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Recent developments and advances in energy storage technologies are making the application of energy storage technologies a viable solution to power system applications. This paper addresses the economical aspects of Vanadium Redox Battery (VRB) energy storage participation in competitive electricity markets as a power producer. The costs including installation, operation & maintenance and the revenues containing energy price, reducing transmission access cost and deferring facility investment are among economic parameters considered here. In order to achieve this goal, an appropriate self-scheduling approach must be developed to determine its maximum potential of expected profit among multi-markets such as energy and ancillary service markets. The profit maximization problem faced by the VRB is therefore an optimal scheduling problem that is formulated as a mixed-integer non-linear programming (MINLP) problem. Numerical studies have been conducted to evaluate the proposed approach.