The Application of a Water-Based Hybrid Polymer Binder to a High-Voltage and High-Capacity Li-Rich Solid-Solution Cathode and Its Performance in Li-Ion Batteries

Abstract

Recently, water-soluble and aqueous polymers (water-based polymers) have attracted much attention as binders for lithium ion batteries (LIBs) because of the need for low-cost materials and environmentally compatible electrode fabrication processes. For example, N-methyl-2-pyrrolidone (NMP), which is listed as a carcinogenic chemical with reproductive toxicity is often used as a solvent to prepare a slurry (cathode material particle/conducting carbon additive/conventional polyvinylidene difluoride (PVdF) binder/ NMP solvent) employed in the fabrication process of electrode films on current collectors; this slurry should be recycled without releasing it to the atmospheric environment. Therefore, switching from a nonaqueous-based fabrication process to an aqueous-based process has been widely investigated. The hurdles in developing water-soluble and aqueous polymer binders for use in cathodes in LIBs are still high; improvements are necessary to increase the resistance to electrochemical oxidation and dissolution of metal oxide surfaces in water. In order to overcome these problems, a variety of polymer materials have been applied in the fabrication of cathodes with water-based slurries. In recent years, Li-rich solid-solution layered cathode materials comprising layered LiMO2 (M: transition metals) and Li2MnO3 have attracted much interest because some materials exhibit capacities as high as 250 mAh g-1 in the voltage range of 2.0 and 4.8 V. These materials are charged to above 4.5 V (vs. Li/Li+) to fully activate the Li2MnO3 component, and after activation, the cathodes are charged to 4.5 V to reach discharge capacities over 250 mAh g-1. To use these promising high-voltage and high-capacity cathodes in the next-generation Li-ion batteries prepared in environmentally compatible electrode fabrication processes with a water-based binder, water-based binders having high resistances to electrochemical oxidation during charging process should be developed. In this study, an aqueous hybrid polymer (TRD202A, JSR), which was composed of acrylic polymer and fluoropolymer, was selected as a binder for the Li-rich solid-solution layered cathode material Li[Ni0.18Li0.20Co0.03Mn0.58]O2. A cathode prepared with Li[Ni0.18Li0.20Co0.03Mn0.58]O2 particles, TRD202A binder, CMC and conductive carbon additive was tested and analyzed for charge/discharge capacity, cycle stability, rate performance, mechanical resistance, resistance of electrochemical oxidation, and changes of the surface composition and structure after water-treatment used for preparing water-based slurry. The water-based TRD202A cathode binder is a water-based emulsion and is designed with a unique hybrid polymer developed from acrylic polymer and fluoropolymer to satisfy both the requirements of high adhesion and chemical and electrochemical resistances. Wu and co-workers have already reported an application of the TRD202 binder in a Li-rich solid-solution cathode. They mentioned that the TRD202A binder can be used for high-voltage cathodes in the voltage range of 2.0-4.6 V [1], and its thermal stability is equivalent to that of PVdF. However, they have not examined the water-based binders for charge/discharge capacities, long cycle stability, rate performance, mechanical resistance, resistance of electrochemical oxidation, or changes of the surface composition and structure after water-treatment used for preparing the water-based slurry. We have examined in depth the above points with the Li-rich solid-solution cathode (3/5)Li2MnO3·(1/5)Li[Ni0.5Mn0.5]O2 ·(1/5)Li[Ni1/3Co1/3Mn1/3]O2. [1] Wu Q, Ha S, Prakash J, Dees DW, Lu W (2013) Electrochim. Acta 114:1-6