Reproducing Zn-Br flow batteries using Sodium Sulfamate

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A recent Chinese Nature paper showed how Sodium sulfamate can be used in Zn-Br batteries to sequester active Br2 into an N-bromosulfamate that is much less aggressive, much more water soluble and even more easily electrochemically reversible than elemental bromine. I also wrote a recent post discussing the potential use of nicotinamide to achieve this (plot twist, it doesn’t work as the nicotinamide Zn complex is not very soluble). In today’s post I want to share with you my attempts at reproducing this chemistry of the Chinese paper using our open source flow battery dev kit.

The paper is very extensive and shares multiple formulations, they share a formulation for normal asymmetric cells as well as formulations to run the batteries using microporous Daramic membranes. Thankfully I have a bunch of 900um Daramic (thanks a lot to Daramic who donated these membranes to us for research). I bought some Sodium sulfamate (NaSA), Zinc bromide (ZnBr2), Potassium bromide (KBr) and potassium acetate (KAc) and proceeded to run some tests.

Tests using 1M ZnBr2, 1M KBr, 2M KAc, 1M NaSA. Charge and discharge were both done at 30mA/cm2.

My tests using the formulations that they disclose exclusively for daramic were not very successful. Formulations using only ZnBr2, KAc and NaSA suffer from either lower capacities because of lower conductivity or issues with hydrogen evolution. This was specially the case when I tried the ZnBr2 1M, KAc 1.5M, NaSA1.5M formulation, which they suggest in the supporting information to reach >50Ah/L. However I think this is a typo and they meant 2M ZnBr2. If you read that paragraph in the supporting information closely you’ll realize why this is the case (they previously refer to a ZnBr2 1M solution and then say this is basically 2x that, but still write it as ZnBr2 1M).

I then proceeded to test using some of the electrolytes they suggest for asymmetric cells, which were much more successful. In particular the 1M ZnBr2, 2M KAc, 1M KBr and 1M NaSA was great, with high CE values and decent EE values (see graph above). I didn’t experience dendrites before reaching the Nernst limit of the cells when using the 900um thick Daramic, which suggests plating is not as aggressively dendritic as with other electrolytes. However dendrites are quite evident when using 300um Daramic, suggesting you need around 300um of Daramic for every 30mAh/cm2. This might explain why the paper restricts most plating to below 90mAh/cm2 when using the 900um Daramic. I have yet to reproduce the Chinese group capacity or cycling stability values, but I believe I have validated the electrochemical principles well.

Clear evidence of dendrites at 78-79mAh (using 8mL of total electrolyte) using a 2M ZnBr2, 1.5M KAc, 1.5M NaSA electrolyte.

It is also worth noting that the Chinese group does some fancy functionalization of their felt with both nitrogen containing groups and carbon nanotubes, which aggressively boosts the conductivity and energy efficiency of the felt for the Br reactions. This is an important different that might justify why they get energy efficiencies closer to 75-80% while mine are just shy of 60%. I also haven’t optimized the compression ratio of my felt, which means that my felt might be under or over-compressed to extract the max EE in this setup. I also lack an oven to properly do air activation of the felt, so my felt is quite suboptimal and just used as-is.

Furthermore, the paper successfully tested a true flow battery setup using Ti-Br. I cannot easily buy TiOSO4 but I decided to try to innovate and test this chemistry in a fully symmetric setup coupled with 0.5M of Fe-DTPA. While Fe-DTPA isn’t expected to be fully resistant to N-bromosulfamate, I figured it might last enough to provide me with some data. Given that the redox potential of the Fe-DTPA redox couple is quite lower than Fe2+/Fe3+, I figured it should give some appreciable voltage in an Fe-DTPA/N-Br-sulfamate battery. Fe-DTPA is also quite soluble and stable at the near neutral pH that favors the N-Br-sulfamate chemistry, so it should work nicely.

Fe-DTPA 0.5M, NaSA 1M, KBr 1M, KAc 1M. Cycled at a current of 30mA/cm2.

The results above, which have never been published before, show that this chemistry works to some extent. The low CE does suggest that a significant portion of the Fe-DTPA is somehow lost, perhaps to oxidation by atmospheric oxygen (I cannot purge my cells with N2 or Argon at the moment), but also likely from just interactions with N-Bromosulfamate across the microporous membrane. With that said, it does show that the new stabilized bromosulfamate chemistry opens up the window to some very interesting options that just didn’t exist before. Perhaps I can test nicotinamide in this setup, where there is no Zn to cause it to precipitate out of solution.

Finally, I wanted to dedicate the above post to Robert Murray-Smith, a fellow chemist in the UK who passed away recently and was a key inspiration for the start of this blog. I know his passing has been very sad for a lot of us in the DIY community, the curiosity and inspiration he instilled in a lot of us will live on. Thank you Robert!

Could we create a Zn-Br flow battery using Nicotinamide?

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Zinc bromide flow batteries have been researched very extensively during the past 30 years. There are many advantages to this chemistry, very high potential (~1.8V), high efficiencies, symmetric electrolyte and low reagent costs. Nonetheless, the disadvantages are also huge: zinc dendrites, hydrogen evolution, bromine corrosion, etc. Despite all the development, a lot of these disadvantages remain insurmountable.

A recent nature paper has disrupted the field by using sulfamate ions as a bromine scavenger. Unlike previously used complexing agents that sequestered Bromine as reactive Br3- species, the new scavenging method sequesters Bromine as an N-bromosulfamate, which is stable in solution in the timescales necessary for energy storage. Furthermore, the N-bromosulfamate is chemically much milder than elemental Br2 or Br3-, making the use of cheaper gasketing materials possible and preventing a lot of issues associated with the high reactivity of elemental bromine species.

A model of the nicotinamide molecule. The Br reacts primarily with the amide group (NH2) under mildly acidic conditions.

I have been very excited by these findings and have ordered some sodium sulfamate to test this chemistry myself in our FBRC development kit. However, the development of this technology is likely not open source and it is very likely that the people involved with it want to patent it and lock down the technology. This made me think about potential alternatives that could be used outside of the sulfamate family that could also exploit the mechanism of Br storage in N-Br bonds. Such a technology might be outside the scope of their original paper and therefore be exempt from intellectual property registration.

Thinking about the stability of N-Br compounds (usually not stable at all), I immediately think about NBS and analogous chemical compounds. These are very stable reagents that are routinely used in chemical synthesis, although their aqueous solubility is very low and therefore not useful in the creation of a ZnBr2 aqueous battery.

With that said, nicotinamide (vitamin B3) is a very water soluble and readily available material that also forms a stable N-Br compound in mildly acidic conditions. This 2007 paper describes how N-bromonicotinamide can be created using elemental bromine. While N-bromine compounds from amines like this would often go through a Hoffman rearrangement to yield the corresponding amine, this doesn’t happen under mildly acidic condition in the case of nicotinamide. In fact, the 2007 paper mentions that a concentrated solution of this N-Br compound was stored for months without degradation. The solubility of nicotinamide is also very high (5-6M), compared to sodium sulfamate’s solubility limit of 1.3M at 25C.

An example of a nicotinamide-Zn complex. Check this paper to learn more.

Furthermore, nicotinamide forms mono and dimeric complexes with Zn atoms through the nitrogen in their pyridine ring, which makes this nitrogen unavailable for potential deactivation with direct bromination of this N to yield the corresponding quaternary nitrogen salt (irreversible and undesirable in the context of a battery).

Given that vitamin B3 is very soluble, very low cost, already produced industrially, has a stable amide N-Br compound and is unlikely to undergo Hoffman rearrangement or similar decomposition modes, it is a great candidate to serve as a Br2 scavenger in a ZnBr2 battery. I am going to buy some vitamin B3 to test this idea out. Stay tuned for some tests of this and the sodium sulfamate chemistry.

Studying a WiSE based all-Fe chemistry using our flow battery kit

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All-Fe flow batteries are very promising due to iron’s high abundance, low toxicity and low cost. In these batteries, FeCl2 is used as the main active salt in solution. When charging Fe2+ gets reduced to Fe metal on the anode while Fe2+ gets oxidized to Fe3+ on the cathode. However, these batteries suffer from a fundamental problem that has made their large scale adoption very difficult up until now.

Cyclic voltammetry of 1M FeCl2 and 4.5M CaCl2 using an Ag/AgCl reference electrode and a glassy carbon working electrode.

The main limiting problem of these batteries is H2 evolution at the anode. Since Fe plating happens at a lower potential than H2 evolution, there is always some hydrogen generation when the battery is charged. This H2 evolution causes an increase in the pH of the battery which then causes iron hydroxides and oxides to precipitate out of solution. This causes passivation of Fe metal surfaces, loss of capacity and potentially clogging of the battery.

A few years ago, Tao Gao’s group in Utah discovered that CaCl2 and MgCl2 water-in-salt-electrolytes (WiSE) (read the paper here) could substantially improve Fe plating behavior. While they didn’t test this in flow batteries, they showed that very high Coulomb efficiencies with very low hydrogen evolution rates were possible when using these salts. This is because these salts bond with water and therefore make it substantially harder for water to get reduced at the anode. We are talking about very highly concentrated solutions though, around 4.5M CaCl2, which is around 660g/L of CaCl2.2H2O.

Plate/strip experiment using the 1M FeCl2, 4.5M CaCl2 electrolyte.

We recently obtained some of these reagents to test these chemistries in our flow battery kit. I first ran CV experiments of the 4.5M CaCl2 electrolyte with 1M FeCl2 and obtained the curves showed above. This reveals standard potentials of -0.71V and 0.55V for the two half reactions, which means our battery should have a max potential of around 1.26V. I then ran plate/strip experiments (using different plating times), which generated the second curve above. Using the slope of this plot we can extract the plating efficiency, which is >99% in this case. This means that very little hydrogen evolution is happening within this electrolyte, a result I had never seen with FeCl2 solutions and which is in agreement with the Tao Gao group paper.

After doing this I then ran a flow battery using this electrolyte and noticed some problems with capacity loss because of undissolved metallic Fe on the anode using a Daramic separator. It seems that the above electrolyte has some issues with the reversibility of the plating reaction. While little hydrogen is generated on plating, there still seem to be some important losses of capacity due to passivation of the Fe. To fix this problem I then added 1M NH4Cl into the electrolyte, which helped me fix this issue when dealing with Zn-I flow batteries.

Cycling of an all-Fe battery using 1M FeCl2, 4.5M CaCl2 and 1M NH4Cl. Cycling was done at 20mA/cm2 Charging was done to 4Ah/L and discharge was done to 0V.

I cycled the battery at 4Ah/L, which generated the results above. You can see that we get extremely good CE values (97.88%) which are even better than those we were obtaining with the Zn-I system, even though we’re using a microporous separator. The energy efficiency is lower than for Zn-I but still reaches a value of 53.27%. Given a concentration of 1M FeCl2 , 4Ah/L represents a state-of-charge (SOC) of ~30%. The cycling is stable, although some increase of the charging voltage is indeed happening through time (although this is also matched by an increase in the discharge voltage). The mean discharge potential is quite low though, at 0.7V, which means we have considerable ohmic losses at this current density.

I am now testing the electrolyte at higher SOC values and will continue testing MgCl2 and other modifications, such as additions of ascorbic acid and thiosulfate to remove oxygen from the initial solutions and improve the initial state of the battery (as some capacity is lost due to the presence of oxidized Fe in the initial solution). Make sure to follow our progress on this forum thread.

This flow battery kit work is being funded by the Financed by Nlnet’s NGI0 Entrust Fund. We are also collaborating with the FAIR Battery project.

Our v2 Open Source Flow Battery Small Scale Kit is now stable

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After a lot of work on our small scale flow battery kit, the kit has now reached a form factor that is stable and will only require minor cosmetic changes from now on (to do things like hide exposed cabling, etc). The instructions for assembly of the kit are available at fbrc.dev. The kit is the culmination of 2 years of hard work from our team at the Flow Battery Research Collective, especially Kirk Smith and Josh Hauser, who both worked tirelessly with me in the design and fabrication of the kit.

Final form factor of the flow battery kit v2.
The back of the kit now features a box for the storage of the Arduino, to minimize the possibility of any solutions damaging the board. In the future we will add some modifications to better route the wiring.

Our final design uses Kaomer KPK200 24B pumps, polypropylene reservoirs and what Kaomer calls “Tygon Chemical Tubing” which seems to be a PTFE lined BPT tubing material. These materials are all compatible with the Zn-I chemistry and are also expected to be compatible with chemistries like Vanadium, Fe-Zn, pure Fe and even non-aqueous chemistries. The 24V pumps are driven using PWM signals coming directly from the Arduino, they also send digital signals back to the arduino that provide us with RPM information. This allows us to control the speed of the pumps quantitatively and achieve more robust experimentation. The mystat software has also been modified to allow direct control of the pumps from the software as well as monitoring of these readings.

Box design for the flow cell educational kit

As you can see above, we have also created a box design for the flow battery kit, which we have titled “Flow Cell Educational Kit” as applications for it can go beyond flow batteries. We may start publicly selling kits sometime in the near future, if there is enough interest from people wanting a plug-and-play solution (especially for academic environments). If you’re an academic researcher, battery enthusiast or professor looking to provide low cost flow battery setups for your students, feel free to let us know is such a kit would interest you.

These are some recent results using the latest kit setup using Zn-I chemistry. This test was ran at 2M KI, 1M ZnCl2, 2M NH4Cl with a 5% Triethylene glycol addition at 60mA/cm2 for both charge and discharge current.

Above you can see some experimental results using the kit and Zn-I chemistry. We are able to reproducibly cycle Zn-I chemistries to very decent SOC values, even though the above tests have been carried out without any nitrogen purging of the system. This is a testament to the robustness of the system and the Zn-I chemistry we are using as a showcase for it.

With all that said, none of the above would have been possible without the support of our financial sponsor for this project, the nlNet foundation. We are ever thankful for all their support in this endeavor. Thanks to them, we are also building a large scale, fully open source kit, that we also hope to release later this year.

This flow battery kit work is being funded by the Financed by Nlnet’s NGI0 Entrust Fund. We are also collaborating with the FAIR Battery project.

Working on a large scale open source flow battery design and kit

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During the past couple of years we have been working on the design of a small flow battery kit for the study of flow batteries (you can read a previous post about it here). With the help of an NLNet grant, we have fully developed the first two versions of our small scale kit – with the second one achieving even longer scale tests – and are now working on the development of a larger surface area kit that can be used to study flow batteries or build flow battery applications at a relevant scale for practical power storage.

A flowframe being printed on our Prusa Core One on Polypropylene. Such a large flat area piece is very hard to print without warping in non-heated chambers.

This new large area setup – which we have discussed in our forum – is now moving out of the design stage thanks to the acquisition of new systems for both 3D printing (Prusa Core One) and vinyl cutting (Cricut Maker4) that are allowing us to move to their in-house fabrication and testing. The new cell is designed to be compatible with the area of 3D printing beds and features an active area of 13.5×13.5cm, which is 182.5cm2. In practice this means a single cell will be able to handle a capacity of nearly 22Wh when using the Zn-I chemistry used in our small scale design.

We borrow some of the features that worked great for our small scale kit – like using a polypropylene enclosed flow frame – and add features that are needed for a scalable design (like all entry/exit points on the same side, stacking compatible design, etc).

Finished flow frame held against light so that you can see the flow field design. This design is not final and will change as we do fluid testing.

The fabrication of these pieces is especially challenging due to their size and the complexity of the flow fields in them. The flow fields have to follow complex paths to prevent the creation of large shunt currents within the device. A really good 3D printer with a heated enclosure is required to be able to print this in polypropylene with no warping and good enough resolution. Even with such a printer, a lot of fine tuning is still required to achieve the low level of surface roughness and high level of water tightness that is needed for this particular application.

While we are thinking about the potential of using heat welding or even adhesives to be able to put the cell together, the easiest first approach will be to use the same silicon gaskets as we used for the fabrication of our initial cells. To cut our gaskets in house we are using a Cricut Maker4 vynil cutter, which is able to make this high precision cuts without any problems.

One of our 3D printed polypropylene flow frames next to a silicone gasket

With these materials now fabricated, we are now close to putting together our first tests of a larger scale flow battery cell. The idea of these initial tests will be to test the cell for leaks and make sure we can circulate water without problems before we try to run any active materials. We will be using thick wood as endplates for this initial test, as this is the easiest to source, hard material, that can be used. Thanks to our use of fully enclosed gaskets, the end plates will also have zero contact with any water or active materials.

This flow battery kit work is being funded by the Financed by Nlnet’s NGI0 Entrust Fund. We are also collaborating with the FAIR Battery project.