The role of triallyl phosphate as an electrolyte additive in Li(Ni0.42Mn0.42Co0.16)O-2/graphite pouch cells was studied using ex-situ gas measurements, ultra high precision coulometty, automated storage experiments, electrochemical impedance spectroscopy, long-term cycling and X-ray photoelectron spectroscopy. Cells containing triallyl phosphate produced less gas during formation, cycling and storage than control cells. The use of triallyl phosphate led to higher coulombic efficiency and smaller charge endpoint capacity slippage during ultra high precision charger testing. Cells containing triallyl phosphate showed smaller potential drop during 500 h storage at 40 degrees C and 60 degrees C and the voltage drop decreased as the triallyl phosphate content in the electrolyte increased. However, large amounts of triallyl phosphate (>3% by weight in the electrolyte) led to large impedance after cycling and storage. Symmetric cell studies showed large amounts of triallyl phosphate (5% or more) led to significant impedance increase at both negative and positive electrodes. X-ray photoelectron spectroscopy studies suggested that the high impedance came from the polymerization of triallyl phosphate molecules which formed thick solid electrolyte interphase films at the surfaces of both negative and positive electrodes. An optimal amount of 2%-3% triallyl phosphate led to better capacity retention during long term cycling. (C) 2015 Elsevier B.V. All rights reserved.