Reduced Graphene Oxide-Incorporated SnSb@CNF Composites as

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Reduced Graphene Oxide Incorporated SnSb@CNF Composites as Anodes for High Performance Sodium Ion Batteries Hao Jia, Mahmut Dirican, Chen Chen, Jiadeng Zhu, Pei Zhu, Chaoyi Yan, Ya Li, Xia Dong, Jiansheng Guo, and Xiangwu Zhang ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.7b18921 • Publication Date (Web): 22 Feb 2018 Downloaded from http://pubs.acs.org on February 23, 2018

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ACS Applied Materials & Interfaces

Reduced Graphene Oxide Incorporated SnSb@CNF Composites as Anodes for High Performance Sodium Ion Batteries

Hao Jiaa,b, Mahmut Diricanb,*, Chen Chenb, Jiadeng Zhub,c, Pei Zhub, Chaoyi Yanb, Ya Lib,d, Xia Dong b, Jiansheng Guoa and Xiangwu Zhangb,*

a

Key Laboratory of Textile Science and Technology, Ministry of Education, College of Textiles, Donghua University, Shanghai, 201620, China

b

Fiber and Polymer Science Program, Department of Textile Engineering, Chemistry and Science, North Carolina State University, Raleigh, NC 27695-8301, USA

c

Department of Forest Biomaterials, North Carolina State University, Raleigh, NC 27695-8005, USA

d

National Engineering Laboratory for Modern Silk, College of Textile and Clothing Engineering, Soochow University, 199 Ren-Ai Road, Suzhou, 215123, China

*Corresponding authors: - Xiangwu Zhang, E-mail: [email protected]

- Mahmut Dirican, E-mail: [email protected]

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Abstract Sodium-ion batteries (SIBs) are promising alternative to lithium-ion batteries due to the low cost and natural abundance of sodium resources. Nevertheless, low energy density and poor cycling stability of current SIBs unfavorably hinder their practical implementation for smart power grid and stationary storage applications. Antimony tin (SnSb) is one of the most promising anode materials for next-generation SIBs attributing to its high capacity, high abundance, and low toxicity. However, the practical application of SnSb anodes in SIBs is currently restricted because of their large volume changes during cycling, which results in serious pulverization and loss of electrical contact between the active material and carbon conductor. Herein, we apply reduced graphene oxide (rGO) incorporated SnSb@carbon nanofiber (SnSb@rGO@CNF) composite anodes in SIBs that can sustain their structural stability during prolonged charge-discharge cycles. Electrochemical performance results shed light on that the combination of rGO, CNF, and SnSb alloy led to a high-capacity anode (capacity of 490 mAh·g-1 at 10th cycle) with high capacity retention of 87.2% and large coulombic efficiency of 97.9% at the 200th cycle. This work demonstrates that SnSb@rGO@CNF composite is a potential and attractive anode material for next-generation, high-energy SIBs.

Keywords: Sodium-ion battery; Antimony tin; Carbon nanofiber; Reduced graphene oxide; Cycling stability; Capacity retention


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1. Introduction Storage of the energy harvested from natural sources such as solar radiation, wind, tide and even mechanical vibration has become a key issue, and electrochemical energy storage has been widely regarded as the most appropriate method for storing the energy1-5. This is mainly because the electrochemical energy exhibit encouraging features such as high power, long cycle life, good reliability, and more importantly it can hardly be affected by unpredictable environmental conditions. Hence, the market and applications for rechargeable batteries have been steadily and promptly increasing in last few decades6-8. In addition to the widely commercialized lithium-ion batteries (LIBs), current sodium-ion batteries (SIBs) have drawn great attention and have been regarded as promising candidate for wide-scale renewable energy storage attributed to the low price and huge reserves of sodium resources9-11. In order to achieve high capacity and stable cycling stability, considerable research has been devoted to find proper anode materials for SIBs. However, today’s high-capacity sodium-ion anodes still suffer from the combined weakness of unstable cycling performance and low Coulombic efficiency (CE)12. Hence, exploring novel anode materials and demonstrating high cycling stability and Coulombic efficiency has positive significance and potentially wide application prospect for future SIBs.

Antimony tin (SnSb) alloy-based materials have become increasingly attractive as a potential anode material candidate for SIBs because of their high capacity, high safety as well as low cost. As the calculated theoretical specific capacities of Sn and Sb are 847 mAhg-1 (Na15Sn4) and 660 mAhg-1 (Na3Sb), respectively13, of the SnSb alloy is expected to reach a prominent theoretical specific capacity of 750 mAhg-1 when the molar ratio of Sn and Sb is 1:1. Besides, it has been reported that intermetallic alloy anodes can keep a rather stable microstructure during cycling



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because different components in the alloy can disperse into each other uniformly at an atomic or nanometer scale14-15, hence the volume changes of individual elements during cycling could be effectively accommodated by each other. Furthermore, compared to pure Sn or Sb, SnSb alloy has higher plasticity and ductility, leading to a higher resistance to volume change16. However, the relatively large radius of sodium ions would still bring high volume expansion during cycling and this has an extremely negative effect on preserving the electronic conductivity in the electrode, thereby leading to the gradual loss of electrical contact within the electrode and ultimate fast capacity degradation17. In recent years, intensive efforts have been exerted to improve the stability and cycling performance of SnSb based anodes. Combining them with carbonaceous materials is the most preferred approach to achieve improved cycling stability. Liu et al18 evaluated the performance of porous carbon nanofiber (CNF)-incorporated SnSb nanocomposite anodes in SIBs and showed that capacity retention could only reach 80% over 50 cycles. They further attempted to include fluoroethylene carbonate (FEC) in the electrolyte solution and found that it could effectively prevent electrolyte decomposition and eventually controls solid electrolyte interphase (SEI) formation on the cycled electrode surfaces, which can lead to lower kinetics impedance for the long time sodiation–desodiation processes19. In addition, Chen et al20 introduced SnSb@CNF composite anode fabricated by simple electrospinning method and demonstrated that the carbon nanofiber matrix with porous structure works synergistically to accommodate the volume change of the SnSb alloy on the cycling process. Nevertheless, the SnSb-based anode materials with more stable architecture and excellent cycling performance are still highly demanded and deserve further exploration for SIBs.


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Figure 1. Schematic illustration of the fabrication process of SnSb@rGO@CNF composites.

In this study, we introduce reduced graphene oxide (rGO) incorporated SnSb@CNF composites as high-performance anodes for SIBs. The rGO component not only improves the electrical conductivity of the composites but also accommodates the volume changes, and thus ensures the integrity of the electrodes during cycling due to its proper layer distance and flexibility. As schematically shown in Figure 1, the SnSb@rGO@CNF composites were prepared

from

the

electrospun

Sn(CH3COO)2

(Sn(Ac)2)/Sb(CH3COO)3

(Sb(Ac)3)/GO/polyacrylonitrile (PAN)/polymethyl methacrylate (PMMA) precursor composite nanofibers followed by subsequent thermal treatment. Specifically, PAN serves as the carbon precursor while PMMA works as the pore-forming agent. During the high-temperature carbonization process, GO was deoxidized to rGO and SnSb alloy was synthesized from Sn(Ac)2 and Sb(Ac)3 salts. Galvanostatic charge-discharge measurement results presented that the SnSb@rGO@CNF anode with 6 wt. % rGO presents better electrochemical properties, including enhanced

reversible

capacity,

cycling

stability,

and

rate

performance,

than

the

SnSb@rGO@CNF anode with 3 wt. % rGO and the SnSb@CNF anode without rGO. These 5 ACS Paragon Plus Environment


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results demonstrated that the introduced rGO and the carbon nanofiber matrix could work synthetically to accommodate the volume variation of the SnSb alloy during the charge/discharge processes, which enables the fabricated SIBs to work with compelling features such as high reversible capacity, good cycling performance, and improved rate performance.

2. Experimental 2.1. Chemicals and reagents Polyacrylonitrile (PAN, Mw = 150000, Sigma–Aldrich), polymethyl methacrylate (PMMA, average Mw = 120 000, Aldrich), N, N-dimethylformamide (DMF, >99.5%, Sigma–Aldrich), tin(II) acetate (Sn(Ac)2, anhydrous, Sigma–Aldrich), antimony(III) acetate (Sb(Ac)3, anhydrous, Sigma–Aldrich), graphite powder (99.99% purity,

Reduced Graphene Oxide-Incorporated SnSb@CNF Composites as

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