Supporting Information

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1 Electronic Supplementary Material (ESI) for Journal of Materials Chemistry A. This journal is The Royal Society of Chemistry 2018 Supporting Information Directly anchoring 2D NiCo metal-organic frameworks on few-layer black phosphorus for advanced lithium-ion batteries Jun Jin, a, b Yun Zheng, c Shao-zhuan Huang, d Ping-ping Sun, a Narasimalu Srikanth, b Ling Bing Kong, c Qingyu Yan, c Kun Zhou a, * a School of Mechanical and Aerospace Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore, Singapore; * kzhou@ntu.edu.sg b Energy Research Institute, Nanyang Technological University, 50 Nanyang Avenue, Singapore, Singapore c School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore, Singapore d Pillar of Engineering Product Development, Singapore University of Technology and Design, 8 Somapah Road, Singapore, Singapore 1

2 Table S1. The comparison of electrochemical properties of MOF-based anode materials. Electrode materials Capacity (mah g -1 ) (cycle number) Current density Co MOF/rGO 1185 (50) 0.1 A g -1 1 Mn MOF 390 (50) 0.05 A g -1 2 Co MOF 601 (500) 0.5 A g -1 3 F-doped Mn MOF 620 (500) 0.5 A g -1 4 Fe MOF (400) 0.06 A g -1 5 Al MOF 392 (100) A g -1 6 Ref. BP/NiCo MOF 1211 (10) 853 (100) 569 (250) 398 (1000) 0.1 A g A g -1 2 A g -1 5 A g -1 This work 2

3 Figure S1. (a-b) Cross-sectional SEM images of pristine BP/NiCo MOF electrode. 3

4 Figure S2. (a) XRD pattern and (b-c) TEM images of the pure 2D few-layer BP. In the XRD pattern, three peaks at 16.9 o, 34.2 o, and 52.4 o are indexed to the (002), (004), and (006) planes of BP (JCPDS ), respectively. 4

5 Figure S3. SEM-EDX mapping images of the BP/NiCo MOF hybrid: (a) SEM, (b) Ni element, (c) Co element, (d) P element, (e) C element, and (f) O element. 5

6 Figure S4. (a) N2 adsorption-desorption isotherm and (b) pore size distribution of the BP/NiCo MOF hybrid. 6

7 Figure S5. (a-b) SEM images of BP/NiCo MOF-15 and (c) XRD pattern of BP/NiCo MOF

8 Figure S6. SEM-EDX mapping images of the BP/NiCo MOF-15 hybrid: (a) SEM, (b) Ni element, (c) Co element, (d) P element, (e) C element, and (f) O element. 8

9 Figure S7. (a-b) SEM images of BP/NiCo MOF-35 and (c) XRD pattern of BP/NiCo MOF

10 Figure S8. SEM-EDX mapping images of the BP/NiCo MOF-35 hybrid: (a) SEM, (b) Ni element, (c) Co element, (d) P element, (e) C element, and (f) O element. 10

11 Figure S9. (a-b) SEM images, (c-d) TEM images, (e) XRD pattern, and (f) Raman spectrum of the NiCo MOF sample. 11

12 Figure S10. SEM-EDX mapping images of the NiCo MOF sample: (a) SEM, (b) Ni element, (c) Co element, (d) C element, and (e) O element. 12

13 Figure S11. (a) N2 adsorption-desorption isotherm and (b) pore size distribution of the NiCo MOF sample. 13

14 Figure S12. XPS spectra of the NiCo MOF sample: (a) survey, (b) Ni 2p, (c) Co 2p, (d) C 1s, and (e) O 1s. The XPS spectra in Figure S12a demonstrates the presence of Ni, Co, C, and O elements in the NiCo MOF. The Ni 2p spectrum (Figure S12b) shows two main peaks centered at and ev, which are assigned to Ni 2p3/2 and Ni 2p1/2, together with two corresponding satellite peaks at and ev. The Co 2p spectrum (Figure S12c) shows two main peaks centered at and ev, which are assigned to Co 2p3/2 and Co 2p1/2, together with two corresponding satellite peaks located at and ev. For C spectrum (Figure S12d), three peaks located at 284.9, and ev are assigned to C=C, C-C and O=C- O, respectively. Finally, the O 1s spectrum (Figure S12e) can be divided into two peaks centered at and ev, which are ascribed to the hydroxyl and chemisorbed water. 14

15 Figure S13. (a) SEM image and (b) XRD pattern of the BP/Co MOF hybrid. 15

16 Figure S14. SEM-EDX mapping images of the BP/Co MOF hybrid: (a) SEM, (b) Co element, (c) P element, (d) C element, and (e) O element. 16

17 Figure S15. (a) N2 adsorption-desorption isotherm and (b) pore size distribution of the BP/Co MOF hybrid. 17

18 Figure S16. XPS spectra of the BP/Co MOF hybrid: (a) survey, (b) Co 2p, (c) P 2p, (d) C 1s, and (e) O 1s. The XPS survey spectrum (Figure S16a) demonstrates the presence of Co, P, C, and O elements in the BP/Co MOF composite. The Co 2p spectrum (Figure S16b) shows two main peaks centered at and ev, which are assigned to Co 2p3/2 and Co 2p1/2, together with two corresponding satellite peaks at and ev. The P 2p spectrum (Figure S16c) exhibits the 2p3/2 and 2p1/2 doublet at and ev, which are the characteristics of the P-P within BP. For C spectrum (Figure S16d), three peaks located at 285.0, and ev are assigned to C=C, C-C and O=C-O, respectively. The O 1s spectrum (Figure S16e) possesses two peaks centered at and ev, which are assigned to the hydroxyl and chemisorbed water. 18

19 Figure S17. (a) SEM images of BP/Ni MOF and (b) XRD pattern of BP/Ni MOF. 19

20 Figure S18. SEM-EDX mapping images of the BP/Ni MOF hybrid: (a) SEM, (b) Ni element, (c) P element, (d) C element, and (e) O element. 20

21 Figure S19. (a) CV profiles of the NiCo MOF electrode at a scan rate of 0.1 mv s -1 and (b) CV profiles at various scan rates (0.1, 0.2, 0.3, 0.4, 0.5, 1, 2, 3, 4 and 5 mv s -1 ). (c) logi~logv plots at each redox peak with various scan rates. Peak 1 and 2: 1.2 and 1.05 V. 21

22 Figure S20. (a) rate performance of BP/NiCo MOF-15 electrode at various rates and (b) cycling performance of BP/NiCo MOF-15 electrode at 0.5 A g

23 Figure S21. (a) rate performance of BP/NiCo MOF-35 electrode at various rates and (b) cycling performance of BP/NiCo MOF-35 electrode at 0.5 A g

24 Figure S22. Electrochemical performances of the NiCo MOF electrode: (a) discharge/charge profiles at various rates, (b) rate performance at various rates, and (c) cycling performance at 0.5 A g

25 Figure S23. Electrochemical performances of the BP/Co MOF electrode: (a) discharge/charge profiles at various rates, (b) rate performance at various rates, and (c) cycling performance at 0.2 A g

26 Figure S24. (a) rate performance of BP/Ni MOF electrode at various rates and (b) cycling performance of BP/Ni MOF electrode at 0.5 A g

27 Figure S25. (a-b) Post-mortem SEM images of the BP/NiCo MOF electrode after 100 cycles. 27

28 Figure S26. Ex-situ XRD patterns of BP/NiCo MOF electrode at different discharge states (1.1 V and 0.02 V). LiP: JCPDS No , Li3P: JCPDS No

29 Figure S27. XPS spectra of the BP/NiCo MOF electrode on the state of discharge after 100 cycles: (a) Ni 2p, (b) Co 2p, and (c) P2p. 29

30 References 1. C. Dong, L. Xu, ACS Appl. Mater. Interfaces, 2017, 9, Q. Liu, L. Yu, Y. Wang, Y. Ji, J. Horvat, M.-L. Cheng, X. Jia, G. Wang, Inorg. Chem., 2013, 52, C. Li, X. Hu, X. Lou, L. Zhang, Y. Wang, J.-P. Amoureux, M. Shen, Q. Chen, B. Hu, J. Mater. Chem. A, 2016, 4, S. He, X. Zhou, Z. Li, J. Wang, L. Ma, S. Yang, ACS Appl. Mater. Interfaces, 2017, 9, L. Shen, H. Song, C. Wang, Electrochim. Acta, 2017, 235, Y. Wang, Q. Qu, G. Liu, V. S. Battaglia, H. Zheng, Nano Energy, 2017, 39,