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Frontiers in Energy

Front. Energy    2018, Vol. 12 Issue (2) : 198-224
Redox flow batteries—Concepts and chemistries for cost-effective energy storage
Matthäa Verena HOLLAND-CUNZ, Faye CORDING, Jochen FRIEDL, Ulrich STIMMING()
Chemistry-School of Natural and Environmental Sciences, Newcastle University, Newcastle upon Tyne NE1 7RU, United Kingdom
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Electrochemical energy storage is one of the few options to store the energy from intermittent renewable energy sources like wind and solar. Redox flow batteries (RFBs) are such an energy storage system, which has favorable features over other battery technologies, e.g. solid state batteries, due to their inherent safety and the independent scaling of energy and power content. However, because of their low energy-density, low power-density, and the cost of components such as redox species and membranes, commercialised RFB systems like the all-vanadium chemistry cannot make full use of the inherent advantages over other systems. In principle, there are three pathways to improve RFBs and to make them viable for large scale application: First, to employ electrolytes with higher energy density. This goal can be achieved by increasing the concentration of redox species, employing redox species that store more than one electron or by increasing the cell voltage. Second, to enhance the power output of the battery cells by using high kinetic redox species, increasing the cell voltage, implementing novel cell designs or membranes with lower resistance. The first two means reduce the electrode surface area needed to supply a certain power output, thereby bringing down costs for expensive components such as membranes. Third, to reduce the costs of single or multiple components such as redox species or membranes. To achieve these objectives it is necessary to develop new battery chemistries and cell configurations. In this review, a comparison of promising cell chemistries is focused on, be they all-liquid, slurries or hybrids combining liquid, gas and solid phases. The aim is to elucidate which redox-system is most favorable in terms of energy-density, power-density and capital cost. Besides, the choice of solvent and the selection of an inorganic or organic redox couples with the entailing consequences are discussed.

Keywords electrochemical energy storage      redox flow battery      vanadium     
Corresponding Authors: Ulrich STIMMING   
Just Accepted Date: 12 February 2018   Online First Date: 04 April 2018    Issue Date: 04 June 2018
 Cite this article:   
Matthäa Verena HOLLAND-CUNZ,Faye CORDING,Jochen FRIEDL, et al. Redox flow batteries—Concepts and chemistries for cost-effective energy storage[J]. Front. Energy, 2018, 12(2): 198-224.
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Fig.1  Schematics of different electrochemical energy storage devices (The location where the active material is stored is highlighted in red)
Fig.2  Ragone plot for four electrochemical devices, supercapacitors, batteries, redox flow batteries, and fuel cells
Fig.3  Figure illustrating the creation of a RFB system through the building up of individual cells into modular stacks (Reprinted with permission from Ref. [29])
Fig.4  A schematic diagram of the all-vanadium RFB in discharge mode
Type Advantages Challenges Ref.
Solid- liquid
(e.g. Zn/Br)
High energy density due to solid state • Internal short-circuits;
• High self-discharge
(e.g. LiCoO2/Li4Ti5O12)
High energy density due to high concentration of redox species • Limited conductivity of the slurries;
• High viscosities;
• Potentially sluggish kinetics of non-dissolved species
Mediated FB (Ferrocene as shuttle and LiFePO4 as storage material) • Low viscosity of shuttles;
• Good conductivity
• Limited variety of suitable redox mediators;
• Complicated reaction mechanism
(e.g. Fe/Cr)
Capacity that is only limited by the size of the tank Lower concentration of charge carriers than in the solid state [46]
(e.g. V/O2 or H2/V)
• Low costs for gaseous species;
• High concentrations of gaseous species can be reached, therefore high energy density
• Low energy efficiency;
• Self-discharge;
• Oxygen gas permeation through membrane need for catalyst loading on electrode;
• Pt leaching into the cell
Tab.1  Summary of advantages and drawbacks of various RFB concepts
Electrolyte Advantages Challenges Ref.
Aqueous • Environmental friendly;
• Inexpensive;
• High conductivities;
• Often high solubilities for redox species
• Small potential window
• Restriction by temperature range
• Corrosion processes by chloride ions
Non-Aqueous • Larger potential window than aqueous electrolytes;
• Larger temperature range than aqueous electrolytes
• Potential window limited by decomposition of additives;
• Safety risks;
• Low conductivity;
• Environmental hazards;
• Higher (maintenance) costs
Room temperature ionic liquids • Non-volatile;
• Non-flammable;
• Highly conductive;
• Chemically stable;
• Wide potential window;
• Environmental friendly?
• High viscosity;
• High (maintenance) costs;
• Low conductivity
Tab.2  Summary of advantages and challenges of various types of electrolytes used in RFBs
Fig.5  Performance data of a VRFB employing 3 M vanadium in 5 M total sulfate electrolyte with 1 wt% H3PO4 + 2 wt% ammonium sulphate additives
Fig.6  Cyclic voltammograms recorded at 0.5 V/s at a glassy carbon electrode in 0.5 M TEABF4 in CH3CN (dashed line) and 0.01 M V(acac)3 and 0.5 M TEABF4 in CH3CN (solid line) (Measurements were taken at room temperature. Reprinted with permission from Ref. [105])
Fig.7  A co-laminar flow cell by Goulet et al. [111]
Fig.8  Schematic representation of the polymer-based RFB and the fundamental electrode reactions of the TEMPO and viologen radicals
Fig.9  Performance data of a polymer-based RFB presented by Winsberg et al. [118]
Fig.10  Chemical structure of 9,10-anthraquinone-2,7-disulphonic acid
Fig.11  Alloxazine 7/8-carboxylic acid (ACA)
Fig.12  Redox reactions in the negative and positive electrolyte during charge and discharge in a hybrid TEMPO – Li RFB
Redox couples U0 vs. SHE Aqueous/non-aqueous k0/(cm s1) Concentration Number of electrons Energy content realized Reference
Br/Br2 1.09 V Aqueous 2 3 MWh [32,135]
Zn/Zn2+ −0.76 V Aqueous - 2
Fe2+/Fe3+ 0.77 V Aqueous 6 × 105 2 M 1 12 kWh in 1981 [136,137]
Cr2+/Cr3+ −0.41 Aqueous 2.2 × 105 2 M 1
VO2+/VO2+ 1.0 V Aqueous 106 1.6 – 2 M 1 800 MWh contract signed in 2016 [26,138]
V2+/V3+ −0.25 V Aqueous 106 1.6 – 2 M 1
Br3/Br +1.09 V Aqueous 4 × 105 1 M NaBr saturated with Br 2 120 MWh in 2002 [42,139,140]
S42–/S22 −0.265 V Aqueous 3 × 106 2 M Na2S 2
I3/I +0.54 V Aqueous - 5.0 M ZnI2 2 Approx. 0.01 Wh in 2015 [116]
Zn/Zn2+ −0.76 V Aqueous - 5.0 M ZnI2 2
Ce3+/Ce4+ +1.28 to+1.72 V Aqueous - 0.2 M Ce(III) methanesulfonate
(0.5 M methanesulfonic acid)
1 Approx. 3 Wh in 2011 [141]
Zn/Zn2+ −0.76 V Aqueous - 1.5 M zinc methanesulfonate
(0.5 M methanesulfonic acid)
Mn2+/Mn3+ +1.3 V vs Ag/AgCl Aqueous - 1 M MnSO4 + 1.5 M TiOSO4
(3 M H2SO4)
1 Approx. 20 Wh in 2015 [142]
Ti3+/TiO22+ ~–0.09 V vs Ag/AgCl Aqueous - 1 M MnSO4 + 1.5 M TiOSO4
(3 M H2SO4)
Fe2+/Fe3+ +0.77 V Aqueous 6 × 105 1 M FeCl2 + 0.5 M CdSO4
(3 M HCl)
No flow cell demonstrated. [143]
Cd/Cd2+ −0.40 V Aqueous - 1 M FeCl2 + 0.5 M CdSO4
(3 M HCl)
NiOOH/Ni(OH)2 0.490 V Aqueous - 1 M ZnO (10 M KOH) 2 Approx. 0.3Wh in 2007 [144]
Zn/Zn(OH)42– −1.215 V - 1 M ZnO (10 M KOH) 2
VIII(acac)3/[VIV(acac)3]+ +0.45 V vs. Ag/Ag+ Non-aqueous 1.3 × 104 0.01 M
(0.5 M TEABF4/acetonitrile)
1 No flow cell demonstrated. [66,105]
VIII(acac)3/[VII(acac)3] −1.8 V vs. Ag/Ag+ Non-aqueous - 1
RuIII(acac)3/[RuIV(acac)3]+ +1.0 V vs. SCE Non-aqueous 3.4 × 103 0.1 M
(0.5 M TEABF4/acetonitrile)
1 Approx 0.2 Wh in 2011 [145,146]
RuIII(acac)3/[RuII(acac)3] −0.85 V vs. SCE Non-aqueous 1
MnIII(acac)3/[MnIV(acac)3]+ +0.7 V vs. Ag/Ag+ Non-aqueous - 0.05 M
(0.5 M TEABF4/acetonitrile)
1 No flow cell demonstrated. [67]
MnIII(acac)3/[MnII(acac)3] −0.4 V vs. Ag/Ag+ Non-aqueous - 1
CrIII(acac)3/[CrIV(acac)3]+ +1.2 V vs. Ag/Ag+ Non-aqueous - 0.05 M
(0.5 M TEABF4/acetonitrile)
1 No flow cell demonstrated. [105]
CrIII(acac)3/[CrII(acac)3]/ −2.2 vs. Ag/Ag+ Non-aqueous - 1
[RuII(bpy)3]2+ /[RuIII(bpy)3]3+ +1.0 V vs. Ag/Ag+ Non-aqueous - 0.02 M
(0.1 M Et4NBF4/acetonitrile)
1 n.a. [68]
[RuII(bpy)3]2+/[RuI(bpy)3]+ −1.6 V vs. Ag/Ag+ Non-aqueous 1
[V(mnt)3]2–/[V(mnt)] 0.856 V Non-aqueous - 0.02 M
(0.1 M TBAPF6/acetonitrile)
1 No flow cell demonstrated. [147]
[V(mnt)3]2–/[V(mnt)3]3– −0.227 V Non-aqueous - 1
Fc/Fc+ (Fc= ferrocene) 0.041 V vs. Ag/Ag+ Non-aqueous - 0.01 M
(1 M TEAPF6/acetonitrile)
1 Approx. 0.3 mWh [148]
Cc/Cc+ (Cc= cobaltocene) −1.290 V vs. Ag/Ag+ Non-aqueous - 1
CoII(acacen)/[CoI(acacen)] −0.2 V vs. Ag/Ag+ Non-aqueous - 0.01 M
(0.1 M TEAPF6/acetonitrile)
1 No flow cell demonstrated. [149]
CoII(acacen)/[CoIII(acacen)]+ −2.2 V vs Ag/Ag+ Non-aqueous - 1
(QCl4 = Tetrachloro-p-benzoquinone)
0.71 V Aqueous - 0.5 M CdSO4
(1 M (NH4)2SO4 + 0.5 M H2SO4)
2 Approx. 0.2 Wh [150]
Cd/Cd2+ −0.402 Aqueous - 2
(BQDS= 1,2-benzoquinone-3,5-disulfonic acid)
0.85 V Aqueous 1.55 × 104 0.2 M
(1 M H2SO4)
2 Approx. 0.1 Wh [151]
(AQS= anthraquinone-2-sulfonic acid)
0.09 V 2.25 × 104 0.2 M
(1 M H2SO4)
TEMPO/TEMPO+ 0.30 V vs. Ag Non-aqueous - 0.1 M
(1 M NaClO4/acetonitrile)
1 <1 mWh [69]
−1.30 V vs. Ag Non-aqueous - 0.1 M
(1 M NaClO4/acetonitrile)
TEMPTMA/TEMPTMA+ 0.79 vs. AgCl/Ag Aqueous 4.2 × 103 2 M
(in NaCl)
1 Approx. 0.6 Wh [117]
Methyl Viol2+ /Methyl Viol+• −0.63 V vs. AgCl/Ag 3.3 × 103 1
Polythiophene/Polythiophene+ +0.5 V vs. Ag/Ag+ Non-aqueous - Suspension of polythiophene (0.1 eq. L1 of thiophene repeating units)
(1 M TEABF4/propylene carbonate)
1 Approx. 1.5 mWh [152]
Polythiophene/Polythiophene −2.0 V vs. Ag/Ag+ Non-aqueous - 1
TEMPO/TEMPO+ +0.7 V vs. Ag/AgCl Aqueous (4.5±0.1) × 104 polymer solutions
(2 M NaCl)
1 Approx. 80 mWh [89]
Viol2+/Viol+• ~–0.4 V vs. Ag/AgCl (9±2) × 105 1
Poly(BODIPY)/Poly(BODIPY)+ 0.69 V vs. AgNO3/Ag Non-aqueous - polymer solution
(0.5 M Bu4NClO4/propylene carbonate)
1 Approx. 0.006 mWh [118]
Poly(BODIPY)/Poly(BODIPY) −1.51 V vs. AgNO3/Ag Non-aqueous - 1
Tab.3  Overview of redox reactions of importance for RFBs
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