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This design has proved reliable form 70 charge/discharge cycles at 80 mA cm–2 [255], during which the overall energy efficiency was 75%. Later, the same group demonstrated the feasibility of Zn electrodeposition on a 3-D porous nickel foam electrode [238]. This type of electrode material limits the operational negative electrode current density to values just over 50 mA cm–2. Below this value, uniform Zn deposits were observed on the substrate but, as the current density increases, spongy and dendritic deposits are formed instead. Nanostructured materials have been applied to increase the capacity of the Zn-Ni system by extending the surface area of the nickel electrode. Zhang et al. [258] have filed a patent for the implementation of double bilayer nanotubes as positive electrode material. The nanotubes comprised a zinc oxide inner structure covered by a nickel hydroxide layer. The energy density of the battery was claimed to be enhanced by approximately 10%. He et al. [260] have recently studied the use of a positive electrode consisting of nickel tubes with a wall thickness of 0.6 mm and an inner diameter of 5 mm. This was found the have a specific capacity of 35.7 mA h cm–2 and retained 82% of this capacity after 480 cycles. The reported coulombic and energy efficiencies were quite high, at 96.0% and 83.8% respectively. 5.3 Cell developments The membrane-free Zn-Ni RFB system was first proposed by a Chinese group in 2007 [27]. A concept cell was presented, with a cell potential over 1.6 V and an overall efficiency over 85%. This cell design was later improved by employing cadmium electroplated nickel as negative electrode [236], which resulted in energy efficiencies of 88% over 220 cycles. A second Chinese group patented nanostructured materials for the positive electrode (see section 5,2) [258] and subsequently developed a serpentine flow-field Zn-Ni RFB with a power density of 83 W kg–1, which sustained an energy efficiency of 80% over 200 charge/discharge cycles [254, 255]. The effect of temperature over this cell was also studied [257], showing 47PDF Image | hybrid redox flow batteries with zinc negative electrodes
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