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Development of magnesium sulfur battery is accompanied with all known difficulties present in Li–S batteries, however with even more limited choice of electrolytes. In the present work, the influence of current collector on electrochemical mechanism was investigated in light of different reports where improved behavior was ascribed to electrolyte. Notable differences in cycling behavior are reported when Al current collector is replaced by Cu current collector independent of electrolyte. The initial reduction of sulfur follows similar reaction path no mater of current collector, but formation of MgS can be in competition with formation of CuS in the presence of Cu cations. With the subsequent cycling cells prepared from cathodes deposited on Cu current collector show decrease in the voltage and formation of single plateau during cycling. The change corresponds to the involvement of Cu into the reaction and formation of redox couple Mg/CuS as determined by Cu K-edge XANES measurements. Corrosion of Cu foil is identified by SEM and serves as a source of Cu cations for the chemical reaction between Cu and polysulfides. Mg/CuS redox couple shows improved cycling stability, but theoretical energy density is severely reduced due to substitution of S with CuS as cathode active material. Image 1 • Influence of current collectors on electrochemistry of Mg–S battery is shown. • Increased stability and rate capability can be achieved with Cu current collector. • Formation of CuS was confirmed when using Cu current collector. • Severe degradation of Cu current collector was observed in different electrolytes. • Cu current collectors can not be used in combination with sulfur cathode. [ABSTRACT FROM AUTHOR]