Poly(acrylonitrile-methyl methacrylate) as a non-fluorinated binder for the graphite anode of Li-ion batteries

Abstract

Poly(vinylidene fluoride) (PVDF) has been a choice of the binder for both cathode and graphite anode in stateof-the-art Li-ion batteries [1, 2]. However, there is currently a demand to replace PVDF with non-fluorinated binder since at elevated temperatures the fluorinated polymers react with lithiated graphite (LixC6) and metal lithium to form more stable LiF and >C@CF– double bonds. In particular, the reaction of PVDF and metal lithium produces an enthalpy as high as 7180 J (g PVDF) [1]. It has been reported that in the presence of electrolytes, PVDF and lithiated graphite undergo a series of exothermic reactions, including (i) temperature-induced degradation of the solid electrolyte interface (SEI) at 120–140 C, (ii) reactions of lithiated graphite and electrolyte at 210–230 C, and (iii) dehydrofluorination of PVDF initiated by LixC6 at >260 C [1, 2]. Among these reactions, the last one is known to be very exothermic and is believed to be a potential source for the thermal runaway of Li-ion batteries under abuse conditions. Therefore, safety concerns with Li-ion batteries may arise from the use of PVDF in the graphite anode. To replace the rather reactive PVDF, we attempt to evaluate poly(acrylonitrile-methyl methacrylate) (AMMA) as a non-fluorinated binder for the graphite anode of Li-ion batteries. Differential scanning calorimetry (DSC) study has shown that the heat of reaction of the lithiated graphite and electrolyte can be reduced significantly by using AMMA instead of PVDF [3]. That is, total enthalpies for the reactions (as indicated by two exothermic peaks in DSC curves) of the fully lithiated graphite (MAG-10, Hitachi Chemical) and electrolyte (1.2 M LiPF6 3:7 EC/EMC) in the temperature range 280–340 C can be reduced to 1211 J (g AMMA) from 2699 J (g PVDF). In this paper, we will electrochemically evaluate AMMA as a binder of the graphite anode of Li-ion batteries. 2. Experimental details