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Nanomaterials 2021, 11, 810 diglyme. A mid-point discharge voltage of about 0.75 V and a specific capacity of 90 mAh g−1 were observed. The full cell also exhibited a 92.3% capacity retention after 200 cycles (Figure 7D). X-ray diffraction (XRD) analysis confirmed the high reversibility of magne- sium ions insertion. A weakness, though, was the large voltage hysteresis between mag- nesiumalloyinganddealloying,whichresultedinenergylosses.Otherdrawback1s0wofe2r9e the exotic nature of the anodic material and its manufacturing costs, which made it diffi- cult to be used in large scale commercial systems [110]. Figure 7. Electrochemical performances of bismuth NTs as anodes for MIBs: (a) Cyclic voltammo- Figure 7. Electrochemical performances of bismuth NTs as anodes for MIBs: (a) Cyclic voltammo- grams (CV) of magnesium ions insertion/deinsertion; (b) Discharge/charge profile of a cell; (c) grams (CV) of magnesium ions insertion/deinsertion; (b) Discharge/charge profile of a cell; (c) Rate Rate performance of a cell; (d) Cycling stability and Coulombic efficiency of bismuth NTs for re- performance of a cell; (d) Cycling stability and Coulombic efficiency of bismuth NTs for reversible versible magnesium ions insertion/deinsertion (C-rate was not reported by the authors). Cell con- magnesium ions insertion/deinsertion (C-rate was not reported by the authors). Cell configura- figuration: Mg/Mg(BH4)2 0.1 M + LiBH4 1.5 M in diglyme/Bi. A comparison with the corresponding tion: Mg/Mg(BH ) 0.1 M + LiBH 1.5 M in diglyme/Bi. A comparison with the corresponding microstructured a4n2odes is also sho4wn in each plot. Adapted with permission from [161]. Copy- microstructured anodes is also shown in each plot. Adapted with permission from [161]. Copyright right American Chemical Society, 2014. American Chemical Society, 2014. The bismuth-based anode was also studied by Murgia et al. by electrochemical meas- The bismuth-based anode was also studied by Murgia et al. by electrochemical mea- urements coupled with XRD [162]. The experiments were conducted in two-electrode surements coupled with XRD [162]. The experiments were conducted in two-electrode cells, which contained metallic magnesium as counter and reference electrodes and an cells, which contained metallic magnesium as counter and reference electrodes and an organometallic-based electrolyte solution. An unexpected phenomenon was observed: a biphasic process occurred between bismuth and Mg3Bi2 without any intermediate amor- phization, that is the rule for alloy-type electrodes. Micrometric bismuth and Mg3Bi2 prepared by ball-milling delivered specific capacity of 300 mAh g−1 at a discharge rate of 2C, with Coulombic efficiency of 98.5% after 50 cycles (Figure 8A). Moreover, a full cell composed by a Mg3Bi2 anode and a Mo6S8 cathode in a conventional electrolyte solution of Mg(TFSI)2 0.5 M in dyglime was developed. The full cell showed a voltage profile with a discharge plateau at around 0.6 V. Both the intercalation process on the cathodic side and the de-alloying process of the anode during discharge were corroborated through ex situ XRD measurements. However, full de-magnesiation of Mg3Bi2 was not achieved. Moreover, by 25Mg nuclear magnetic resonance spectroscopy, aimed at understanding the mechanism and diffusion pathway for magnesium ions in the bismuth anode [163], two-phase alloying reactions of magnesium and bismuth were demonstrated, and such spectroscopy studies enlightened a fast exchange between the two magnesium sites in the Mg3Bi2 alloy. Di Leo et al. proposed the synthesis of bismuth/carbon nanotubes (CNTs) com- posite [159]. Electrochemical deposition of bismuth on CNTs from aqueous solution of Bi(NO3)3 was adopted to obtain the composite material. They observed a specific capacity of 180 mAh g−1 through CV at a rate of 0.5 mV s−1 in acetonitrile-based solution containing Mg(ClO4)2 0.5 M and dipropylene glycol dimethyl ether 0.5 M. However, the capacity decreased to 80 mAh g−1 at the second cycle and to 49 mAh g−1 at the third. This sharp capacity fading excluded the material from any further investigation.PDF Image | Overview on Anodes for Magnesium Batteries
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