A Comparative Mechanistic Study on the Intercalation Reactions of Mg<sup>2+</sup> and Li<sup>+</sup> Ions into (Mg<sub>0.5</sub>Ni<sub>0.5</sub>)<sub>3</sub>(PO<sub>4</sub>)<sub>2</sub>
Magnesium-ion batteries represent promising environmentally sustainable energy-storage systems with higher energy densities than their lithium counterparts. In this work, the charge storage mechanisms of the olivine-related compound (Mg<sub>0.5</sub>Ni<sub>0.5</sub>)<sub&g...
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| Format: | Article |
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MDPI AG
2023-06-01
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| Series: | Batteries |
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| Online Access: | https://www.mdpi.com/2313-0105/9/7/342 |
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| author | Martina Romio Yuri Surace Andreas Mautner Raad Hamid Marcus Jahn Damian M. Cupid Isaac Abrahams |
| author_facet | Martina Romio Yuri Surace Andreas Mautner Raad Hamid Marcus Jahn Damian M. Cupid Isaac Abrahams |
| author_sort | Martina Romio |
| collection | DOAJ |
| description | Magnesium-ion batteries represent promising environmentally sustainable energy-storage systems with higher energy densities than their lithium counterparts. In this work, the charge storage mechanisms of the olivine-related compound (Mg<sub>0.5</sub>Ni<sub>0.5</sub>)<sub>3</sub>(PO<sub>4</sub>)<sub>2</sub> using Mg<sup>2+</sup> and Li<sup>+</sup> ions were investigated and compared for the first time when copper was chosen as the current collector. A comprehensive physicochemical and electrochemical characterization was performed on the pristine powder and electrodes at different states of charge. Although (Mg<sub>0.5</sub>Ni<sub>0.5</sub>)<sub>3</sub>(PO<sub>4</sub>)<sub>2</sub> is electrochemically active, it undergoes irreversible conversion reactions in both Mg and Li chemistries. The conversion reactions proceed with an ionic exchange between structural Ni<sup>2+</sup> and Mg<sup>2+</sup> or Li<sup>+</sup> cations, which results in the formation of sarcopside-Mg<sub>3</sub>(PO<sub>4</sub>)<sub>2</sub>, a Cu–Ni alloy and poorly crystalline Li<sub>3</sub>PO<sub>4</sub>, respectively. A capacity of 600 mA h g<sup>−1</sup> was achieved with a Li metal counter electrode in the Li cell since the conversion reaction could go to completion. A capacity of 92 mA h g<sup>−1</sup> was delivered in the Mg cell using an activated carbon counter electrode. These findings shed light on the fundamental mechanism of activity in olivine-related compounds, underlining the importance of performing systematic studies to unveil the complex interactions between both single-valent and multivalent ions with novel structures. |
| first_indexed | 2024-03-11T01:18:35Z |
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| institution | Directory Open Access Journal |
| issn | 2313-0105 |
| language | English |
| last_indexed | 2024-03-11T01:18:35Z |
| publishDate | 2023-06-01 |
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| record_format | Article |
| series | Batteries |
| spelling | doaj.art-6561d4bcb646404999995691bef9668f2023-11-18T18:18:37ZengMDPI AGBatteries2313-01052023-06-019734210.3390/batteries9070342A Comparative Mechanistic Study on the Intercalation Reactions of Mg<sup>2+</sup> and Li<sup>+</sup> Ions into (Mg<sub>0.5</sub>Ni<sub>0.5</sub>)<sub>3</sub>(PO<sub>4</sub>)<sub>2</sub>Martina Romio0Yuri Surace1Andreas Mautner2Raad Hamid3Marcus Jahn4Damian M. Cupid5Isaac Abrahams6AIT Austrian Institute of Technology GmbH, Centre for Low-Emission Transport, Giefinggasse 2, 1210 Vienna, AustriaAIT Austrian Institute of Technology GmbH, Centre for Low-Emission Transport, Giefinggasse 2, 1210 Vienna, AustriaDepartment of Materials Chemistry, Universität Wien, Währinger Straße 42, 1090 Vienna, AustriaAIT Austrian Institute of Technology GmbH, Centre for Low-Emission Transport, Giefinggasse 2, 1210 Vienna, AustriaAIT Austrian Institute of Technology GmbH, Centre for Low-Emission Transport, Giefinggasse 2, 1210 Vienna, AustriaAIT Austrian Institute of Technology GmbH, Centre for Low-Emission Transport, Giefinggasse 2, 1210 Vienna, AustriaDepartment of Chemistry, Queen Mary University of London, Mile End Rd, London E1 4NS, UKMagnesium-ion batteries represent promising environmentally sustainable energy-storage systems with higher energy densities than their lithium counterparts. In this work, the charge storage mechanisms of the olivine-related compound (Mg<sub>0.5</sub>Ni<sub>0.5</sub>)<sub>3</sub>(PO<sub>4</sub>)<sub>2</sub> using Mg<sup>2+</sup> and Li<sup>+</sup> ions were investigated and compared for the first time when copper was chosen as the current collector. A comprehensive physicochemical and electrochemical characterization was performed on the pristine powder and electrodes at different states of charge. Although (Mg<sub>0.5</sub>Ni<sub>0.5</sub>)<sub>3</sub>(PO<sub>4</sub>)<sub>2</sub> is electrochemically active, it undergoes irreversible conversion reactions in both Mg and Li chemistries. The conversion reactions proceed with an ionic exchange between structural Ni<sup>2+</sup> and Mg<sup>2+</sup> or Li<sup>+</sup> cations, which results in the formation of sarcopside-Mg<sub>3</sub>(PO<sub>4</sub>)<sub>2</sub>, a Cu–Ni alloy and poorly crystalline Li<sub>3</sub>PO<sub>4</sub>, respectively. A capacity of 600 mA h g<sup>−1</sup> was achieved with a Li metal counter electrode in the Li cell since the conversion reaction could go to completion. A capacity of 92 mA h g<sup>−1</sup> was delivered in the Mg cell using an activated carbon counter electrode. These findings shed light on the fundamental mechanism of activity in olivine-related compounds, underlining the importance of performing systematic studies to unveil the complex interactions between both single-valent and multivalent ions with novel structures.https://www.mdpi.com/2313-0105/9/7/342magnesium-ion batteryorthophosphateolivine-related structureconversion reaction |
| spellingShingle | Martina Romio Yuri Surace Andreas Mautner Raad Hamid Marcus Jahn Damian M. Cupid Isaac Abrahams A Comparative Mechanistic Study on the Intercalation Reactions of Mg<sup>2+</sup> and Li<sup>+</sup> Ions into (Mg<sub>0.5</sub>Ni<sub>0.5</sub>)<sub>3</sub>(PO<sub>4</sub>)<sub>2</sub> Batteries magnesium-ion battery orthophosphate olivine-related structure conversion reaction |
| title | A Comparative Mechanistic Study on the Intercalation Reactions of Mg<sup>2+</sup> and Li<sup>+</sup> Ions into (Mg<sub>0.5</sub>Ni<sub>0.5</sub>)<sub>3</sub>(PO<sub>4</sub>)<sub>2</sub> |
| title_full | A Comparative Mechanistic Study on the Intercalation Reactions of Mg<sup>2+</sup> and Li<sup>+</sup> Ions into (Mg<sub>0.5</sub>Ni<sub>0.5</sub>)<sub>3</sub>(PO<sub>4</sub>)<sub>2</sub> |
| title_fullStr | A Comparative Mechanistic Study on the Intercalation Reactions of Mg<sup>2+</sup> and Li<sup>+</sup> Ions into (Mg<sub>0.5</sub>Ni<sub>0.5</sub>)<sub>3</sub>(PO<sub>4</sub>)<sub>2</sub> |
| title_full_unstemmed | A Comparative Mechanistic Study on the Intercalation Reactions of Mg<sup>2+</sup> and Li<sup>+</sup> Ions into (Mg<sub>0.5</sub>Ni<sub>0.5</sub>)<sub>3</sub>(PO<sub>4</sub>)<sub>2</sub> |
| title_short | A Comparative Mechanistic Study on the Intercalation Reactions of Mg<sup>2+</sup> and Li<sup>+</sup> Ions into (Mg<sub>0.5</sub>Ni<sub>0.5</sub>)<sub>3</sub>(PO<sub>4</sub>)<sub>2</sub> |
| title_sort | comparative mechanistic study on the intercalation reactions of mg sup 2 sup and li sup sup ions into mg sub 0 5 sub ni sub 0 5 sub sub 3 sub po sub 4 sub sub 2 sub |
| topic | magnesium-ion battery orthophosphate olivine-related structure conversion reaction |
| url | https://www.mdpi.com/2313-0105/9/7/342 |
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