Aqueous Manufacturing of Ni-Rich Cathodes Using Polyacrylic Acid As Binder for Lithium-Ion Batteries
Authors: Boz Buket , Vuksanovic Miljana , Neidhart Lukas , Höchtl Micheal , Fröhlich Katja , Jahn Marcus 
Published: November 2022

In the field of secondary batteries, the lithium-ion battery (LIB) is one of the most promising candidates for future electric vehicle (EV) applications, due to its high specific energy and good specific power [1]. However, to meet the demands in large scale storage, not only higher energy and power density and lower cost are needed, but environmentally friendly processing of LiBs is getting more in the focus of research.
To meet the desirable requirements, one necessity is to tune the cathode in terms of sustainable production and materials. Ni-rich layered LiNi
x
Mn
y
Co1−x−y
O2 (NMCs, x ≥ 0.8) cathodes are poised to be the dominating cathode materials for lithium-ion batteries for the foreseeable future due to its high energy density [2]. The state-of-the-art NMC based cathode production in both industrial and lab scale is with polyvinylidene fluoride (PVDF) in organic solvent N-methyl-2-pyrrolidone (NMP). NMP is a toxic, expensive, and highly flammable organic solvent [3]. Replacing NMP with water in the production of LiB cathodes is critical in terms of process cost savings and environmental concerns. Aqueous processes of NMC based cathodes are highly favorable as well as challenging due to the high reactivity of NMC particles. During the slurry preparation, the surface of Ni-rich particles undergoes Li leaching via exchange between H+ from water and Li+ from the active material which leads to increase in pH of the slurry. Li leaching leads to capacity fade and reduces the specific capacity of the cathode. The high pH of the slurry causes corrosion on the aluminum current collector. Surface treatment of NMC particles is a way to prevent Li leaching as well as using carbon coated Al current collector to resist the corrosion, but in terms of production cost these methods are not favorable.
In this study, our fundamental aim is to demonstrate the manufacturing of large scale water based NMC811-PAA cathodes. We therefore employ a well-known binder material, polyacrylic acid (PAA), which is water soluble and an anionic polymer. During the mixing processes of the slurry, H+ from PAA can drive Li+ leaching, the leached Li+ reacts with carboxylic groups of PAA and binds to the PAA backbone. Thus, the reaction of H+ and OH- neutralizes the pH of the slurry. Bonded Li+ on PAA creates an active binder in which these Li ions can participate as an additional Li source to aid to prevent capacity decrease. This method has been successfully implemented in the lab scale [4]. Our main target is to investigate the slurry behavior and scalability of the cathodes with a PAA binder. Herein, we report high solid content of slurry behavior of NMC with PAA and the comparison to the conventionally produced slurry for the first time. Also, we show how the slurry behavior is affected by the mixing techniques from lab scale to pilot scale, which is an important parameter for later transfer to industrial production. The electrodes and successfully formed LiPAA as binder are shown by Fourier transformed infrared (FTIR) and Raman spectroscopy. The electrochemical tests are performed both in half and full cell configuration for NMC811-PAA and NMC811-PVDF cathodes.

References

[1] Tao, Yanqiu, et al. "Second life and recycling: Energy and environmental sustainability perspectives for high-performance lithium-ion batteries." Science advances 7.45 (2021): eabi7633. https://doi.org10.1126/sciadv.abi7633.
[2] Lu, Yanying, et al. "Single‐crystal LiNixMnyCo1− x− yO2 cathodes for extreme fast charging." Small 18.12 (2022): 2105833. https://doi.org/10.1002/smll.202105833.
[3] Zou, Feng, and Arumugam Manthiram. "A review of the design of advanced binders for high‐performance batteries." Advanced Energy Materials 10.45 (2020): 2002508. https://doi.org/10.1002/aenm.202002508.
[4] Hawley, W. Blake, Harry M. Meyer III, and Jianlin Li. "Enabling aqueous processing for LiNi0. 80Co0. 15Al0. 05O2 (NCA)-based lithium-ion battery cathodes using polyacrylic acid." Electrochimica Acta 380 (2021): 138203. https://doi.org/10.1016/j.electacta.2021.138203.