The use of hybrid cyclic phosphazene polymer/graphite anodes, where the phosphazene serves as distributed loci for Li deposition, has been investigated. Capacity within the hybrid system was found to occur reversibly in distinct regions. At the most positive voltages, above 0.06 V vs Li/Li+, the capacity was associated mostly with Li+ intercalation into graphite. In the most negative region, deposition of Li within the polymer was the predominate mechanism. A transitional region is inferred by the data whereby bulk aggregation or clustering of Li atoms occurs in proximity to the phosphazene sites that then serve as a template for more widespread population of Li within the anode at higher voltages, akin to a nucleation process. In full cells with a mixed oxide cathode, controlling the extent of Li deposition by limiting the charging voltage to 4.45 V enabled repeated cycling with no loss in capacity. Capacities as high as 183 mAh g(-1) have been achieved for systems containing as little as 10% graphite while retaining coulombic efficiencies of 98% over 50 cycles. This level of cycling equates to the deposition of 7.4 Li per cyclic phosphazene. (C) 2014 Elsevier B.V. All rights reserved.