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A magnesium–sulfur battery is a rechargeable battery that uses magnesium ion as its charge carrier, magnesium metal as anode and sulfur as cathode. To increase the electronic conductivity of cathode, sulfur is usually mixed with carbon to form a cathode composite. Magnesium–sulfur battery is an emerging energy storage technology and now is still in the stage of research. It is of great interest since in theory the Mg/S chemistry can provide 1722 Wh/kg energy density with a voltage at ~1.7 V.
Magnesium is abundant, non-toxic and doesn't degrade in air. Most importantly, magnesium does not form dendrites during deposition/stripping process, which is attributed to be the main cause for the safety issue in lithium-ion battery and rechargeable lithium battery. A first review on Mg–S batteries has been published in MRS Communications[1]
Research
editToyota
editIn 2011, Toyota Motor announced a research project in this area,[2] and in the same year they reported a new electrolyte that is chemically compatible with sulfur.[3] The electrolyte was prepared as a Lewis acid-base complex from the Hauser base (HMDS)MgCl, where HMDS = hexamethyldisilazide,[4] introduced by C. Liebenow et al. in 2000[5] and AlCl3, conceptionally similar to Aurbach's binuclear electrolyte complex from 2001.[6] Although the complex had to be refined by recrystallization and only THF could be used as solvent, a discharge voltage of 1 V was obtained over two cycles, demonstrating the principle feasibility.
Currently, efforts on rechargeable magnesium battery research are known to be underway at Apple, Toyota, and Pellion Technologies,[7] as well as in several universities.
Helmholtz-Institute Ulm and KIT
editIn 2013, researchers announced a new electrolyte and accompanying magnesium-based batteries.[8] The electrolyte is more stable and works well with various solvents and at high concentrations. It supports sulfur cathodes. Two commercial chemicals, a magnesium amide and aluminum chloride were mixed in a solvent, the product can then be used directly as an electrolyte.[9][10]
In 2015, a Mg rechargeable battery was presented built with a graphene–sulfur nanocomposite cathode, a Mg–carbon composite anode and a non-nucleophilic Mg-based complex in tetraglyme solvent as the electrolyte. The graphene–sulfur nanocomposites were prepared with a combination of thermal and chemical precipitation. The Mg/S cell delivers 448 mA h g−1 and 236 mA h g−1 after 50 cycles. The graphene–sulfur composite cathode, with a high surface area, porous morphology and oxygen functional groups, along with a non-nucleophilic Mg electrolyte, gives improved performance.[11]
Recently, a new class of sulfur-compatible and Cl-free electrolytes was introduced.[12] It is based on a weakly coordinated Mg salt with big anions (fluorinated alkoxyborate) which can be prepared by a simple reaction and used in-situ.
University of Maryland
editIn 2015, a team at University of Maryland discovered that Li ion additive can enhance the reversibility of the electrochemical reaction in a Mg/S battery. The Mg/S cell delivers ~1000 mAh/g capacity for 30 cycles with two discharge plateau at 1.75 V and 1.0 V.[13] The obtainable energy density of the cell at material level is 874 Wh/kg, about half of its theoretical value.
In 2017, the same team successfully increases the cycling stability of a Mg/S cell to 110 cycles, by suppressing the dissolution of polysulfide with a concentrated electrolyte, a major reason for the loss of active material and capacity fading in Mg/S batteries. They also demonstrate that the MgTFSI2-MgCl2-DME electrolyte is compatible with sulfur cathode. Unlike the complex electrolytes made through Lewis acid-base reaction or the electrolytes using Mg salts with big anions, this electrolyte can be simply made by blending dried MgTFSI2, MgCl2 with DME. This facile synthesis procedure enables this electrolyte to be a convenient platform for the community to further study the Mg/S chemistry.[14]
References
edit- ^ Zhao-Karger, Zhirong; Fichtner, Maximilian (September 2017). "Magnesium–sulfur battery: its beginning and recent progress". MRS Communications. 7 (4): 770–784. doi:10.1557/mrc.2017.101. ISSN 2159-6859. S2CID 49309970.
- ^ Fletcher, Seth (January 18, 2011). "The Truth About Toyota's New Magnesium Battery". Popular Science. Retrieved April 9, 2015.
- ^ Kim, Hee Soo; Arthur, Timothy S.; Allred, Gary D.; Zajicek, Jaroslav; Newman, John G.; Rodnyansky, Alexander E.; Oliver, Allen G.; Boggess, William C.; Muldoon, John (2011-08-09). "Structure and compatibility of a magnesium electrolyte with a sulphur cathode". Nature Communications. 2: 427. Bibcode:2011NatCo...2..427K. doi:10.1038/ncomms1435. ISSN 2041-1723. PMC 3266610. PMID 21829189.
- ^ Wang, Peiwen; Buchmeiser, Michael R. (September 6, 2019). "Rechargeable Magnesium–Sulfur Battery Technology: State of the Art and Key Challenges". Advanced Functional Materials. 29 (49). Wiley. doi:10.1002/adfm.201905248. S2CID 202886015. Retrieved December 10, 2022.
- ^ Liebenow, C; Yang, Z; Lobitz, P (2000-09-01). "The electrodeposition of magnesium using solutions of organomagnesium halides, amidomagnesium halides and magnesium organoborates". Electrochemistry Communications. 2 (9): 641–645. doi:10.1016/S1388-2481(00)00094-1.
- ^ Aurbach, Doron; Gizbar, Haim; Schechter, Alex; Chusid, Orit; Gottlieb, Hugo E.; Gofer, Yossi; Goldberg, Israel (2002-02-01). "Electrolyte Solutions for Rechargeable Magnesium Batteries Based on Organomagnesium Chloroaluminate Complexes". Journal of the Electrochemical Society. 149 (2): A115–A121. Bibcode:2002JElS..149A.115A. doi:10.1149/1.1429925. ISSN 0013-4651.
- ^ Jaffe, Sam (April 10, 2014). "Next-Generation Batteries: Problems and Solutions". Retrieved April 9, 2015.
- ^ Zhao-Karger, Zhirong; Zhao, Xiangyu; Fuhr, Olaf; Fichtner, Maximilian (2013-08-28). "Bisamide based non-nucleophilic electrolytes for rechargeable magnesium batteries". RSC Advances. 3 (37): 16330. Bibcode:2013RSCAd...316330Z. doi:10.1039/C3RA43206H. ISSN 2046-2069.
- ^ Zhao-Karger, Zhirong; Zhao, Xiangyu; Wang, Di; Diemant, Thomas; Behm, R. Jürgen; Fichtner, Maximilian (2015-02-01). "Performance Improvement of Magnesium Sulfur Batteries with Modified Non-Nucleophilic Electrolytes". Advanced Energy Materials. 5 (3): n/a. doi:10.1002/aenm.201401155. ISSN 1614-6840. S2CID 96659406.
- ^ Mack, Eric (November 30, 2014). "New electrolyte to enable cheaper, less toxic magnesium-sulfur-based batteries". Retrieved April 9, 2015.
- ^ Vinayan, B. P.; Zhao-Karger, Zhirong; Diemant, Thomas; Chakravadhanula, Venkata Sai Kiran; Schwarzburger, Nele I.; Cambaz, Musa Ali; Behm, R. Jürgen; Kübel, Christian; Fichtner, Maximilian (2016-02-05). "Performance study of magnesium–sulfur battery using a graphene based sulfur composite cathode electrode and a non-nucleophilic Mg electrolyte". Nanoscale. 8 (6): 3296–3306. Bibcode:2016Nanos...8.3296V. doi:10.1039/c5nr04383b. PMID 26542750.
- ^ Zhao-Karger, Zhirong; Bardaji, Maria Elisa Gil; Fuhr, Olaf; Fichtner, Maximilian (2017-06-06). "A new class of non-corrosive, highly efficient electrolytes for rechargeable magnesium batteries". Journal of Materials Chemistry A. 5 (22): 10815–10820. doi:10.1039/C7TA02237A. ISSN 2050-7496.
- ^ Gao, Tao; Noked, Malachi; Pearse, Alex J; Gillette, Eleanor; Fan, Xiulin; Zhu, Yujie; Luo, Chao; Suo, Liumin; Schroeder, Marshall A (2015-09-30). "Enhancing the Reversibility of Mg/S Battery Chemistry through Li+ Mediation". Journal of the American Chemical Society. 137 (38): 12388–12393. doi:10.1021/jacs.5b07820. ISSN 0002-7863. PMID 26360783.
- ^ Gao, Tao; Hou, Singyuk; Wang, Fei; Ma, Zhaohui; Li, Xiaogang; Xu, Kang; Wang, Chunsheng (2017). "Reversible S0/MgSx Redox Chemistry in a MgTFSI2/MgCl2/DME Electrolyte for Rechargeable Mg/S Batteries". Angewandte Chemie International Edition. 56 (43): 13526–13530. doi:10.1002/anie.201708241. ISSN 1521-3773. PMID 28849616.