Coulometric ion sensing with Li+-selective LiMn2O4 electrodes

[Display omitted] •A new constant potential coulometric method based on ISM-free SC-ISE was proposed.•LiMn2O4 was used as a combined ion-recognition and signal-transduction layer.•The sensor has exhibited excellent signal amplification for detecting small Li+ activity changes. A coulometric signal readout method, which was originally developed for solid-contact ion-selective electrodes, was investigated in this work using LiMn2O4 (LMO) as a combined ion-recognition and signal-transduction layer. The redox process of LMO, which is associated with reversible intercalation/expulsion of Li+ ions, allowed coulometric sensing of Li+ ions in aqueous solutions. On increasing the active area (mass loading) of LMO, the coulometric signal increased for a given change in Li+ ion activity. The excellent redox reversibility of LMO and its relatively low resistance were instrumental in achieving a high signal amplification together with a relatively fast response. Coating the LMO layer with a conventional Li+-selective plasticized PVC membrane was found to dramatically lower the coulometric response. Hence, the application of LMO as a combined Li+-selective electrode material and ion-to-electron transducer was found to be highly compatible with the coulometric signal readout method, especially for detecting small Li+ activity changes at high Li+ concentrations.