To understand the relationship between the specific energy and power of lithium (Li)-ion batteries, the dependence of the internal resistance of porous electrodes with high loading weight on thickness was systematically investigated. The ionic resistance in pores (Rion) and chargetransfer resistance for Li intercalation (Rct) normalized per unit electrode geometric area were assessed using a combination of electrochemical impedance spectroscopy with symmetric cells and the transmission line model for cylindrical pores. The changes of Rion and Rct and their magnitude show opposite trends with respect to electrode thickness. For thin electrodes, Rion is lower than Rct. The specific power decreases slightly as the electrodes become thicker because the total internal resistance is predominantly affected by the charge-transfer resistance, and there is no delay of the response in the depth direction. In contrast, for thick electrodes, Rion is higher than or approximately equal to Rct, so there is a delay of the reaction in the depth direction. As a result, the power of the battery is dramatically reduced because the total internal resistance is strongly influenced by both Rion and Rct.

Memory effects are well known to users of nickel-cadmium and nickel-metal-hydride batteries. If these batteries are recharged repeatedly after being only partially discharged, they gradually lose usable capacity owing to a reduced working voltage. Lithium-ion batteries, in contrast, are considered to have no memory effect. Here we report a memory effect in LiFePO4-one of the materials used for the positive electrode in Li-ion batteries-that appears already after only one cycle of partial charge and discharge. We characterize this memory effect of LiFePO4 and explain its connection to the particle-by-particle charge/discharge model. This effect is important for most battery uses, as the slight voltage change it causes can lead to substantial miscalculations in estimating the state of charge of batteries.

We used a suite of transmission electron microscopy (TEM) and associated electron spectroscopy methods to examine the local structure and changes in the electronic structure of LinormalNi0.8normalCo0.15normalAl0.05normalO2 positive electrode material. We found a scattered rock-salt phase near grain surfaces and grain boundaries, where Ni3+ turned to Ni2+ , deduced from relative intensity ratios and fine structures of the L2,3 white-line peaks of the transition metals. The spatial distribution of the degraded phase throughout the secondary particle was found using a scanning TEM-electron energy loss spectroscopy spectral imaging technique and multivariate analysis. The degradation process and its relationship to the surface reactions with electrolytes is discussed based on the spatial-distribution map of the degraded phases.

No abstract

No abstract