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Frontiers of Materials Science

ISSN 2095-025X

ISSN 2095-0268(Online)

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Front. Mater. Sci.    2020, Vol. 14 Issue (2) : 133-144    https://doi.org/10.1007/s11706-020-0500-1
RESEARCH ARTICLE
Double core---shell nanostructured Sn---Cu alloy as enhanced anode materials for lithium and sodium storage
Luoyang LI, Tian CHEN, Fengbin HUANG, Peng LIU(), Qingrong YAO, Feng WANG, Jianqiu DENG()
School of Materials Science and Engineering & Guangxi Key Laboratory of Information Materials, Guilin University of Electronic Technology, Guilin 541004, China
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Abstract

Sn-based alloy materials are considered as a promising anode candidate for lithium-ion batteries (LIBs) and sodium-ion batteries (SIBs), whereas they suffer from severe volume change during the discharge/charge process. To address the issue, double core–shell structured Sn–Cu@SnO2@C nanocomposites have been prepared by a simple co-precipitation method combined with carbon coating approach. The double core–shell structure consists of Sn–Cu multiphase alloy nanoparticles as the inner core, intermediate SnO2 layer anchored on the surface of Sn–Cu nanoparticle and outer carbon layer. The Sn–Cu@SnO2@C electrode exhibits outstanding electrochemical performances, delivering a reversible capacity of 396 mA·h·g−1 at 100 mA·g−1 after 100 cycles for LIBs and a high initial reversible capacity of 463 mA·h·g−1 at 50 mA·g−1 and a capacity retention of 86% after 100 cycles, along with a remarkable rate capability (193 mA·h·g−1 at 5000 mA·g−1) for SIBs. This work provides a viable strategy to fabricate double core–shell structured Sn-based alloy anodes for high energy density LIBs and SIBs.
Keywords lithium-ion battery      sodium-ion battery      Sn-based alloy      anode      double core–shell structure     
Corresponding Author(s): Peng LIU,Jianqiu DENG   
Online First Date: 06 May 2020    Issue Date: 27 May 2020
 Cite this article:   
Luoyang LI,Tian CHEN,Fengbin HUANG, et al. Double core---shell nanostructured Sn---Cu alloy as enhanced anode materials for lithium and sodium storage[J]. Front. Mater. Sci., 2020, 14(2): 133-144.
 URL:  
https://academic.hep.com.cn/foms/EN/10.1007/s11706-020-0500-1
https://academic.hep.com.cn/foms/EN/Y2020/V14/I2/133
Fig.1  Schematic illustration of the synthesis process for Sn–Cu@SnO2 and Sn–Cu@SnO2@C nanocomposites.
Fig.2  SEM, TEM and HRTEM images of (a)(b)(c) Sn-Cu@SnO2 and (d)(e)(f) Sn-Cu@SnO2@C nanocomposites.
Fig.3  (a) Elemental mapping images based on TEM of Sn–Cu@SnO2@C nanocomposites. (b) SEM–EDS spectra of Sn–Cu@SnO2 and Sn-Cu@SnO2@C nanocomposites.
Fig.4  Electrochemical performances of Sn–Cu@SnO2 and Sn–Cu@SnO2@C electrodes for LIBs: (a) the initial three CV curves of the Sn–Cu@SnO2@C electrode at a scan rate of 0.5 mV·s−1; (b) discharge/charge profiles plotted for initial three cycles of the Sn–Cu@SnO2@C electrode at a current density of 100 mA·g−1; (c) cycling performance of Sn–Cu@SnO2 and Sn–Cu@SnO2@C electrodes at a current density of 100 mA·g−1; (d) rate capability of Sn–Cu@SnO2 and Sn–Cu@SnO2@C electrodes.
Fig.5  Electrochemical performance of Sn–Cu@SnO2@C nanocomposites as an anode for SIBs: (a) the initial three CV curves at a scan rate of 0.1 mV·s−1; (b) the discharge/charge curves at 50 mA·g−1; (c) cycling performance at 50 mA·g−1; (d) rate capability at different rates from 0.1 to 10 C (1 C= 500 mA·g−1); (e) long cycle life at 250 mA·g−1; (f) Nyquist plots of the fresh and cycled Sn–Cu@SnO2@C electrodes.
  Fig. S1 XRD patterns of Sn–Cu@SnO2 and Sn–Cu@SnO2@C nanocomposites.
  Fig. S2 Particle diameter distribution curves of (a) Sn–Cu@SnO2 and (b) Sn–Cu@SnO2@C nanocomposites.
  Fig. S3(a) The initial three CV curves of the Sn–Cu@SnO2 electrode at a scan rate of 0.5 mV·s−1 for LIBs. (b) Discharge/charge curves at 100 mA·g−1 of the Sn–Cu@SnO2 electrode for LIBs.
  Fig. S4 The Nyquist plots of the fresh Sn–Cu@SnO2 and Sn–Cu@SnO2@C electrodes for LIBs. The inset is the equivalent circuit and fitting results.
  Fig. S5 Nyquist plots of the fresh and cycled Sn–Cu@SnO2@C electrodes for SIBs. The equivalent circuit and fitting results are illustrated in the inset.
Electrode material Reversible capacity ICE Rate capability Cycle performance Refs.
Cu6Sn5@C 504.9 mA·h·g−1 at 200 mA?g−1 56.5% 203 mA·h?g−1 at 10 A?g−1 366.4 mA?h?g−1 at 1 A·g−1 over 200 cycles, capacity retention is 92.3% [S1]
RGO/Cu6Sn5 895.5 mA·h?g−1 at 500 mA?g−1 70.1% 220 mA·h?g−1 at 10 A?g−1 186.5 mA·h?g−1 at 500 mA?g−1 over 3000 cycles, capacity retention is 21% [S2]
Sn–Cu–CNFs 562 mA·h?g−1 at 50 mA?g−1 74% ca. 180 mA·h?g−1 at 6.4 A?g−1 400 mA·h·g−1 at 1.0 A·g−1 after 1200 cycles [S3]
Cu6Sn5/Cu 578 mA·h?g−1 at 100 mA?g−1 73.6% 200 mA·h?g−1 at 1 A?g−1 326 mA·h?g−1 at 0.1 A?g−1 after 50 cycles, capacity retention is 41.5% [S4]
SnO2–SnCu@C–Felt 885 mA·h?g−1 at 83 mA?g−1 – 305 mA·h?g−1 at 1.333 A?g−1 681 mA·h?g−1 at 0.15 A?g−1 after 140 cycles [S5]
Sn–Cu@SnO2@C 668 mA·h?g−1 at 100 mA?g−1 70% 349 mA·h?g−1 at 5 A?g−1 396 mA·h?g−1 at 0.1 A?g−1 after 100 cycles this work
  Table S1 A comparison of the electrochemical performance for Sn–Cu@SnO2@C nanocomposites in this work with previous Sn-based alloy anodes for LIBs
Electrode material Reversible capacity ICE Rate capability Cycle performance Refs.
Cu/Sn/C fiber 142 mA?h?g−1 at 156 mA·g−1 36% – 220 mA?h?g−1 at 155 mA·g−1 over 200 cycles [S6]
Cu6Sn5–TiC–C 146 mA·h?g−1 at 100 mA?g−1 56% 120 mA·h?g−1 at 5000 mA?g−1 Capacity retention is ~94% at 100 mA·g−1 over 250 cycles [S7]
Sn/SnO2 562 mA·h?g−1 at 50 mA?g−1 46.8% 209.8 mA·h?g−1 at 1000 mA?g−1 372.3 mA·h?g−1 at 50 mA?g−1 after 50 cycles, capacity retention is 70.8% [S8]
Sn/SnO2/C 655 mA·h?g−1 at 20 mA?g−1 59% 120 mA?h?g−1 at 1000 mA·g−1 245 mA·h?g−1 at 20 mA?g−1 after 100 cycles [S9]
Cu6.26Sn5 alloy 573 mA·h?g−1 at 50 mA?g−1 65.7% 270 mA·h?g−1 at 200 mA?g−1 233 mA?h?g-1 at 50 mA·g-1 after 100 cycles [S10]
Sn–Co alloy 306.4 mA·h?g−1 at 25 mA?g−1 38.4% 228.4 mA·h?g−1 at 1000 mA?g−1 276.2 mA·h?g−1 at 100 mA?g−1 after 120 cycles, capacity retention is 87% [S11]
Ni0.9Sn alloy 300 mA?h?g−1 at 100 mA·g−1 – 88 mA·h?g−1 at 2000 mA?g−1 160 mA?h?g−1 at 100 mA·g−1 after 120 cycles [S12]
Sn–Cu@SnO2@C 420 mA·h?g−1 at 50 mA?g−1 61% 193 mA·h?g-1 at 5000 mA?g-1 157 mA·h?g−1 at 250 mA?g−1 after 300 cycles this work
  Table S2 A comparison of the electrochemical performance for Sn–Cu@SnO2@C nanocomposites in this work with previous Sn-based alloy anodes for SIBs
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