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Metal–air electrochemical cell

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A metal–air electrochemical cell is an electrochemical cell that uses an anode made from pure metal and an external cathode of ambient air, typically with an aqueous or aprotic electrolyte.[1][2]

During discharging of a metal–air electrochemical cell, a reduction reaction occurs in the ambient air cathode while the metal anode is oxidized.

The specific capacity and energy density of metal–air electrochemical cells is higher than that of lithium-ion batteries, making them a prime candidate for use in electric vehicles. While there are some commercial applications, complications associated with the metal anodes, catalysts, and electrolytes have hindered development and implementation of metal–air batteries.[3][4]

Types by anode element

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Lithium

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Main article: Lithium–air battery

The remarkably high energy density of lithium metal (up to 3458 Wh/kg) inspired the design of lithium–air batteries. A lithium–air battery consists of a solid lithium electrode, an electrolyte surrounding this electrode, and an ambient air electrode containing oxygen. Current lithium–air batteries can be divided into four subcategories based on the electrolyte used and the subsequent electrochemical cell architecture. These electrolyte categories are aprotic, aqueous, mixed aqueous/aprotic, and solid state, all of which offer their own distinct advantages and disadvantages.[5] Nonetheless, efficiency of lithium–air batteries is still limited by incomplete discharge at the cathode, charging overpotential exceeding discharge overpotential, and component stability.[6] During discharge of lithium–air batteries, the superoxide ion (O2−) formed will react with the electrolyte or other cell components and will prevent the battery from being rechargeable.[7]

Sodium

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Sodium–air batteries were proposed with the hopes of overcoming the battery instability associated with superoxide in lithium–air batteries. Sodium, with an energy density of 1605 Wh/kg, does not boast as high an energy density as lithium. However, it can form a stable superoxide (NaO2) as opposed to the superoxide undergoing detrimental secondary reactions. Since NaO2 will decompose reversibly to an extent back to the elemental components, this means sodium–air batteries have some intrinsic capacity to be rechargeable.[8] Sodium–air batteries can only function with aprotic, anhydrous electrolytes. When a DMSO electrolyte was stabilized with sodium trifluoromethanesulfonimide, the highest cycling stability of a sodium–air battery was obtained (150 cycles).[9]

Potassium

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Potassium–air batteries were also proposed with the hopes of overcoming the battery instability associated with superoxide in lithium–air batteries. While only two to three charge-discharge cycles have ever been achieved with potassium–air batteries, they do offer an exceptionally low overpotential difference of only 50 mV.[10]

Zinc

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Main article: Zinc–air battery

Zinc–air batteries are used for hearing aids and film cameras.

Magnesium

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A variety of metal–air chemistries are currently being studied. The homogeneous deposition of Mg metal makes Mg–air systems interesting.[11][12][13] However, aqueous Mg–air batteries are seriously limited by the Mg electrode's dissolution. The use of a number of ionic aqueous electrolytes in magnesium–air devices has been recommended. Nevertheless, electrochemical fragility affects them all.[14] However, the cell's reversibility is limited, and the especially visible during recharging.[14]

Main article: Magnesium–air fuel cell

Calcium

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Calcium–air(O2) batteries have been reported.[15][16]

Aluminium

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Main article: Aluminium–air battery

Aluminium–air batteries have the highest energy density of any other battery, with a theoretical maximum energy density of 6–8 kWh/kg, however, as of 2003, a maximum of only 1.3 kWh/kg has been achieved. Aluminium battery cells are not rechargeable, so new aluminium anodes must be installed to continue getting power from the battery, which makes them expensive to use and limited to mostly military applications.[17]

Aluminium–air batteries have been used for prototypes of electric cars, with one claiming 2000 km of range on a single charge, however none have been available to the public. However, aluminium–air batteries maintain a stable voltage and power output until they run out of power, which could make them useful for electric planes, where full power is always required in case of emergency landings. Due to not having to carry a separate metal anode, the natural low density of aluminium, and the high energy density of aluminium–air batteries, the batteries are very lightweight, which is also beneficial for electric aviation. The scale of airports could also allow for on-site recycling of anodes, which would not be feasible for cars where many small stations are necessary.[18]

Aluminium–air batteries are better for the environment compared to traditional lithium-ion batteries. Aluminium is the most abundant metal in the Earth's crust, so mines would not have to be as invasive to find a similar amount of aluminium compared to lithium. Another factor is that aluminium recycling plants already exist, while lithium recycling plants are just starting to emerge and become profitable. Aluminium is a lot more economical to recycle with current technology.[18]

Iron

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Iron–air rechargeable batteries are an attractive technology with the potential of grid-scale energy storage. The main raw-material of this technology is iron oxide (rust), a material that is abundant, non-toxic, inexpensive, and environmentally friendly.[19] Most of the batteries currently being developed utilize iron oxide powders to generate and store hydrogen via the Fe/FeO reduction/oxidation (redox) reaction (Fe + H2O ⇌ FeO + H2).[20] In conjunction with a fuel cell, this enables the system to behave as a rechargeable battery, creating H2O/H2 via the production and consumption of electricity.[21] Furthermore, this technology has minimal environmental impact, as it could be used to store energy from intermittent or variable energy sources, such as solar and wind, developing an energy system with low carbon dioxide emissions.

One way the system can start is by using the Fe/FeO redox reaction. Hydrogen created during the oxidation of iron and of oxygen from the air can be consumed by a fuel cell to create electricity. When electricity must be stored, hydrogen generated from water by operating the fuel cell in reverse is consumed during the reduction of the iron oxide to metallic iron.[20][21] The combination of both of these cycles is what makes the system operate as an iron–air rechargeable battery.

Limitations of this technology come from the materials used. Generally, iron oxide powder beds are selected; however, rapid sintering and pulverization of the powders limit the ability to achieve a high number of cycles, which results in diminished capacity. Other methods currently under investigation, such as 3D printing[22] and freeze-casting,[23][24] seek to enable the creation of architecture materials to allow for high surface area and volume changes during the redox reaction.

Comparison

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Anode element Theoretical specific energy, Wh/kg
(including oxygen) 		Theoretical specific energy, Wh/kg
(excluding oxygen) 		Calculated open-circuit voltage, V
Aluminium 4300[25] 8140[26] 1.2
Germanium[citation needed] 1480 7850 1
Calcium 2990 4180 3.12
Iron 1431 2044 1.3
Lithium 5210 11140 2.91
Magnesium 2789 6462 2.93
Potassium 935[27][28] 1700[Note 1] 2.48[27][28]
Sodium 1677 2260 2.3[29][30]
Tin[31] 860 6250 0.95
Zinc[citation needed] 1090 1350 1.65

See also

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Notes

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  1. ^ Calculated from the specific energy density (including oxygen) value and 39.1 and 16 atomic weight data for K and O respectively for KO2

References

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  1. ^ "Metal air". December 27, 2010. Archived from the original on 2010-12-27.
  2. ^ "Metal–Air Batteries Lithium, Aluminum, Zinc, and Carbon" (PDF). Retrieved 2013-04-04.
  3. ^ Li, Y.; Lu, J. (2017). "Metal–Air Batteries: Will They Be the Future Electrochemical Energy Storage Device of Choice?". ACS Energy Letters. 2 (6): 1370–1377. doi:10.1021/acsenergylett.7b00119. OSTI 1373737.
  4. ^ Zhang, X.; Wang, X.; Xie, Z.; Zhou, Z. (2016). "Recent progress in rechargeable alkali metal–air batteries". Green Energy & Environment. 1 (1): 4–17. doi:10.1016/j.gee.2016.04.004.
  5. ^ Girishkumar, G.; McCloskey, B.; Luntz, C.; Swanson, S.; Wilcke, W. (2010). "Lithium–Air Battery: Promise and Challenges". The Journal of Physical Chemistry Letters. 1 (14): 2193–2203. doi:10.1021/jz1005384.
  6. ^ Kraytsberg, Alexander; Ein-Eli, Yair (2011). "Review on Li–air batteries—Opportunities, limitations and perspective". Journal of Power Sources. 196 (3): 886–893. Bibcode:2011JPS...196..886K. doi:10.1016/j.jpowsour.2010.09.031.
  7. ^ Zyga, Lisa. "Sodium–air battery offers rechargeable advantages compared to Li–air batteries". Phys.org. Retrieved 1 March 2018.
  8. ^ Hartmann, P.; Bender, C.; Vracar, M.; Durr, A.; Garsuch, A.; Janek, J.; Adelhelm, P. (2012). "A rechargeable room-temperature sodium superoxide (NaO2) battery". Nature Materials Letters. 12 (1): 228–232. Bibcode:2013NatMa..12..228H. doi:10.1038/NMAT3486. PMID 23202372.
  9. ^ He, M.; Lau, K.; Ren, X.; Xiao, N.; McCulloch, W.; Curtiss, L.; Wu, Y. (2016). "Concentrated Electrolyte for the Sodium–Oxygen Battery: Solvation Structure and Improved Cycle Life". Angewandte Chemie. 55 (49): 15310–15314. doi:10.1002/anie.201608607. OSTI 1352612. PMID 27809386.
  10. ^ Ren, X.; Wu, Y. (2013). "A Low-Overpotential Potassium−Oxygen Battery Based on Potassium Superoxide". Journal of the American Chemical Society. 135 (8): 2923–2926. doi:10.1021/ja312059q. PMID 23402300.
  11. ^ Rahman, Md. Arafat; Wang, Xiaojian; Wen, Cuie (2013). "High Energy Density Metal–Air Batteries: A Review". Journal of the Electrochemical Society. 160 (10): A1759–A1771. doi:10.1149/2.062310jes. ISSN 0013-4651.
  12. ^ Zhang, Tianran; Tao, Zhanliang; Chen, Jun (2014). "Magnesium–air batteries: from principle to application". Mater. Horiz. 1 (2): 196–206. doi:10.1039/c3mh00059a. ISSN 2051-6347.
  13. ^ Li, Yifei; Zhang, Xiaoxue; Li, Hao-Bo; Yoo, Hyun Deog; Chi, Xiaowei; An, Qinyou; Liu, Jieyu; Yu, Meng; Wang, Weichao; Yao, Yan (September 2016). "Mixed-phase mullite electrocatalyst for pH-neutral oxygen reduction in magnesium–air batteries". Nano Energy. 27: 8–16. doi:10.1016/j.nanoen.2016.06.033. ISSN 2211-2855.
  14. ^ a b Li, Chun-Sheng; Sun, Yan; Gebert, Florian; Chou, Shu-Lei (2017-08-22). "Current Progress on Rechargeable Magnesium–Air Battery". Advanced Energy Materials. 7 (24): 1700869. Bibcode:2017AdEnM...700869L. doi:10.1002/aenm.201700869. ISSN 1614-6832. S2CID 102825802.
  15. ^ Shiga, Tohru; Kato, Yuichi; Hase, Yoko (2017-06-27). "Coupling of nitroxyl radical as an electrochemical charging catalyst and ionic liquid for calcium plating/stripping toward a rechargeable calcium–oxygen battery". Journal of Materials Chemistry A. 5 (25): 13212–13219. doi:10.1039/C7TA03422A. ISSN 2050-7496.
  16. ^ Reinsberg, Philip; Bondue, Christoph J.; Baltruschat, Helmut (2016-10-06). "Calcium–Oxygen Batteries as a Promising Alternative to Sodium–Oxygen Batteries". The Journal of Physical Chemistry C. 120 (39): 22179–22185. doi:10.1021/acs.jpcc.6b06674. ISSN 1932-7447.
  17. ^ Yang, Shaohua; Knickle, Harold (2002-10-24). "Design and analysis of aluminum/air battery system for electric vehicles". Journal of Power Sources. 112 (1): 162–173. Bibcode:2002JPS...112..162Y. doi:10.1016/S0378-7753(02)00370-1. ISSN 0378-7753.
  18. ^ a b "Can Aluminium–air batteries outperform Li-ion for EVs?". Energy Post. 2021-09-08. Retrieved 2023-01-08.
  19. ^ Narayanan, S. R.; Prakash, G. K. Surya; Manohar, A.; Yang, Bo; Malkhandi, S.; Kindler, Andrew (2012-05-28). "Materials challenges and technical approaches for realizing inexpensive and robust iron–air batteries for large-scale energy storage". Solid State Ionics. "Fuel Cells-Energy Conversion" Proceedings of Symposium X EMRS Spring Meeting 2011E-MRS / MRS BILATERAL CONFERENCE on ENERGY,"Held at the E-MRS 2011 SPRING MEETING IUMRS ICAM 2011. 216: 105–109. doi:10.1016/j.ssi.2011.12.002.
  20. ^ a b Requies, J.; Güemez, M. B.; Gil, S. Perez; Barrio, V. L.; Cambra, J. F.; Izquierdo, U.; Arias, P. L. (2013-04-19). "Natural and synthetic iron oxides for hydrogen storage and purification". Journal of Materials Science. 48 (14): 4813–4822. Bibcode:2013JMatS..48.4813R. doi:10.1007/s10853-013-7377-7. ISSN 0022-2461. S2CID 93103339.
  21. ^ a b Ju, Young-Wan; Ida, Shintaro; Inagaki, Toru; Ishihara, Tatsumi (2011-08-01). "Reoxidation behavior of Ni–Fe bimetallic anode substrate in solid oxide fuel cells using a thin LaGaO3 based film electrolyte". Journal of Power Sources. 196 (15): 6062–6069. Bibcode:2011JPS...196.6062J. doi:10.1016/j.jpowsour.2011.03.086.
  22. ^ Jakus, Adam E.; Taylor, Shannon L.; Geisendorfer, Nicholas R.; Dunand, David C.; Shah, Ramille N. (2015-12-01). "Metallic Architectures from 3D-Printed Powder-Based Liquid Inks". Advanced Functional Materials. 25 (45): 6985–6995. doi:10.1002/adfm.201503921. ISSN 1616-3028. S2CID 15711041.
  23. ^ Sepúlveda, Ranier; Plunk, Amelia A.; Dunand, David C. (2015-03-01). "Microstructure of Fe2O3 scaffolds created by freeze-casting and sintering". Materials Letters. 142: 56–59. doi:10.1016/j.matlet.2014.11.155.
  24. ^ Durán, P.; Lachén, J.; Plou, J.; Sepúlveda, R.; Herguido, J.; Peña, J. A. (2016-11-16). "Behaviour of freeze-casting iron oxide for purifying hydrogen streams by steam-iron process". International Journal of Hydrogen Energy. The 5th Iberian Symposium on Hydrogen, Fuel Cells and Advanced Batteries (HYCELTEC 2015), 5–8 July 2015, Tenerife, Spain. 41 (43): 19518–19524. doi:10.1016/j.ijhydene.2016.06.062.
  25. ^ "Electrically Rechargeable Metal–Air Batteries (ERMAB)". Archived from the original on 3 March 2016. Retrieved 25 March 2012.
  26. ^ "Batteries for Oxygen Concentrators". NASA.gov. Archived from the original on 26 February 2014.
  27. ^ a b Wu, Yiying; Ren, Xiaodi (2013). "A Low-Overpotential Potassium−Oxygen Battery Based on Potassium Superoxide". Journal of the American Chemical Society. 135 (8): 2923–2926. doi:10.1021/ja312059q. PMID 23402300.
  28. ^ a b Ren, Xiaodi; Wu, Yiying (2013). "A Low-Overpotential Potassium−Oxygen Battery Based on Potassium Superoxide". Journal of the American Chemical Society. 135 (8): 2923–2926. doi:10.1021/ja312059q. PMID 23402300.
  29. ^ Sun, Qian (2012). "Electrochemical properties of room temperature sodium–air batteries with non-aqueous electrolyte". Electrochemistry Communications. 16: 22–25. doi:10.1016/j.elecom.2011.12.019.
  30. ^ "BASF investigating sodium–air batteries as alternative to Li–air; patent application filed with USPTO". Green Car Congress.
  31. ^ Ju, HyungKuk; Lee, Jaeyoung (2015). "High-temperature liquid Sn–air energy storage cell". Journal of Energy Chemistry. 24 (5): 614–619. doi:10.1016/j.jechem.2015.08.006.
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