Supporting Information

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1 Supporting Information Bi-functional MnO 2 coated Co 3 O 4 Hetero-structured Catalysts for Reversible Li-O 2 Batteries Young Joo Lee,, Do Hyung Kim,, Tae-Geun Kang, Youngmin Ko, Kisuk Kang*,, and Yun Jung Lee*, Department of Energy Engineering, Hanyang University, , Republic of Korea Department of Materials Science and Engineering, Seoul National University, 1 Gwanak-ro, Gwanak-gu, Seoul , Republic of Korea KEYWORDS: Lithium-oxygen battery, Bi-functional, Co3O4, MnO2, Hetero-structured, Reversible 1

2 Title cathode Electrolyte Cell test Cycle No. A Co 3 O 2 /Ni nanocomposite as a carbon and Co 3 O 4 and MnO 2 0.5M LiTFSI 300 ma/g 170 cycles binder-free cathode for rechargeable Li-O 2 batteries 1 Synthesis of α-mno 2 nanowires modified by Co 3 O 4 nanoparticles as a high-performance catalyst for rechargeable Li O 2 batterie 2 Co 3 O 4 and MnO 2 : KB : PVDF NMP (6:3:1) 125 ma/g 50 cycles Carbon-Free O 2 Cathode with Three-Dimensional Ul- Freestanding ultralight Ni foam@ru TEMDME/LiCF ma/g 100 cycles tralight Nickel Foam-Supported Ruthenium Electro- SO 3 (1500 catalysts for Li O 2 Batteries 3 Porous Perovskite La 0.6 Sr 0.4 Co 0.8 Mn 0.2 O 3 Nanofibers RuO2@LSCM NFs:SuperP:PVDF 50 ma/g 100 cycles Loaded with RuO 2 Nanosheets as an Efficient and Du- (4:5:1) (500 rable Bifunctional Catalyst for Rechargeable Li O 2 Batteries 4 Ruthenium-Functionalized Hierarchical Carbon Ru-hCNCs:PVDF NMP 1M LiCF 3 SO 3 78 cycles Nanocages as Efficient Catalysts for Li-O 2 Batteries 5 (8:2) (500 Toward Highly Efficient Electrocatalyst for Li BND-Co@G-MCH:PVDF NMP 1M LiCF 3 SO 3 30 cycles O 2 Batteries Using Biphasic N-Doping Cobalt@Gra- (8:2) phene Multiple-Capsule Heterostructures 6 IrO 2 nanoparticles highly dispersed on nitrogen- IrO 2 -N/CNT:PVDF NMP 500 ma/g 80 cycles doped carbon nanotubes as an efficient cathode cata- (9:1) lyst for high-performance Li-O 2 batteries 7 Positive role of oxygen vacancy in electrochemical CoMn 2 O 4 :KB:CMC DI water 0.5M LiTFSI 200 ma/g 41 cycles performance of CoMn 2 O 4 cathodes for Li-O2 batter- (4:5:1) (500 ies 8 Yolk shell Co 2 CrO 4 nanospheres as highly active cat- CCO catalyst:sp:pvdf NMP 200 ma/g 237 cycles alysts for Li O 2 batteries: understanding the electro- (6:3:1) catalytic mechanism 9 Three-Dimensional Array of TiN@Pt 3 Cu Nanowires TiN@Pt 3 Cu:PTFE 1M LiClO cycles as an Efficient Porous Electrode for the Lithium Ox- (9:1) 0.1mM TTF ygen Battery 10 DMSO One-Dimensional RuO 2 /Mn 2 O 3 Hollow Architectures RM catalysts:kb:pvdf 121 cycles as Efficient Bifunctional Catalysts for Lithium Oxy- (3:6:1) gen Batteries 11 Bifunctional Au Pd decorated MnO x nanomembranes Catalyst(AMP):Super P:PVDF NMP 1M LiCF 3 SO ma/g 120 cycles as cathode materials for Li O 2 batteries 12 (6:2:2) 2

3 Table S1. A summary of the most recent literatures on diverse electro-catalysts for Li-O2 batteries (a) Element Weight % Atomic % O K MnK CoK Co : Mn = 6.89 (b) Element Weight % Atomic % O K MnK CoK Co : Mn = 5.21 (c) Element Weight % Atomic % O K MnK CoK Co : Mn = 3.10 Figure S1 Elemental analysis from energy dispersive X-ray spectroscopy (a) HSC-3, (b) HSC-2 and (c) HSC-3. The ratios of OER and ORR catalysts were different depending on the concentration of graphitic carbon coated onto the Co3O4 surface in the synthesis process. The white scale bar in the SEM images denotes 300 nm. Figure S2 Lattice-resolved HR-TEM images and fast Fourier transform (FFT) of Co3O4 and HSC. The same lattice results proves that the surface morphology and crystal structure of the hexagonal Co3O4 were maintained during the formation of MnO2. 3

4 Figure S3 Nitrogen adsorption -desorption isotherm curve. The flower like morphology of MnO2 might increase the surface of catalysts. Figure S4 XPS Co 2p spectra of the catalysts. As the MnO2 covered the surface of Co3O4, XPS Co 2p peak intensity decreased especially illustrating the change in the Co 2+ and Co 3+ ratio. 4

5 Voltage(V) Voltage(V) Current Density (ma cm -2 ) KB Co 3 O 4 MnO 2 HSC-1 HSC-2 HSC-3 Working: (catalyst) + KB Counter: Li Foil Reference: 0.01 M Ag/Ag + Acetonotrile Electrolyte: 1 M LiTFSI Ar atmosphere Voltage (vs. Li/Li + ) Figure S5 Cyclic Voltammetry (CV) result form V in Ar atmosphere with a three-electrode system. There were large peaks indicative of Li + ion intercalation and/or capacitive interaction in MnO2 and HSC (a) HSC-1 1st 2nd 3th 5th 10th 15th 20th 25th 30th 35th 40th 45th 50th 51th Specific Capacity(mAh/gc) (c) Discharge capacity (b) HSC-3 1st 2nd 3rd 5th 10th 15th 20th 25th 30th 35th 36th 37th 38th Specific Capacity(mAh/gc) (d) Charge capacity Specific Capacity (mah/g c ) KB Co 3 O 4 MnO 2 HSC-1 HSC-2 HSC-3 Specific Capacity (mah/g c ) KB Co 3 O 4 MnO 2 HSC-1 HSC-2 HSC Cycle Number (#) Cycle Number (#) Figure S6 Cycling performance of (a) HSC-1, (b) HSC-3, (c) discharge and (d) charge capacity versus cycle number for each cycle. (1) Han, X.; Cheng, F.; Chen, C.; Li, F.; Chen, J., A Co3O4@MnO2/Ni nanocomposite as a carbon-and binder-free cathode for rechargeable Li O2 batteries. Inorg. Chem. Front. 2016, 3 (6),

6 (2) Wang, F.; Wen, Z.; Shen, C.; Wu, X.; Liu, J., Synthesis of α-mno2 nanowires modified by Co3O4 nanoparticles as a high-performance catalyst for rechargeable Li O2 batteries. Phys. Chem. Chem. Phys. 2016, 18 (2), (3) Liu, Z.; Feng, N.; Shen, Z.; Li, F.; He, P.; Zhang, H.; Zhou, H., Carbon Free O2 Cathode with Three Dimensional Ultralight Nickel Foam Supported Ruthenium Electrocatalysts for Li O2 Batteries. ChemSusChem (4) Zhang, X.; Gong, Y.; Li, S.; Sun, C., Porous Perovskite La0. 6Sr0.4Co0.8Mn0.2O3 Nanofibers Loaded with RuO2 Nanosheets as an Efficient and Durable Bifunctional Catalyst for Rechargeable Li-O2 Batteries. ACS Catal (5) Wang, L.; Lyu, Z.; Gong, L.; Zhang, J.; Wu, Q.; Wang, X.; Huo, F.; Huang, W.; Hu, Z.; Chen, W., Ruthenium Functionalized Hierarchical Carbon Nanocages as Efficient Catalysts for Li O2 Batteries. ChemNanoMat (6) Tan, G.; Chong, L.; Amine, R.; Lu, J.; Liu, C.; Yuan, Y.; Wen, J.; He, K.; Bi, X.; Guo, Y., Toward Highly Efficient Electrocatalyst for Li O2 Batteries Using Biphasic N-Doping Cobalt@ Graphene Multiple-Capsule Heterostructures. Nano Lett. 2017, 17 (5), (7) Zhang, Y.; Li, X.; Zhang, M.; Liao, S.; Dong, P.; Xiao, J.; Zhang, Y.; Zeng, X., IrO2 nanoparticles highly dispersed on nitrogen-doped carbon nanotubes as an efficient cathode catalyst for high-performance Li-O2 batteries. Ceram. Int. 2017, 43 (16), (8) Sadighi, Z.; Huang, J.; Qin, L.; Yao, S.; Cui, J.; Kim, J.-K., Positive role of oxygen vacancy in electrochemical performance of CoMn2O4 cathodes for Li-O2 batteries. J. Power Sources 2017, 365, (9) Zhao, Q.; Wu, C.; Cong, L.; Zhang, Y.; Sun, G.; Xie, H.; Sun, L.; Liu, J., Yolk shell Co2CrO4 nanospheres as highly active catalysts for Li O 2 batteries: understanding the electrocatalytic mechanism. J. Mater. Chem. A 2017, 5 (2), (10) Luo, W.-B.; Pham, T. V.; Guo, H.-P.; Liu, H.-K.; Dou, S.-X., Three-Dimensional Array of TiN@Pt3Cu Nanowires as an Efficient Porous Electrode for the Lithium Oxygen Battery. ACS nano 2017, 11 (2), (11) Yoon, K. R.; Lee, G. Y.; Jung, J.-W.; Kim, N.-H.; Kim, S. O.; Kim, I.-D., One-Dimensional RuO2/Mn2O3 Hollow Architectures as Efficient Bifunctional Catalysts for Lithium Oxygen Batteries. Nano lett. 2016, 16 (3), (12) Lu, X.; Zhang, L.; Sun, X.; Si, W.; Yan, C.; Schmidt, O. G., Bifunctional Au Pd decorated MnOx nanomembranes as cathode materials for Li O2 batteries. J. Mater. Chem. A 2016, 4 (11),