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Figure 1. Characterization of pristine ZnO-ALD-E: (a) X-ray diffraction pattern; (b) Room temperature photoluminescence (PL) spectra, indicating sharp near band edge (NBE) and broad deep level (DLE) emissions; (c) and (d) FESEM image of ZnO-ALD-E in two different magnifications.

Figure 1 Characterization of pristine ZnO-ALD-E: (a) X-ray diffraction pattern; (b) Room temperature photoluminescence (PL) spectra, indicating sharp near band edge (NBE) and broad deep level (DLE) emissions; (c) and (d) FESEM image of ZnO-ALD-E in two different magnifications.

Related Figures (7)

Figure 2. Electrochemical characterizations of Al/ZnO-ALD-E batteries. (a) Initial discharge/charge curves of ZnO-ALD-E1 at a current density of 400 mA g~'. (b) Galvanostatic discharge-charge profiles of ZnO-ALD-E1 at a current density of 400 mA g™' for the 4% 5" and 8 cycle. (c) Cyclic voltammogram (CV) of ZnO- ALD-E1 for the 4", 5" and 8" cycle at the scan rate of 0.1 mV s~'. (d) Cycle performance and Coulombic Efficiency plot of ZnO-ALD-E1 from the second cycle onwards at a current density of 400 mA g™'. All capacity calculations are based on the mass of ZnO. (e) Representation of ALD grown binder-free ZnO cathode, ZnO-ALD-E1. Optical image of the steel current collector (SS) before and after the growth of thin ZnO film by ALD technique and the open circuit potential of the Al/ZnO-ALD-E battery; corresponding assembled coin cell by the series connection of three Al/ZnO-ALD-E1 batteries, which lights up an LED indicator (f).
Figure 2. Electrochemical characterizations of Al/ZnO-ALD-E batteries. (a) Initial discharge/charge curves of ZnO-ALD-E1 at a current density of 400 mA g~'. (b) Galvanostatic discharge-charge profiles of ZnO-ALD-E1 at a current density of 400 mA g™' for the 4% 5" and 8 cycle. (c) Cyclic voltammogram (CV) of ZnO- ALD-E1 for the 4", 5" and 8" cycle at the scan rate of 0.1 mV s~'. (d) Cycle performance and Coulombic Efficiency plot of ZnO-ALD-E1 from the second cycle onwards at a current density of 400 mA g™'. All capacity calculations are based on the mass of ZnO. (e) Representation of ALD grown binder-free ZnO cathode, ZnO-ALD-E1. Optical image of the steel current collector (SS) before and after the growth of thin ZnO film by ALD technique and the open circuit potential of the Al/ZnO-ALD-E battery; corresponding assembled coin cell by the series connection of three Al/ZnO-ALD-E1 batteries, which lights up an LED indicator (f).
Figure 3. (a) Initial discharge/charge curve of ZnO nano-E and ZnO bulk-E at a current density of 100 mA g~'. (b) Cycle performance of ZnO nano-E and ZnO bulk-E at a current density of 100 mA g~'. (c) Galvanostatic discharge- charge profiles of ZnO-ALD-E, ZnO nano-E and ZnO bulk-E for the 6" cycle. ZnO nano-E and ZnO bulk-E, with respect to ZnO-ALD-E as cathodes (shown in Figure 2d). The discharge/charge capacity for a given cycle (e.g., the sixth cycle) of the cells using ZnO- ALD-E, ZnO nano-E and ZnO bulk-E as the cathode are shown in Figure 3c, for the comparison purpose. ZnO nano-E and ZnO bulk-E delivered an initial discharge capacity 226 mAh g' and 59 mAh g' respectively as cathodes in Al-ion batteries, much lesser (order of magnitude less) than that of cell fabricated using ZnO-ALD-E as the cathode. The discharge voltage plateau at about 0.45 V in the galvanostatic discharge curves of the ZnO-ALD-E cathode is much higher than that of the ZnO nano-E and ZnO bulk-E cathodes. This improvement is attributed to the properties of the binder-free cathode, as
Figure 3. (a) Initial discharge/charge curve of ZnO nano-E and ZnO bulk-E at a current density of 100 mA g~'. (b) Cycle performance of ZnO nano-E and ZnO bulk-E at a current density of 100 mA g~'. (c) Galvanostatic discharge- charge profiles of ZnO-ALD-E, ZnO nano-E and ZnO bulk-E for the 6" cycle. ZnO nano-E and ZnO bulk-E, with respect to ZnO-ALD-E as cathodes (shown in Figure 2d). The discharge/charge capacity for a given cycle (e.g., the sixth cycle) of the cells using ZnO- ALD-E, ZnO nano-E and ZnO bulk-E as the cathode are shown in Figure 3c, for the comparison purpose. ZnO nano-E and ZnO bulk-E delivered an initial discharge capacity 226 mAh g' and 59 mAh g' respectively as cathodes in Al-ion batteries, much lesser (order of magnitude less) than that of cell fabricated using ZnO-ALD-E as the cathode. The discharge voltage plateau at about 0.45 V in the galvanostatic discharge curves of the ZnO-ALD-E cathode is much higher than that of the ZnO nano-E and ZnO bulk-E cathodes. This improvement is attributed to the properties of the binder-free cathode, as
Figure 4. Schematic illustration of the Al/AICI3-[EMIm]Cl/ZnO-ALD-E battery during the discharge process. well as the effect of oriented growth of ZnO through ALD technique, which not only enhanced the charge exchange between the ZnO active material and the stainless steel collector, but may have also improved the migration of the ions within the large-scale textured ZnO cathode (ZnO-ALD-E), as shown schematically in Figure 4. The comparison study
Figure 4. Schematic illustration of the Al/AICI3-[EMIm]Cl/ZnO-ALD-E battery during the discharge process. well as the effect of oriented growth of ZnO through ALD technique, which not only enhanced the charge exchange between the ZnO active material and the stainless steel collector, but may have also improved the migration of the ions within the large-scale textured ZnO cathode (ZnO-ALD-E), as shown schematically in Figure 4. The comparison study
Figure 5. (a) XRD data of ZnO-ALD-E (i) pristine, (ii) after 1st discharge, (iii) after 50th charge; and (b) Reference data. Standard Diffraction pattern of hexagonal wurtzite ZnO with a space group of P63mc (JCPDS PDF Card No. 01-079-2205). The two dashed vertical lines show shifted ZnO (100) and ZnO (002) peaks in 1st discharge and 50th charged samples.
Figure 5. (a) XRD data of ZnO-ALD-E (i) pristine, (ii) after 1st discharge, (iii) after 50th charge; and (b) Reference data. Standard Diffraction pattern of hexagonal wurtzite ZnO with a space group of P63mc (JCPDS PDF Card No. 01-079-2205). The two dashed vertical lines show shifted ZnO (100) and ZnO (002) peaks in 1st discharge and 50th charged samples.
Figure 6. Gaussian fits for the room temperature photoluminescence (PL) spectra of ZnO-ALD-E1 at different states: Left panel: (a) pristine, (b) after 1* discharge, (c) after 50" discharge, and (d) after 50" charge. The sum of the Gaussian components is indicated by the thicker solid line as resultant fit for the experimental data (in circles). Right panel represents the corresponding data in log scale to clearly indicate the band edge shifts, shown in black dashed line:
Figure 6. Gaussian fits for the room temperature photoluminescence (PL) spectra of ZnO-ALD-E1 at different states: Left panel: (a) pristine, (b) after 1* discharge, (c) after 50" discharge, and (d) after 50" charge. The sum of the Gaussian components is indicated by the thicker solid line as resultant fit for the experimental data (in circles). Right panel represents the corresponding data in log scale to clearly indicate the band edge shifts, shown in black dashed line:
Figure 7. (a) Side view and top view of bilayer structure of ZnO (0 0 2)*; (b) Band structure and (c) Density of states (DOS) of ZnO (0 0 2) 2D bilayer structure. * (0 0 2) indicates the 2D plane.
Figure 7. (a) Side view and top view of bilayer structure of ZnO (0 0 2)*; (b) Band structure and (c) Density of states (DOS) of ZnO (0 0 2) 2D bilayer structure. * (0 0 2) indicates the 2D plane.
Figure 8. (a) Side view and top view of bilayer structure of Al-ion intercalated ZnO (0 0 2); (b) Band structure and (c) Density of states (DOS) of Al-ion intercalated ZnO (0 0 2).
Figure 8. (a) Side view and top view of bilayer structure of Al-ion intercalated ZnO (0 0 2); (b) Band structure and (c) Density of states (DOS) of Al-ion intercalated ZnO (0 0 2).
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