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Electrochemical strain microscopy (ESM) is a powerful atomic force microscopy (AFM) mode for the investigation of ion dynamics and activities in energy storage materials. Here we compare the changes in commercial LiFePO 4 cathodes due to ageing and its influence on the measured ESM signal. Additionally, the ESM signal dynamics are analysed to generate characteristic time constants of the diffusion process, induced by a dc-voltage pulse, which changes the ionic concentration in the material volume under the AFM tip. The ageing of the cathode is found to be governed by a decrease of the electrochemical activity and the loss of available lithium for cycling, which can be stored in the cathode.

Comparison of fresh and aged lithium iron phosphate cathodes using a tailored electrochemical strain microscopy technique