Scanning Probe Microscopy Facility for Operando Study of Redox Processes on Lithium ion Battery Electrodes

An Atomic Force Microscope (AFM) is combined with a special designed glovebox system and coupled to a Galvanostat/Potentiostat to allow measurements on electrochemical properties for battery research. An open cell design with electrical contacts makes it possible to reach the electrode surface with the cantilever so as to perform measurements during battery operation. A combined AFM-Scanning Electro-Chemical Microscopy (AFM-SECM) approach makes it possible to simultaneously obtain topological information and electrochemical activity. Several methods have been explored to provide the probe tip with an amount of lithium so that it can be used as an active element in a measurement. The "wet methods" that use liquid electrolyte appear to have significant drawbacks compared to dry methods, in which no electrolyte is used. Two dry methods were found to be best applicable, with one method applying metallic lithium to the tip and the second method forming an alloy with the silicon of the tip. The amount of lithium applied to the tip was measured by determining the shift of the resonance frequency which makes it possible to follow the lithiation process. A FEM-based probe model has been used to simulate this shift due to mass change. The AFM-Galvanostat/Potentiostat set-up is used to perform electrochemical measurements. Initial measurements with lithiated probes show that we are able to follow ion currents between tip and sample and perform an electrochemical impedance analysis in absence of an interfering Redox-probe. The active probe method developed in this way can be extended to techniques in which AFM measurements can be combined with mapping electrochemical processes with a spatial resolution.