Probing Anode Degradation in Automotive Li-ion Batteries
Open Access
- Author:
- Kwon, Ou Jung
- Graduate Program:
- Materials Science and Engineering
- Degree:
- Doctor of Philosophy
- Document Type:
- Dissertation
- Date of Defense:
- August 27, 2010
- Committee Members:
- Chao Yang Wang, Dissertation Advisor/Co-Advisor
Chao Yang Wang, Committee Chair/Co-Chair
Michael Anthony Hickner, Committee Member
Christopher Rahn, Committee Member
Donghai Wang, Committee Member - Keywords:
- Thermal effect at low temperature
Li-ion battery
Electric vehicle
Rapid charge
Lithium deposition
Anode degradation - Abstract:
- The lithium-ion battery is drawing attention as a power source for future clean and fuel-efficient vehicles. Although the Li-ion battery presently shows best performance for energy density and power density compared to other rechargeable batteries, some degradation problems still remain as key challenges for long-term durability in automotive applications. Among those problems, Li deposition is well known for causing permanent capacity loss. Fundamental mechanisms of Li deposition in the carbon anode are, however, not fully understood, especially at subzero temperature and/or under high rate charge. This dissertation introduces comprehensive study of Li deposition using automotive 18650 Li-ion cells. The mechanism and relevant diagnostic methods as well as preventive charging protocol are discussed. In part one, a new diagnostic tool is introduced utilizing 3-electrode cell system, which measures thermodynamic and kinetic parameters of cathode and anode, respectively, as a function of temperature and SOC (state of charge): open circuit potential (OCP); Li diffusion coefficient in active particles; and internal resistance. These data are employed to understand electrochemical reaction and its thermal interaction under charging conditions that result in Li deposition. Part two provides a threshold parameter for the onset of Li deposition, which is not commonly used anode potential but charge capacity, or more specifically the amount of Li+ ions participating in intercalation reaction without Li deposition at given charging circumstances. This is called the critical charge capacity in this thesis, beyond which capacity loss at normal operating condition is observed, which becomes more serious as temperature is lowered and/or charge C-rate increases. Based on these experimental results, the mechanism of Li deposition is proposed as the concept of anode particle surface saturation, meaning that once the anode particle surface is saturated with Li in any charging circumstances, no more Li+ ions can be intercalated but should be reduced to metallic form on the anode particle surface. This is validated by calculating the distribution of Li concentration inside the anode particle with electrochemical modeling. In part three, a novel pulse charge protocol is developed, which consists of two steps. First high current charge/discharge pulses increase the cell temperature from a subzero temperature up to above room temperature in a short time, and next, high current charge provides the net charge capacity. Sluggish Li diffusion at low temperature becomes fast thanks to cell temperature elevation by high current pulses (1st step), which plays a role of preventing surface saturation during high current charge (2nd step). Thus, this charge protocol is not only Li deposition-free but also leads to rapid charge at subzero temperatures.