Monthly Archives: February 2026

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.