Improved Cycle Life and Determination of Li Ion Transport Parameters in Mixed Cation Doped Ni-Rich NMC
Authors: Williams Ethan , Kendrick Emma 
Published: February 2024

Ni-rich Li-ion cathode materials like NMC-9.5.5 (LiNi0.9Mn0.05Co0.05O2) are of interest due to their higher energy density and limited cobalt content, aiding the transition away from critical raw materials, when compared to materials like NMC111 - 622. This has the advantage of reducing production costs while maintaining a high working voltage and capacity. However, the high nickel content of these materials can be detrimental due to disorder brought by Li+/Ni2+ cation mixing, lithium residuals, and irreversible phase changes during operation resulting in significant capacity fade during cycling. Similarly, the different synthesis methods and treatments drastically affect the morphological, structural, and electrochemical properties
We present a structural and electrochemical study of NMC-9.5.5 prepared at scale via a hydroxide coprecipitation synthesis in a 5 L continuous stirred reactor tank (CSTR). In this work, bulk doping and co-doping with two metal cations are investigated with a simple and scalable method to achieve mixed metal and mixed valence doped NMC-9.5.5 with the aim to further improve cycle life and stability. Additionally, the effect of bulk doping on the thermodynamic and kinetic properties of the cathode material are investigated in both half-cells and full-cells using galvanostatic intermittent titration technique (GITT) and electrical impedance spectroscopy (EIS), where a 3-electrode configuration is used to elucidate the individual electrode potentials and stoichiometries.
The bulk doping of the transition metal layer was found to significantly reduce the capacity fade in the NMC-9.5.5, increasing the capacity retention after 100 cycles from 78% in the undoped material to 92% and 89% in the doped and co-doped NMC-9.5.5 half-cells. The mixed metal co-doped material was also effective in delivering a higher specific capacity than the baseline throughout the full cycling range. The improved cycling performance can be understood by the inspection of the differential capacity plots, which show a suppression of the H2-H3 irreversible phase transition in the doped material and stabilisation of the peak to a higher voltage compared to the baseline. The effect of doping on the structural stabilisation is similarly reflected in the XRD characterisation, in which the introduction of the metal cation acts to constrain the detrimental Li+/Ni2+ cation mixing due to a widening of the transition metal channel. This is also supported by the EXAFS characterisation that indicate the dopants may act to stabilise the local Ni environment. These structural changes appear to be further beneficial in facilitating improved Li ion transport properties in the doped material as evidenced by the lower charge transfer resistances during cycling and increased diffusion coefficient.
This research illustrates the high capacity performance of low cobalt cathode materials thus reducing the reliance on critical materials, as well as the ability to produce Ni-rich cathode material at large scale and further stabilise its cycle life by simple structural engineering. Improved materials manufacturing processes will enable a greater understanding of the synthesis process and enable more sustainable methods of synthesis. There are also benefits for cell makers with improvement in processability and additional stabilisation knowledge for battery manufacturers, as well as the consumers that benefit from longer driving ranges and battery life in their EV’s.

Figure 1