Vanadium redox battery

The vanadium redox battery (VRB), also known as the vanadium flow battery (VFB) or vanadium redox flow battery (VRFB), is a type of rechargeable flow battery. It employs vanadium ions as charge carriers.[5] The battery uses vanadium's ability to exist in a solution in four different oxidation states to make a battery with a single electroactive element instead of two.[6] For several reasons, including their relative bulkiness, vanadium batteries are typically used for grid energy storage, i.e., attached to power plants/electrical grids.

Vanadium redox battery
Specific energy10–20 Wh/kg (36–72 J/g)
Energy density15–25 Wh/L (54–65 kJ/L)
Charge/discharge efficiency75–80%<.[1][2]
Time durability20-30 years
Cycle durability>12,000-14,000 cycles[3]
Nominal cell voltage1.15–1.55 V
Schematic design of a vanadium redox flow battery system[4]
1 MW 4 MWh containerized vanadium flow battery owned by Avista Utilities and manufactured by UniEnergy Technologies
A vanadium redox flow battery located at the University of New South Wales, Sydney, Australia

Pissoort explored the possibility of VRFB's in the 1930s.[7] NASA researchers and Pellegri and Spaziante followed suit in the 1970s,[8] but neither was successful. Maria Skyllas-Kazacos presented the first successful demonstration of dissolved vanadium in a solution of sulfuric acid in the 1980s.[9][10] Her design used sulfuric acid electrolytes, and was patented by the University of New South Wales in Australia in 1986.[2]

Numerous companies and organizations are involved in funding and developing vanadium redox batteries.

Advantages and disadvantages

Advantages

VRFB's main advantages over other types of battery:[11]

  • no limit on energy capacity
  • can remain discharged indefinitely without damage
  • mixing electrolytes causes no permanent damage
  • single charge state across the electrolytes avoids capacity degradation
  • safe, non-flammable aqueous electrolyte;[12]
  • wide operating temperature range including passive cooling[13][14]
  • long charge/discharge cycle lives: 15,000-20,000 cycles.
  • low levelized cost: (a few tens of cents), approaching the 2016 $0.05 target stated by the US Department of Energy and the European Commission Strategic Energy Technology Plan €0.05 target.[15]

Disadvantages

VRFB's main disadvantages compared to other types of battery:[11]

  • high and volatile prices of vanadium minerals (i.e. the cost of VRFB energy) ;
  • relatively poor round trip efficiency (compared to lithium-ion batteries) ;
  • heavy weight of aqueous electrolyte ;
  • relatively poor energy-to-volume ratio compared to standard storage batteries ;
  • toxicity of vanadium (V) compounds.

Materials
Diagram of a vanadium flow battery

A vanadium redox battery consists of an assembly of power cells in which two electrolytes are separated by a proton exchange membrane. The electrodes in a VRB cell are carbon based. The most common types are carbon felt, carbon paper, carbon cloth, and graphite felt. Recently, carbon nanotube-based electrodes have attracted interest from the scientific community.[16][17][18]

Both electrolytes are vanadium-based. The electrolyte in the positive half-cells contains VO2+ and VO2+ ions, while the electrolyte in the negative half-cells consists of V3+ and V2+ ions. The electrolytes can be prepared by several processes, including electrolytically dissolving vanadium pentoxide (V2O5) in sulfuric acid (H2SO4). The solution remains strongly acidic in use.

The membrane is another critical component. The most common membrane material is perfluorinated sulfonic acid (PFSA) (Nafion). However, vanadium ions tend to penetrate the membrane and destabilize the cell. A 2021 Chinese study found that this penetration is reduced with hybrid sheets made by growing tungsten trioxide nanoparticles on the surface of single-layered graphene oxide sheets. These hybrid sheets are then embedded into a sandwich structured PFSA membrane reinforced with polytetrafluoroethylene (Teflon). The tungsten trioxide nanoparticles also promote proton transport, offering high Coulombic efficiency and energy efficiency of more than 98.1 percent and 88.9 percent, respectively.[19]

Operation
Cyclic voltammogram of vanadium (IV) solution in sulfuric acid solution

The reaction uses the half-reactions:[20]

VO+2 + 2H+ + e− → VO2+ + H2O (E° = +1.00 V[21])
V3+ + e− → V2+ (E° = −0.26 V[22])

Other useful properties of vanadium flow batteries are their very fast response to changing loads and their extremely large overload capacities. Studies by the University of New South Wales have shown that they can achieve a response time of under half a millisecond for a 100% load change, and allowed overloads of as much as 400% for 10 seconds. The response time is mostly limited by the electrical equipment. Unless specifically designed for colder or warmer climates, most sulfuric acid-based vanadium batteries work only between about 10 and 40 °C. Below that temperature range, the ion-infused sulfuric acid crystallizes.[23] Round trip efficiency in practical applications is around 65–75 %.[24]

Proposed improvements

The original VRFB design by Skyllas-Kazacos employed sulfate (added as vanadium sulfate(s) and sulfuric acid) as the only anion in VRFB solutions, which limited the maximum vanadium concentration to 1.7 M of vanadium ions.[25] Around 2010 a team from Pacific Northwest National Laboratory proposed a mixed sulfate-chloride electrolyte, that allowed for the use in VRFBs solutions with the total vanadium concentration of 2.5 M over a whole temperature range between −20 and +50 °C.[26] It is worth noting, that the based on the standard equilibrium potential of the V(+5)/V(+4) couple it is expected to oxidize chloride, and for this reason chloride solutions were avoided in earlier VRFB studies. The surprising oxidative stability (albeit only at the state of charge below ca. 80%) of V(+5) solutions in the presence of chloride was explained on the basis of activity coefficients.[27] Nevetheless, because of a high vapor pressure of HCl solutions, such mixed electrolytes have not been widely adopted by the VRFB industry.

Another VRFB chemistry variation is the use of vanadium bromide salts. Since the redox potential of Br2/2Br- couple is more negative than that of V(5+/4+), the positive electrode operates via the bromine process. Such solutions were expected to approximately double the energy density and increase the temperature range in which the battery can operate.[28] However, due to the problems with volatility and corrosivity of Br2, they did not gain much popularity (see zinc-bromine battery for a similar problem). The vanadium/cerium flow battery has also been proposed .[29]

Typically, perfluorinated sulfonic acid (PFSA) is used as the separator membrane. However, vanadium ions can cross the membrane and destabilize the battery. Researchers grew tungsten trioxide nanoparticles on the surface of graphene oxide sheets and embedded them in a polytetrafluoroethylene-reinforced, sandwich-structured PFSA system. This reduced penetration and promoted proton transport, yielding Coulumbic efficiency and energy efficiency of greater than 98.1% and 88.9%, respectively.[30]

Specific energy and energy density

Current production vanadium redox batteries achieve a specific energy of about 20 Wh/kg (72 kJ/kg) of electrolyte. More recent research at UNSW indicates that the use of precipitation inhibitors can increase the density to about 35 Wh/kg (126 kJ/kg), with even higher densities made possible by controlling the electrolyte temperature. The current specific energy is quite low compared to other rechargeable battery types (e.g., lead–acid, 30–40 Wh/kg (108–144 kJ/kg); and lithium ion, 80–200 Wh/kg (288–720 kJ/kg)). However, using precipitation inhibitors would place vanadium redox batteries on par with lead-acid batteries.

Applications

VRFB's large potential capacity may be best-suited to buffer the irregular output of utility-scale wind and solar systems.[11]

Their reduced self-discharge makes them potentially appropriate in applications that require long-term battery storage with little maintenance as in military equipment, such as the sensor components of the GATOR mine system.[31][11]

They feature rapid response times well suited to uninterruptible power supply (UPS) applications, where they can replace lead–acid batteries or diesel generators. Fast response time is also appropriate for frequency regulation. These capabilities make VRBF's an effective "all-in-one" solution for microgrids, frequency regulation and load shifting.[11]

Largest vanadium grid batteries
Largest operational vanadium redox batteries
Name Commissioning date Energy (MWh) Power (MW) Duration (hours) Country
Minami Hayakita Substation[32][33]December 201560154Japan
Pfinztal, Baden-Württemberg[34][35][36] September 2019 20 2 10 Germany
Woniushi, Liaoning[37][38]1052China
Tomamae Wind Farm[39]2005641:30Japan
Zhangbei Project[40]2016824China
SnoPUD MESA 2 Project[41][42]March 2017824USA
San Miguel Substation[43]2017824USA
Pullman Washington[44]April 2015414USA
Dalian Battery[45] May 2021 (Final Capacity) 400 (800) 100 (200) 4 China

A 200 MW, 800 MWh (4 hours) vanadium redox battery is under construction in China; it was expected to be completed by 2018[46] and its 250 kW/ 1 MWh first stage was in operation in late 2018[47]

Companies funding or developing vanadium redox batteries

Companies include CellCube (Enerox),[48] UniEnergy Technologies,[49] StorEn Technologies,[50][51] Largo Energy[52] and Ashlawn Energy[53] in the United States; H2 in South Korea; Renewable Energy Dynamics Technology,[54] Invinity Energy[55] and VoltStorage[56] in Europe; Prudent Energy in China;[57] Australian Vanadium in Australia;[58] EverFlow Energy JV SABIC SCHMID Group in Saudi Arabia[59] and Bushveld Minerals in South Africa.[60]

See also
Wikimedia Commons has media related to Vanadium redox batteries.

References
  1. Vanadium Battery Group University of New South Wales
  2. M. Skyllas-Kazacos, M. Rychcik and R. Robins, in AU Patent 575247 (1986), to Unisearch Ltd.
  3. Electricity Storage and Renewables: Costs and Markets to 2030. IRENA (2017), Electricity Storage and Renewables: Costs and Markets to 2030, International Renewable Energy Agency, Abu Dhabi.
  4. Qi, Zhaoxiang; Koenig, Gary M. (July 2017). "Review Article: Flow battery systems with solid electroactive materials". Journal of Vacuum Science & Technology B, Nanotechnology and Microelectronics: Materials, Processing, Measurement, and Phenomena. 35 (4): 040801. Bibcode:2017JVSTB..35d0801Q. doi:10.1116/1.4983210. ISSN 2166-2746.
  5. Laurence Knight (14 June 2014). "Vanadium: The metal that may soon be powering your neighbourhood". BBC. Retrieved 2 March 2015.
  6. Alotto, P.; Guarnieri, M.; Moro, F. (2014). "Redox Flow Batteries for the storage of renewable energy: a review". Renewable & Sustainable Energy Reviews. 29: 325–335. doi:10.1016/j.rser.2013.08.001. hdl:11577/2682306.
  7. P. A. Pissoort, in FR Patent 754065 (1933)
  8. A. Pelligri and P. M. Spaziante, in GB Patent 2030349 (1978), to Oronzio de Nori Impianti Elettrochimici S.p.A.
  9. M. Rychcik and M. Skyllas-Kazacos, J. Power Sources, 22 (1988) 59–67
  10. "Discovery and invention: How the vanadium flow battery story began". Energy Storage News. 18 October 2021. Archived from the original on 18 October 2021.
  11. Ragsdale, Rose (May 2020). "Vanadium fuels growing demand for VRFBs". Metal Tech News. Retrieved 15 November 2021.
  12. UniEnergy Technologies Products Accessed 21 Jan 2016.
  13. "Vanadium Redox Flow Batteries" (PDF). Pacific Northwest National Laboratory. October 2012.
  14. Miller, Kelsey. UniEnergy Technologies Goes from Molecules to Megawatts Archived 31 January 2016 at the Wayback Machine, Clean Tech Alliance, 7 July 2014. Accessed 21 Jan 2016.
  15. Spagnuolo, G.; Petrone, G.; Mattavelli, P.; Guarnieri, M. (2016). "Vanadium Redox Flow Batteries: Potentials and Challenges of an Emerging Storage Technology". IEEE Industrial Electronics Magazine. 10 (4): 20–31. doi:10.1109/MIE.2016.2611760. hdl:11577/3217695. S2CID 28206437.
  16. Mustafa, Ibrahim; Lopez, Ivan; Younes, Hammad; Susantyoko, Rahmat Agung; Al-Rub, Rashid Abu; Almheiri, Saif (March 2017). "Fabrication of Freestanding Sheets of Multiwalled Carbon Nanotubes (Buckypapers) for Vanadium Redox Flow Batteries and Effects of Fabrication Variables on Electrochemical Performance". Electrochimica Acta. 230: 222–235. doi:10.1016/j.electacta.2017.01.186. ISSN 0013-4686.
  17. Mustafa, Ibrahim; Bamgbopa, Musbaudeen O.; Alraeesi, Eman; Shao-Horn, Yang; Sun, Hong; Almheiri, Saif (1 January 2017). "Insights on the Electrochemical Activity of Porous Carbonaceous Electrodes in Non-Aqueous Vanadium Redox Flow Batteries". Journal of the Electrochemical Society. 164 (14): A3673–A3683. doi:10.1149/2.0621714jes. hdl:1721.1/134874. ISSN 0013-4651.
  18. Mustafa, Ibrahim; Al Shehhi, Asma; Al Hammadi, Ayoob; Susantyoko, Rahmat; Palmisano, Giovanni; Almheiri, Saif (May 2018). "Effects of carbonaceous impurities on the electrochemical activity of multiwalled carbon nanotube electrodes for vanadium redox flow batteries". Carbon. 131: 47–59. doi:10.1016/j.carbon.2018.01.069. ISSN 0008-6223.
  19. Lavars, Nick (12 November 2021). "Hybrid membrane edges flow batteries toward grid-scale energy storage". New Atlas. Retrieved 14 November 2021.
  20. Jin, Jutao; Fu, Xiaogang; Liu, Qiao; Liu, Yanru; Wei, Zhiyang; Niu, Kexing; Zhang, Junyan (25 June 2013). "Identifying the Active Site in Nitrogen-Doped Graphene for the VO 2+ /VO 2 + Redox Reaction". ACS Nano. 7 (6): 4764–4773. doi:10.1021/nn3046709. PMID 23647240.
  21. Cotton, F. Albert; Wilkinson, Geoffrey; Murillo, Carlos A.; Bochmann, Manfred (1999), Advanced Inorganic Chemistry (6th ed.), New York: Wiley-Interscience, ISBN 0-471-19957-5
  22. Atkins, Peter (2010). Inorganic Chemistry (5th ed.). W. H. Freeman. p. 153. ISBN 978-1-42-921820-7.
  23. DOE/Pacific Northwest National Laboratory (17 March 2011). "Electric Grid Reliability: Increasing Energy Storage in Vanadium Redox Batteries by 70 Percent". Science Daily. Retrieved 2 March 2015.
  24. VRB Power Systems FAQ Archived 13 February 2010 at the Wayback Machine
  25. M. Skyllas-Kazacos, M. Rychcik and G. Robins Robert, "All vanadium redox battery." 1986AU-0055562 1986-04-02. M. Skyllas-Kazacos, "All-vanadium redox battery and additives." 1988WO-AU00472 1988-12-091989AU-0028153 1989-12-09. M. Skyllas-Kazacos, M. Kazacos and C. Mcdermott Rodney John, "Vanadium charging cell and vanadium dual battery system." 1989AU-0028152 1989-12-09. M. Kazacos and S. Kazacos Maria, "High energy density vanadium electrolyte solutions, methods of preparation thereof and all-vanadium redox cells and batteries containing high energy vanadium electrolyte solutions." 1996AT-0911853T 1996-05-031996AU-0054914 1996-05-031996US-08945869 1996-05-031996WO-AU00268 1996-05-031996NZ-0306364 1996-05-031996ES-0911853T 1996-05-031996EP-0911853 1996-05-031996DE-6030298 1996-05-031996CA-2220075 1996-05-031998HK-0110321 1998-08-312002US-10226751 2002-08-22
  26. L. Li, S. Kim, W. Wang, M. Vijayakumar, Z. Nie, B. Chen, J. Zhang, et al., "A stable vanadium redox-flow battery with high energy density for large-scale energy storage." Adv. Energy Mater., 1, 394 (2011) 10.1002/aenm.201100008 || Y. Yang, Y. Zhang, L. Tang, T. Liu, J. Huang, S. Peng and X. Yang, "Investigations on physicochemical properties and electrochemical performance of sulfate-chloride mixed acid electrolyte for vanadium redox flow battery." J Power Sources, 434 (2019) 10.1016/j.jpowsour.2019.226719
  27. N. Roznyatovskaya, J. Noack, H. Mild, M. Fühl, P. Fischer, K. Pinkwart, J. Tübke, et al., "Vanadium electrolyte for all-vanadium redox-flow batteries: The effect of the counter ion." Batteries, 5 (2019) 10.3390/batteries5010013
  28. Vafiadis, Helen, and Maria Skyllas-Kazacos. "Evaluation of membranes for the novel vanadium bromine redox flow cell." Journal of Membrane Science 279.1-2 (2006): 394-402
  29. Sankarasubramanian, Shrihari; Zhang, Yunzhu; Ramani, Vijay (2019). "Methanesulfonic acid-based electrode-decoupled vanadium–cerium redox flow battery exhibits significantly improved capacity and cycle life". Sustainable Energy & Fuels. 3 (9): 2417–2425. doi:10.1039/C9SE00286C. ISSN 2398-4902. S2CID 199071949.
  30. Lavars, Nick (12 November 2021). "Hybrid membrane edges flow batteries toward grid-scale energy storage". New Atlas. Retrieved 15 November 2021.
  31. Allbright, Greg, et al. A Comparison of Lead Acid to Lithium-ion in Stationary Storage Applications All Cell, March 2012
  32. Stone, Mike (3 February 2016). "A Look at the Biggest Energy Storage Projects Built Around the World in the Last Year". Retrieved 12 August 2017.
  33. "DOE Global Energy Storage Database". www.energystorageexchange.org. Archived from the original on 9 November 2017. Retrieved 9 November 2017.
  34. "Redox-Flow-Batterien". Retrieved 27 July 2014.
  35. "Der Rotor steht noch still".
  36. "Großprojekt "RedoxWind"". Fraunhofer-Institut für Chemische Technologie.
  37. "Energy Storage in China". www.ees-magazine.com. Retrieved 12 August 2017.
  38. Zonghao, L. I. U.; Huamin, Zhang; Sujun, G. a. O.; Xiangkun, M. A.; Yufeng, L. I. U.; 刘宗浩, 张华民. "The world's largest all-vanadium redox flow battery energy storage system for a wind farm, 风场配套用全球最大全钒液流电池储能系统". 储能科学与技术. 3 (1): 71–77. doi:10.3969/j.issn.2095-4239.2014.01.010.
  39. "DOE Global Energy Storage Database". www.energystorageexchange.org. Retrieved 9 November 2017.
  40. "DOE Global Energy Storage Database". www.energystorageexchange.org. Archived from the original on 31 August 2018. Retrieved 9 November 2017.
  41. "UET and Snohomish County PUD Dedicate the World's Largest Capacity Containerized Flow Battery". Energy Storage News. 29 March 2017. Archived from the original on 18 August 2018. Retrieved 29 December 2017.
  42. "PUD invests $11.2 million in energy-storing units". Everett Herald. 2 November 2016. Retrieved 29 December 2017.
  43. "SDG&E and Sumitomo unveil largest vanadium redox flow battery in the US". Energy Storage News. 17 March 2017. Retrieved 12 August 2017.
  44. Wesoff, Eric, St. John, Jeff. Largest Capacity Flow Battery in North America and EU is Online, Greentech Media, June 2015. Accessed 21 Jan 2016.
  45. "World's largest flow battery connected to the grid in China". New Atlas. 3 October 2022. Retrieved 12 October 2022.
  46. "It's Big and Long-Lived, and It Won't Catch Fire: The Vanadium Redox-⁠Flow Battery". IEEE Spectrum: Technology, Engineering, and Science News. Retrieved 12 November 2017.
  47. "First phase of China's biggest flow battery put into operation by VRB Energy". Energy Storage News. Retrieved 4 May 2019.
  48. "CellCube - the versatile energy storage system of the future". Cellcube. Retrieved 14 December 2022.
  49. Steve Wilhelm (3 July 2014). "Liquid battery the size of a truck, will give utilities a charge". Puget Sound Business Journal. Retrieved 2 May 2015.
  50. Entrepreneur, Office of the Queensland Chief (3 February 2021). "How Queensland can supercharge the future of batteries". Office of the Queensland Chief Entrepreneur. Retrieved 3 February 2021.
  51. "StorEn Tech Provides First Of Its Kind Vanadium Flow Battery To Australia". CleanTechnica. 19 December 2020. Retrieved 3 February 2021.
  52. "Vanadium producer Largo prepares 1.4GWh of flow battery stack manufacturing capacity". 6 May 2021.
  53. BILL HAGSTRAND (23 August 2013). "Vanadium redox: powering up local communities". Crain's Cleveland Business. Retrieved 2 May 2015.
  54. "US clean-tech investments leap to US$1.1bn. Where's Ireland at?". Silicon Republic. 11 April 2011. Retrieved 2 May 2015.
  55. "'UK's first' grid-scale battery storage system comes online in Oxford". 24 June 2021.
  56. "Voltstorage develops a safe and ecological storage solution". 16 January 2018.
  57. Jeff St. John (2 March 2010). "Made in China: Prudent Energy Lands $22M For Flow Batteries". GigaOm. Retrieved 2 May 2015.
  58. "Australian Vanadium Ltd ships first vanadium flow battery from Austria". Proactive Investors. 13 July 2016. Retrieved 24 November 2017.
  59. "3GWh flow battery manufacturing facility to be constructed in Saudi Arabia". 16 May 2020.
  60. "Vanadium producer Bushveld Minerals begins building flow battery electrolyte plant in South Africa". 15 June 2021.

Additional references
This article is issued from Wikipedia. The text is licensed under Creative Commons - Attribution - Sharealike. Additional terms may apply for the media files.