Is this a magic pot, or a self-healing Li-Ion battery?

[RoGeorge]

Found last months a 10Ah Li-Ion cell.  It was swollen, like a pillow, about 2-3 times its normal thickness.  Charged it to 4.2V, out of curiosity, and it seemed to take charge just fine.  Then I've stored it in a thick metal pot with a normal lid, for just in case the battery will vent.

Next day measured its voltage again, still 4.1V, and the swollen was almost gone.  Back then I thought the battery's plastic bag cover might have developed a microscopic puncture/rupture somewhere and the gasses vented.

Stored it back inside the pot, put the lidded pot on the balcony for just in case more gases will vent.  Today looked at the battery again, and it is very, very flat.  The external cover looks like there was some suction from the inside. 

The battery measures now 4.06V.  Temperature was about the same at all times, ~25*C.

In phones battery, I've never seen a battery to recover by itself.  This 10Ah is not from a phone, looks like a bulk Li-Po cell somebody discarded because it was so bulged.

Is the bulging reversible?  What conditions are needed for that to happen?
How come that the mobile phones batteries never recover once bulged?

[AVGresponding]

Maybe the heatsinking effect of the iron pot allowed the gases to recombine into the electrolyte by cooling it to condensation point?   

[RoGeorge]

It was all at room-temperature. 

The battery being that bulged when I found it, I was afraid it might vent.  Charged it at first at 10mA for a few hours, then let it at about 100mA for 10 more hours or so, then charged it at 1A for another 10-20 hours.  I don't recall the exact charging time, but I've kept charging it for a whole weekend, until it finally reached 4.2V.  Then finally disconnected it at 4.2V, after the charging current dropped under 0.1A or so.

It didn't heat during charging, and it was stored in the pot only many hours later after charging.

[james_s]

I've never seen that happen, but if the cell is self-discharging in such a short period then it's obviously damaged and you really don't want to use a damaged LiPo cell, they have a nasty habit of failing spectacularly at some random later time. The self discharge should be negligible, a few percent a year perhaps.

[RoGeorge]

For now it is store inside that 3mm thick cast iron pot with a lid, in a concrete balcony with nothing else around.

I've write down the voltage a few times.  Measured max thickness of the pillow-like shape at first was 2cm and under small pressure inside (now it is 1.25cm everywhere, flat as a plank and under vacuum inside).
4.1873V - right after disconnected from the 4.2V charging, bulged as a pillow, some pressure inside but not much
4.1813V - 30 minutes later
4.1599V - 5 hours later
4.1390V - 15 hours later
4.1062V - 3 days later  <--  here it was de-bulged but no signs of internal vacuum, only a flask plastic cover
4.0935V - 5 days later
4.0663V - 20 days later  <--  today, as seen in the pics

The plan was to discharge it later and measure its capacity.  Because back then I've thought the plastic cover has ruptured, I've just let it there and never measured the capacity.

Maybe the bulging gasses did escaped, and something else entered and started another chemical reaction, and that absorbed the remaining gases and made the plastic cover stick to the battery material, thus self-sealing whatever micro-puncture might have been there before.

Another observation is I remember the internal material softer 3 weeks ago than it is now.  Not sure if this is because of the vacuum inside, or if the battery material started to harden itself.

[RoGeorge]

Made a chart with voltage over time, after a slow full charging terminated at 4.200V and 100mA.

[RoGeorge]

Just for the records, still showing suction-like from inside, the inside material feels more stiff/hardened when pressed with the fingers, added 2 more data points, after 34 days 4.0605V, and today 2023-06-08, after 52 days 4.0571V.  Voltage was measured at all times at a battery temperature of about 24...25 Celsius.

[tom66]

My understanding is that the bulging of a Li-Po cell is due to the buildup of carbon dioxide. It doesn't automatically mean the cell is dead, but it likely means it is somewhat degraded and liable to future failure.  I'm not sure if it means the cell is likely to combust though - but I'd still be very cautious around them.

This is common apparently on certain Nissan Leafs (which use a battery chemistry which is utter s***) but the vehicles will usually still drive okay for some time before a cell goes totally out of balance or open circuit.
Example - https://www.speakev.com/threads/swollen-battery-pack.169831/

[Jeroen3]

The chemistry is complicated. a common electrolyte is lithiumhexafluorophosphate, my understanding is that it takes some of the lithium cobaltoxide away when turning gasseous, which is in my basic chemistry not reversible?

[tunk]

I think I would try maybe 2-3-4 discharge/charge cycles,
and then monitor the voltage for a few weeks. The drop
between the two last points isn't too bad.

[Infraviolet]

If you want to charge/discharge cycle it any more I'd keep it outside on a concrete surface well away from buildings and well away from dry grass/vegetation. Perhaps place bets on which iteration of charging, or even discharging, it will be in when it combusts.

[AndyBeez]

No mysterous chemistry foo, it went down because the plastic pouch burst along a seam. Next time it will not bulge because the hydrocarbon and carbon monoxide gases that causes inflation (sometimes to 50psi) will be able to vent freely into the room. Discharge this battery and bin it.
Interesting paper for the EEs - "Calendar Aging and Gas Generation in Commercial Graphite/NMC-LMO Lithium-Ion Pouch Cells"
 https://iopscience.iop.org/article/10.1149/2.0241714jes

[RoGeorge]

Could be so, though the outside pouch looks sealed now, just like there would be some suction from inside the cell.  Interesting paper, thank you.

[amyk]

Since you put the lid on the pot, if any electrolyte vented it should contain the vapours.

If it deflated because it burst, the electrolyte smell is very noticeable, fruity and not unpleasant.

[SiliconWizard]

Are you working at Abbott, by any chance?

[RoGeorge]

2 years later... 
For the curious, the voltage of the same 10Ah cell while sitting disconnected on a shelf since last recharged 628 days ago:

Code: [Select]

Days Voltage
0.000 4.1873 2023-04-17
0.021 4.1813
0.208 4.1599
0.625 4.1390
3.000 4.1062
5.000 4.0935
19.000 4.0663 2023-05-06
34.000 4.0605 2023-05-21
52.000 4.0571 2023-06-08
99.000 4.0521 2023-07-25
562.000 4.0330 2024-10-30
628.000 4.0318 2025-01-04

To recap the story, I've found this cell in the EE waste basket about 2 years ago, it was so bulged it was 2-3 times thicker than normal, and the solid body of the battery (under the gasses inside the plastic pouch) was somehow soft, like a putty, but I didn't insist pressing on it.

Then after charging to 4.2V, I've let it sit, and found it deflated a few days later.  In fact, judging by the external plastic pouch it was looking like there was some vacuum inside.  And the putty-like material inside became hard as a plank. Still is.

Would be interesting to measure the current mAh, just that I didn't do that two years ago, so can't appreciate if, or by how much, that bulging incident from 2 years ago affected the cell.  Now I have the SW and HW setup to measure the mAh while discharging a battery, just that I have to do that while sitting in the same room for about 10-20 hours (it's a raw cell, no protection whatsoever, with at least one bulging incident in the past, and of an unknown provenience, and has a lot of Li inside - 10Ah nominal).  Don't want to risk a fire by letting it to discharge unsupervised, not even for a minute.

[Jeroen3]

You can discharge outdoors with a simple resistor if you intend te reycle it.

[RoGeorge]

Discharged the battery already.  Put it in the same thick metal pot, with a lid, and discharged under a constant current of 1A while logging the I, V and T.  The battery didn't heat at all.

The surprise was to drain yesterday more than 6.4Ah out from that battery (stopped at 2.5V).
That is for a 10Ah battery last charged 20 months ago, when it was as bulged as a pillow! 

After discharging, put it to charge overnight, with 1A and top 4.2V.  Stopped from charging when the current dropped to 80mA.  About 9.1Ah were put into the battery during the last night charging.  Now it is discharging again under 1A (0.1C) constant load, and so far it looks like a battery in good condition.

(Topic moved note:  This topic started as a curiosity, but turned into a long term experiment, so moved it from 'General Technical Chat' to 'Projects, Designs, and Technical Stuff'.)

[ArchieAltz]

Discharged the battery already.  Put it in the same thick metal pot, with a lid, and discharged under a constant current of 1A while logging the I, V and T.  The battery didn't heat at all.

The surprise was to drain yesterday more than 6.4Ah out from that battery (stopped at 2.5V).
That is for a 10Ah battery last charged 20 months ago, when it was as bulged as a pillow! 

After discharging, put it to charge overnight, with 1A and top 4.2V.  Stopped from charging when the current dropped to 80mA.  About 9.1Ah were put into the battery during the last night charging.  Now it is discharging again under 1A (0.1C) constant load, and so far it looks like a battery in good condition.

(Topic moved note:  This topic started as a curiosity, but turned into a long term experiment, so moved it from 'General Technical Chat' to 'Projects, Designs, and Technical Stuff'.)

Interesting how it didn't turn into a fireworks show during the discharging , seems like you got a magic pot on your hands 

[RoGeorge]

Meanwhile, did 5 cycles of charging/discharging at 1A.

Depending on how much it was charged (the stop current at 4.2V), and depending on how much it was drained during discharge (first at 1A stopping at 2.5V, then wait for voltage to recover and drain some more current at less than 1A, but with the same Vmin=2.5V limit) measured about 7-8Ah.  Logged and plotted the I and V during charging/discharging.


Regarding the bulging, it didn't happen at the first charge/discharge cycles.  But at the last discharge, I've insisted to repeatedly drain the battery down to 2.5V, wait for it to recover, then drain again at a smaller current, and so on, until I've drained out almost as much energy as it was put in during the previous charging.

As an effect to over-discharging, at the end it was a layer of about 1mm of gas between the solid body of the battery and its plastic pouch (the solid body of the cell is about 10mm, factory packed in a plastic pouch).

Then recharged it all night (limited 2A and 4.2V max), and until the next morning the charging current dropped to only 6mA, and the 1mm of gas was gone.

The battery looks again like there is some vacuum inside its plastic pouch.  My best guess so far is that somehow, this battery produces gases when discharged too much, and can absorb back the gasses into its solid body during charging.


P.S.
All these charge/discharge cycles were made inside the same container, so the magic pot theory is not yet disproved.