Cobalt and Vanadium Trimetaphosphate Polyanions: Synthesis, Characterization, and Electrochemical Evaluation for Non-aqueous Redox-Flow Battery Applications
An electrochemical cell consisting of cobalt ([Co[superscript II/III](P₃O₉)₂]4⁻/3⁻) and vanadium ([V[superscript III/II](P₃O₉)₂]3⁻/4⁻) bistrimetaphosphate complexes as catholyte and anolyte species, respectively, was constructed with a cell voltage of 2.4 V and Coulombic efficiencies >90% for up...
| Main Authors: | , , , , , , |
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| Other Authors: | |
| Format: | Article |
| Language: | en_US |
| Published: |
American Chemical Society (ACS)
2018
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| Online Access: | http://hdl.handle.net/1721.1/119623 https://orcid.org/0000-0001-9783-907X https://orcid.org/0000-0003-3497-181X https://orcid.org/0000-0001-9557-0281 https://orcid.org/0000-0003-2568-3269 |
| Summary: | An electrochemical cell consisting of cobalt ([Co[superscript II/III](P₃O₉)₂]4⁻/3⁻) and vanadium ([V[superscript III/II](P₃O₉)₂]3⁻/4⁻) bistrimetaphosphate complexes as catholyte and anolyte species, respectively, was constructed with a cell voltage of 2.4 V and Coulombic efficiencies >90% for up to 100 total cycles. The [Co(P₃O₉)₂]4⁻ (1) and [V(P₃O₉)₂]3⁻ (2) complexes have favorable properties for flow-battery applications, including reversible redox chemistry, high stability toward electrochemical cycling, and high solubility in MeCN (1.09 ± 0.02 M, [PPN]₄[1]·2MeCN; 0.77 ± 0.06 M, [PPN]3[2]·DME). The [PPN]₄[1]·2MeCN and [PPN]₃[2]·DME salts were isolated as crystalline solids in 82 and 68% yields, respectively, and characterized by 31P NMR, UV/vis, ESI-MS(−), and IR spectroscopy. The [PPN]₄[1]·2MeCN salt was also structurally characterized, crystallizing in the monoclinic P21/c space group. Treatment of 1 with [(p-BrC₆H₄)₃N]⁺ allowed for isolation of the one-electron-oxidized spin-crossover (SCO) complex, [Co(P3O₉)₂]₃– (3), which is the active catholyte species generated during cell charging. The success of the 1-2 cell provides a promising entry point to a potential future class of transition-metal metaphosphate-based all-inorganic non-aqueous redox-flow battery electrolytes. |
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