Developing new techniques to synthesize layered cathode materials for lithium-ion batteries
Authors:   , Hamad Khaleel Idan 
Published: April 2021

Many synthesis techniques like sol-gel, co-precipitation, hydrothermal, pyrolysis, and many more have been used to synthesize batteries' active electrode materials. High surface area cathode materials with smaller nanoparticles are favored for their higher reactivity compared to materials with particles of larger size. Sol-gel and co-precipitation methods have been primarily adopted because they can produce the desirable particle size easily and on a large scale. This dissertation details an efficient and cost-effective process for using a newly developed sol-gel method that uses glycerol solvent instead of the conventionally used water. Glycerol has three hydroxyl groups (OH) instead of one in water. These can play an important role in nanoparticle formation at earlier stages by speeding up the reaction. One of the main reasons for capacity fade in batteries is cationic mixing between Ni2+ and Li+. This results in blocking of the Li+ path and ultimately poor cyclability. This capacity fade has been successfully minimized in our current work by taking advantage of the high heat released from glycerol to get partially crystalline nanoparticles that could mitigate cationic mixing at high temperatures. The first cathode material synthesized using glycerol solvent was LiMn1/3Ni1/3Co1/3O2 (LMNC) layered oxide cathode material. Temperature's effects on the particles' morphologies, sizes, and electrochemical performances have been studied at four different temperatures. LMN2 was annealed at 900 ï¿½C/8hr and shows desirable particles size of ~ 0.3 (ï¿½_m), an initial discharge capacity of 177.1 mAh/g in the first cycle, and a superior capacity retention of 83.7% after 100 cycles. The process takes eight hours, rather than >12hr when using other solvents to prepare LMNC material at high temperatures. The results also demonstrate the higher stability and lower cationic mixing after 100 cycles. To increase capacity and voltage, lithium-rich cathode materials with the formula Li1.2Mn0.51Ni0.145+xCo0.145-xO2 (x = 0 (LR2), 0.0725 (LR1)) have been successfully synthesized. In this material, cobalt (Co) content has been decreased by half and the larger produced particles have suppressed the total activation of Li2MnO3 phase in the first charge cycle. The specific discharge capacity retention of LR1 at 1C between 2 and 4.8 V was more than 100% after 100 cycles. Further improvements to LR1 cathode materials have led to an increase in the initial discharge capacity to 248 mAh/g at 0.1C. This is achieved by using an equimolecular combination of acetate and nitrate salt anions (LRACNI) with cornstarch. Cornstarch acts as a capping agent with the nitrate salt anions, and a gelling agent with acetate based anions. LRACNI shows an intermediate particle size with satisfactory capacity retention upon cycling and the lowest cationic mixing. LiNi0.8Co0.15Al0.05O2 (NCA) is one of the most commercialized cathode materials for lithium-ion batteries. It is challenging to have a high Ni content with Li in one combination electrode because cationic mixing increases proportionally. The use of glycerol has diminished the cationic mixing. High capacity retentions of 97% at 1C after 50 cycles, 87.6% at 0.3C after 100 cycles, and 93.6% at 0.1C after 70 cycles have been successfully achieved, which are better than those previously reported.