In my previous posts about cation exchange membranes, I created a membrane using cross-linked PVA over a cellulose support. For this purpose, I used a filter paper and then applied successive layers of a solution with PVA, phosphoric acid and citric acid, which I then heated to 150C to create the final cross-linked membrane. This procedure created a membrane that had high permselectivity, decent in-plane conductivity and that could be produced for very low cost.

The problem however, came from the fact that the membrane degraded in the presence of Mn³⁺ , which was generated when the Mn|Fe chemistry I am testing is cycled. The degradation became apparent as the red color of the Mn³⁺ faded with time, although no crossing of the Mn³⁺ across the membrane happened. There were also a lot of bubbles generated on the membrane on the Mn side, which is further evidence supporting this degradation mechanism.

I think that this degradation happened mainly because of the cellulose, which is the most reactive part of the structure. To try to alleviate this problem, I decided to move away from the cellulose support and try to cross-link the PVA over a more stable substrate. To achieve this I performed the same cross-linking process, but this time doing it over a daramic polyethylene separator as support.

The Daramic is a microporous polyethylene separator – commonly used in lead acid batteries – which can be purchased for very little cost (only a few dollars per square meter). The daramic has a well defined pore size that can be filled with the PVA solution. Upon heating and reapplication of the solution, the pores can be filled with the cross-linked cation exchange material, with the daramic matrix providing the main source of structural support.

After the material has been saturated, heated to dryness and resaturated/redried multiple times with the polymer solution (10mL 14% H₂SO₄, 15g PVA, 8g citric acid, 250mL of water), the Daramic is then heated to 150C for one hour to finalize the process. The Daramic film created is black and has a permselectivity greater than 95%, measured in a cell with 0.1M KCl | 0.5M KCl. The first image in this post also shows how absolutely no cross-over of an Fe-EDTA salt is seen after running by this PVA+Daramic separator for more than 24 hours. When using just the Daramic microporous separator, cross-over is seen within minutes.

The great news is that the Daramic support is made of polyethylene, so it is very unreactive. The crosslinked PVA is also way less reactive than the cellulose, enough so that it now doesn’t react with Mn³⁺. I generated some of this material through electrolysis of an Mn-EDTA solution, and the crosslinked daramic didn’t bubble or degrade the Mn³⁺ after a couple of hours.

Sadly my potentiostat broke due to a small lab accident (spilled liquid over it), so I am waiting for a new potentiostat to be delivered to perform the first cycling experiments using this new cation exchange separator.