A simple glass cell has been constructed for in situ Raman characterization of discharge products in Li/SOCl2 batteries with polyvinyl chloride (PVC) and LiAl(SO3Cl)(4) additives. The assembly enables the characterization of catholyte-soluble discharge products in the electrolyte as well as products on the lithium and carbon electrode surfaces. The effect of the additives was also examined by scanning electron microscoyy/energy dispersive spectroscopy and impedance spectroscopy and correlated to the voltage delay in batteries. The best results, as regards to the elimination of the delay effect, were obtained with a new electrolyte consisting of LiAlCl4/SOCl2 with an admixture of PVC and LiAl(SO3Cl)(4).