DOE OSTI2011
Path dependence is emerging as a premier issue of how electrochemical cells age in conditions that are diverse and variable in the time domain. For example, lithium-ion cells in a vehicle configuration will experience a variable combination of usage and rest periods over a range of temperature and state of charge (SOC). This is complicated by the fact that some aging can actually become worse (or better) when a lithium-ion cell is idle for extended periods under calendar-life (calL) aging, as opposed to cycle-life (cycL) conditions where the cell is used within a predictable schedule. The purpose of this study is to bridge the gap between highly idealized and controlled laboratory test conditions and actual field conditions regarding PHEV applications, so that field-type aging mechanisms can be mimicked and quantified in a repeatable laboratory setting. The main parameters are the magnitude and frequency of the thermal cycling, looking at isothermal, mild, and severe scenarios. To date, little is known about Li-ion aging effects caused by thermal cycling superimposed onto electrochemical cycling, and related path dependence. This scenario is representative of what Li-ion batteries will experience in vehicle service, where upon the typical start of a HEV/PHEV, the batteries will be cool or cold, will gradually warm up to normal temperature and operate there for a time, then will cool down after the vehicle is turned off. Such thermal cycling will occur thousands of times during the projected life of a HEV/PHEV battery pack. We propose to quantify the effects of thermal cycling on Li-ion batteries using a representative chemistry that is commercially available. The secondary Li-ion cells used in this study are of the 18650 configuration, have a nominal capacity rating of 1.9 Ah, and consist of a {LiMn2O4 + LiMn(1/3)Ni(1/3)Co(1/3)O2} cathode and a graphite anode. Electrochemical cycling is based on PHEV-relevant cycle-life protocols that are a combination of charge depleting (CD) and charge sustaining (CS) modes discussed in the Battery Test Manual for Plug-in Hybrid Electric Vehicles (INL, March 2008, rev0). A realistic duty cycle will involve both CD and CS modes, the proportion of each defined by the severity of the power demands. We assume that the cells will start each cycling day at 90% SOC, and that they will not be allowed to go below 35% SOC, with operation around 70% SOC being a nominal condition. The 35, 70, and 90% SOC conditions are also being used to define critical aspects of the related reference performance test (RPT) for this investigation. There are three primary components to the RPT, all assessed at room temperature: (A) static and residual capacity (SRC) over a matrix of current, (B) kinetics and pulse performance testing (PPT) over current for SOCs of interest, and (C) EIS for SOCs of interest. The RPT is performed on all cells every 30 day test interval, as well as a pulse-per-day to provide a quick diagnostic snapshot. Where feasible, we utilize various elements of Diagnostic Testing (DT) to characterize performance of the cells and to gain mechanistic-level knowledge regarding both performance features and limitations. We will present the rationale behind the experimental design, early data, and discuss the fundamental tools used to elucidate performance degradation mechanisms.