NASA's Mars Rovers, Spirit and Opportunity, have been roving on the surface of Mars, capturing impressive images of its terrain and analyzing the drillings from Martian rocks, to answer the ever -puzzling questions of life beyond Earth and origin of our planets. These rovers are being enabled by an advanced rechargeable battery system, lithium-ion, for the first time on a space mission of this scale, for keeping the rover electronics warm, and for supporting nighttime experimentation and communications. These rover Li-ion batteries are characterized by their unique low temperature capability, in addition to the usual advantages associated with Li-ion chemistry in terms of mass, volume and energy efficiency. To enable a rapid insertion of this advanced Li-ion chemistry into flight missions, we have performed several performance assessment studies on several prototype cells over the last few years. These tests mainly focused primarily on the long-term performance characteristics, such as cycling and storage, as described in our companion paper. In addition, various tests have been performed on MER cells and engineering and proto flight batteries; under conditions relevant to these missions. For example, we have examined the performance of the cells in: a) an inverted orientation, as during integration and launch, and b) conditions of low rate discharge, between 3.0-2.5 V to support the mission clock. Likewise, we have determined the impedance of the proto-flight Rover battery assembly unit in detail, with a view to asses whether a current-limiting resistor would be unduly stressed, in the event of a shorting induced by a failed pyro. In this paper we will describe these studies in detail, as well as the performance of Li-ion batteries in Spirit and Opportunity rovers, during cruise and on Mars.