An aqueous, polymer-based redox-flow battery using non-corrosive, safe, and low-cost materials

Janoschka, Tobias; Martin, Norbert; Martin, Udo; Friebe, Christian; Morgenstern, Sabine; Hiller, Hannes; Hager, Martin D.; Schubert, Ulrich S.

doi:10.1038/nature18909

Cited by 97 publications

(136 citation statements)

References 3 publications

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“…5,6 Further disadvantages of classical RFBs are the deficient civil and environmental standards associated with ore mining, the applied hazardous and highly corrosive acidic electrolytes, and the expensive membranes such as the commonly used Nafion (DuPont, Wilmington, DE, USA) cation-exchange membrane. [6][7][8][9][10] The development of an all-organic RFB with inexpensive and sustainable redox-active materials and low-cost membranes may overcome these drawbacks. 7,[10][11][12][13][14] Among others, Darling et al 15 conducted cost analyses, which revealed that the price of the active material itself and the membrane represent the main costs of these systems.…”

Section: Introductionmentioning

confidence: 99%

“…[6][7][8][9][10] The development of an all-organic RFB with inexpensive and sustainable redox-active materials and low-cost membranes may overcome these drawbacks. 7,[10][11][12][13][14] Among others, Darling et al 15 conducted cost analyses, which revealed that the price of the active material itself and the membrane represent the main costs of these systems. Cost-efficient organic charge-storage materials can feature a price advantage compared with metal-based RFBs; in particular, if the raw materials are affordable, no synthesis or fewer synthesis procedures are required and the avoidance of elaborate purification steps can be achieved.…”

Section: Introductionmentioning

confidence: 99%

“…For example, a brief calculation for the anthraquinone disulphonate/bromine system yields a price of $27 per kW h for the redox-active organic charge-storage materials used, which is significantly lower than the price of $81 per kW h for vanadium systems. 16 In recent years, several semi-organic, [17][18][19][20][21][22][23][24][25][26][27][28][29] metal-free organic/ inorganic 16,30 and all-organic RFBs 7,[11][12][13][31][32][33][34][35] have been reported. Commonly, two different redox-active materials are used as chargestorage materials, one within the catholyte and the other within the anolyte.…”

Section: Introductionmentioning

confidence: 99%

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A bipolar nitronyl nitroxide small molecule for an all-organic symmetric redox-flow battery

et al. 2017

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An all-organic symmetric redox-flow battery (RFB) that employs nitronyl nitroxide (NN) units as a bipolar redox-active chargestorage material was designed and investigated. An organic molecule possessing two bipolar redox-active NN units connected via a tetraethylene glycol chain was synthesized for this purpose. Owing to the ethylene glycol chain, this molecule demonstrates good solubility in organic solvents. The electrochemical behavior of the obtained compound was investigated via cyclic voltammetry (CV) measurements and it features quasi-reversible redox reactions of the NN + /NN redox couple at E ½ = 0.37 V and the NN/NN − redox couple at E ½ = − 1.25 V versus AgNO 3 /Ag, which led to a promising cell voltage of 1.62 V in a subsequent battery application. A static solution-based battery exhibits a stable charge/discharge performance over 75 consecutive cycles with a high energy efficiency of 82% and an overall energy density of the electrolyte system of 0.67 W h l − 1 . In addition, a pumped RFB test demonstrates an overall energy density of the electrolyte system of 4.1 W h l − 1 and an energy efficiency of 79%.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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A bipolar nitronyl nitroxide small molecule for an all-organic symmetric redox-flow battery

et al. 2017

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“…15,16 Whereas previous studies have used such membranes to prevent electrolyte mixing, this work investigates battery operation using mixed electrolytes in order to simplify the battery hardware and to reduce capital costs. As with the all-iron flow battery, moderate amounts of electrolyte crossover in this configuration would not cause irreversible performance loss.…”

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confidence: 99%

Zinc-Iron Flow Batteries with Common Electrolyte

Selverston

Savinell

Wainright

2017

J. Electrochem. Soc.

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The feasibility of zinc-iron flow batteries using mixed metal ions in mildly acidic chloride electrolytes was investigated. Iron electrodeposition is strongly inhibited in the presence of Zn 2+ and so the deposition and stripping processes at the negative electrode approximate those of normal zinc electrodes. In addition, the zinc ions have no significant effect on the Fe(II/III) couple at the positive electrode. This enables the use of mixed Zn-Fe electrolytes and microporous separators in place of expensive ion-exchange membranes. Considering the low-cost materials and simple design, zinc-iron chloride flow batteries represent a promising new approach in grid-scale energy storage. The preferential deposition of zinc occurs with similar behavior on titanium, graphite and glassy carbon substrates. A proof-of-concept zinc-iron chloride battery starting with mixed electrolytes was demonstrated and maintains a consistent open-circuit voltage of about 1.5 V and stable performance during over 10 days and 100 cycles of continuous charge-discharge cycling. Zinc-based hybrid flow batteries are being widely-developed due to the desirable electrochemical properties of zinc such as its fast kinetics, negative potential (E 0 = −0.76 V SHE ) and high overpotential for the hydrogen evolution reaction (HER). Many groups are developing zinc-bromine batteries, and they address challenges associated with bromine toxicity and the organic complexing agents used to reduce its vapor pressure.1,2 Other positive electrode couples using cerium, vanadium, nickel and iron are also being investigated. 3-5Zinc-ferricyanide flow batteries using alkaline electrolytes were developed in the late 1970 s, but progress was reportedly hindered by high membrane costs and challenges with handling solid zinc oxide precipitates.6 Currently, zinc-ferricyanide flow batteries are also being developed by ViZn, Inc.7 Some of the challenges of using the Fe(CN) 3−/4− 6 couple include its low solubility on the order of 0.2-0.5 mol L −1 , and the possible generation of toxic gas if it mixes with acid. [8][9][10] More recently, a zinc-iron flow battery based on deep eutectic solvents (DES) with an open-circuit potential of 1.02 V was described, but it operated at a low current density of 0.5 mA cm −2 and so it was concluded that high-temperature operation would be required in order to obtain useful power densities. 11Of the possible reactions to use for a positive electrode, the aqueous Fe(II/III) redox couple is among the safest and cheapest, and it has high solubility and fast kinetics even on uncatalyzed carbon materials.12 However, most studies of zinc-iron batteries have focused on the alkaline chemistry (using Fe(CN) 3−/4− 6 at the positive electrode), and there are only a few reports of zinc-iron flow batteries based on the acidic chemistry. A recent study combined an alkaline (2.4 M NaOH) negative electrode with an acidic (1 M HCl) positive electrode to achieve high performance, but this required the use of two ion-exchange membranes as well as a third e...

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“…These organic molecules can be tailored to have certain properties, such as fast kinetics, high solubility and high associated cell voltage in the resulting flow battery [25][26][27][28]. They typically dissolve in either aqueous or non-aqueous electrolytes and can be incorporated in polymers [29] or appear as solid electrodes mixed with porous carbon and binders [30].…”

Section: Figurementioning

confidence: 99%

Membrane-less hybrid flow battery based on low-cost elements

Leung

Martin

Shah

et al. 2017

Journal of Power Sources

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The capital cost of conventional redox flow batteries is relatively high (> USD$ 200 /kWh) due to the use of expensive active materials and ion-exchange membranes. This paper presents a membrane-less hybrid organic-inorganic flow battery based on the low-cost elements zinc (< USD$ 3 Kg -1 ) and para-benzoquinone (< USD$ 8 Kg -1 ). Redox potential and voltammetric studies show that the open-circuit voltage of the battery is 1.17 -1.59 V over a wide range of pH. Half-cell charge-discharge and dissolution experiments indicate that the negative electrode reaction is limiting due to the presence of chemical side reactions on the electrode surface. The positive electrode redox reactions are not affected and exhibit (half-cell) coulombic efficiencies of > 92.7 % with the use of carbon felt electrodes. In the presence of a fully oxidized active species close to its solubility limit, dissolution of the deposited anode is relatively slow (< 2.37 g h -1 cm -2 ) with an equivalent corrosion current density of < 1.9 mA cm -2 . In a parallel plate flow configuration, the resulting battery was charge-discharge cycled at 30 mA cm -2 with average coulombic and energy efficiencies of c.a. 71.8 and c.a. 42.0 % over 20 cycles, respectively.

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An aqueous, polymer-based redox-flow battery using non-corrosive, safe, and low-cost materials

Cited by 97 publications

References 3 publications

A bipolar nitronyl nitroxide small molecule for an all-organic symmetric redox-flow battery

A bipolar nitronyl nitroxide small molecule for an all-organic symmetric redox-flow battery

Zinc-Iron Flow Batteries with Common Electrolyte

Membrane-less hybrid flow battery based on low-cost elements

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