A Nonflammable Fluorinated Carbonate Electrolyte for Sodium-Ion Batteries

1.
SDU & Rice Joint Center for Carbon Nanomaterials, Key Laboratory for Liquid Solid Structural, Evolution & Processing of Materials (Ministry of Education), School of Materials Science and Engineering, Shandong University, Jinan 250061, P. R. China
2.
School of Physical Science and Technology, Jiangsu Key Laboratory of Thin Films, Soochow University, Suzhou 215006, Jiangsu Province, P. R. China

Corresponding author: Feng Jinkui, jinkui@sdu.edu.cn Ni Jiangfeng, jjeffni@suda.edu.cn

Received Date: 02 May 2019
Accepted Date: 25 June 2019
Revised Date: 06 June 2019
Available Online: 15 May 2020
Fund Project:

The project was supported by the Shandong Provincial Natural Science Foundation, China (ZR2017MB001), the Shandong Provincial Science and Technology Key Project, China (2018GGX104002), the National Natural Science Foundation of China (61633015), the Young Scholars Program of Shandong University, China (2016WLJH03) and the Project of the Taishan Scholar, China (tsqn201812002, ts201511004)

Abstract: Lithium-ion batteries (LIBs) are widely used in cellphones, laptops, and electric cars owing to their high energy density and long operational lifetime. However, their further deployment in large-scale energy storage systems is restricted by the uneven distribution of lithium resources (~0.0017% (mass fraction, w) in the Earth's crust). Therefore, alternative energy storage systems composed of abundant elements are of urgent need. Recently, sodium-ion batteries (SIBs) have attracted significant attention and are considered to be a potential alternative for next-generation batteries owing to abundant sodium resources (~2.64% (w) of the Earth's crust), suitable potential (−2.71 V), and low cost. SIBs are similar to LIBs in terms of their physical and electrochemical properties. Previous studies have mainly focused on SIB storage materials, including hard carbon, alloys, and hexacyanoferrate, while the safety of SIBs remains largely unexplored. Similar to LIBs, the current electrolytes used in SIBs are mainly composed of flammable organic carbonate solvents (or ether solvents), sodium salts, and functional additives, which pose possible safety issues. Moreover, the chemical activity of sodium is much higher than that of lithium, leading to a higher risk of fire, thermal runaway, and explosion. To overcome this problem, herein we propose a fluorinated non-flammable electrolyte composed of 0.9 mol∙L⁻¹ NaPF₆ (sodium hexafluorophosphate) in an intermixture of di-(2, 2, 2 trifluoroethyl) carbonate (TFEC) and fluoroethylene carbonate (FEC) in a 7 : 3 ratio by volume. Its physical and electrochemical properties were studied by ionic conductivity, direct ignition, cyclic voltammetry, and charge/discharge measurements, demonstrating excellent flame-retarding ability and outstanding compatibility with sodium electrodes. The electrochemical tests showed that the Prussian blue cathode retained a capacity of 84 mAh∙g⁻¹ over 50 cycles in the prepared electrolyte, in contrast to the rapid capacity degradation in a flammable conventional carbonate electrolyte (74 mAh∙g⁻¹ with 57% capacity retention after 50 cycles). To test the practical application of the proposed electrolyte, a hard carbon anode was used and exhibited exceptional performance in this system. The enhancement mechanism was further verified by Fourier transform infrared (FTIR), X-ray diffraction (XRD), and scanning emission microscopy (SEM) investigations. Polycarbonate on the surface of the cathode played an important role for the studied electrolyte system. The polycarbonate may originate from FEC decomposition, which can enhance the ionic conductivity of the solid electrolyte interface (SEI) layer and reduce impedance. Hence, we believe that this proposed electrolyte may provide new opportunities for the design of robust and safe SIBs for next-generation applications.

Key words:

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

不可燃氟代碳酸酯基钠离子电池电解液

通讯作者: 冯金奎, jinkui@sdu.edu.cn
倪江锋, jjeffni@suda.edu.cn

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