Predicting the potentials, solubilities and stabilities of metal-acetylacetonates for non-aqueous redox flow batteries using density functional theory calculations

Kucharyson, Jonathan F.; Cheng, Lei; Tung, Siu On; Curtiss, Larry A.; Thompson, Levi T.

doi:10.1039/c7ta01285c

Cited by 58 publications

(54 citation statements)

References 51 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…The D values reported in acetonitrile ranged from 0.56 © 10 ¹5 to 1.5 © 10 ¹5 cm 2 s ¹1 , depending on the electrochemical techniques. 14,15,22,26 The D value of Fe(acac) 3 in BMPTFSA was much smaller than those in acetonitrile, reflecting the higher viscosity (73 mPa s) of BMPTFSA containing 10 mM Fe(acac) 3 . As abovementioned, the negative redox potentials of [Fe(CN) 6 ] 3¹ and Fe(acac) 3 are considered suitable for the anolyte of the redox flow batteries.…”

Section: ¹1mentioning

confidence: 99%

“…In the electrochemical field, the redox reaction using tris(acetylacetonato)iron complex (Fe(acac) 3 ) has been examined in organic electrolytes and deep eutectic solvents for such applications as redox flow batteries and photoelectrochemical cells. [14][15][16] We have reported that the metal complexes with acac ¹ , such as Pd(acac) 2 and Pt(acac) 2 , are stable in TFSA ¹ -based ionic liquids. [17][18][19] In the present study, the redox properties of Fe(acac) 3 were investigated in BMPTFSA.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Redox Reaction of Tris(acetylacetonato)iron(III) Complex in an Amide-type Ionic Liquid

et al. 2018

View full text Add to dashboard Cite

The redox reaction of tris(acetylacetonato)iron(III) (Fe(acac) 3 ) on a glassy carbon electrode was investigated in 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide (BMPTFSA). A one-electron transfer redox reaction of [Fe(acac) 3 ] 0/− showed the relatively negative potential of −1.4 V vs. Ag|Ag(I). The diffusion coefficient of Fe(acac) 3 estimated by chronoamperometry was (1.4 + 0.1) × 10 −7 cm 2 s −1 . The redox properties examined in this study suggested that the redox reaction of [Fe(acac) 3 ] 0/− can be utilized in the negative half-cell reaction of redox flow batteries.

show abstract

Section: ¹1mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Redox Reaction of Tris(acetylacetonato)iron(III) Complex in an Amide-type Ionic Liquid

et al. 2018

View full text Add to dashboard Cite

show abstract

“…High-throughput computational screening offers the possibility of exploring thousands of molecules for desirable properties without the need for experimental trial and error. [23][24][25] The computational results can provide key insights into structureactivity properties that may be used in the design and tuning of new molecules for electrochemical energy storage. The majority of theoretical studies have been conducted on the quinone family (benzoquinone, naphthoquinone, and anthraquinone) whose redox potential and solvation free energies strongly depend on the chemical nature of electron donating groups (EDGs) and electron withdrawing groups (EWGs) attached to the basic quinoyl skeleton.…”

Section: Introductionmentioning

confidence: 99%

New insights into phenazine-based organic redox flow batteries by using high-throughput DFT modelling

Cruz

Molina

Patil

et al. 2020

Sustainable Energy Fuels

View full text Add to dashboard Cite

show abstract

“…Milestone examples of non-aqueous metal-based RFBs include Ru- [32], Fe- [32], U- [33], V- [34,35], Mn- [36], Cr- [37], Ni- [38], Co- [39], and W [40]-containing systems. It is worthy to note that efforts to develop more efficient electrolytes for non-aqueous RFBs have mostly been empirical, from both theoretical and experimental perspectives, with limited attempts toward the rational design of structural, electronic, and other RFB-relevant properties [41][42][43][44]. It is clear that there is an urgent need to develop more affordable and efficient RFBs to meet the world's growing energy storage demands.…”

Section: Introductionmentioning

confidence: 99%

Catalyst-Inspired Charge Carriers for High Energy Density Redox Flow Batteries

et al. 2019

View full text Add to dashboard Cite

We introduce a theoretical design approach aiming at improving energy density of redox flow batteries (RFBs) via the utilization of redox non-innocent ligands capable of stabilizing a metal center in a wide range of oxidation states. Our findings suggest that this promotes the possibility of multiple redox events as well as high open circuit voltages. Specifically, we have proposed two Fe-coordination complexes (I, Fe(Me2 Pytacn)(C 2 N 3 H 2), and II, Fe(H 2 pmen)(C 2 N 3 H 2)) combining two different types of ligands, i.e., catalyst-inspired scaffolds and triazole ring, which were previously shown to promote high and low oxidation states in transition metals, respectively. These complexes exhibit as many as six theoretical redox events in the full range of charge states +4 → −2, several of which reside within the electrochemical window of acetonitrile. Electronic structure calculations show that the Fe center exhibits oxidation states ranging from the very rare Fe 4+ to Fe 1+. Values of the reduction potentials as well as nature of the redox events of both complexes is found to be similar in their high +4 → +1 charge states. In contrast, while exhibiting qualitatively similar redox behavior in the lower 0 → −2 range, some differences in the electronic ground states, delocalization patterns as well as reduction potential values are also observed. The calculated open circuit voltages can reach values of 5.09 and 6.14 V for complexes I and II, respectively, and hold promise to be experimentally accessible within the electrochemical window of acetonitrile expanded by addition of ionic liquids. The current results obtained for these two complexes are intended to illustrate a more general principle based on the simultaneous utilization of two types of ligands responsible for the stabilization of high and low oxidation states of the metal that can be used to design the next-generation charge carriers capable of supporting multi-electron redox and operating in a broad range of charge states, leading to RFBs with greater energy density.

show abstract

Predicting the potentials, solubilities and stabilities of metal-acetylacetonates for non-aqueous redox flow batteries using density functional theory calculations

Abstract: New active materials are needed to improve the performance and reduce the cost of non-aqueous redox flow batteries (RFBs) for grid-scale energy storage applications.

Cited by 58 publications

References 51 publications

Redox Reaction of Tris(acetylacetonato)iron(III) Complex in an Amide-type Ionic Liquid

Redox Reaction of Tris(acetylacetonato)iron(III) Complex in an Amide-type Ionic Liquid

New insights into phenazine-based organic redox flow batteries by using high-throughput DFT modelling

Catalyst-Inspired Charge Carriers for High Energy Density Redox Flow Batteries

Contact Info

Product

Resources

About