Unexpected electrochemical behavior of an anolyte redoxmer in flow battery electrolytes: solvating cations help to fight against the thermodynamic–kinetic dilemma

Zhao, Yuyue; Zhou, Yu; Robertson, Lily A.; Zhang, Jingjing; Shi, Zhangxing; Bheemireddy, Sambasiva R.; Shkrob, Ilya A.; Zhang, Yang; Li, Tao; Zhang, Zhengcheng; Cheng, Lei; Zhang, Lu

doi:10.1039/d0ta02214d

Cited by 20 publications

(30 citation statements)

References 49 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…A Ag pseudoelectrode has been reported to exhibit little potential drift in nonaqueous systems . On the other hand, a similar shift in the redox potential of a redox couple has been reported when using Li + - and K + -containing supporting electrolytes, due to different solvating interactions . Therefore, we consider the change in the solvation structure as the major contributor to the redox potential shift, which we will further discuss using Raman spectroscopy.…”

Section: Resultsmentioning

confidence: 53%

“…29 On the other hand, a similar shift in the redox potential of a redox couple has been reported when using Li + -and K + -containing supporting electrolytes, due to different solvating interactions. 30 Therefore, we consider the change in the solvation structure as the major contributor to the redox potential shift, which we will further discuss using Raman spectroscopy. Compared with the 1 m LiTFSI, the CVs exhibit more of a rectangular shape at the reversal potentials (0 and 0.35 V vs Ag/Ag + ).…”

Section: ■ Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Potential-Dependent Layering in the Electrochemical Double Layer of Water-in-Salt Electrolytes

Zhang

Han

et al. 2020

ACS Appl. Energy Mater.

View full text Add to dashboard Cite

Water-in-salt electrolytes (WiSE) are concentrated aqueous electrolytes recently developed that are of great interest because of their possible relevance for batteries. The origin for their promising application has been ascribed to the formation of percolating nanodomains in the bulk. However, the interfacial structure of WiSE still remains to be understood. In this paper, we characterize the potential-dependent double layer of a LiTFSIbased electrolyte on a charged electrode surface. Ultramicroelectrode (UME) measurements reveal a surface-confinement effect for a ferricyanide redox species at the electrode/WiSE interface. Potential-dependent atomic force microscopy (AFM) shows the presence of layers, the structure of which changes with the applied potential. Thicker layers (6.4 and 6.7 Å) are observed at positive potentials, associated with [Li(H 2 O) x ] + ([TFSI] − ) y ion pairs, while thinner layers (2.8 and 3.3 Å) are found at negative potentials and associated with [Li(H 2 O) x ] + alone. Vibrational spectroscopy shows that the composition of the double layer also changes with potential, where [TFSI] − is enriched at positive and [Li(H 2 O) x ] + enriched at negative potentials.

show abstract

Section: Resultsmentioning

confidence: 53%

Section: ■ Introductionmentioning

confidence: 99%

Potential-Dependent Layering in the Electrochemical Double Layer of Water-in-Salt Electrolytes

Zhang

Han

et al. 2020

ACS Appl. Energy Mater.

View full text Add to dashboard Cite

show abstract

“…Dynamic interactions between solvent, supporting electrolyte, and ROMs at various concentrations play an important role in determining the properties of an electrolyte. 30 This is particularly important in modeling nonaqueous systems as these interactions tend to be complex due to the large and diverse chemical space of the organic components and their various possible combinations. In contrast, water as the only solvent can alleviate some of the difficulties of simulating the aqueous electrolyte environment.…”

Section: Identification Of Electroactive Molecule Candidates By Simul...mentioning

confidence: 99%

“…In addition to comparing spectra at specific times, EPR can also be used to follow radical cation intensity over time, allowing half-lives to be extrapolated. 27,30…”

Section: Investigation Of Physicochemicalmentioning

confidence: 99%

“…Several limitations exist in DFT simulations for studying electrolytes in O-NRFBs. Dynamic interactions between solvent, supporting electrolyte, and ROMs at various concentrations play an important role in determining the properties of an electrolyte . This is particularly important in modeling nonaqueous systems as these interactions tend to be complex due to the large and diverse chemical space of the organic components and their various possible combinations.…”

Section: Identification Of Electroactive Molecule Candidates By Simul...mentioning

confidence: 99%

See 1 more Smart Citation

Experimental Protocols for Studying Organic Non-aqueous Redox Flow Batteries

Odom

Pancoast

et al. 2021

ACS Energy Lett.

Self Cite

View full text Add to dashboard Cite

Fusing Thiadiazole and Terephthalate: A Concept to Promote the Electrochemical Performance of Conjugated Dicarboxylates

et al. 2023

View full text Add to dashboard Cite

Organic electrode materials based on conjugated dicarboxylate moieties are particularly attractive to develop metal-ion organic batteries. Exhibiting good stability properties in liquid electrolytes, such organic electrode materials can reversibly store alkali metal ions (Li, Na or K) at low working potential. Although many molecular designs have been investigated in the last decade, conjugated dicarboxylates are impeded by low coulombic efficiencies, especially at the first cycle, and sluggish kinetics in most cases. Herein, a new strategy in the design of conjugated carboxylates by fusing a thiadiazole heterocycle to the terephthalate core is reported. The synthesis and electrochemical performance of dilithium-2,1,3-benzothiadiazole-4,7-dicarboxylate (Li 2 -DCBTZ) as positive electrode material is investigated for the first time. Next to being a new structural design, the presence of the thiadiazole ring enables (i) a better conjugation of π-n electrons leading to a benefit in terms of rate capability, and (ii) a better stabilizing coordination network for Li ions through both oxygen and nitrogen atoms. In addition, the reduced state in Li 4 -DCBTZ is stabilized due to a maintained aromaticity in the heteroaromatic core in comparison to the parent terephthalate. Theoretical calculations on the Li-ion storage mechanism and bonding character support the experimental work.

show abstract

Unexpected electrochemical behavior of an anolyte redoxmer in flow battery electrolytes: solvating cations help to fight against the thermodynamic–kinetic dilemma

Abstract: Solvating cations help to lift the thermodynamic-kinetic constrain of an anolyte redoxmer by achieving a synergetic improvement of two conflicting properties: a lower redox potential AND a higher stability of the charged radical anion.

Cited by 20 publications

References 49 publications

Potential-Dependent Layering in the Electrochemical Double Layer of Water-in-Salt Electrolytes

Potential-Dependent Layering in the Electrochemical Double Layer of Water-in-Salt Electrolytes

Experimental Protocols for Studying Organic Non-aqueous Redox Flow Batteries

Fusing Thiadiazole and Terephthalate: A Concept to Promote the Electrochemical Performance of Conjugated Dicarboxylates

Contact Info

Product

Resources

About