This paper discusses the possible application of an innovative set of binary sequences, the De Bruijn ones, for spread spectrum applications, in which it may be useful to have a quite huge set of sequences to allocate different users, in order to avoid interference among them. The sequences are evaluated and compared to more traditional sets (Gold and Chaotic sequences) by means of the Periodic Ambiguity Function tool, and in a specific scenario related to the Entry, Descent and Landing stage of a Mars rover. The scenario is selected based on the critical Doppler phenomena it involves on signals transmitted from the lander to the Earth. Simulations show that De Bruijn sequences provide Doppler and Range performance comparable to those of the other sets, with the advantage of a much greater cardinality.