Lithium electrochemistry and cycling behaviour of ionic liquids using cyano based anions

Lithium based battery technologies are increasingly being considered for large-scale energy storage applications such as grid storage associated with wind and solar power installations. Safety and cost are very significant factors in these large scale devices. Ionic liquid (IL) electrolytes that are inherently non-volatile and non-flammable offer a safer alternative to mainstream lithium battery electrolytes, which are typically based on volatile and flammable organic carbonates. Hence, in recent years there have been many investigations of ionic liquid electrolytes in lithium batteries with some highly promising results to date, however in most cases cost of the anion remains a significant impediment to widespread application. Amongst the various possible combinations the dicyanamide (DCA) anion based ionic liquids offer exceptionally low viscosities and high conductivities – highly desirable characteristics for Li electrolyte solvents. DCA ILs can be manufactured relatively inexpensively because DCA is already a commodity anion, containing only carbon and nitrogen, which is produced in large amounts for the pharmaceutical industry. In this study we use the non-fluorinated ionic liquid N-methyl-N-butylpyrrolidinium dicyanamide to form non-volatile lithium battery electrolytes. We demonstrate good capacity retention for lithium metal and LiFePO4 in such electrolytes and discharge capacities above 130 mAh.g−1 at 50 °C. We show that it is important to control moisture contents in this electrolyte system in order to reduce capacity fade and rationalise this observation using cyclic voltammetry and lithium symmetrical cell cycling. Having approximately 200 ppm of moisture content produces the optimum cycling ability. We also describe plastic crystal solid state electrolytes based on the DCA anion in the lithium metal–LiFePO4 battery configuration and demonstrate over 150 mAh.g−1 discharge capacity without any significant capacity fading at 80 °C.