The role of phosphate additive in stabilization of sulphuric-acid-based vanadium(V) electrolyte for all-vanadium redox-flow batteries

Roznyatovskaya, Nataliya; Roznyatovsky, Vitaly A.; Höhne, Carl‐Christoph; Fühl, Matthias; Gerber, Tobias; Küttinger, Michael; Noack, Jens; Fischer, P.; Pinkwart, Karsten; Tübke, Jens

doi:10.1016/j.jpowsour.2017.07.100

Cited by 42 publications

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“…The electrolyte samples were prepared in H 2 SO 4 and HCl acids using either V(IV) or V 3.5+ solution containing equimolar mixtures of V(IV) and V(III) as the initial electrolyte (Section 3.2). The abbreviations of the vanadium electrolyte samples used in the study and their analysis data are given in Table 1 and are defined in Section 3.2.…”

Section: Electrolyte Preparationmentioning

confidence: 99%

“…Total sulfate concentration in I-V4-H 2 SO 4 solution was 4.7 M and corresponded to the common total sulfate concentration of some commercial electrolytes. Though the exact vanadium speciation in electrolyte solution is unknown and can involve dimeric V(V) species [4], the process of V(IV) electrolysis can be commonly represented by the following conversions:…”

Section: Electrolyte Preparationmentioning

confidence: 99%

“…Otherwise, the limit of the SoC of less than 100% in the case of HCl-based electrolytes (at least at 1.6 M vanadium and 6-7.6 M total chloride concentrations) appears to be the easiest condition to avoid chlorine evolution due to the reaction of V(V) with chloride ions. A VRFB operated with H 2 SO 4 -containing electrolyte is also known to have a limit of less than 80% SoC due to the thermal aging of the catholyte at elevated temperatures [4].…”

Section: Thermal Stabilitymentioning

confidence: 99%

“…Provided that the total vanadium concentration and the conductivity of electrolytes are comparable for both acids, respective energy efficiencies of 77% and 72-75% were attained at a current density of 50 mA·cm −2 . All electrolytes in the oxidation state V(V) were examined for chemical stability at room temperature and +45 • C by titrimetric determination of the molar ratio V(V):V(IV) and total vanadium concentration.Batteries 2019, 5, 13 2 of 16 sulfuric acid VRFB electrolytes [1][2][3][4]. Therefore, the electrochemical kinetics of vanadium reactions, and ultimately the activation losses during battery operation, are likely also dependent on the nature of the counter ion or battery chemistry.…”

mentioning

confidence: 99%

“…Batteries 2019, 5, 13 2 of 16 sulfuric acid VRFB electrolytes [1][2][3][4]. Therefore, the electrochemical kinetics of vanadium reactions, and ultimately the activation losses during battery operation, are likely also dependent on the nature of the counter ion or battery chemistry.…”

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Vanadium Electrolyte for All-Vanadium Redox-Flow Batteries: The Effect of the Counter Ion

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In this study, 1.6 M vanadium electrolytes in the oxidation forms V(III) and V(V) were prepared from V(IV) in sulfuric (4.7 M total sulphate), V(IV) in hydrochloric (6.1 M total chloride) acids, as well as from 1:1 mol mixture of V(III) and V(IV) (denoted as V3.5+) in hydrochloric (7.6 M total chloride) acid. These electrolyte solutions were investigated in terms of performance in vanadium redox flow battery (VRFB). The half-wave potentials of the V(III)/V(II) and V(V)/V(IV) couples, determined by cyclic voltammetry, and the electronic spectra of V(III) and V(IV) electrolyte samples, are discussed to reveal the effect of electrolyte matrix on charge-discharge behavior of a 40 cm2 cell operated with 1.6 M V3.5+ electrolytes in sulfuric and hydrochloric acids. Provided that the total vanadium concentration and the conductivity of electrolytes are comparable for both acids, respective energy efficiencies of 77% and 72–75% were attained at a current density of 50 mA∙cm−2. All electrolytes in the oxidation state V(V) were examined for chemical stability at room temperature and +45 °C by titrimetric determination of the molar ratio V(V):V(IV) and total vanadium concentration.

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Section: Electrolyte Preparationmentioning

confidence: 99%

Section: Electrolyte Preparationmentioning

confidence: 99%

Section: Thermal Stabilitymentioning

confidence: 99%

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Vanadium Electrolyte for All-Vanadium Redox-Flow Batteries: The Effect of the Counter Ion

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Vanadium Electrolytes and Related Electrochemical Reactions

2023

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Material Design of Aqueous Redox Flow Batteries: Fundamental Challenges and Mitigation Strategies

2020

Advanced Materials

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redox flow systems to date. [7] However, their high chemical cost (V 2 O 5 , $24 kg −1) and low energy density (E d < 50 Wh L −1 , normalized based on both side of the electrolytes, unless specified otherwise) limit their wide implementation for large-scale grid storage. To boost the energy density of RFBs, nonaqueous RFBs with a wider potential window were developed. However, nonaqueous RFBs face intrinsic challenges such as high cost, flammability, and low ionic conductivity of organic electrolytes. [8] Here, we review recent developments of advanced materials for electrolyte design in ARFBs. We further classified ARFBs based on the type of active material: inorganic ARFBs (i.e., AIRFBs, including vanadium-, zinc-, iron-, polysulfide-based, and two other emerging systems); and organic ARFBs (i.e., AORFBs, including viologen-, 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO)-, quinone-, and N-centered heteroaromatic-mole culebased systems). We first summarize the fundamental physicochemical properties of redox couples in each ARFB system and then discuss critical challenges and mitigation design strategies to shed light on the design guidelines for future RFBs. Finally, assessment methodologies and metrics for evaluating battery stability among different ARFBs are discussed. 2. Aqueous Inorganic Redox Flow Batteries (AIRFBs) 2.1. Vanadium-Based AIRFBs 2.1.1. Fundamental Physicochemical Properties All-vanadium redox flow batteries (VRFBs, Figure 1a) are the most developed and widely used RFB system to date. Applying a vanadium element with diverse valence states (i.e., +2, +3, +4, and +5) effectively minimizes cross contamination, facilitates electrolyte regeneration, and provides long-term durability (Figure 1b-e). For example, a 200 MW/800 MWh system has been under construction by Dalian Rongke Power since 2016. [9] The reversible cell voltage of a VRFB is 1.26 V. The nominal cell voltage of VRFBs ranges from 1.15 to 1.55 V in acidic electrolytes, since the catholyte potential is pH-dependent. [10] The redox reactions on both sides are shown in the cyclic voltammetry (CV) analysis in Figure 1f. [11] Redox flow batteries (RFBs) are critical enablers for next-generation grid-scale energy-storage systems, due to their scalability and flexibility in decoupling power and energy. Aqueous RFBs (ARFBs) using nonflammable electrolytes are intrinsically safe. However, their development has been limited by their low energy density and high cost. Developing ARFBs with higher energy density, lower cost, and longer lifespan than the current standard is of significant interest to academic and industrial research communities. Here, a critical review of the latest progress on advanced electrolyte material designs of ARFBs is presented, including a fundamental overview of their physicochemical properties, major challenges, and design strategies. Assessment methodologies and metrics for the evaluation of RFB stability are discussed. Finally, future directions for material design to realize practical applications and achieve the comme...

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The role of phosphate additive in stabilization of sulphuric-acid-based vanadium(V) electrolyte for all-vanadium redox-flow batteries

Cited by 42 publications

References 32 publications

Vanadium Electrolyte for All-Vanadium Redox-Flow Batteries: The Effect of the Counter Ion

Vanadium Electrolyte for All-Vanadium Redox-Flow Batteries: The Effect of the Counter Ion

Vanadium Electrolytes and Related Electrochemical Reactions

Material Design of Aqueous Redox Flow Batteries: Fundamental Challenges and Mitigation Strategies

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