Green, Template-Less Synthesis of Honeycomb-Like. Porous Micron-Sized Red Phosphorus for High- Performance Lithium Storage

Transcription

1 Supporting Information (SI) Green, Template-Less Synthesis of Honeycomb-Like Porous Micron-Sized Red Phosphorus for High- Performance Lithium Storage Junlu Zhu, Zhonggang Liu, Wei Wang, Liguo Yue, Wenwu Li, Haiyan Zhang, Ligong Zhao, He Zheng, Jianbo Wang, Yunyong Li,, * Guangdong Provincial Key Laboratory of Functional Soft Condensed Matter, School of Materials and Energy, Guangdong University of Technology, No. 100 Waihuan Xi Road, Guangzhou Higher Education Mega Center, Guangzhou, , China School of Physics and Technology, Center for Electron Microscopy, MOE Key Laboratory of Artificial Micro- and Nano-structures, and Institute for Advanced Studies, Wuhan University, Wuhan, , China S-1

2 Additional results: Figure S1. SEM images of Raw RP. S-2

3 Figure S2. More SEM images of HPRP-36. Figure S3. The XPS survey spectrum of HPRP-36 and Raw RP. Figure S4. N 2 adsorption-desorption isotherms (A) and pore size distribution (B) of S-3

4 Raw RP and HPRP samples with different hydrothermal reacted time. Figure S5. Raman spectra of the supernatant after reaction. Specific capacity (mah g -1 ) HPRP-24 HPRP-36 HPRP-48 HPRP Cycle Numbers Figure S6. Cycling stability of HPRP anodes with different hydrothermal reaction time in LIBs at 0.05 A g -1. S-4

5 Capacity Utilization(%) Cycle Numbers Figure S7. The capacity utilization of the HPRP-36 anode for 2 nd -80 th cycle. Figure S8. Nyquist plots and the relationship between -Z im and ω -1/2 of Raw RP and HPRP-36 electrodes (measured in the frequency range of 100 khz Hz at open circuit potential with an ac perturbation of 5 mv). The inset in Fig. S8A shows the equivalent circuit used for data fitting (R s : Ohmic resistance including electrolyte and contact resistance; R f : SEI film resistance; R ct : charge transfer resistance; W: Warburg impedance; CPE 1 and CPE 2 : constant phase element). S-5

6 Figure S9. Electrode morphologies of HPRP-36 ((A-C) SEM images, (D) TEM and (E) STEM images) after 500 cycles at 0.5 A g -1. Table S1. BET total surface areas and Total pore volumes of different samples. Samples BET total surface area (m 2 g -1 ) Total pore volume (cm 3 g -1 ) Raw RP HPRP HPRP HPRP HPRP S-6

7 HPRP Table S2. Impedance parameters of HPRP-36 and Raw RP electrodes in different cycle number. Samples R s (Ω) R ct (Ω) Fresh cell 5 th cycle 10 th cycle 20 th cycle Raw RP HPRP Raw RP HPRP Raw RP HPRP Raw RP HPRP Table S3. Electrochemical performance comparison with some reported representative pure red phosphorus and red phosphorus-based composite anodes in LIBs. Material Preparation method RP content in active materials (%) Proportion of active materials, conductive agent and binder ICE (%) Cycling performance (ma h g -1 ) (Based on the whole electrode) Ref. red phosphorus films high energy sonication 100 8:1: /0.1 A g -1 /100 th S1 hollow P nanospheres solvothermal reaction 100 6:3: /1.3 A g -1 /80 th S2 red phosphorus nanoparticles solution-phase approach 100 5:3: /0.4 A g -1 /150 th S3 S-7

8 red phosphorus/ti 3 C 2 T x high-energy ball-milling 25 7:2:1 ~67 ~500/0.05 A g -1 /80 th ~590/0.2 A g -1 /500 th S4 N Ti 3 C 2 T x /P vaporizationcondensation :1: ~455/0.5 A g -1 /500 th S5 vaporization-conversion 39 freestanding No mention 996.8/0.1 A g -1 /300 th 802.3/1 A g -1 /500 th S6 red phosphorus/crumpled nitrogen-doped graphene ball-milling 63 7:1.5: /0.78 A g -1 /100 th S7 ball-milling 52 freestanding /0.75 A g -1 /25 th S8 red P/porous carbon vaporizationcondensation :2: /0.1 A g -1 /50 th S9 P-MWCNTs wet ball-milling 70 7:2: /0.05 A g -1 /50 th S10 RGO-RP solution route :1: /0.160 A g -1 /70th S11 50F composites amorphous red phosphorus/carbon nanotube Vaporizationadsorption 47 7:2: /0.3 A g -1 /100 th S12 high-pressure-assisted spraying method 70 8:1: /0.1 A g -1 /50 th S13 planetary ball-milling 80 8:1: /0.130 A g -1 /50 th S14 red P/mesoporous carbon matrix vaporization condensation conversion process :1: /0.648 A g -1 /85 th S15 red P-porous carbon nanofiber electrospinning freestanding /0.26 A g -1 /100 th S16 red phosphorus/carbon composite vaporization/adsorption strategy :1: /0.1 A g -1 /55 th S17 P/TiN/Gnps ball-milling 60 8:1: ~520/0.1 A g -1 /300 th S18 HPRP-36 Hydrothermal 100 7:2: /0.05 A g -1 /80th 841.0/0.5 Ag -1 /500th This work References (S1) Subramaniyam, C. M.; Tai, Z.; Mahmood, N.; Zhang, D.; Liu, H. K.; Goodenough, J. B.; Dou, S. X., Unlocking the Potential of Amorphous Red Phosphorus Films as a Long-Term Stable Negative Electrode for Lithium Batteries. J. Mater. Chem. A 2017, 5, (S2) Zhou, J.; Liu, X.; Cai, W.; Zhu, Y.; Liang, J.; Zhang, K.; Lan, Y.; Jiang, Z.; Wang, S-8

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