Flow Battery - Wikipedia

12/07/2021 Flow battery - Wikipedia
Flow battery
A flow battery, or redox flow battery (after
reduction–oxidation), is a type of electrochemical
cell where chemical energy is provided by two
chemical components dissolved in liquids that are
pumped through the system on separate sides of
a membrane.[2][3] Ion exchange (accompanied by
flow of electric current) occurs through the
membrane while both liquids circulate in their
own respective space. Cell voltage is chemically
determined by the Nernst equation and ranges, in
practical applications, from 1.0 to 2.43 volts.
A flow battery may be used like a fuel cell (where

the spent fuel is extracted and new fuel is added A typical flow battery consists of two tanks of liquids
to the system) or like a rechargeable battery which are pumped past a membrane held between two
(where an electric power source drives electrodes.[1]
regeneration of the fuel). While it has technical
advantages over conventional rechargeables, such
as potentially separable liquid tanks and near unlimited longevity, current implementations are
comparatively less powerful and require more sophisticated electronics.
The energy capacity is a function of the electrolyte volume and the power is a function of the surface
area of the electrodes.
Contents
Construction principle
Types
Redox
Hybrid
Membraneless
Organic
Metal hydride
Metal-organic
Nano-network
Other flow-type batteries
Chemistries
Advantages
Disadvantages
Applications
See also
References
External links
https://en.wikipedia.org/wiki/Flow_battery 1/14
Construction principle
A flow battery is a rechargeable fuel cell in which an electrolyte containing one or more dissolved
electroactive elements flows through an electrochemical cell that reversibly converts chemical energy
directly to electricity. Electroactive elements are "elements in solution that can take part in an
electrode reaction or that can be adsorbed on the electrode."[4] Additional electrolyte is stored
externally, generally in tanks, and is usually pumped through the cell (or cells) of the reactor,
although gravity feed systems are also known.[5] Flow batteries can be rapidly "recharged" by
replacing the electrolyte liquid (in a similar way to refilling fuel tanks for internal combustion
engines) while simultaneously recovering the spent material for recharging. Many flow batteries use
carbon felt electrodes due to its low cost and adequate electrical conductivity, although these
electrodes somewhat limit power density due to their low inherent activity towards many redox
couples.[6][7]
In other words, a flow battery is an electrochemical cell, with the property that the ionic solution
(electrolyte) is stored[8] outside of the cell (instead of in the cell around the electrodes) and can be fed
into the cell in order to generate electricity. The total amount of electricity that can be generated
depends on the volume of electrolyte in the tanks.
Flow batteries are governed by the design principles established by electrochemical engineering.[9]
Types
Various types of flow cells (batteries) have been developed,[10] including redox, hybrid and
membraneless. The fundamental difference between conventional batteries and flow cells is that
energy is stored in the electrode material in conventional batteries, while in flow cells it is stored in
the electrolyte.
Redox
The redox (reduction–oxidation) cell is a reversible cell in which electrochemical components are
dissolved in the electrolyte. Redox flow batteries are rechargeable (secondary cells).[11] Because they
employ heterogeneous electron transfer rather than solid-state diffusion or intercalation they are
more appropriately called fuel cells rather than batteries. In industrial practice, fuel cells are usually,
and unnecessarily, considered to be primary cells, such as the H
2/O
2 system. The unitized
regenerative fuel cell on NASA's Helios Prototype is another reversible fuel cell. The European Patent
Organisation classifies redox flow cells (H01M8/18C4) as a sub-class of regenerative fuel cells
(H01M8/18). Examples of redox flow batteries are the vanadium redox flow battery, polysulfide
bromide battery (Regenesys), and uranium redox flow battery.[12] Redox fuel cells are less common
commercially although many systems have been proposed.[13][14][15][16]
Vanadium redox flow batteries are the most marketed flow batteries at present, due to a number of
advantages they provide over other chemistries, despite their limited energy and power densities.
Since they use vanadium at both electrodes, they do not suffer cross-contamination issues. For the
same reason, they have unparalleled cycle lives (15,000–20,000 cycles), which in turns results in
record levelized cost of energy (LCOE, i.e. the system cost divided by the usable energy, the cycle life,
and round-trip efficiency), which are in the order of a few tens of $ cents or € cents per kWh, namely
much lower than other solid-state batteries and not so far from the targets of $0.05 and €0.05, stated
by US and EC government agencies.[17]
A prototype zinc-polyiodide flow battery has been demonstrated with an energy density of 167 Wh/l
(watt-hours per liter). Older zinc-bromide cells reach 70 Wh/l. For comparison, lithium iron
phosphate batteries store 233 Wh/l. The zinc-polyiodide battery is claimed to be safer than other flow
batteries given its absence of acidic electrolytes, nonflammability and operating range of −4 to 122 °F
(−20 to 50 °C) that does not require extensive cooling circuitry, which would add weight and occupy
space. One unresolved issue is zinc build-up on the negative electrode that permeated the membrane,
reducing efficiency. Because of the Zn dendrite formation, the Zn-halide batteries cannot operate at
high current density (> 20 mA/cm2) and thus have limited power density. Adding alcohol to the
electrolyte of the ZnI battery can slightly control the problem.[18]
When the battery is fully discharged, both tanks hold the same electrolyte solution: a mixture of
2+
−
positively charged zinc ions (Zn ) and negatively charged iodide ion, (I ). When charged, one tank
holds another negative ion, polyiodide, (I−
3 ). The battery produces power by pumping liquid from
external tanks into the battery's stack area where the liquids are mixed. Inside the stack, zinc ions
pass through a selective membrane and change into metallic zinc on the stack's negative side.[19] To
further increase the energy density of the zinc-iodide flow battery, bromide ions (Br
–) are used as the
−
complexing agent to stabilize the free iodine, forming iodine-bromide ions (I

2Br ) as a means to free
up iodide ions for charge storage.[20]
Traditional flow battery chemistries have both low specific energy (which makes them too heavy for
fully electric vehicles) and low specific power (which makes them too expensive for stationary energy
storage). However a high power of 1.4 W/cm2 was demonstrated for hydrogen-bromine flow
batteries, and a high specific energy (530 Wh/kg at the tank level) was shown for hydrogen-bromate
flow batteries[21][22][23]
One system uses organic polymers and a saline solution with a cellulose membrane. The prototype
withstood 10000 charging cycles while retaining substantial capacity. The energy density was 10
Wh/l.[24] Current density reached 100 milliamperes/cm2.[25]
Hybrid
The hybrid flow battery uses one or more electroactive components deposited as a solid layer.[26] In
this case, the electrochemical cell contains one battery electrode and one fuel cell electrode. This type
is limited in energy by the surface area of the electrode. Hybrid flow batteries include the zinc-
bromine, zinc–cerium,[27] lead–acid,[28] and iron-salt flow batteries. Weng et al.[29] reported a
Vanadium-Metal hydride rechargeable hybrid flow battery with an experimental OCV of 1.93 V and
operating voltage of 1.70 V, very high values among rechargeable flow batteries with aqueous
electrolytes. This hybrid battery consists of a graphite felt positive electrode operating in a mixed
solution of VOSO4 and H2SO4, and a metal hydride negative electrode in KOH aqueous solution. The
two electrolytes of different pH are separated by a bipolar membrane. The system demonstrated good
reversibility and high efficiencies in coulomb (95%), energy (84%), and voltage (88%). They reported
further improvements of this new redox couple with achievements of increased current density,
operation of larger 100 cm2 electrodes, and the operation of 10 large cells in series. Preliminary data
using a fluctuating simulated power input tested the viability toward kWh scale storage.[30] Recently,
a high energy density Mn(VI)/Mn(VII)-Zn hybrid flow battery has been proposed.[31]
Membraneless
A membraneless battery[32] relies on laminar flow in which two liquids are pumped through a
channel, where they undergo electrochemical reactions to store or release energy. The solutions
stream through in parallel, with little mixing. The flow naturally separates the liquids, eliminating the
need for a membrane.[33]
Membranes are often the most costly and least reliable components of batteries, as they can be
corroded by repeated exposure to certain reactants. The absence of a membrane enables the use of a
liquid bromine solution and hydrogen: this combination is problematic when membranes are used,
because they form hydrobromic acid that can destroy the membrane. Both materials are available at
low cost.[34]
The design uses a small channel between two electrodes. Liquid bromine flows through the channel
over a graphite cathode and hydrobromic acid flows under a porous anode. At the same time,
hydrogen gas flows across the anode. The chemical reaction can be reversed to recharge the battery —
a first for any membraneless design.[34]
One such membraneless flow battery published in August
2013 produced a maximum power density of 7950 W/m2, three times as much power as other
membraneless systems— and an order of magnitude higher than lithium-ion batteries.[34]
Recently, a macroscale membraneless redox flow battery capable of recharging and recirculation of
the same electrolyte streams for multiple cycles has been demonstrated. The battery is based on
immiscible organic catholyte and aqueous anolyte liquids, which exhibits high capacity retention and
Coulombic efficiency during cycling.[35]
Organic
Compared to redox flow batteries that are inorganic, such as vanadium redox flow batteries and Zn-
Br2 batteries, which have been developed for decades, organic redox flow batteries emerged in 2009.
The primary appeal of organic redox flow batteries lies in the tunable redox properties of the redox-
active components.
Organic redox flow batteries can be further classified into aqueous (AORFBs) and non-aqueous
(NAORFBs).[36][37] AORFBs use water as solvent for electrolyte materials while NAORFBs employ
organic solvents. AORFBs and NAORFBs can be further divided into total and hybrid organic
systems. The former use only organic electrode materials, while the latter use inorganic materials for
anode or cathode. In larger-scale energy storage, lower solvent cost and higher conductivity give
AORFBs greater commercial potential, as well as offering safety advantages from water-based
electrolytes. NAORFBs instead provide a much larger voltage window and occupy less physical space.
Quinones and their derivatives are the basis of many organic redox systems.[38][39][40] In one study,
1,2-dihydrobenzoquinone-3,5-disulfonic acid (BQDS) and 1,4-dihydrobenzoquinone-2-sulfonic acid
(BQS) were employed as cathodes, and conventional Pb/PbSO4 was the anolyte in a hybrid acid
AORFB. The quinones accept two units of electrical charge, compared with one in conventional
catholyte, implying that such a battery could store twice as much energy in a given volume.
9,10-Anthraquinone-2,7-disulfonic acid (AQDS), also a quinone, has been evaluated.[41] AQDS

undergoes rapid, reversible two-electron/two-proton reduction on a glassy carbon electrode in
sulfuric acid. An aqueous flow battery with inexpensive carbon electrodes, combining the
−
quinone/hydroquinone couple with the Br

2/Br redox couple, yields a peak galvanic power density
exceeding 6,000 W/m2 at 13,000 A/m2. Cycling showed > 99% storage capacity retention per cycle.
Volumetric energy density was over 20 Wh/L.[42] Anthraquinone-2-sulfonic acid and anthraquinone-
2,6-disulfonic acid on the negative side and 1,2-dihydrobenzoquinone- 3,5-disulfonic acid on the
positive side avoids the use of hazardous Br2. The battery was claimed to last for 1,000 cycles without
degradation although no data were published.[43] While this total organic system appears robust, it
has a low cell voltage (ca. 0.55 V) and a low energy density (< 4 Wh/L).
Hydrobromic acid used as an electrolyte has been replaced with a far less toxic alkaline solution (1 M
KOH) and ferrocyanide.[44] The higher pH is less corrosive, allowing the use of inexpensive polymer
tanks. The increased electrical resistance in the membrane was compensated by increasing the
voltage. The cell voltage was 1.2 V.[45][46] The cell's efficiency exceeded 99%, while round-trip
efficiency measured 84%. The battery has an expected lifetime of at least 1,000 cycles. Its theoretic
energy density was 19 Wh/L.[47] Ferrocyanide's chemical stability in high pH KOH solution without
forming Fe(OH)2 or Fe(OH)3 needs to be verified before scale-up.
Another organic AORFB used methyl viologen as anolyte and 4-hydroxy-2,2,6,6-

tetramethylpiperidin-1-oxyl as catholyte, plus sodium chloride and a low-cost anion exchange
membrane. This MV/TEMPO system has the highest cell voltage, 1.25 V, and, possibly, lowest capital
cost ($180/kWh) reported for AORFBs. The water-based liquid electrolytes were designed as a drop-
in replacement for current systems without replacing existing infrastructure. A 600-milliwatt test
battery was stable for 100 cycles with nearly 100 percent efficiency at current densities ranging from
20 to 100 mA/cm2, with optimal performance rated at 40–50 mA, at which about 70% of the
battery's original voltage was retained.[48][49] Neutral AORFBs can be more environmentally friendly
than acid or alkaline AORFBs while showing electrochemical performance comparable to corrosive
RFBs. The MV/TEMPO AORFB has an energy density of 8.4 Wh/L with the limitation on the TEMPO
side.
One flow-battery concept is based on redox active, organic polymers. It employs viologen and
TEMPO with dialysis membranes. The polymer-based redox-flow battery (pRFB) uses functionalized
macromolecules (similar to acrylic glass or Styrofoam) dissolved in water as active material for the
electrodes. Thereby, simple dialysis membranes can be employed. The membrane works like a
strainer and is produced much more easily and at lower cost than conventional ion-selective
membranes. It retains the big "spaghetti"-like polymer molecules, while allowing the small
counterions to pass.[50] The concept may solve the high cost of traditional Nafion membrane, but the
design and synthesis of redox active polymer with high water solubility is not trivial.
Aligned with the tunability of the redox-active components as the main advantage of organic redox
flow batteries, the idea of integrating both anolyte and catholyte in the same molecule has been
developed. Those so called, bifunctional analytes[51] or combi-molecules[52] allow the same material
to be used in both tanks, which has relevant advantages such as diminishing the effect of
crossover.[53] Thus, diaminoanthraquinone,[53] also a quinone, and indigo-based[51] molecules as
well as TEMPO/phenazine[52] combining molecules have been presented as potential electrolytes for
the development of symmetric redox-flow batteries (SRFB).
Another anolyte candidate is fluorenone, reengineered to increase its water solubility. A reversible
ketone (de)hydrogenation demonstration cell operated continuously for 120 days over 1,111 charging
cycles at room temperature without the use of a catalyst, retaining 97% percent of its capacity. The
cell offers more than double the energy density of vanadium-based systems.[54][55]
Metal hydride
Proton flow batteries (PFB) integrate a metal hydride storage electrode into a reversible proton
exchange membrane (PEM) fuel cell. During charging, PFB combines hydrogen ions produced from
splitting water with electrons and metal particles in one electrode of a fuel cell. The energy is stored
in the form of a solid-state metal hydride. Discharge produces electricity and water when the process
is reversed and the protons are combined with ambient oxygen. Metals less expensive than lithium
can be used and provide greater energy density than lithium cells.[56][57]
Metal-organic
Metal-organic flow batteries use organic ligands to provide more favorable properties to redox-active
metals. The ligands can be chelates like EDTA, and can enable electrolyte to be in neutral or alkaline
pH, conditions under which metal aquo complexes would otherwise precipitate. By blocking the
coordination of water to the metal, organic ligands can also inhibit metal-catalyzed water-splitting
reactions, resulting in some of the highest voltage all-aqueous systems ever reported. For example,
the use of chromium coordinated to 1,3-propanediaminetetraacetate (PDTA), gave cell potentials of
1.62 V vs. ferrocyanide and a record 2.13 V vs. bromine.[58] Metal-organic flow batteries are
sometimes known as coordination chemistry flow batteries, which represents the technology behind
Lockheed Martin's Gridstar Flow technology.[59]
Nano-network
Lithium–sulfur system arranged in a network of nanoparticles eliminates the requirement that

charge moves in and out of particles that are in direct contact with a conducting plate. Instead, the
nanoparticle network allows electricity to flow throughout the liquid. This allows more energy to be
extracted.[60]
Other flow-type batteries
Other flow-type batteries include the zinc–cerium hybrid flow battery, the zinc–bromine hybrid flow
battery, and the hydrogen bromine battery.
Semi-solid
In a semi-solid flow cell, the positive and negative

electrodes are composed of particles suspended
in a carrier liquid. The positive and negative
suspensions are stored in separate tanks and
pumped through separate pipes into a stack of
adjacent reaction chambers, where they are
separated by a barrier such as a thin, porous
membrane. The approach combines the basic
structure of aqueous-flow batteries, which use
electrode material suspended in a liquid
Semi-solid flow battery[61]
electrolyte, with the chemistry of lithium-ion
batteries in both carbon-free suspensions and
slurries with conductive carbon network.[1][62][63]
The carbon free semi-solid redox flow battery is also sometimes referred to as Solid Dispersion Redox
Flow Battery.[64] Dissolving a material changes its chemical behavior significantly. However,
suspending bits of solid material preserves the solid's characteristics. The result is a viscous
suspension that flows like molasses.[65]
Chemistries
A wide range of chemistries have been tried for flow batteries.[2]
Max. cell Average electrode power Average fluid

Couple Cycles
voltage (V) density (W/m2) energy density
Hydrogen–lithium
1.1 15,000 750 Wh/kg
bromate
Hydrogen–lithium
1.4 10,000 1400 Wh/kg
chlorate
Bromine-hydrogen 1.07 7,950
Iron–tin 0.62 < 200
Iron–titanium 0.43 < 200
Iron–chromium 1.07 < 200
Organic (2013) 0.8 13,000 21.4 Wh/L 10
Organic (2015) 1.2 7.1 Wh/L 100
MV-TEMPO 1.25 8.4 Wh/L 100
Metal-organic–
1.62 2000 21.7 Wh/L 75
ferrocyanide[58]
Metal-organic–
2.13 3000 35 Wh/L 10
bromine[58]
Vanadium–vanadium
1.4 ~800 25 Wh/L
(sulphate)
Vanadium–vanadium
50 Wh/L 2000[2]
(bromide)
Sodium–bromine
1.54 ~800
polysulfide
Sodium–potassium[66]
Sulfur-oxygen-salt[67]
Zinc–bromine 1.85 ~1,000 75 Wh/kg > 2000
Lead–acid
1.82 ~1,000
(methanesulfonate)
Zinc–cerium
2.43 < 1,200–2,500
(methanesulfonate)
Zn-Mn(VI)/Mn(VII) 1.2 60 Wh/L[31]
Advantages
Redox flow batteries, and to a lesser extent hybrid flow batteries, have the advantages of
flexible layout (due to separation of the power and energy components)

long cycle life (because there are no solid-to-solid phase transitions)
quick response times
no need for "equalisation" charging (the overcharging of a battery to ensure all cells have an
equal charge)
no harmful emissions.
Some types also offer easy state-of-charge determination (through voltage dependence on charge),
low maintenance and tolerance to overcharge/overdischarge.
They are safe because
they typically do not contain flammable electrolytes

electrolytes can be stored away from the power stack.
These technical merits make redox flow batteries a well-suited option for large-scale energy storage.
Disadvantages
The two main disadvantages are
low energy density (you need large tanks of electrolyte to store useful amounts of energy)
low charge and discharge rates (compared to other industrial electrode processes). This means
that the electrodes and membrane separators need to be large, which increases costs.
Compared to non-reversible fuel cells or electrolyzers using similar electrolytic chemistries, flow
batteries generally have somewhat lower efficiency.
Applications
Flow batteries are normally considered for relatively large (1 kWh – 10 MWh) stationary
applications.[68] These are for:
Load balancing – where the battery is attached to an electrical grid to store excess electrical
power during off-peak hours and release electrical power during peak demand periods. The
common problem limiting the use of most flow battery chemistries in this application is their low
areal power (operating current density) which translates into a high cost of power.
Storing energy from renewable sources such as wind or solar for discharge during periods of
peak demand.[69]
Peak shaving, where spikes of demand are met by the battery.[70]
UPS, where the battery is used if the main power fails to provide an uninterrupted supply.
Power conversion – because all cells share the same electrolyte(s). Therefore, the electrolyte(s)
may be charged using a given number of cells and discharged with a different number. Because
the voltage of the battery is proportional to the number of cells used the battery can therefore act
as a very powerful DC–DC converter. In addition, if the number of cells is continuously changed
(on the input and/or output side) power conversion can also be AC/DC, AC/AC, or DC–AC with
the frequency limited by that of the switching gear.[71]
Electric vehicles – Because flow batteries can be rapidly "recharged" by replacing the electrolyte,
they can be used for applications where the vehicle needs to take on energy as fast as a
combustion engined vehicle.[72][73] A common problem found with most RFB chemistries in the
EV applications is their low energy density which translated into a short driving range. Flow
batteries based on highly soluble halates are a notable exception.[74]
Stand-alone power system – An example of this is in cellphone base stations where no grid
power is available. The battery can be used alongside solar or wind power sources to
compensate for their fluctuating power levels and alongside a generator to make the most
efficient use of it to save fuel.[75][76] Currently, flow batteries are being used in solar micro grid
applications throughout the Caribbean.
See also
Glossary of fuel cell terms
Hydrogen technologies
Redox electrode
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External links
Electropaedia on Flow Batteries (http://www.mpoweruk.com/flow.htm)
Research on the uranium redox flow battery (https://web.archive.org/web/20050220030937/http://
www.imr-oarai.jp/en/research/research4-5.html)
How flow batteries work (https://www.youtube.com/watch?v=lAW-mMsCNlU) on YouTube
South Australian Flow Battery Project (https://arena.gov.au/blog/south-australia-goes-with-the-flo
w-battery/)
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A flow battery may be used like a fuel cell (where

complexing agent to stabilize the free iodine, forming iodine-bromide ions (I

9,10-Anthraquinone-2,7-disulfonic acid (AQDS), also a quinone, has been evaluated.[41] AQDS

quinone/hydroquinone couple with the Br

Another organic AORFB used methyl viologen as anolyte and 4-hydroxy-2,2,6,6-

Lithium–sulfur system arranged in a network of nanoparticles eliminates the requirement that

Other flow-type batteries

In a semi-solid flow cell, the positive and negative

Max. cell Average electrode power Average fluid

Zn-Mn(VI)/Mn(VII) 1.2 60 Wh/L[31]

flexible layout (due to separation of the power and energy components)

They are safe because

they typically do not contain flammable electrolytes

Retrieved from "https://en.wikipedia.org/w/index.php?title=Flow_battery&oldid=1033074675"

This page was last edited on 11 July 2021, at 12:37 (UTC).

Text is available under the Creative Commons Attribution-ShareAlike License;

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