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Electrode degradation in LiFePO 4 /mesocarbon microbead graphite (MCMB) pouch cells aged at 55 °C by a synthetic hybrid drive cycle or storage is diagnosed and put into context with previous results of aging at 22 °C. The electrode degradation is evaluated by means of electrochemical impedance spectroscopy (EIS), measured separately on electrodes harvested from the cells, and by using a physics-based impedance model for aging evaluation. Additional capacity measurements, scanning electron microscopy (SEM), and energy dispersive X-ray spectroscopy (EDX) are used in the evaluation. At 55 °C the LiFePO 4 electrode shows increased particle/electronic conductor resistance, for both stored and cycled electrodes. This differs from results obtained at 22 °C, where the electrode suffered lowered porosity, particle fracture, and loss of active material. For graphite, only cycling gave a sustained effect on electrode performance at 55 °C due to lowered porosity and changes of surface properties, and to greater extent than at low temperature. Furthermore, increased current collector resistance also contributes to a large part of the pouch cell impedance when aged at increased temperatures. The result shows that increased temperature promotes different degradation on the electrode level, and is an important implication for high temperature accelerated aging. In light of the electrode observations, the correlation between full-cell and electrode impedances is discussed. [ABSTRACT FROM AUTHOR]

Abstract: This study investigates aging in LiFePO4/mesocarbon microbead graphite cells that have been subjected to either a synthetic hybrid drive cycle or calendar aging, at 22°C. The investigation involves detailed examination and comparison of harvested fresh and aged electrodes. The electrode properties are determined using a physics-based electrochemical impedance spectroscopy (EIS) model that is fitted to three-electrode EIS measurements, with input from measured electrode capacity and scanning electrode microscopy (SEM). Results from the model fitting provide a detailed insight to the electrode degradation and is put into context with the behavior of the full cell aging. It was established that calendar aging has negligible effect on cell impedance, while cycle aging increases the impedance mainly due to structural changes in the LiFePO4 porous electrode and electrolyte decomposition products on both electrodes. Further, full-cell capacity fade is mainly a consequence of cyclable lithium loss caused by electrolyte decomposition. [Copyright &y& Elsevier]

Abstract: This study presents an extensive characterization of a standard Li-ion battery (LiB) electrolyte containing different concentrations of the flame retardant triphenyl phosphate (TPP) in the context of high power applications. Electrolyte characterization shows only a minor decrease in the electrolyte flammability for low TPP concentrations. The addition of TPP to the electrolyte leads to increased viscosity and decreased conductivity. The solvation of the lithium ion charge carriers seem to be directly affected by the TPP addition – as evidenced by Raman spectroscopy and increased mass-transport resistivity. Graphite/LiFePO4 full cell tests show the energy efficiency to decrease with the addition of TPP. Specifically, diffusion resistivity is observed to be the main source of increased losses. Furthermore, TPP influences the interface chemistry on both the positive and the negative electrode. Higher concentrations of TPP lead to thicker interface layers on LiFePO4. Even though TPP is not electrochemically reduced on graphite, it does participate in SEI formation. TPP cannot be considered a suitable flame retardant for high power applications as there is only a minor impact of TPP on the flammability of the electrolyte for low concentrations of TPP, and a significant increase in polarization is observed for higher concentrations of TPP. [Copyright &y& Elsevier]