Understanding the Initial Stages of Reversible Mg Deposition and Stripping in Inorganic Nonaqueous Electrolytes
Multivalent (MV) battery architectures based on pairing a Mg metal anode with a high-voltage (∼3 V) intercalation cathode offer a realistic design pathway toward significantly surpassing the energy storage performance of traditional Li-ion-based batteries, but there are currently only few electrolyt...
| Main Authors: | , , , , , , , |
|---|---|
| Other Authors: | |
| Format: | Article |
| Language: | en_US |
| Published: |
American Chemical Society (ACS)
2016
|
| Online Access: | http://hdl.handle.net/1721.1/102239 https://orcid.org/0000-0002-8987-8500 https://orcid.org/0000-0002-1303-0976 |
| _version_ | 1826191901897785344 |
|---|---|
| author | Canepa, Pieremanuele Malik, Rahul Jayaraman, Saivenkataraman Rong, Ziqin Zavadil, Kevin R. Persson, Kristin Ceder, Gerbrand Gopalakrishnan, Sai Gautam |
| author2 | Massachusetts Institute of Technology. Department of Materials Science and Engineering |
| author_facet | Massachusetts Institute of Technology. Department of Materials Science and Engineering Canepa, Pieremanuele Malik, Rahul Jayaraman, Saivenkataraman Rong, Ziqin Zavadil, Kevin R. Persson, Kristin Ceder, Gerbrand Gopalakrishnan, Sai Gautam |
| author_sort | Canepa, Pieremanuele |
| collection | MIT |
| description | Multivalent (MV) battery architectures based on pairing a Mg metal anode with a high-voltage (∼3 V) intercalation cathode offer a realistic design pathway toward significantly surpassing the energy storage performance of traditional Li-ion-based batteries, but there are currently only few electrolyte systems that support reversible Mg deposition. Using both static first-principles calculations and ab initio molecular dynamics, we perform a comprehensive adsorption study of several salt and solvent species at the interface of Mg metal with an electrolyte of Mg[superscript 2+] and Cl[superscript –] dissolved in liquid tetrahydrofuran (THF). Our findings not only provide a picture of the stable species at the interface but also explain how this system can support reversible Mg deposition, and as such, we provide insights in how to design other electrolytes for Mg plating and stripping. The active depositing species are identified to be (MgCl)[superscript +] monomers coordinated by THF, which exhibit preferential adsorption on Mg compared to possible passivating species (such as THF solvent or neutral MgCl[subscript 2] complexes). Upon deposition, the energy to desolvate these adsorbed complexes and facilitate charge transfer is shown to be small (∼61–46.2 kJ mol[superscript –1] to remove three THF from the strongest adsorbing complex), and the stable orientations of the adsorbed but desolvated (MgCl)[superscript +] complexes appear to be favorable for charge transfer. Finally, observations of Mg–Cl dissociation at the Mg surface at very low THF coordinations (0 and 1) suggest that deleterious Cl incorporation in the anode may occur upon plating. In the stripping process, this is beneficial by further facilitating the Mg removal reaction. |
| first_indexed | 2024-09-23T09:03:04Z |
| format | Article |
| id | mit-1721.1/102239 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T09:03:04Z |
| publishDate | 2016 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/1022392022-09-26T10:08:21Z Understanding the Initial Stages of Reversible Mg Deposition and Stripping in Inorganic Nonaqueous Electrolytes Canepa, Pieremanuele Malik, Rahul Jayaraman, Saivenkataraman Rong, Ziqin Zavadil, Kevin R. Persson, Kristin Ceder, Gerbrand Gopalakrishnan, Sai Gautam Massachusetts Institute of Technology. Department of Materials Science and Engineering Canepa, Pieremanuele Gopalakrishnan, Sai Gautam Malik, Rahul Jayaraman, Saivenkataraman Rong, Ziqin Multivalent (MV) battery architectures based on pairing a Mg metal anode with a high-voltage (∼3 V) intercalation cathode offer a realistic design pathway toward significantly surpassing the energy storage performance of traditional Li-ion-based batteries, but there are currently only few electrolyte systems that support reversible Mg deposition. Using both static first-principles calculations and ab initio molecular dynamics, we perform a comprehensive adsorption study of several salt and solvent species at the interface of Mg metal with an electrolyte of Mg[superscript 2+] and Cl[superscript –] dissolved in liquid tetrahydrofuran (THF). Our findings not only provide a picture of the stable species at the interface but also explain how this system can support reversible Mg deposition, and as such, we provide insights in how to design other electrolytes for Mg plating and stripping. The active depositing species are identified to be (MgCl)[superscript +] monomers coordinated by THF, which exhibit preferential adsorption on Mg compared to possible passivating species (such as THF solvent or neutral MgCl[subscript 2] complexes). Upon deposition, the energy to desolvate these adsorbed complexes and facilitate charge transfer is shown to be small (∼61–46.2 kJ mol[superscript –1] to remove three THF from the strongest adsorbing complex), and the stable orientations of the adsorbed but desolvated (MgCl)[superscript +] complexes appear to be favorable for charge transfer. Finally, observations of Mg–Cl dissociation at the Mg surface at very low THF coordinations (0 and 1) suggest that deleterious Cl incorporation in the anode may occur upon plating. In the stripping process, this is beneficial by further facilitating the Mg removal reaction. United States. Dept. of Energy. Office of Basic Energy Sciences. Joint Center for Energy Storage Research (Subcontract 3F-31144) 2016-04-15T14:22:14Z 2016-04-15T14:22:14Z 2015-04 2015-04 Article http://purl.org/eprint/type/JournalArticle 0897-4756 1520-5002 http://hdl.handle.net/1721.1/102239 Canepa, Pieremanuele, Gopalakrishnan Sai Gautam, Rahul Malik, Saivenkataraman Jayaraman, Ziqin Rong, Kevin R. Zavadil, Kristin Persson, and Gerbrand Ceder. “Understanding the Initial Stages of Reversible Mg Deposition and Stripping in Inorganic Nonaqueous Electrolytes.” Chem. Mater. 27, no. 9 (May 12, 2015): 3317–3325. https://orcid.org/0000-0002-8987-8500 https://orcid.org/0000-0002-1303-0976 en_US http://dx.doi.org/10.1021/acs.chemmater.5b00389 Chemistry of Materials Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. application/pdf American Chemical Society (ACS) arXiv |
| spellingShingle | Canepa, Pieremanuele Malik, Rahul Jayaraman, Saivenkataraman Rong, Ziqin Zavadil, Kevin R. Persson, Kristin Ceder, Gerbrand Gopalakrishnan, Sai Gautam Understanding the Initial Stages of Reversible Mg Deposition and Stripping in Inorganic Nonaqueous Electrolytes |
| title | Understanding the Initial Stages of Reversible Mg Deposition and Stripping in Inorganic Nonaqueous Electrolytes |
| title_full | Understanding the Initial Stages of Reversible Mg Deposition and Stripping in Inorganic Nonaqueous Electrolytes |
| title_fullStr | Understanding the Initial Stages of Reversible Mg Deposition and Stripping in Inorganic Nonaqueous Electrolytes |
| title_full_unstemmed | Understanding the Initial Stages of Reversible Mg Deposition and Stripping in Inorganic Nonaqueous Electrolytes |
| title_short | Understanding the Initial Stages of Reversible Mg Deposition and Stripping in Inorganic Nonaqueous Electrolytes |
| title_sort | understanding the initial stages of reversible mg deposition and stripping in inorganic nonaqueous electrolytes |
| url | http://hdl.handle.net/1721.1/102239 https://orcid.org/0000-0002-8987-8500 https://orcid.org/0000-0002-1303-0976 |
| work_keys_str_mv | AT canepapieremanuele understandingtheinitialstagesofreversiblemgdepositionandstrippingininorganicnonaqueouselectrolytes AT malikrahul understandingtheinitialstagesofreversiblemgdepositionandstrippingininorganicnonaqueouselectrolytes AT jayaramansaivenkataraman understandingtheinitialstagesofreversiblemgdepositionandstrippingininorganicnonaqueouselectrolytes AT rongziqin understandingtheinitialstagesofreversiblemgdepositionandstrippingininorganicnonaqueouselectrolytes AT zavadilkevinr understandingtheinitialstagesofreversiblemgdepositionandstrippingininorganicnonaqueouselectrolytes AT perssonkristin understandingtheinitialstagesofreversiblemgdepositionandstrippingininorganicnonaqueouselectrolytes AT cedergerbrand understandingtheinitialstagesofreversiblemgdepositionandstrippingininorganicnonaqueouselectrolytes AT gopalakrishnansaigautam understandingtheinitialstagesofreversiblemgdepositionandstrippingininorganicnonaqueouselectrolytes |