Hou, JingGirod, RobinNianias, NikolaosShen, Tzu-HsienFan, JialiangTileli, Vasiliki2020-07-302020-07-302020-07-302020-01-0810.1149/1945-7111/ab9eeahttps://infoscience.epfl.ch/handle/20.500.14299/170454WOS:000549363700001Electrochemical liquid-phase transmission electron microscopy (TEM) is showing excellent promise in fundamental studies of energy-related processes including lithium-ion battery (LIB) cycling. A key requirement to accurately interpret the measurements and acquire quantitative information is the implementation of a reliable reference electrode. Quasi-reference electrodes (QRE) remain commonly used due to microfabrication constraints of the electrochemical cell, however, they typically yield dramatic potential drifts making the electrochemical results inconclusive. Here, we present a method of producing a stable and readily interpretable lithium-gold alloy micro-reference electrode, which exhibits a reference potential of 0.1 V vs Li/Li+. We first examine the feasibility of electrochemically alloying a pristine gold electrode, patterned on a chip forin situTEM, using a benchtop setup, and investigate various sources to support the lithiation. We confirm the presence of the Li-Au alloy using chronopotentiometry (CP) and open circuit voltage (OCV) measurements, and by scanning electron microscopy (SEM), electron energy loss spectroscopy (EELS) and high-resolution (HR) TEM. Finally, we apply this methodologyin situand use LiFePO(4)as a model cathode material to demonstrate the merit of the Li-Au alloy reference electrode for obtaining reproducible cyclic voltammetry (CV) measurements on a liquid cell microelectrode system.ElectrochemistryMaterials Science, Coatings & FilmsElectrochemistryMaterials Sciencein situtemlithium-ion batteryreference electrodeli-au alloyin-situelectrochemical measurementsanodeslifepo4lipf6fepo4text::journal::journal article::research article