Chemistry of Flow Batteries

Technology is progressing more and more with each passing day. In order to support these changes, advancements regarding power supply must also be made. At the moment, the trend is moving towards more efficient and sustainable sources of energy. The rechargeable, low-cost, and long-lasting flow battery seems to fit the bill perfectly. Of course, it is not as well known as the common lithium-ion battery because it is used on a larger scale rather than for small everyday items. It can be used to store excess electrical grid power which is then released during periods of high demand.

When you hear the word “battery”, the first thing that comes to mind is probably a package of AA or AAA batteries — you know, the ones with the adorable Energizer bunny on the front? Flow batteries are neither portable nor small. In fact, they consist of two liquid-filled tanks that are separated from the actual cell of the battery. These “tanks”, or electrolyte reservoirs, pump liquid electrolytes into two half cells separated by a membrane, as can be seen in the image below.

A reduction reaction takes place on one side and an oxidation reaction in the other, similar to the reactions within the fuel cells we mentioned in our last post. The membrane between the two half cells  keeps  the electrolytes separate, but is thin enough to allow certain ions to pass through in order to complete the redox reaction. Ions from both sides flow through the membrane and react with the electrodes on both sides of the cell, drawing energy from them. To store more power, the batteries can be stacked in a bipolar arrangement. At this point, they essentially provide unlimited electrical storage capacity. The only limit is the capacity of the electrolyte reservoirs.

Sounds pretty simple, right? Now for the interesting, and slightly more complex, part: how the actual energy storage takes place. The liquid electrolytes that flow through the cell are mixed with energy storing materials such as iron, vanadium, zinc, or bromine. Zinc-bromine flow batteries, for example, have a zinc anode in one half cell and a bromine cathode in the other. Aqueous zinc bromide is circulated through the two half cells. In discharge, (bottom image on right) a load is applied to the cell and the zinc metal on the anode is oxidized (Zn(s)↔ Zn2+(aq) + 2e) to form zinc ions and bromine is reduced to bromide ions at the cathode (Br2(aq)+ 2e ↔ 2Br(aq)). When the battery is completely discharged, the metal zinc on the anode dissolves in the electrolyte. It is stored there until the battery is recharged (top image on right), during which the reactions involving zinc and bromine are reversed. The zinc ions are reduced back to metal (Zn2+(aq) + 2e– ↔ Zn(s)), thus plating metallic zinc back onto the electrode. On the cathode side, bromide ions are oxidized into molecular bromine in the aqueous solution (2Br(aq) ↔ Br2(aq) + 2e) which combines with an oil to form a dense, oily liquid called a polybromide complex. As more polybromide complex is created and more zinc metal is plated onto the anode, the energy stored in the system increases. Because there are always fresh electrolytes in both half cells, the system is always ready to produce full power, even when the pumps are off. The electrodes in the zinc-bromine batteries don’t take part in thereactions but rather function as substrates, so repeated cycling won’t cause the electrode materials to deteriorate, as it would in most other rechargeable batteries.

So far, flow batteries seem like the best option available. The only problem is that they’re not quite available — not commercially, at least. Right now, the main issue is cost. The most commercially developed flow battery utilizes the rather expensive metal vanadium. For this reason, a team of Harvard researchers have recently developed a new type of metal-free flow battery that instead uses organic molecules called quinones, specially those found in rhubarb. According to Harvard author Roy Gordon, there is a limited number of metal ions that can be put into solution and used to store energy, none of which can store large amounts of renewable energy. For this reason, researchers have turned to organic molecules. The quinone used by the Harvard team is known as 9,10-anthraquinone-2,7-disulfonic acid (AQDS). What is unique about AQDS is its capacity for rapid reactions. It is able to undergo quick and reversible two-electron two-proton reduction on a glass-like carbon electrode in sulfuric acid. Although the small battery prototype has only run through about a hundred cycles, so far it has exhibited little to no losses. The model displays nearly the same performance as vanadium flow battery, but is much less expensive.

Flow batteries have a promising future, though they are not widely available at the moment and there are still unresolved issues regarding cost and production. Eventually, large quantities of energy will need to be stored and conserved in order to sustain our population and the great demand for power. Flow batteries will undoubtedly provide the best and most efficient solution.


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