You could say I am fully
capacitated now - my ELV ESR 1 arrived, and I finally bought a lab power supply (PeakTech 6227 - 60 V, 6 A, 150 W). Using the PSU limited to 0.002 A (which really is more like 0.8 mA and 0.001 A is virtually nil, but I mean it's a 6 A supply so what do you expect) and my multimeter's µA range, I conducted some experiments to see how far I could get electrolytic cap leakage down.
Put a few caps old and new to the test:
I always thought the old Elna 1000µ/25 out of my Kenwood KT-80 was in better shape than its counterpart out of the KT-900, but nope. ESR 0.04-0.05 ohms vs. 0.03 ohms, higher leakage (about 3 µA vs. 0.5ish µA at 25 V, things get a bit noisy sub-1 µA) and lower sustained voltage (31 V is really pushing it, the other one does 35 easily). With capacitance measuring about 0.98 mF as well, the KT-900 part could basically pass for a new cap. I did notice that pushing the voltage could worsen leakage once you returned to a lower one, so these old caps may not have much in terms of self-repair abilities left in them and may be living on borrowed time (electrolyte pH gone off - oh well, that sort of thing can happen after 44-45 years I guess).
(EDIT: With the 100k current shunt, leakage of the KT-900 specimen settles at 0.55-0.59 µA at 25 V. The next day, it's at 0.45 µA and still slowly falling... 0.41 µA... 0.335 µA... 0.28 µA... 0.26 µA... seemed pretty stable there. OK, that'll do. The KT-80 specimen has made it to 2.44 µA, but obviously that's still not nearly in the same ballpark.)
I was delighted to find some Nichicon UPW 1200µ/35V (16x20mm) at the local parts store. I was initially disappointed with the first specimen as leakage started out relatively high, however it only seems to have needed some "waking up" as I was able to get it into the 0.5 µA range at 35 V eventually (EDIT: 0.53 µA with a 10k shunt), and the second one behaved more like a new cap. These guys will also sustain 50 V fine. ESR measures 0.03 ohms, in line with the 0.029 ohm spec.
(EDIT 2: Leakage is down to about 0.15 µA after accidentally sitting for a few hours. Superb. Another 9 hours or so later, it has settled at around 0.10 µA. Swapping back in the 100k shunt, things settle to about 0.099 µA. Still seems to be going down veeery slowly, it's around 0.090 µA a good hour later, though at this point changes in ambient temperature seem to have a greater effect than anything else.)
A Jamicon TK 1000µ/63 that's been rolling around in my parts jar for the last 15 years seems like it might be a tad overrated in both capacitance and voltage handling from the way it behaves. It's more like an 820µ/50. ESR is fine at 0.03 ohms though.
Nichicon PL 2200µ/16 also from the parts jar, nothing unusual to note. ESR 0.02 ohms, in line with the <0.028 ohm spec.
NOS 4.7µ/25V Philips axial also from the parts jar (probably old even when I bought them), now that one needed some thorough reforming. These things had always struck me as quite leaky, and that's because they were. (These have a reputation of being crap anyway.) I managed to get this one to calm down to the point of 0.00µA with occasional blips of 0.02 and 0.04 µA on my meter at 38 V (clearly I need a more resolving test setup), things go downhill quickly around 40 V. I cobbled something together using a 100k resistor as a current shunt, that gives me 6.3ish mV or about 0.063 µA at 38 V, dropping to 0.030 µA by 35 V, 0.014 µA by 30 V, 0.006 µA by 25 V and 0.002 µA by 20 V. ESR 2.5 ohms, #2 is a bit better at 1.9 ohms.
Oh no, I just read the print on the cap... these are supposed to be 100V types.

OK, let's try 60 V then.... The cap has slowly made it to sub-0.5 µA and is inching towards 0.3 µA, but that's still hardly exciting. At least it seems to have helped leakage further down... 38 V now shows about 0.012 µA.
Cap #2 is, if anything, even worse. It has now reached
8.0 5.0 2.5 1.5 µA at 60 V, still going down...
You can readily observe the effect of dielectric absorption when going back down with your voltage.
If you are in a bit of a hurry getting the leakage current down, going somewhat above rated voltage can speed this process up. Most caps seem fine at the next higher rating or at least +20%. I would wait with going higher until leakage is firmly in double-digit µA territory though.
Does anyone know what sort of function describes leakage current vs. applied voltage? It seems to be quite extreme when approaching the voltage limit. At times I would go up a volt and it would virtually double. My guess is perhaps something like a*V + b*e^(V-Vth), but what do I know. I guess it's some sort of avalanche breakdown?
Either way, these experiments have confirmed my hunch about why the KT-880L uses a 2200µ/16V cap for +5 V memory backup instead of the 6.3V type found on the older KT-770(L) or misc. low-end models, it must bring leakage down substantially. With electronics obviously in the sub-µA range, capacitor self-discharging may otherwise have a substantial effect on backup times. Plus that cap, even if a bit bulky, still seems to work just fine, which is more than you can say about many of the double layer capacitors (aka goldcaps) that came later. (I still have to replace the one in my Onkyo T-4650 that is
conveniently located underneath the VFD, plus rework the reset/sleep circuit on the main PCB which is known marginal and not helping matters.)