Preparation and characterization of trifluoroethyl aliphatic carboxylates as co-solvents for the carbonate-based electrolyte of lithium-ion batteries

• Published in: Journal of fluorine chemistry Vol. 161; pp. 110 - 119
• Main Authors: Lu, Wei, Xie, Kai, Chen, Zhong xue, Pan, Yi, Zheng, Chun man
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 01.05.2014
• Subjects: Aliphatic compounds; Carbonates; Carboxylates; Co-solvent; Electrochemical impedance spectroscopy; Electrolyte; Electrolytes; Graphite; Lithium-ion batteries; Lithium-ion battery; Low temperature; Performance enhancement; Trifluoroethyl aliphatic carboxylates; Lithium-ion battery; Electrolyte; Co-solvent; Trifluoroethyl aliphatic carboxylates; Low temperature
• ISSN: 0022-1139; 1873-3328
• DOI: 10.1016/j.jfluchem.2014.02.006

The charge curves at 218K demonstrate that the addition of trifluoroethyl n-hexanoate (TFENH) co-solvents can improve the electrochemical performance of graphite at low temperature most effectively. [Display omitted] •An efficient method was provided to synthesize RCOOCH2CF3 esters.•CH3(CH2)4COOCH2CF3 is a new efficient low temperature co-solvent for lithium-ion battery electrolyte.•RCOOCH2CF3with longer acyl group will be helpful to form a SEI film with better low temperature performance. In this work, a series of trifluoroethyl aliphatic carboxylates with different carbon-chain lengths in acyl group are prepared and investigated as the co-solvents for the carbonate-based electrolyte of lithium-ion batteries. The trifluoroethyl aliphatic carbonates are synthesized by a modified one-step approach, using aliphatic carboxylic acid and trifluoroethanol as the raw materials (molar ratio, 1.2:1), hydrogen ion exchange resin as the catalyst and silica gel drier as the de-hydration. The structure and electrochemical properties of the final products have been characterized by FTIR, 1H NMR, GC–MS, viscosity, conductivity meter and electrochemical measurements. The structure characterizations show that the final products have high purity. Electrochemical tests present that the co-solvents are able to improve the electrochemical performances of graphite electrode at low temperature. In particular, we find that an addition of trifluoroethyl n-hexanoate (TFENH) into 1M LiPF6/EC+EMC electrolyte can significantly decrease the Li de-intercalation potential of graphite by 540mV and achieve a high capacity retention of 92% at 218K. The electrochemical impedance spectroscopy (EIS) measurements indicate that the observed performance improvement at low temperature is associated with the decreased surface film resistance (RSEI) by the addition of co-solvents.