image: (a) Irreversible structural changes were observed on the surface after 150 charge/discharge cycles within the voltage range in which the quasi-conversion reaction occurs. (b) The original layered structure was preserved even after 150 cycles within a more stable voltage range. (c) When high nickel pouch-type cells were cycled more than 250 times at 1.9 V (where the quasi-conversion reaction occurs) and 3.15 V (where it does not), capacity retention improved significantly solely by adjusting the discharge cutoff voltage. (d) Increasing the discharge voltage effectively suppressed oxygen loss and subsequent side reactions at the surface, resulting in a significant reduction in the evolution of gases (CO, CO₂, CH₄, and C₂H₄).
Credit: POSTECH
A research team (including Researcher Seungyun Jeon and Dr. Gukhyun Lim) led by Professor Jihyun Hong from the Department of Battery Engineering at POSTECH (Pohang University of Science and Technology), in collaboration with Professor Jongsoon Kim’s group at Sungkyunkwan University, has identified a previously unknown degradation mechanism that occurs during the use of lithium-ion batteries. Their groundbreaking findings have been published as a cover article in Advanced Energy Materials, a leading international journal in the field of energy materials.
Lithium-ion batteries, which are essential for electric vehicles typically use nickel-manganese-cobalt (NMC) ternary cathodes. To reduce costs, recent industry trends have favored increasing the nickel content while minimizing the use of expensive cobalt. However, higher nickel content tends to shorten the overall cycle life of the battery.
Until now, battery performance degradation was primarily attributed to overcharging. However, this explanation failed to account for degradation occurring under seemingly stable voltage conditions. The research team focused on the discharging process—the actual operation of the battery—to solve this mystery.
They discovered that when a battery is used for extended periods without recharging, a phenomenon known as the “quasi-conversion reaction” occurs on the cathode surface. During this reaction, oxygen escapes from the surface and combines with lithium to form lithium oxide (Li₂O) during discharge, particularly around 3.0V. This compound further reacts with the electrolyte, generating gas and accelerating battery degradation.
The quasi-conversion reaction was found to be more severe in high nickel cathodes. The research team confirmed that when batteries are used until most of their capacity is depleted, the effects of the degradation process including battery swelling, become increasingly pronounced.
Importantly, the study also revealed a simple yet effective solution. The research team significantly extended cycle life by optimizing battery usage and avoiding full discharge. In experiments with high-nickel batteries (containing over 90% nickel), those discharged deep enough to trigger the quasi-conversion reaction retained only 3.8% of their capacity after 250 cycles, whereas batteries with controlled usage maintained 73.4% of their capacity even after 300 cycles.
Prof. Jihyun Hong, who led the research, stated, “The impact of discharge—the actual process of using a battery—has been largely overlooked until now,” and added, “This research presents an important direction for the developing longer-lasting batteries.”
This research was supported by the Korea Institute for Advancement of Technology (KIAT) through the Ministry of Trade, Industry & Energy (MOTIE) (HRD Program for Industrial Innovation). It was also funded by the Korea Planning & Evaluation Institute of Industrial Technology (KEIT).
Journal
Advanced Energy Materials
Article Title
Reduction-Induced Oxygen Loss: the Hidden Surface Reconstruction Mechanism of Layered Oxide Cathodes in Lithium-Ion Batteries
Article Publication Date
16-Jan-2025