A redox flow battery system includes a redox flow battery that has a redox flow cell and a supply/storage system. The supply/storage system has first and second electrolytes for circulation through the redox flow cell. At least the first electrolyte is a liquid electrolyte that has electrochemically active species with multiple, reversible oxidation states. A secondary cell is operable to monitor concentration of one or more of the electrochemically active species. The secondary cell has a counter electrode, a flow passage that connects the counter electrode with the redox flow battery to receive the first or second electrolyte, a working electrode, and a separator. The working electrode is isolated from receiving the electrochemically active species of the first and second electrolytes except for a transport passage connecting the flow passage and the working electrode. The transport passage limits movement of the electrochemically active species to the working electrode.