Diagnosis of the Lifetime Performance Degradation of Lithium-Ion Batteries : Focus on Power-Assist Hybrid Electric Vehicle and Low-Earth-Orbit Satellite Applications
Lithium-ion batteries are a possible choice for the energy storage system onboard hybrid electric vehicles and low-earth-orbit satellites, but lifetime performance remains an issue. The challenge is to diagnose the effects of ageing and then investigate the dependence of the magnitude of the deterioration on different accelerating factors (e.g. state-of-charge (SOC), depth-of-discharge (DOD) and temperature).Lifetime studies were undertaken incorporating different accelerating factors for two different applications: (1) coin cells with a LixNi0.8Co0.15Al0.05O2-based positive electrode were studied with a EUCAR power-assist HEV cycle, and (2) laminated commercial cells with a LixMn2O4-based positive electrode were studied with a low-earth-orbit (LEO) satellite cycle. Cells were disassembled and the electrochemical performance of harvested electrodes measured with two- and three-electrode cells. The LixNi0.8Co0.15Al0.05O2-based electrode impedance results were interpreted with a physically-based three-electrode model incorporating justifiable effects of ageing.The performance degradation of the cells with nickelate chemistry was independent of the cycling condition or target SOC, but strongly dependent on the temperature. The positive electrode was identified as the main source of impedance increase, with surface films having a composition that was independent of the target SOC, but with more of the same species present at higher temperatures. Furthermore, impedance results were shown to be highly dependent on both the electrode SOC during the measurement and the pressure applied to the electrode surface. An ageing hypothesis incorporating a resistive layer on the current collector and a local contact resistance (dependent on SOC) between the carbon and active material, both possibly leading to particle isolation, was found to be adequate in fitting the harvested aged electrode impedance data.The performance degradation of the cells with manganese chemistry was accelerated by both higher temperatures and larger DODs. The impedance increase was small, manifested in a SOC-dependent increase of the high-frequency semicircle and a noticeable increase of the high-frequency real axis intercept. The positive electrode had a larger decrease in capacity and increase in the magnitude of the high-frequency semi-circle (particularly at high intercalated lithium-ion concentrations) in comparison with the negative electrode. This SOC-dependent change was associated with cells cycled for either extended periods of time or at higher temperatures with a large DOD. An observed change of the cycling behaviour in the second potential plateau for the LixMn2O4-based electrode provided a possible kinetic-based explanation for the change of the high-frequency semi-circle.
School:Kungliga Tekniska högskolan
Source Type:Doctoral Dissertation
Keywords:NATURAL SCIENCES; Chemistry; Analytical chemistry; Electrochemistry; lithium-ion battery; LixNi0.8Co0.15Al0.05O2; LixMn2O4; LiyC6; ageing; three-electrode measurements; impedance modelling; surface film characterisation; hybrid electric vehicle; low-earth-orbit satellite; litiumjonbatteri; åldring; treelektroduppställning; impedansmodell; ytfilmskarakterisering; hybridfordon; satelliter
Date of Publication:01/01/2008