Zinc Bromine Batteries: How can we increase the solubility of TBABr?

As I mentioned in a previous post, the most important issue with the use of tetrabutylammoniumbromide (TBABr) in static Zn-Br batteries, is that the solubility of TBABr drops very sharply when zinc bromide is also in solution. While you can prepare 50% w/w solutions of TBABr in distilled water, the max concentration drops to around 0.15M when preparing solutions in the presence of 0.5M of zinc bromide. This is very bad because – in order to function as an effective sequestering agent – we would want the concentration of TBABr to be able to be significantly higher in solution.

Tetra-n-butylammonium bromide - Wikipedia
Graphic representation of the TBABr salt. You can see that the TAB+ cation has a strong aliphatic component

The solubility of TBABr drops because of a sharp increase in the polarity of the solution due to the introduction of the Zn+2 ions, which are small and – due to their double charge – substantially increase the dielectric constant of the medium. The TBA+ cation is actually not that polar, being spherical and with a strong aliphatic component, meaning it cannot very successfully interact with this new, much more polar medium. As a consequence the TBABr drops out of solution.

In order to prevent this from happening, we need to find solutions that either make the Zn cation less polar or make the media less polar by introducing a less polar additive that can compensate for the increase in polarity brought by the Zn cation. These two potential solutions however, need to avoid the TBABr3 becoming soluble as the perbromide needs to remain insoluble for the battery to work as designed (create an insoluble perbromide to prevent self-discharge).

To make the solvent less polar by adding something else, we need to consider our potential choices and their polarity. We could add another solvent that doesn’t react with perbromide, like an alcohol, but we would need to be very careful with the amount to ensure that it does not make the perbromide soluble (since we know TBABr3 is slightly soluble in alcohols (see here)). We could also decrease the polarity by adding a polymer – like PEG 200 – which also has the benefit of decreasing the formation of dendrites in the Zinc anode. Both of these solutions are potential avenues for experimentation.

Zn(II)-EDTA | Dojindo
The EDTA complex formed between EDTA and Zinc ions

To decrease the polarity by masking the Zinc ion we can use a chelating agent that can react with the Zinc in order to reduce its effect on the dielectric constant of the medium. We could do this by replacing ZnBr2 with ZnEDTANa2 which replace bromides by the Zn(EDTA)-2 complex and requires the addition of two sodium ions, which are bound to be significantly less polar than the Zn+2 cation. However this would imply we would have less bromide available, so it might require the addition of NaBr to recover the equivalent moles of bromide we have lost. Alternatively we can also just add NaH2EDTA2 but we would require to make pH adjustments to the electrolyte, which is not something we would like to do. Additionally, the ZnEDTANa2 reagent is cheap and easily available – as it’s used as a fertilizer in agriculture – and the NaBr is also really low cost. This solution decreases the specific energy/power of the battery though, as the weight is increased by the use of additional reagents.

So there you have it, three potential experiments to try to make TBABr a viable sequestering agent for high energy/power density Zn-Br static batteries. Will they work? I plan to test them out one by one!

Zinc Bromine Batteries: Is TBABr the best complexing agent?

Secondary Zn-Br batteries suffer from a huge problem of self-discharge due to the formation of elemental Bromine which, although largely insoluble in water, is soluble enough to migrate through the cell and react with the zinc anode, effectively self-discharging the cell.

To circumvent this issue, researchers have used chemicals that sequester the produced bromine into a product that has even less affinity for water — an insoluble or immiscible perbromide. In flow batteries this is done to generate a liquid phase that is immiscible with water, since it still needs to be a liquid to allow proper flow of the reagent. In static batteries this is undesirable, because a liquid is still able to flow through the cell and react with the Zn anode.

This is a figure taken from the Chinese paper. You can see that they do test the TBABr for its perbromide’s solubility

The 2020 Chinese paper we’ve discussed previously in this blog goes around this problem by using a sequestering agent that forms an insoluble perbromide, tetrapropylammonium bromide (TPABr). Notably the paper uses TPABr instead of tetrabutylammonium bromide (TBABr) which is almost an order of magnitude cheaper due to its significantly wider array of industrial uses compared to TPABr. Not only that, but the TBABr perbromide is even more insoluble, so the chemistry should be even better, right?

It is worth noting that they are aware of the above facts. You can see this in the image above – taken from the supporting information of the paper – where they clearly show TBABr forms an insoluble perbromide. So why did they choose to go with a significantly more expensive chemical (TPABr) and not use TBABr when its the obvious choice from a practical standpoint?

Precipitation of TBABr from a completely transparent TBABr 1M solution when in contact with a 0.5M Zinc Bromide solution

The problem – which I have lived through experimentally – is that the solubility of TBABr in the presence of ZnBr2 is quite terrible. The TBABr is extremely soluble in water – you can easily prepare a 50% solution by weight in distilled water – but it precipitates back very aggressively when put it into contact with a solution of zinc bromide. The image above shows you what happens when you mix a 1M solution of TBABr with a 0.5M solution of ZnBr2. The authors of the paper probably saw this issue and immediately recognized this as a potential problem for their batteries, my intuition is that they did run and have results for some cells using TBABr, but the results were probably so much worse than those of TPABr, due to this solubility issue, that they simply did not publish them.

The TPABr is most probably a significantly better sequestering agent because it’s likely significantly more soluble than TPABr in Zinc Bromide solutions. This agent is however unlikely to be soluble enough to support very large capacity solutions (>= 2M ZnBr2).

As I mentioned on a previous post, a better sequestering agent must allow for large solubility, be commercially available and form an insoluble perbromide. The only candidate I can think of to fulfill this role would be trimethylphenylammonium bromide (TMPhABr). I might be tempted enough to test it to order some from Alibaba if I can get a low quantity order for a reasonable price!

Zinc Bromine Batteries: Initial thoughts about a practical battery

During this past week I have been experimenting and thinking more about Zn-Br batteries and how a real practical battery would look like (how it would be built and what its characteristics would be like). Let’s imagine we have found a complexing agent that can be used in highly concentrated ZnBr2 solutions. What would a prototype battery look like and how much would it cost?

The first thing we need to consider is the geometry to build such a battery. Single-cell batteries for Zn-Br chemistry are impractical due to the limits that would impose on current density – and it’s not the 19th century – so the ideal battery would probably follow a configuration similar to modern lead-acid batteries, where multiple cells are put together to achieve better results. The simplest way to do this is to stack materials next to each other within a box, then flood the box with the desired electrolyte solution.

Proposed stacking of layers for a battery built in a 101x54x55mm project box. Note that the cells are laid horizontally (left to right) . Fiberglass separator thickness should be increased so all contents fit tightly inside the box.

In a 101mm x 54mm x 44mm project box you could fit a volume of around 237mL. If we decide to use a very porous carbon felt electrode – which I have experience with – with titanium current collectors, glass fiber separators and zinc anodes, we would create a cell configuration like the one showed above. This would occupy the entire cell with either separator, current collector, anode or cathode material. Given that the materials used take little real volume, as they are either very porous or very thin, I’m going to assume the solution volume we will fit will be equal to 200mL, which is realistic given the characteristics of the materials.

If we use a 2M ZnBr2 solution, this would give a maximum theoretical energy of 40Wh. If the cells are all connected in parallel, this would give us a battery with a voltage of 1.85 at a capacity of 21.6 Ah. The battery would be charged at a constant current of around 2.85A, although depending on the actual kinetics this might need to go down to even 285mA. In the above design you actually have only 6 cells that are each equal to 2 normal cells connected in parallel – as they share a current collector in the cathode – so connecting these 6 in series would give you a voltage of 11.1V with an expected charging current of 475mA.

The main caveat of the above design is that it uses a 2M ZnBr2 solution, assuming we can find a complexing agent that forms an insoluble perbromide that can be in the initial formulation at a concentration equal to at least the same as the ZnBr2 then this should be no problem. After a lot of research about the solubility of perbromides and organic ammonium salts I believe this might be possible using trimethylphenylammonium bromide, but such a complexing agent has never been tried! The 200 mL of solution used here would use 90.07g of ZnBr2 and 86.45g of TMPB.

Note that this configuration would certainly not work without a complexing agent that precipitates the tribromide formed. Without it the bromine would pool at the bottom and discharge the cell – in a horizontal configuration – or just sink and discharge the cell in a vertical configuration.

Cost (USD)ItemURL
3Project boxhttps://www.allelectronics.com/item/mb-132/abs-project-box-3.97-x-2.12-x-1.72/1.html
45Carbon felthttps://www.ceramaterials.com/product/gfe-1-pan-graphite-felt/
10.99Fiberglass tissuehttps://www.amazon.com/Multipurpose-Fiberglass-reinforcing-waterproofing-membranes/dp/B0719KWMJ7/ref=sr_1_5?dchild=1&keywords=fiberglass+paper&qid=1600038562&sr=8-5
11.49High purity Znhttps://www.amazon.com/99-9-Sheet-Plate-Metal-140x140mm/dp/B086FGDW83/ref=sr_1_5?dchild=1&keywords=Zn+sheet&qid=1600038696&sr=8-5
9.01Zinc BromidePrice with shipping confirmed from Alibaba vendor
19.99Titanium foilhttps://www.amazon.com/0-3mm-200mm-300mm-Titanium-Purity/dp/B07G8YYPFV/ref=sr_1_2?dchild=1&keywords=titanium+foil&qid=1600040029&sr=8-2
18.85TMPBPrice with shipping confirmed from Alibaba vendor
Potential materials used to construct a prototype Zn-Br cell

Using all the materials above, the cost of building such a prototype would be in the order of probably 120 USD. Probably around 200 USD after you add shipping for everything. In reality this cell is also unlikely to yield 40Wh and will most likely be in the vicinity of 20Wh if everything works as expected.

It is also important to note that an ABS project box like the one above is a risky first-choice, given that ABS can adversely react with elemental bromine, so a PTFE project box would – although much more expensive – be a safer choice for a prototype. By the time I build something like this, I hope I have already established that TMPB forms insoluble enough perbromide salts under my much more controlled Swagelok cell conditions.

Note that I am still far away from executing something like this! Currently I am even far away from testing a TMPB cell, but I wanted to write this blog post to condense all this theoretical research and serve as a referring point for me or others in the future.

Zinc Bromine Batteries: Can they really be that good?

In my quest to study Zinc-Bromine batteries, I have been diving deep into this 2020 paper published by Chinese researchers, which shows how Zn-Br technology can achieve impressive efficiencies and specific power/capacity values, even rivaling lithium ion technologies. I’ve found some important things when studying this paper, that I think anyone looking into this technology should be aware of.

An example of specific capacity values for different cells measured by the Chinese researchers.

First, let’s talk about the specific capacity values found within this paper. Usually the cells in the study would be charged to a specific capacity of around 500 mAh/g, with Coulombic efficiencies greater than 99% in some cases. The cell used has a diameter of 0.5 inches – which gives us an area of around 1.29032 cm^2 for the electrodes – with the capacity per area at 1.5 mAh/cm^2. This is pretty amazing, because it means we are getting 1.5 mAh out of 3 mg of active material. Wait, what?

The researchers are pretty clear in mentioning that they calculate the specific capacity values given the weight of the cathode but, what they fail to mention explicitly, is that this is not the weight of the entire cathode material but merely the conductive active material within the cathode, which has a carbon loading of 3mg per cathode piece. The real cathode does not weight 3mg, it weights significantly more – probably an order of magnitude more – given that the cathode is prepared using a binder in an 8:1:1 proportion with the carbon sources. This also does not count the weight of the electrolyte or the weight of the anode.

Granted, the above approach is not uncommon in battery research – reporting only capacity values of active materials – but in this case, in the real world, it’s not like you’re going to be getting 250 mAh/g of battery, you’re likely going to be getting a lot less. In the case of the specific power/energy values the researchers take into account the mass of electrolyte and complexing agent (ZnBr2 and TPAB) but they do not account for the mass of the separator, anode, or other materials.

Specific power/energy values published on the paper

The unfair and potentially misleading part about this is that they are comparing a very partial weight of their Zn-Br system, with the actual values for specific energy and power that have been measured for actual production Li-ion systems. We know of commercial Li-ion systems with specific energy values of 150-250 Wh/kg where that is delivered per actual kilogram of actual battery (including packaging and everything else).

Realistically a Zn-Br fully built battery is likely to have a specific energy way lower than what is published in this paper. So – not very surprisingly – realistic battery systems built with this technology will likely have an energy and power more on the low end of what current Li-ion technology has to offer, although they are bound to be superior to current Zn-Br flow battery designs.

The paper and Zn-Br technology are still extremely interesting – at least to me – because of the high efficiencies, way lower discharge rates, higher specific energy/capacities and other advantageous properties over traditional Zn-Br flow batteries, but they are unlikely to be a game-changer in the energy industry. As most of the time, researchers want to make their numbers look as good as they can within the general practices of the field and battery research is not the exception. I’m not saying that the researchers are being unethical or lying, just that the reader must be aware of how researchers report these numbers and how they compare to what you actually get in final products.

With that said, the confusion from how specific capacity/energy/power are measured in battery research is not without controversy. With some important efforts going on (see here) to try to create clearer standards within the field to avoid confusion.

Zinc Bromine Batteries: Think about the electrodes!

In order to study the chemistry of Zinc-Bromine batteries I have been using a swagelok cell that I bought from China that has a central Teflon body with stainless steel electrodes. This has been problematic due to the reactivity of these electrodes with the elemental bromine and tribromide salts produced in the battery, requiring the use of some “improvisation” in order to make the batteries work.

Charge/Discharge curve of a Zn-Br battery built using a zinc anode, carbon felt cathode, fiber glass separator and 0.5M ZnBr2+ 0.2 TBAB electrolyte in a swagelok cell with stainless steel electrodes covered with conductive HDPE.

To be able to generate the necessary chemical reactions without interference from the stainless steel I have coated the electrodes with some conductive HDPE I have, which has a relatively high volume resistance of around 10K ohm. The charge/discharge curve above shows you the type of measurements I have been able to achieve with this setup, with the above curve having a Coulombic efficiency of 88%.

This is lower than what I could achieve with the copper anode I was using previously (which gave me around 96%), but note how the charging voltage is lower and the discharge voltage higher, meaning that the overall energy efficiency is significantly better (around double). This is however not because of the zinc anode, but because with the conductive HDPE now covering both electrodes, I have now been able to tighten the cell more and achieve a lower overall internal resistance.

However the still relative low energy efficiency and voltage drop when going from charge to discharge are still pointing to significant sources of efficiency loss, possibly from the 10K ohm resistance that the conductive HDPE is giving. The weird shapes at the beginning and end of the discharge curve are also pointing to more than one chemical reaction happening, probably because the electrodes are still somehow interfering with the chemistry (maybe some micro holes in the conductive HDPE at points of stress are exposing the electrodes underneath). For this reason I have decided to get graphite electrodes for the Swagelok cell, which I will build from these 0.5 inch diameter graphite rods I found.

I am also going to change the current carbon felt cathode for carbon paper electrodes – which are on the way – but I will refrain from using the paper until I can perform some tests using actual graphite electrodes that are guaranteed to be free of any pesky side reactions, with way less resistance than this conductive HDPE.