 5, Li 2 S -0.829 Si 2 1.320 Li 2 Si 2 5, Si Li 21 Si 5, Li 2-0.454 Li 2 Si 3 0.761 Li 4 Si 4, Si Li 21 Si 5, Li 2-0.295 Li 2 Si 2 5 1.265 Li 2 Si 3, Si Li 21 Si 5, Li 2-0.372 Li 4 Si 4 0.258 Li 13 Si 4, Li 8 Si 6 Li 21 Si 5, Li 2-0.222 Li 8 Si 6 0.227 Li 13 Si 4, Li 2 Li 2, Li 21 Si 5-0.213 Zn 3 2 1.423 Zn, Li 3 LiZn, -0.532 LiZn 0.380, LiZn 3 LiZn, -0.365 ZnF 2 2.441 Zn, Li 2 ZnF 4 LiZn, LiF -1.764 Li 2 ZnF 4 2.428 Zn, LiF LiZn, LiF -1.760 ZnS 1.200 Zn, Li 2 S LiZn, Li 2 S -0.941 Zn 1.364 Li 10 Zn 4 9, Zn Li 2, LiZn -1.014 Li 6 Zn 4 1.179 Li 2, Zn LiZn, Li 2-0.927 Li 10 Zn 4 9 1.318 Li 6 Zn 4, Zn LiZn, Li 2-0.968 In 1.037 Li 3, In, Li 13 In 3-0.376 InF 3 2.625 In, LiInF 4 LiF, Li 13 In 3-1.195 LiInF 4 2.517 LiF, In LiF, Li 13 In 3-1.184 In 2 S 3 1.634 InS, Li 2 S Li 13 In 3, Li 2 S -0.785 In 2 3 1.579 LiIn 2, In Li 13 In 3, Li 2-0.734 LiIn 2 1.363 In, Li 2 Li 13 In 3, Li 2-0.712 Eu -0.051, Eu, Eu 0.051 EuF 3 3.389 EuF 2, LiF Eu, LiF -1.278 Eu 2 3 1.655 Eu, Li 2 Li 2, Eu -0.531 Ta 3 5 1.371 Li 2 Ta 3 5 Ta, 0.073 Li 4 Ta 3-0.016 Li 7 Ta 4, Ta, Ta 0.583 Li 7 Ta 4-0.771, Ta, Ta 0.771 LiTa 2 0.877 Li 2 Ta 3 5, Li 4 Ta 3, Ta 0.250 TaF 5 2.895 Ta, LiTaF 6 LiF, Ta -2.045 LiTaF 6 1.876 LiF, Ta LiF, Ta -1.876 Li 3 TaS 4 1.853 Li 2 S, Li 2 (TaS 2 ) 3 Li 2 S, Ta -1.302 Ta 2 5 1.694 LiTa 3 8, Ta Li 2, Ta -0.758 LiTa 3 1.175 Li 3 Ta 4, Ta Li 2, Ta -0.583 Li 3 Ta 4 0.543 Li 5 Ta 5, Ta Ta, Li 2-0.386 LiTa 3 8 1.591 LiTa 3, Ta Ta, Li 2-0.695 Li 5 Ta 5 0.347 Ta, Li 2 Li 2, Ta -0.347 Li 5 Ti 3-0.828, Ti 2, Ti 0.829 Li 2 Ti 2 0.712 Ti, Li 5 Ti 3, Ti 0.572 TiF 4 2.928 TiF 3, Li 2 TiF 6 Ti, LiF -1.725 Li 2 TiF 6 1.896 TiF 3, LiF Ti, LiF -1.553 8

TiS 2 1.939 Li(TiS 2 ) 3 Ti, Li 2 S -1.050 Li 2 TiS 3 1.717 Li 2 S, LiTiS 2 Ti, Li 2 S -1.009 Ti 2 1.712 LiTi 2 4 Ti, Li 2-0.468 Li 2 Ti 3 0.500 LiTi 2, Li 4 Ti 4 Ti, Li 2-0.167 Li 4 Ti 4 0.123 Ti 3, Li 2 Ti, Li 2-0.095 Li 4 Ti 5 12 1.749 Li 7 Ti 11 24, Li 2 Ti 3 Ti, Li 2-0.347 Li 2 Sn 2 0.473, Li 13 Sn 5 Li 17 Sn 4, -0.424 SnF 4 4.319 SnF 3, Li 2 SnF 6 LiF, Li 17 Sn 4-1.651 Li 2 SnF 6 2.911 SnF 2, LiF LiF, Li 17 Sn 4-1.528 SnS 2 1.945 Li 2 SnS 3, SnS Li 2 S, Li 17 Sn 4-1.058 Li 2 SnS 3 1.822 SnS, Li 2 S Li 17 Sn 4, Li 2 S -1.043 Sn 2 1.986 Li 2 Sn 3, Sn 5 6 Li 17 Sn 4, Li 2-0.955 Li 8 Sn 6 1.243 Li 2, Sn Li 17 Sn 4, Li 2-0.824 Li 2 Sn 3 1.362 Li 8 Sn 6, Sn Li 17 Sn 4, Li 2-0.853 B 0.062 Li 3 B 2, LiB, LiB 0.195 Li 3 B 2-0.453, LiB LiB, 0.453 BF 3 2.933 B, LiBF 4 LiF, LiB -1.720 LiBF 4 1.937 B, LiF LiB, LiF -1.534 B 2 S 3 1.870 B, Li 5 B 7 S 13 Li 2 S, LiB -1.319 Li 3 BS 3 1.589 B, Li 2 S LiB, Li 2 S -1.272 Li 5 B 7 S 13 1.615 Li 3 BS 3, B Li 2 S, LiB -1.280 B 2 3 2.067 B 6, Li 3 B 7 12 LiB, Li 2-0.652 Li 3 B 3 0.284 Li 7 B 18, Li 2 Li 2, LiB -0.249 Li 2 B 4 7 1.291 LiB 2, B 6 Li 2, LiB -0.508 Li 3 B 7 12 1.294 Li 2 B 4 7, B 6 LiB, Li 2-0.519 LiB 2 1.014 B 6, Li 3 B 3 Li 2, LiB -0.436 Ga 0.484 Li 3 Ga 2, LiGa Li 2 Ga, -0.281 Li 3 Ga 2 0.125, Li 2 Ga Li 2 Ga, -0.125 GaF 3 2.581 Li 3 GaF 6, Ga Li 2 Ga, LiF -1.637 Li 3 GaF 6 2.277 Ga, LiF Li 2 Ga, LiF -1.546 Ga 2 S 3 2.099 LiGaS 2, GaS Li 2 Ga, Li 2 S -1.053 LiGaS 2 1.307 Ga, Li 2 S Li 2 Ga, Li 2 S -0.964 Ga 2 3 2.131 LiGa 5 8, Ga Li 2 Ga, Li 2-0.902 LiGa 2 1.046 Li 5 Ga 4, Ga Li 2 Ga, Li 2-0.752 LiGa 5 8 1.892 Ga, LiGa 2 Li 2 Ga, Li 2-0.865 Li 5 Ga 4 0.862 Ga, Li 2 Li 2 Ga, Li 2-0.697 if 2 3.200 i, Li 2 if 4 i, LiF -3.165 Li 2 if 4 3.130 i, LiF i, LiF -3.130 i 2.172 Li 2, i Li 2, i -2.172 Li 7 b 4-0.639, b b, 0.639 Lib 2 0.787 b, Li 7 b 4, b 0.092 bf 5 3.169 b 2 F 5, LibF 6 b, LiF -2.309 LibF 6 2.204 b 2 F 5, LiF b, LiF -2.171 9

bs 4 2.083 Li 2 S, Li 5 (bs 2 ) 7 b, Li 2 S -1.378 b 2 5 2.286 Lib 3 8, b 12 29 Li 2, b -0.970 Lib 3 1.745 b 4, Lib 2 Li 2, b -0.814 Lib 3 8 2.225 b 12 29, Lib 3 b, Li 2-0.917 Li 8 b 2 9 0.623 Lib 2, Li 2 b, Li 2-0.577 b 4 0.937 Li 8 b 2 9, Lib 2 b, Li 2-0.603 Fe 0.630 Fe 3, Li 3 Fe 2, Fe -0.405 Li 3 Fe 2 0.188, Fe Fe, -0.188 FeF 3 3.655 LiFe 2 F 6 Fe, LiF -2.663 Li 3 FeF 6 3.151 FeF 2, LiF Fe, LiF -2.553 Fe 2 3 2.299 Fe 3 4, LiFe 2 Fe, Li 2-1.535 Li 5 Fe 4 1.282 Li 2, Fe Fe, Li 2-1.282 LiFe 2 1.540 Li 2 Fe 2 Fe, Li 2-1.373 Ge 3 4 1.728 LiGe 2 3, Ge, Li 15 Ge 4-0.438 Li 5 Ge 3 0.198 Li 15 Ge 4, Li 15 Ge 4, -0.198 LiGe 2 3 0.735 Li 2 Ge 2, Ge, Li 15 Ge 4-0.356 Li 2 Ge 2 0.500 Li 5 Ge 3, LiGe Li 15 Ge 4, -0.282 GeF 4 3.773 Ge 5 F 12, Li 2 GeF 6 LiF, Li 15 Ge 4-1.735 Li 2 GeF 6 2.710 LiF, Ge Li 15 Ge 4, LiF -1.598 GeS 2 1.913 GeS, Li 2 GeS 3 Li 2 S, Li 15 Ge 4-1.107 Li 4 GeS 4 1.622 Li 2 S, Ge Li 2 S, Li 15 Ge 4-1.037 Li 2 GeS 3 1.865 Li 4 GeS 4, Ge Li 15 Ge 4, Li 2 S -1.068 Ge 2 2.408 Li 2 Ge 7 15, Ge Li 15 Ge 4, Li 2-0.992 Li 4 Ge 4 1.016 Ge, Li 2 Li 2, Li 15 Ge 4-0.724 Li 2 Ge 7 15 2.275 Li 4 Ge 5 12, Ge Li 2, Li 15 Ge 4-0.960 Li 4 Ge 5 12 2.259 Li 2 Ge 3, Ge Li 2, Li 15 Ge 4-0.911 Li 2 Ge 3 1.579 Ge, Li 4 Ge 4 Li 2, Li 15 Ge 4-0.797 CuF 2 3.638 LiF, Cu LiCu 3, LiF -3.136 CuS 1.821 Cu 7 S 4, Li 2 S LiCu 3, Li 2 S -1.569 Cu 2.411 LiCu LiCu 3, Li 2-1.863 W 2 2.056 Li 5 W 7 12, 2, W -0.353 Li 6 W 4-0.465, W, W 0.465 WF 6 3.593 LiWF 6 W, LiF -3.067 W 3 2.564 Li 2 W 4, W 18 49 W, Li 2-1.650 Li 2 W 4 2.097 Li 4 W 5, W Li 2, W -1.394 Li 4 W 5 1.219 W, Li 2 W, Li 2-1.219 YbS 2 2.154 YbS, LiS 4 Yb, Li 2 S -0.947 Yb 2 2.853 Yb, Li 2 Yb, Li 2-1.155 P 3 5 2.286 LiP 2, P Li 3 P, -0.552 LiP 2 0.610 Li 7 P 4, Li 3 P Li 3 P, -0.307 Li 7 P 4 0.005 Li 3 P, Li 3 P, -0.005 PF 5 3.302 P, LiPF 6 Li 3 P, LiF -2.118 LiPF 6 2.735 P, LiF Li 3 P, LiF -2.059 10

P 2 S 5 2.273 Li 3 PS 4, P 4 S 9 Li 3 P, Li 2 S -1.532 Li 3 PS 4 1.719 P, Li 2 S Li 3 P, Li 2 S -1.423 P 2 5 3.274 LiP 3, P Li 3 P, Li 2-1.215 Li 4 P 2 7 2.307 Li 3 P 4, P Li 3 P, Li 2-0.826 Li 3 P 4 0.688 Li 2, Li 3 P Li 3 P, Li 2-0.688 LiP 3 2.479 P, Li 4 P 2 7 Li 3 P, Li 2-0.979 Li 6 Mo 4-0.362, Mo, Mo 0.362 MoF 6 4.335 Li 2 MoF 6 LiF, Mo -3.257 Mo 3 3.350 Mo 8 23, Li 2 Mo 4 Mo, Li 2-1.757 Li 2 Mo 4 1.842 Li 2 Mo 3, Li 4 Mo 5 Li 2, Mo -1.420 Li 4 Mo 5 1.333 Mo, Li 2 Mo, Li 2-1.333 Li 7 V 4-0.718, V, V 0.718 LiV 2 0.841 V, Li 7 V 4, V 0.083 VF 5 5.104 VF 4, LiVF 6 V, LiF -2.968 LiVF 6 4.570 Li 2 VF 6 V, LiF -2.849 Li 3 VS 4 1.795 V 3 S 4, Li 2 S V, Li 2 S -1.433 V 2 5 3.675 LiV 3, V 3 7 V, Li 2-1.493 Li 3 V 4 1.126 Li 2, LiV 2 Li 2, V -0.947 LiV 3 3.229 LiV 2 5, Li 3 V 4 V, Li 2-1.287 Li 2 Mn 2 0.552 Li 7 Mn 4, Mn 2, Mn -0.092 MnF 4 6.030 MnF 3, Li 2 MnF 6 LiF, Mn -3.353 Li 2 MnF 6 4.557 LiF, Li 2 MnF 5 LiF, Mn -3.065 MnS 2 1.830 Li(MnS 2 ) 2 Mn, Li 2 S -1.598 Mn 2 3.711 Mn 2 3, Li 5 Mn 7 16 Li 2, Mn -1.748 Li 2 Mn 3 1.732 Li 2, LiMn 2 Mn, Li 2-1.381 Li 4 Mn 5 12 3.417 Li 5 Mn 7 16, Li 2 Mn 3 Mn, Li 2-1.565 CoF 4 6.635 LiCoF 4 LiF, Co -4.150 CoS 2 1.984 Co 3 S 4, Li 2 S Co, Li 2 S -1.750 Co 2 4.096 Li(Co 2 ) 2 Co, Li 2-2.253 Li 8 Co 6 2.605 Li 5 Co 4, Li 2 Co, Li 2-1.943 11

3. Comparison between DFT calculated and experimental values To evaluate the error of the DFT calculation results, we compared the formation enthalpy of binary nitrides and the potential (referenced to Li/Li + ) of lithium conversion reaction of binary nitrides based on the following reaction M x y + 3y Li y + x M. These results are summarized and compared in Table S5. We found that the calculated conversion reaction potential is general in agreement with the experimental value with an error of less than 0.1 V. Table S5. Experimental and calculated formation enthalpy and conversion reaction potential of binary nitrides. (ev/atom) ΔH cal. (ev/atom) ϕ exp. (V) ϕ cal. (V) -0.428-0.460 - - Ta -1.309-1.366-0.303-0.297 Ca 3 2-0.912-0.946-0.190-0.175 Ga -0.569-0.666 0.191 0.169 V -1.131-1.164-0.184-0.162 b -1.227-1.252-0.248-0.221 Be 3 2-1.224-1.233-0.450-0.414 Hf -1.939-1.940-0.722-0.680 Cr 2-0.434-0.523 0.136 0.091 Ce -1.694-1.684-0.559-0.509 Ta 2-0.942-0.934-0.372-0.321 Zn 3 2-0.047-0.033 0.531 0.586 Ti -1.754-1.906-0.600-0.657 U -1.529-1.501-0.449-0.387 B -1.309-1.472-0.303-0.368 La -1.553-1.517-0.465-0.398 Zr -1.911-1.870-0.704-0.633 Si 3 4-1.104-1.312-0.074-0.152 Al -1.652-1.595-0.531-0.450 Mg 3 2-0.958-0.909-0.228-0.144 Cr -0.608-0.527 0.165 0.262 Th 3 4-1.935-1.829-0.559-0.453 Pu -1.553-1.438-0.465-0.345 Eu -1.129-0.996-0.183-0.051 Y -1.553-1.879-0.465-0.639 Th -1.965-1.761-0.740-0.561 Sc -1.628-2.106-0.515-0.790 In -0.717-0.105 0.092 0.543 * Chase, M. W. IST-JAAF thermochemical tables 4th ed.; ational Institute of Standards and Technology: Gaithersburg, 1998. ΔH exp. * 12

4. Li-M-- grand potential phase diagrams Figure S1. Grand potential phase diagrams in equilibrium with Li metal. The composition ranges that form passivating interphase and that form non-passivating interphase are colored green and red, respectively. (a) Li 2 (b) Li 2 Li 3 B 2 LiB B Li 2 Zr 2 Zr Zr 3 2 Zr Zr (c) Li 2 (d) Li 2 Li 16 (Ta 4 ) 2 (e) Li 7 Ta 4 Li 4 Ta 3 Li 2 Ta Ta (f) Li 5 Ti 3 Ti Ti 2 Li 2 Ti 6 Ti Ti Li 5 Si 3 Li 21 Si 5 Si Li 7 V 4 V 2 V V (g) Li 2 (h) Li 2 Li 6 W 4 W W LiMg Li 5 Mg Mg 13

(i) Li 2 (j) Li 2 Li 4 Cl LiCl Cl Li 10 Br 3 Li 5 Br 2 LiBr Br (k) Li 2 (l) Li 2 Li 7 I 2 LiI I Sn Sn (m) Li 2 (n) Li 2 Li 2 Ga Ga LiZn Zn 14