Khalil Amine

30 Years of Lithium-Ion Batteries

Over the past 30 years, significant commercial and academic progress has been made on Li-based battery technologies. From the early Li-metal anode iterations to the current commercial Li-ion batteries (LIBs), the story of the Li-based battery is full of breakthroughs and back tracing steps. This review will discuss the main roles of material science in the development of LIBs. As LIB research progresses and the materials of interest change, different emphases on the different subdisciplines of material science are placed. Early works on LIBs focus more on solid state physics whereas near the end of the 20th century, researchers began to focus more on the morphological aspects (surface coating, porosity, size, and shape) of electrode materials. While it is easy to point out which specific cathode and anode materials are currently good candidates for the next-generation of batteries, it is difficult to explain exactly why those are chosen. In this review, for the reader a complete developmental story of LIB should be clearly drawn, along with an explanation of the reasons responsible for the various technological shifts. The review will end with a statement of caution for the current modern battery research along with a brief discussion on beyond lithium-ion battery chemistries.

Internally Referenced DOSY-NMR: A Novel Analytical Method in Revealing the Solution Structure of Lithium-Ion Battery Electrolytes

A novel methodology is reported on the use of internally referenced diffusion-ordered spectroscopy (IR-DOSY) in divulging the solution structure of lithium-ion battery electrolytes. Toluene was utilized as the internal reference for 1H-DOSY analysis due to its exceptionally low donor number and reasonable solubility in various electrolytes. With the introduction of the internal reference, the solvent coordination ratio of different species in the electrolytes can be easily determined by 1H-DOSY or 7Li-DOSY. This new technique was applied to different carbonate electrolytes, and the results were consistent with a Fourier transform infrared (FTIR) analysis. Compared to conventional vibrational spectroscopy, this IR-DOSY technique avoids the complicated deconvolution of the spectrum and allows determination of the solvent coordination ratio of different species in electrolyte systems with two or more organic solvents.

Revealing the Rate-Limiting Li-Ion Diffusion Pathway in Ultrathick Electrodes for Li-Ion Batteries

Increasing the loading of active materials by thickening the battery electrode coating can enhance the energy density of a Li-ion cell, but the trade-off is the much reduced Li+ transport kinetics. To reach the optimum energy and power density for thick electrodes, the effective chemical diffusion coefficient of Li+ ( DLi) must be maximized. However, the diffusion of Li+ inside an electrode is a complex process involving both microscopic and macroscopic processes. Fundamental understandings are needed on the rate-limiting process that governs the diffusion kinetics of Li+ to minimize the negative impact of the large electrode thickness on their electrochemical performance. In this work, lithium Ni-Mn-Co oxide (NMC) cathodes of various thicknesses ranging from 100 to 300 μm were used as a model system to study the rate-limiting diffusion process during charge/discharge. The rate-limiting diffusion coefficient of Li+ was investigated and quantified, which was correlated to the electrochemical performance degradation of thick electrodes. It is revealed here that the under-utilization of the active material was caused by the limited diffusion of Li+ inside the porous electrode, leading to a critical electrode thickness, beyond which the specific capacity was significantly reduced.