I am no scientist, and much of this discussion is beyond me, but I do have some experiences with aging cells that might be interesting.
I have an Analox ATA Pro trimix analyzer that was having problems calibrating and was way off at the far end of the scale with both the O2 and the helium sensors. Analox told me that if I was getting readings from both, I probably just needed to do a recalibration within the sensor itself, a process that involves a screwdriver. I opened up the box and decided that as long as I was in there, perhaps I should put in a fresh battery. Lo and behold, both sensors immediately calibrated perfectly, and they had no trouble measuring accurately throughout the full range.
A few weeks ago, I was with a group of divers, and we analyzed all our tanks in the morning before diving. The temperatures each morning were in the 30s F. I had a lot of trouble with both cells, especially the O2, the same ones mentioned in the paragraph above, that incident having occurred a bit more than a year before. Another diver had similar problems with his different brand analyzer, although his was more with the He sensor. We ended up using both analyzers on our tanks. A few days later I used my analyzer again, this time with temperatures in the mid 50s F. They both worked fine, although I had to turn the dial for both cells quite a bit for initial calibration.
In talking with a tech at the shop form which I planned to buy replacement cells, I learned that the O2 cell should last 3-5 years, and the He cell should last 10 years. The O2 cell was at its life expectancy, but the He was not. I replaced the battery again (it was only a year old) and, Bingo, the He cell was back to perfect, but the O2 cell was still calibrating at the far end of the dial. I have ordered a new O2 cell.