Photo of the mass manufacture of the Fe-rich nanofiber film by free-surface electrospinning technique

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1 Supporting Information Design 3D hierarchical architectures of carbon and highly active transition-metals (Fe, Co, Ni) as bifunctional oxygen catalysts for hybrid lithiumair batteries Dongxiao Ji, Shengjie Peng,* Dorsasadat Safanama, Haonan Yu, Linlin Li, Guorui Yang, Xiaohong Qin,* Madhavi Srinivasan, Stefan Adams, and Seeram Ramakrishna * Corresponding author: mpepeng@nus.edu.sg; xhqin@dhu.edu.cn This file includes: Photo of the mass manufacture of the Fe-rich nanofiber film by free-surface electrospinning technique FE-SEM image of the surface morphology of Fe-PAN/CA carbon nanofiber: a) low magnification and b) higher magnification. The optimization experiment showing CA is important for the formation of CNT: a) the surface morphology of FeNO-CNT-CNFF and b) the carbon fiber obtained trough the same procedure only without CA. The optimization experiment showing the carbon fiber using dicyandiamide as the CNT precursor at 800 C. The morphology and XRD purity of the CoNO-CNT-CNFF and NiNO-CNT-CNFF. The FE-SEM show the morphology of FeNO-CNT-CNFFs fabricated from different temperature: a, b) FeNO-CNT-CNFF-700; c, d) FeNO-CNT-CNFF-800; e, f) FeNO-CNT- CNFF-900.

2 Bifunctional activities for MNO-CNT-CNFFs in 0.1M KOH at 1600 rpm. XRD patterns of FeNO-CNT-CNFF-700 and FeNO-CNT-CNFF-900. N 2 adsorption-desorption isotherms and pore distribution of a, b) FeNO-CNT-CNFF-700, c, d) FeNO-CNT-CNFF-800 and e, f) FeNO-CNT-CNFF-900. TGA curve shows the weight loss of FeNO-CNT-CNFF-800 from room temperature to 900. The XPS survey spectra of FeNO-CNT-CNFFs. XPS Element compositions of the FeNO-CNT-CNFFs. The proportion of different N bonding types in three samples. LSVs curves of different catalysts for ORR at different rotating speeds, and corresponding K-L plots of different catalysts at different potentials. The LSVs of FeNO-CNT-CNFF-800 in different 1600 rpm. XPS O1s spectra. The stability of FNO-CNT-CNFF-800 for ORR and OER in 0.1 M KOH. ORR and OER activities for different catalysts in 0.1M KOH. The electrocatalytic activities of the recently reported bifunctional catalysts for ORR/OER in 0.1M KOH. The XRD pattern of FeNO-CNT-CNFF-800 air electrode after 20 cycles

3 Figure S1. Photo of the mass manufacture of the Fe-rich nanofiber film by free-surface electrospinning technique

4 Figure S2. FE-SEM image of the surface morphology of Fe-PAN/CA carbon nanofiber: a) low magnification and b) higher magnification.

5 Figure S3. The optimization experiment showing CA is important for the formation of CNT: a) the surface morphology of FeNO-CNT-CNFF and b) the carbon fiber obtained trough the same procedure only without CA.

6 Figure S4. The optimization experiment showing the carbon fiber using dicyandiamide as the CNT precursor at 800 C.

7 Figure S5. The morphology and XRD purity of the CoNO-CNT-CNFF and NiNO-CNT-CNFF.

8 Figure S6. The FE-SEM show the morphology of FeNO-CNT-CNFFs fabricated from different temperature: a, b) FeNO-CNT-CNFF-700; c, d) FeNO-CNT-CNFF-800; e, f) FeNO-CNTCNFF-900.

9 Figure S7. Bifunctional activities for MNO-CNT-CNFFs in 0.1M KOH at 1600 rpm.

10 Figure S8. XRD patterns of FeNO-CNT-CNFF-700 and FeNO-CNT-CNFF-900. The peaks around 16 and 22 in FeNO-CNT-CNFF-700 should be respectively attributed to carbon (002) 13, 14 plane and carbon (120) plane according to the JCPDS card (No ) and literature

11 Figure S9. N 2 adsorption-desorption isotherms and pore distribution of a, b) FeNO-CNT-CNFF- 700, c, d) FeNO-CNT-CNFF-800 and e, f) FeNO-CNT-CNFF-900.

12 Figure S10. TGA curve shows the weight loss of FeNO-CNT-CNFF-800 from room temperature to 900 in air is 21.96%

13 Figure S11. The XPS survey spectra of FeNO-CNT-CNFFs. Table S1. XPS Element compositions and the conductivity of the FeNO-CNT-CNFFs Sample C% O% N% Fe% Conductivity FeNO-CNT- CNFF-700 FeNO-CNT- CNFF-800 FeNO-CNT- CNFF S m S m S m -1

14 Figure S12. The proportion of different N bonding types in three samples Table S2. proportion of different N bonding types in three samples pyridinic- N Fe-N X pyrrolic- N graphitic- N oxidized pyridinic- N FeNO-CNT-CNFF % 4.2% 4.2% 31.2% 14.6% FeNO-CNT-CNFF % 11.2% 23.4% 12.4% - FeNO-CNT-CNFF % 9.0% 5.4% 18.9% 18.1%

15 Figure S13. LSVs curves of different catalysts for ORR at different rotating speeds, and corresponding K-L plots of different catalysts at different potentials compared to Pt/C at 0.5 V.

16 Figure S14. The LSVs of FeNO-CNT-CNFF-800 in different 1600 rpm.

17 Figure S15. XPS O1s spectra of FeNO-CNT-CNFFs.

18 Figure S16. The stability of FNO-CNT-CNFF-800 for ORR and OER in 0.1 M KOH. a) The stability of FNO-CNT-CNFF-800 for ORR at 0.65V vs. RHE; b) The stability of FNO-CNT- CNFF-800 for OER at 1.65V vs. RHE.

19 Figure S17. The XRD pattern of FeNO-CNT-CNFF-800 air electrode after 20 cycles, the peaks observed in the XRD pattern are identified as Li 2 CO 3, Fe, and Fe 3 C, confirming the formation of Li 2 CO 3 during cell cycling.

20 Table S3. ORR and OER activities for different catalysts in 0.1M KOH. Catalyst E ORR Onset / V / V LCD 1600 rpm for ORR (ma/cm 2 ) V / E / V NiNO-CNT-CNFF- 800 CoNO-CNT-CNFF- 800 FeNO-CNT-CNFF- 700 FeNO-CNT-CNFF- 800 FeNO-CNT-CNFF Pt/C (20%) Ir/C (20%) a: LCD equals to limiting current density at 0.4V vs. RHE.

21 Table S4. The electrocatalytic activities of the recently reported bifunctional catalysts for ORR/OER in 0.1M KOH. Catalyst / V / V E / V electrolyte Ref. FeNO-CNT-CNFF Mn oxide film M KOH 0.1M KOH This work 2 Nanoporous carbon nanofiber films M KOH 3 Co 4 N carbon fibers network and carbon cloth M KOH 4 P-doped g-c 3 N 4 grown on carbon-fiber paper M KOH 5 Ni3Fe-N doped carbon sheets 0.78 (-3 ma / cm 2 ) M KOH 6 Fe/N-CNTs N-C Co@ Co 3 O 4 /NC Mn x O y /N-carbon M KOH 0.1M KOH 0.1M KOH 0.1M KOH N, S, O-carbon nanosheet M KOH 11 CoO/N-graphene M KOH 12

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