SUPPORTING INFORMATION: Cerium Oxide Nanocrystal Embedded Bimodal. Micro-Mesoporous Nitrogen-Rich Carbon Nanospheres as

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1 SUPPORTING INFORMATION: Cerium Oxide Nanocrystal Embedded Bimodal Micro-Mesoporous Nitrogen-Rich Carbon Nanospheres as Effective Sulfur Host for Lithium-Sulfur Batteries Lianbo Ma, a Renpeng Chen, a Guoyin Zhu, a Yi Hu, a Yanrong Wang, a Tao Chen, a Jie Liu, ab and Zhong Jin a * a Key Laboratory of Mesoscopic Chemistry of MOE and Collaborative Innovation Center of Chemistry for Life Sciences, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, Jiangsu, , China. b Department of Chemistry, Duke University, Durham, North Carolina, 27708, USA. * Address correspondence to: zhongjin@nju.edu.cn (Prof. Z. Jin)

2 Ref. This work Sulfur materials (Morphology) CeO 2 /MMNC nanospheres Table S1. Performance comparison of CeO 2 /MMNC nanospheres with other representative sulfur host materials for Li-S batteries in the literatures. host Sulfur content (wt.%) Sulfur loading in (mg cm -2 ) electrodes Current density (C, 1675 ma g -1 ) Cycle number Discharge capacity (mah g -1 ) Capacity % % % retention (From the first cycle) S1 Carbon/TiN ~800 ~69.0% S2 Layered doubled hydroxide/graphene oxide ~45.0% S3 CNTs/V 2 O 5 layer ~ % S4 S5 S6 S7 Nb 2 O 5 /mesoporous carbon microspheres Polypyrrole-MnO 2 coaxial nanotubes TiO 2 hollow nanospheres Ti 3 C carbon ~ % ~70 1.0~ % ~61 0.4~ % % S8 CNTs/V 2 O 5 layer ~ % S9 S10 S11 S12 S13 S14 S15 S16 MXene Nanosheet/Carbon- Nanotube Si/SiO al Porous Carbon Spheres TiO 2 /nitrogen-dope graphene Activated carbon cloth/al 2 O 3 layer Cobalt/N-doped graphitic carbon Co-doped porous carbon polyhedrons Hollow sulfide polyhedra Titanium cobalt monoxide@carbon hollow spheres ~ % % % ~70% ~ % % ~60% %

3 S17 S18 S19 Porous graphene/fe 2 O 3 MnO Hollow Nanoboxes TiO 2 /porous N-doped carbon ~361 54% ~ % %

4 Figure S1. XRD pattern of Zn 3 [Co(CN) 6 ] 2 nh 2 O/PVP precursor nanospheres in accordance with cubic-phase Zn 3 [Co(CN) 6 ] 2 nh 2 O (JCPDS card, No , space group: Fm-3m, a = 9.940, b = 9.940, c = 9.940).

5 Figure S2. SEM image of Zn 3 [Co(CN) 6 ] 2 nh 2 O/PVP precursor nanospheres, revealing an average size of ~600 nm.

6 Figure S3. The optimized structures of S 8 and polysulfides, exhibiting the three-dimensional cluster shapes.

7 Figure S4. Binding geometric configurations and binding energies of S 8 and Li 2 S x species with pristine MMNC material. The binding energies between S 8 /Li 2 S x with pristine MMNC are much lower than those between the sulfur species and CeO 2 nanocrystals, suggesting the weak interactions.

8 Figure S5. (a) CV curve of CeO 2 /MMNC composite at 0.05 mv s -1. (b) High-resolution XPS spectrum at S 2p region after the adsorption test of Li 2 S 4 with CeO 2 /MMNC.

9 Figure S6. Raman spectra of MMNC and CeO 2 /MMNC materials. The Raman spectrum of CeO 2 /MMNC product exhibits the typical Raman peak of CeO 2 (F 2g mode) at ~458 cm -1.

10 Figure S7. Survey XPS spectrum of CeO 2 /MMNC material, showing the co-existence of C, N, Ce and O elements.

11 Figure S8. High-resolution XPS spectra at (a) N 1s region and (b) Ce 3d region.

12 Figure S9. TGA curves of CeO 2 /MMNC-S-x composites measured under N 2 atmosphere from room temperature to 600 C with a heating rate of 10 C/min.

13 Figure S10. Morphology and composition characterizations of MMNC-S-70% composite. (a,b) SEM images, (c) TEM image and (d) EDX spectrum of MMNC-S-70%.

14 Figure S11. TGA curves of MMNC-S-x composites measured under N 2 atmosphere from room temperature to 600 C with a heating rate of 10 C min -1.

15 Figure S12. CV curves of MMNC-S-70% and CeO 2 /MMNC-S-70% composite cathodes with a scan rate of 0.2 mv s -1.

16 Figure S13. Electrochemical performance of CeO 2 /MMNC-S-x cathodes. (a,c) CV curves (at a scanning rate of 0.2 mv s -1 ) and (b,d) galvanostatic charge/discharge profiles (at a current density of 0.2 C) of CeO 2 /MMNC-S-60% and CeO 2 /MMNC-S-80% cathodes, respectively.

17 Figure S14. Nyquist plots of CeO 2 /MMNC-S-x cathodes. These plots show low resistance characteristics, suggesting that the CeO 2 /MMNC-S-x cathodes possess good electrical conductivity.

18 Figure S15. Cycling performance of CeO 2 /MMNC-S-70% cathode under 1.0 and 2.0 C in the electrolyte without LiNO 3 additive.

19 Figure S16. (a,b) SEM images of CeO 2 /MMNC-S-70% composite after long-term cycling test at 2.0 C for 1,000 cycles. The CeO 2 /MMNC-S-70% composite well maintains the original morphology before cycling, indicating the high structural integrity.

20 Figure S17. Electrochemical performances of MMNC-S-x cathodes. (a) CV curves at 0.2 mv s -1 and (b) galvanostatic charge/discharge profiles at 0.2 C of MMNC-S-70% cathode. (c) Cycling performances of MMNC-S-x cathodes at 0.2 C. (d) Rate performances of MMNC-S-x cathodes.

21 Figure S18. (a) Long-term cycling performance of MMNC-S-x cathodes at 1.0 C. (b) Long-term cycling performance and corresponding Coulombic efficiency of MMNC-S-70% cathode at 2.0 C.

22 Figure S19. Electrochemical performance of soft-packaged Li-S batteries (~24 cm 2 in area, sulfur loading is 3.8 mg cm -2 ) with CeO 2 /MMNC-S-70% composite as the cathode. (a) The initial charge/discharge profile of the soft-packaged Li-S batteries at 0.1 C. (b) Photograph that shows the soft-packaged Li-S battery powering a LED device.

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