Aqueous Processing of Ni-Rich NMC Electrodes with High Areal Capacity and Excellent Long-Term Cycling Stability
Authors: Surace Yuri , Eshraghi Nicolas , Cupid Damian Marlon 
Published: February 2024

Research efforts in the last three decades have resulted in a steady increase in the energy density of Li-ion batteries (LIBs), leading to their integration into electric vehicles (EVs). Therefore, car manufacturers have increased the number of EVs in their fleets and successfully introduced them to the mass market, with 200M of EVs expected to be sold by 2025 [1] . In such a fast-growing market, the cost and environmental impact of LIB production play major roles. A crucial step in battery manufacturing is the processing of active materials to produce electrode coatings. Commercial cathode electrodes (i.e. LiNixMnxCoxO2 (NMC), LiNi0.5Mn1.5O4 (LNMO) etc.) are still largely processed using organic solvents, specifically N-methyl-2-pyrrolidone (NMP), with poly(vinylidene difluoride) (PVDF) as a binder. However, the NMP-PVDF combination has many disadvantages [2]. Firstly, the binder is considerably more expensive than water-soluble binders and not easy to dispose of at the end of the battery life. Secondly, NMP is costly and toxic, and being a volatile organic compound (VOC), needs solvent recovery at commercial scale. On the other hand, water-soluble binders such as Na-carboxymethylcellulose (Na-CMC) and styrene butadiene rubber (SBR) are not only cheaper but also easier-to-recycle [3]. Additionally, the use of water as a solvent would remove the need for solvent recovery. It is then clear that switching to water-based processing for cathode materials would decrease cost and improve the environmental sustainability of LIB production. Nevertheless, aqueous cathode processing has many challenges [2], the major one being the instability of the active material in water. The leaching of Li+ ions gives rise to very high pH (~ 12) values which, in turn, leads to the corrosion of the current collector (aluminium) and gas evolution during coating. Consequently, electrodes usually show cracks and pinhole defects and exhibit poor flexibility. These issues are even more enhanced for thick coatings, which are needed to achieve high energy density cells. Therefore, the electrochemical performance of water-based cathode electrodes is generally poorer than that for NMP-based electrodes.
In this work, the effect of additions of phosphoric acid (H3PO4) on slurry rheology, adhesion strength, electrode morphology and the electrochemical performance of Ni-rich NMC cathodes prepared via water-based processing was investigated. To effectively bridge the gap between lab-scale investigations and industrially applicable procedures, pH control of the slurries and roll-to-roll electrode coating were performed at the pilot scale, and only electrodes exhibiting commercially relevant areal capacities (~ 4-4.5 mAh cm-2), high active material contents (> 90%) and low binder amounts (3 wt.%) were investigated. Phosphoric acid was added in amounts between 1.5 and 3 wt.%, and a fast-mixing procedure was developed to minimize the contact time between the NMC particles and water. The pH evolution over time showed that at least 2 wt.% of H3PO4 is required to keep the pH below the corrosion threshold of aluminium (pH < 9) for 6-8 hours, which is a usual time scale for industrial electrode processing. All slurries showed shear thinning behaviour with the viscosity of the water-based slurries being slightly lower than that for NMP-based slurries at the shear rate used for coating. Optical micrographs of coated electrodes showed no evidence of defects or agglomerates and good homogeneity. The adhesion to the current collector decreased with increasing amount of acid, e.g., electrodes prepared using 3 wt.% H3PO4 showed cracks at the edges of the coating and delamination.The long-term performance and rate capability of the electrodes were investigated in full-cell configuration vs graphite (coin-cell setup). NMC cathodes prepared with 1.5 wt.% acid showed a specific capacity of around 180 mAh g-1 at C/10 and 165 mAh g-1 at C/3. The specific capacity of the cells decreased with increasing amount of acid. The water-based and NMP electrodes retained around 50% and 60% of the initial capacity at 1C, respectively. Furthermore, electrodes prepared with 1.5 wt.% and 2.25 wt.% acid achieved a capacity retention above 90% after 500 cycles, which is comparable to NMP-based electrodes. In a further step, the production of the electrodes was upscaled in order to manufacture NMC/graphite pouch cells of 10 Ah capacity. These cells showed excellent cycling stability, reaching 80% SoH after 1500 cycles.
References:
[1] I. Tsiropoulos et al., Publ. Off. Eur. Union, no. December, pp. 1–72, 2018.
[2] R. Sahore et al., ACS Sustain. Chem. Eng., vol. 8, no. 8, pp. 3162–3169, 2020.
[3] D. Bresser et al, Energy Environ. Sci., vol. 11, no. 11, pp. 3096–3127, 2018.