Supporting Information for

Transcription

1 Supporting Information for Stable Li Plating/Stripping Electrochemistry Realized by a Hybrid Li Reservoir in Spherical Carbon Granules with 3D Conducting Skeletons Huan Ye,, Sen Xin, Ya-Xia Yin,, Jin-Yi Li,, Yu-Guo Guo,,, * Li-Jun Wan, * CAS Key Laboratory of Molecular Nanostructure and Nanotechnology, Institute of Chemistry, Chinese Academy of Sciences (CAS), Beijing , (P. R. China). School of Chemistry and Chemical Engineering, University of Chinese Academy of Sciences (CAS), Beijing , (P. R. China). Department of Mechanical Engineering, The University of Texas at Austin, Austin, Texas 78712, United States *Corresponding author. ygguo@iccas.ac.cn (Y.G.G.); wanlijun@iccas.ac.cn (L.J.W.) S-1

2 Figure S1. (a) Ex-situ Raman measurements for the CMN electrodes. (b) Comparison of the voltage profiles of the Li plating on the CMN with different areal loadings of C granules at 0.5 ma cm 2. S-2

3 Figure S2. Morphology of Li metal deposited on the BNF under different current densities. Plating 2 ma h cm 2 of Li under the current density of (a) 0.5 ma cm 2, (b) 1 ma cm 2, (c) 2 ma cm 2. S-3

4 Figure S3. Evolution of Li dendrite growth on the BNF at 2 ma cm 2. (a) The discharge voltage profile. The corresponding morphology of Li metal on the BNF after plating (b) 0.5 ma h cm 2, corresponding to stage b in Figure S3a, (c) 1 ma h cm 2, corresponding to stage c in Figure S3a, (d) 2 ma h cm 2, corresponding to stage d in Figure S3a, (e) 4 ma h cm 2, corresponding to stage e in Figure S3a, (f) 8 ma h cm 2, corresponding to stage f in Figure S3a. S-4

5 Figure S4. Morphology of Li metal deposited on the CMN under different current densities. Plating 2 ma h cm 2 of Li under the current density of (a) 0.5 ma cm 2, (b) 1 ma cm 2, and (c) 2 ma cm 2. S-5

6 Figure S5. Morphology of Li metal deposited on the CMN under 2 ma cm 2. Top-view SEM images of Li metal on the CMN after plating (a) 0.8 ma h cm 2, (b) 2 ma h cm 2 and (c) 4 ma h cm 2 of Li. S-6

7 Figure S6. Surface morphologies and corresponding energy-dispersive X-ray patterns of the pure spherical C and Li-CMNs. Pristine spherical C (a) (d), CMN after plating 2 ma h cm 2 of Li at 0.5 ma cm 2 (b) (e) and plating 2 ma g cm 2 at 2 ma cm 2 (c) (f). S-7

8 Figure S7. XRD patterns of CMN and Li-CMN. (a) CMN without plating Li metal and after plating 2 ma h cm 2 of Li metal into the CMN at 2 ma cm 2. (b) The corresponding discharge voltage profile. S-8

9 Figure S8. HRTEM images of spherical C after plating 2 ma h cm 2 of Li metal into the CMN at 2 ma cm 2. S-9

10 Figure S9. Electrochemical performance of Li anode on the CMN at 0.5, 1.0 ma cm 2 for 2 ma h cm 2. (a) Comparison of the Coulombic efficiency of Li deposition on the BNF and the CMN under current density of 0.5 ma cm 2. (b) Coulombic efficiency and voltage hysteresis of Li anode on the CMN at 1 ma cm 2 for 2 ma h cm 2. S-10

11 Figure S10. Electrochemical performance of Li anode on the CMN for high areal capacity cycling at high rate of 2 and 4 ma cm 2 respectively. (a) Coulombic efficiency of Li anode on the CMN for 4 ma h cm 2. (b) Voltage hysteresis of the Li anode on the CMN for 4 ma h cm 2. (c) Coulombic efficiency of Li anode on the CMN for 8 ma h cm 2. (d) Voltage hysteresis of the Li anode on the CMN for 8 ma h cm 2. S-11

12 Figure S11. Electrochemical performance of Li anode on the CMN at 55 C at 1.0 ma cm 2. The voltage profiles of plating 4 ma h cm 2 (a) and 8 ma h cm 2 (c). The corresponding Coulombic efficiency and voltage hysteresis of plating 4 ma h cm 2 (b) and 8 ma h cm 2 (d). S-12

13 Figure S12. Electrochemical performance of Li anode on the CMN for high areal capacity cycling at 0.5 and 1.0 ma cm 2 respectively. (a) Coulombic efficiency of the Li anode on the CMN for 4 ma h cm 2. (b) Voltage hysteresis of the Li anode on the CMN for 4 ma h cm 2. (c) Coulombic efficiency of the Li anode on the CMN for 8 ma h cm 2. (d) Voltage hysteresis of the Li anode on the CMN for 8 ma h cm 2. S-13

14 Figure S13. Average Coulombic efficiency of Li anode on the BNF at high areal capacity. Plating 2, 4 and 8 ma h cm 2 of Li on the BNF at 0.5 ma cm 2. S-14

15 Figure S14. Symmetrical cell testing of Li Li-CMN electrode at 2 and 4 ma cm 2. The amount of Li plated in each cycle is 1 ma h cm 2. S-15

16 Figure S15. EIS tests of the Li-BNF electrode and the Li-CMN electrode. (a) The Li-BNF and (b) the Li-CMN electrode with different states at 1.0 ma cm 2 for 4 ma h cm 2. S-16

17 Figure S16. XPS spectra of the Li-CMN electrode for the initial and 5 th cycles. (a) C1s spectra (b) F1s spectra. S-17

18 Figure S17. Electrochemical performance of Li-BNF LiFePO 4 full cells at 0.2 C. (a) Voltage profiles of full cell with the cathode/anode capacity ratio of 1:1. (b) Voltage profiles of full cell with the cathode/anode capacity ratio of 1:1.05. (c) Cycling performance of the assembled full cells. S-18

19 Figure S18. Morphology of the cycled Li-BNF electrode after 100 cycles. Ex situ SEM was performed to investigate the Li-BNF anode in the cycled Li-BNF LiFePO 4 full battery at 0.2 C. S-19

20 Figure S19. Morphology of the cycled Li-CMN electrode after 100 cycles. Ex situ SEM was performed to investigate the Li-CMN anode in the cycled Li-CMN LiFePO 4 full battery at 0.2 C. Most C spheres were still decorated with petal-like Li and with no filament and tubular-shaped Li dendrites, implying the C spheres have excellent capability to uniformize the Li + flux and thus accommodate Li without the growth of Li dendrite in practical cell system. S-20

21 Figure S20. Voltage profiles of Li-CMN LiFePO 4 full cell with the cathode/anode capacity ratio of 1:1.05, after 20 cycles (a) and 100 cycles (b). S-21

22 Figure S21. Electrochemical performance of Li-CMN LiFePO 4 full cell. (Based on the LiFePO 4 cathode, CMN anode with 5% Li surplus anode, the areal capacity of LiFePO 4 is of~2.5 ma h cm 2 ). (a) Voltage profiles of Li-CMN LiFePO 4 full cell at 0.2 C. (b) Cycling performance. S-22

23 Figure S22. Electrochemical performance of Li anode on the CMN at 0.5 ma cm 2 for 0.8 ma h cm 2. (a) Discharge/charge voltage profiles. (b) Coulombic efficiency and voltage hysteresis. S-23