High Voltage Magnesium-ion Battery Enabled by Nanocluster Mg3Bi2

Transcription

1 Supporting Information High Voltage Magnesium-ion Battery Enabled by Nanocluster Mg3Bi2 Alloy Anode in Noncorrosive Electrolyte Yi-Hong Tan,, Wei-Tang Yao,*, Tianwen Zhang, Tao Ma, Lei-Lei Lu, Fei Zhou, Hong-Bin Yao,*, Shu-Hong Yu Division of Nanomaterials & Chemistry, Hefei National Research Center for Physical Sciences at the Microscale, CAS Center for Excellence in Nanoscience, Hefei Science Center of CAS, Collaborative Innovation Center of Suzhou Nano Science and Technology, Department of Chemistry, University of Science and Technology of China, Hefei , China. Key Subject Laboratory of National Defense for Radioactive Waste and Environmental Security, Southwest University of Science and Technology, Mianyang , China. *To whom correspondence should be addressed. s: 1

2 Figure S1. Schematical illustration of experimental procedures. The alloying synthesis of Mg3Bi2 anode materials. Figure S2. The initial charge and discharge voltage profiles of the MB-300, MB-500, MB-650 and MB- 750 with LiCl-APC electrolyte at 0.1 A g -1. 2

3 Figure S3. HAADF-STEM image and the corresponding EDX elementary mappings of MB

4 Figure S4. Nyquist plot of the impedance spectra of the MB-300, MB-500, MB-650 and MB-750 with LiCl-APC electrolyte by applying a sine wave with an amplitude of 5.0 mv over the frequency range from 100 khz to 100 mhz at room temperature. Figure S5. TEM image of (a) MB-300 and (b) MB-500, respectively. The inset shows the SAED patterns of the corresponding area denoted by red cycle. 4

5 Figure S6. Electrochemical characterizations of MB-650 electrode in half-cells. (a) CV curves of MB- 650 electrode from first to tenth cycle. (b) The corresponding galvanostatic charge/discharge voltage profiles with cut-off voltage range from V at the current density of 0.1 A g -1. (c) Rate performance of MB-650 electrode. (d) Cycling performance of MB-650 electrode at 0.38 A g -1. 5

6 Figure S7. XPS analysis of MB-650 electrode after discharging to 0.05V. (a) full spectrum. (b) Mg 2+ 2p and Li + 1s. Figure S8. EDX spectra of MB-650 anode particles at (a) open-circuit voltage, charging to (b) 0.75 V, (c) 1.6 V, and then discharging to (d) 0.05 V, respectively. 6

7 Figure S9. TEM image of MB-650 at different charge/discharge states. (a) pristine, (b) 0.75 V, (c) 1.6 V and (d) 0.05 V. Figure S10. PXRD patterns of Mg3Bi2 anodes at the fully discharged states obtained at different numbers of cycles. 7

8 Figure S11. Material characterizations of PB. (a) SEM and (b) TEM image of as-synthesized high quality PB nanocubes, respectively. (c) The PXRD pattern of PB. (d) TGA profile of PB nanoparticles showing a 6.8% weight loss due to the crystalline water, corresponding to the formula of Na0.61Fe[Fe(CN)6] H2O. Figure S12. Discharge specific capacities and CEs versus cycling numbers of PB-MB-650 full cells with different mass ratios of anode to cathode (RMB/PB) at 0.1 ma g -1 in 2 M Mg(TFSI)2-1 M LiTFSI/AN electrolyte. 8

9 Figure S13. PXRD patterns of pristine PB cathodes. After the 1st discharge to 1.0 V and the 1st charge to 2.5 V. 9

10 Figure S14. STEM characterizations of PB cathode at the discharge state of 1.0 V (a) and corresponding EDX elementary mappings of (b) Fe, (c) Na and (d) Mg, respectively. 10

11 Figure S15. Material characterization of VO and electrochemical performance of MB-VO full cell using 2 M Mg(TFSI)2-1 M LiTFSI/AN electrolyte. (a) SEM image and (b) TEM image of the VO nanosheets, respectively. (c) The PXRD pattern of VO prepared by annealing at 400 o C in air. (d) CV curves of VO electrode between 0.8 and 2.7 V vs. Mg 2+ /Mg at a scan rate of 0.1 mv s -1. (e) Galvanostatic discharge/charge voltage profiles and (f) cycling performance of VO cathode at 0.2 A g -1, respectively. 11

12 Figure S16. Material characterization of MO and electrochemical performance of MB-MO full cell using 2 M Mg(TFSI)2-1 M LiTFSI/AN electrolyte. (a) SEM image and (b) TEM image of the MO, respectively. (c) The PXRD pattern of MO. (d) CV curves of MB-VO full cell between 1.0 and 2.6 V vs. Mg 2+ /Mg at a scan rate of 0.1 mv s -1. (e) Galvanostatic discharge-charge voltage profiles and (f) cycling performance of MO at 0.2 A g -1, respectively. 12

13 Figure S17. Nyquist plot of the impedance spectra of the MB-PB, MB-VO and MB-MO full cells with 2 M Mg(TFSI)2-1 M LiTFSI/AN electrolyte by applying a sine wave with an amplitude of 5.0 mv over the frequency range from 100 khz to 100 mhz at room temperature. 13

14 Table S1. The capacity and voltage of typical rechargeable Mg batteries Anode Material Cathode Material Electrolyte Discharge Plateau vs. Mg 2+ / Mg (V) Discharge Capacity (mah g -1 ) Energy Density (Wh kg -1 ) 80% Capacity Retention (cycles) Reference Mg (Taking the capacity of the Mg metal anode as 2205 mah g -1 ) Mo 6X 8 (X=S or Se) H 2V 3O 8 Mg(AlCl 2B uet) 2/THF APC-LiCl/ THF LiFePO 4 [Mg 2Cl 2(D ME) 4][AlCl 4] 2 - LiTFSI (0.015A g -1 ) 1.5 and (0.05A g - 1 ) (0.085A g -1 ) 115 > ~ ~50 3 NaV 2(PO 4) 3 NaAlCl 4- [Mg 2Cl 2][Al Cl 4] 2/ DME (0.058A g -1 ) Fe[Fe(CN) 6] 0.95 APC-LiCl/ THF (0.01 A g -1 ) 270 ~7 5 I 2 (HMDS) 2M g-alcl 3- MgCl 2/TEG DME (0.1 A g - 1 ) 330 >120 6 MgNaTi 3O 7 V 2O 5 Mg(ClO 4) 2/ diglyme 1.15 and and 35 (0.02 A g -1 ) Sn (1C=903 mah g -1 ) Mg xv 2O 5 Mg(ClO 4) 2/ AN (0.03A g - 1 ) Mg 2Sn (1C 300 mah g -1 ) Mo 6S 8 Mg(TFSI) 2/ DME ~ ~ Mg-SnSb (1C 400 mah g -1 ) Mg(TFSI) 2/ diglyme 0.8 ~70 (0.01A g - 1 ) ~ Mg-Bi Mg(TFSI) 2/ diglyme Mg 3Bi 2 δ-mno 2 Mg(TFSI) 2- LiTFSI/AN 0.8 ~65 ~ (0.2A g -1 ) 72 5 This work V 2O and and 151 (0.2A g -1 ) This work PB (0.1A g -1 ) 83 >200 This work 14

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