Metal Organic Framework-Derived Metal Oxide Embedded in Nitrogen-Doped Graphene Network for High-Performance Lithium-Ion Batteries

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1 Supporting Information for Metal Organic Framework-Derived Metal Oxide Embedded in Nitrogen-Doped Graphene Network for High-Performance Lithium-Ion Batteries Zhu-Yin Sui, Pei-Ying Zhang,, Meng-Ying Xu, Yu-Wen Liu, Zhi-Xiang Wei,*,, and Bao-Hang Han*,, CAS Key Laboratory of Nanosystem and Hierarchical Fabrication, CAS Center for Excellence in Nanoscience, National Center for Nanoscience and Technology, Beijing , China Department of Environment and Chemical Engineering, Yanshan University, Qinhuangdao , China University of Chinese Academy of Sciences, Beijing , China Tel: Tel: S 1

2 Experimental Section Preparation of NGA NGA was obtained from a hydrothermal process as our previous work reported. S1 In a typical procedure, the mixture of aqueous graphene oxide dispersion (18 ml, 5 mg ml 1 ) and ammonia solution (4 ml, 28 wt %) was sealed in a Teflon-lined autoclave and heated at 180 C for 12 h, thus producing a black nitrogen-doped graphene hydrogel. After that, nitrogen-doped graphene hydrogel was dialyzed for 3 days to remove the impurities and freeze-dried for 24 h under vacuum to obtain the product, NGA. S 2

3 Figure S1. The digital pictures of NGA, which was immersed into water, methanol, and N,N-dimethylformamide (DMF), respectively. S 3

4 Figure S2. SEM images (a and b) of NGA treated in a hydrothermal condition (at 120 C for 24 h in water); SEM images (c and d) of NGA treated in a solvothermal condition (at 120 C for 24 h in DMF). S 4

5 Figure S3. SEM images of (a and b) and (c and d) at different magnifications. S 5

6 Intensity / a.u. NGA ZIF-67@NGA ZIF theta / degree Intensity / a.u. NGA ZIF-8@NGA ZIF theta / degree Intensity / a.u. NGA UiO-66@NGA UiO theta / degree Figure S4. XRD patterns of NGA, pristine MOFs (ZIF-67, ZIF-8, and UiO-66), and MOF-containing NGA (ZIF-67@NGA, ZIF-8@NGA, and UiO-66@NGA). S 6

7 100 Mass Remaining / % Co 3 O 40 ZIF ZIF-67@NGA NGA Temperature / o C Figure S5. TGA curves of NGA, ZIF-67, ZIF-67@NGA, and Co 3 O in air. The mass remaining of NGA, ZIF-67, and ZIF-67@NGA is 0, 38.7, and 13.3 wt %, respectively. It can be concluded that the mass ratio of NGA and ZIF-67 in the ZIF-67@NGA composite is ~2:1. In addition, the weight percentage of NGN in the Co 3 O composite is estimated to be ~56.6 wt %. S 7

8 Figure S6. SEM images of ZIF-67 (a), ZIF-67 derived Co 3 O 4 (b), NGA (c) and NGN (d). S 8

9 Figure S7. TEM images of Co 3 O at low (a) and high (b) magnifications (Inset is the high-resolution TEM image of Co 3 O 4. S 9

10 Adsorbed Volume / cm 3 (STP) g a ZIF-67@NGA 200 Co 3 O Relative Pressure (P/P 0 ) Pore Volume, dv/dd (cm 3 g -1 nm -1 ) b Pore Width (nm) Figure S8. (a) Nitrogen adsorption desorption isotherm at 77 K of ZIF-67@NGA and Co 3 O 4 ; (b) Barret Joyner Halenda desorption PSD profile of Co 3 O composite. S 10

11 N 1s Intensity / a.u. Pyridinic N Pyrrolic N Quaternary N Binding Energy / ev Figure S9. N 1s spectrum of Co 3 O composite. S 11

12 2000 Capacity / ma h g Cycle Number Figure S10. Rate capability of Co 3 O 4 /NGN composite at various charge/discharge rates (100, 200, 400, 600, and 1000 ma g 1 ). S 12

13 Capacity / ma h g ma g -1 Co 3 O 4 /NGA Cycle Number Figure S11. Cycling stability of Co 3 O 4 /NGA at 200 ma g 1. S 13

14 -Z'' / Ohm Co 3 O Co 3 O 4 NGN Z' / Ohm Figure S12. Nyquist plots of Co 3 O composite, NGN, and Co 3 O 4 electrodes. S 14

15 Table S1. Electrochemical performance comparison of the Co 3 O electrode with graphene or MOF-derived materials for LIBs. Electrode Current (ma g 1 ) Capacity retention (Capacity in mah g 1 ) Cycle number Ref. Co 3 O This work Co 3 O This work NPGM a [S2] NGS b [S3] graphene nanosheets [S4] MWCNTs/Co 3 O [S5] MWCNTs/ZnCo 2 O [S5] NiFe 2 O 4 /Fe 2 O 3 nanotubes [S6] hollow Zn x Co 3 x O [S7] Fe 2 O 2 O 4 nanocages [S8] hierarchical Fe 2 O 3 microboxes [S9] Co 3 O 4 /ZnO hybrids 1000 ~ [S10] porous Co 3 O 4 /N C c [S11] a nitrogen-doped porous graphene; b nitrogen-doped graphene sheet; c porous nitrogen-doped carbon coated Co 3 O 4 fish-scale structures. References [S1] Sui, Z.-Y.; Meng, Y.-N.; Xiao, P.-W.; Zhao, Z.-Q.; Wei, Z.-X.; Han, B.-H. Nitrogen-Doped Graphene Aerogels as Efficient Supercapacitor Electrodes and Gas Adsorbents. ACS Appl. Mater. Interfaces 2015, 7 (3), [S2] Sui, Z.-Y.; Wang, C.; Yang, Q.-S.; Shu, K.; Liu, Y.-W.; Han, B.-H.; Wallace, G. A S 15

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17 Their Lithium Storage Properties. J. Am. Chem. Soc. 2012, 134 (42), [S10] Fang, G. Z.; Zhou, J.; Cai, Y. S.; Liu, S. N.; Tan, X. P.; Pan, A. Q.; Liang, S. Q. Metal Organic Framework-Templated Two-Dimensional Hybrid Bimetallic Metal Oxides with Enhanced Lithium/Sodium Storage Capability. J. Mater. Chem. A 2017, 5 (27), [S11] Han, X.; Chen, W. M.; Han, X. G.; Tan, Y. Z.; Sun, D. Nitrogen-Rich MOF Derived Porous Co 3 O 4 /N C Composites with Superior Performance in Lithium-Ion Batteries. J. Mater. Chem. A 2016, 4 (34), S 17