Sodium-ion-batteries (NIBs) are promising energy storage devices with advantages
like low cost and highly abundant raw materials. In order to probe the electrochemical
properties  of  NIBs,  sodium  metal  is  most  frequently  applied  as  reference  and/or
counter  electrode  in  state-of-the-art  literature.  However,  the  high  reactivity  of  the
sodium metal and its impact on the electrochemical performance is usually neglected.
In our  study,  we  demonstrate  spontaneous reactions  of sodium metal  with  organic
electrolytes and emphasize the importance of critical interpretation of electrochemical
experiments.  When  using  sodium-metal  half-cells,  decomposition  products
contaminate the electrolyte during the electrochemical measurement and can easily
lead to wrong conclusions on the stability of active materials. We prove that the cycling
stability is highly affected by these electrolyte contaminations by comparing sodium
metal  free  with  sodium  metal  containing  cells.  Interestingly,  a  more  stable  cycling
performance of the Li4Ti5O12  half-cells can be observed when replacing the Na metal
counter  and  reference electrodes  by  activated  carbon  electrodes. We attribute  this
difference  to  the altered  properties  of the electrolyte  due  to  contaminations  and to
different surface chemistries.