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Author: Subject: Problems with Lithium Batteries
Abromination
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[*] posted on 28-7-2018 at 13:24
Problems with Lithium Batteries


This morning I was attempting to extract the lithium metal from an energizer lithium battery. First off, I tried using a method highlighted by NurdRage, invoving taking the cap off with nettle nosed plyers. I ended up failing and taking so much metal off of the cap end that I couldn't hold it anymore, the damn thing is impossible to remove.

Next, I tryed the method given by NileRed which involves cutting the steel casing with a pipe cutter. It was just dull enough to push the steel into the lithium and cause a reaaly bad short. I latter tryed to pull the casing apart but couldn't. I also started to notice a very concentrated rotten egg smell, the characteristic smell of hydrogen sulfide. I got out of there really fast and quickly gave up. I heard something about iron (ii) sulfide in lithium batteries (in NurdRage's video) but thought that iron sulfides only formed H2S when mixed with hydrochloric acid. Does anyone know why H2S (or some other damn thing smelling like rotten eggs in a lithium battery) would be formed and how I could open the batteries easier? Ive done this with the button lithium batteries before but never with AA lithiums.




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[*] posted on 28-7-2018 at 22:22


To take the metal off the cap try a pair of vice grips. Just be careful not to short them to the casing, i'd leave the plastic coating on to prevent this. I've taken the caps off them in one motion with a good pair of vice grips.



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[*] posted on 29-7-2018 at 01:26


You get much more Li from A123 cells, if you can find them cheap enough. The chemistry is different, too, so this problem will be avoided.




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For all your phlogiston needs.
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[*] posted on 29-7-2018 at 10:14


Well Im using these cause I had some older (not dead) AAs because I bought some fresh ones the other day and thought "hey why dont I dismantle these for lithium!"
And you are sure they wont short with the lining still on?
I will try vice grips later today.




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[*] posted on 29-7-2018 at 13:26


Thanks for the tip! It took me about two hours, but I managed to recover most of the lithium from the battery. The vice grips worked well but i lost a bit cause I somehow managed to fling the battery into a water puddle and lost about 3 cm of lithium. Thanks!


It still oxidises even under my vacuum deoxygenated mineral oil
Also the rotten egg smell has gotton unbearable and I think its from the iron disulfide. Is that correct?


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[*] posted on 29-7-2018 at 16:24


Glad it worked for you!
I keep my Na, K, and Li under toluene. It's a lot easier to remove from the metal than mineral oil, and is not miscible with water so there's no contamination.




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[*] posted on 29-7-2018 at 17:40


I preferably would but I dont have access to any right now. Ive decided that most of the oxidation on the bottom is from when I was unwraping it from the other stufd (the carbon disulfide got real damn hot) and some from air bubbles that got stuck underneath the lithium when I put it under the mineral oil. Also, is it possible that the air in the jar could completely react with the exposed lithium and pull a vacuum in the jar? It wouldnt be a full vacuum because of other non reactive stuff like nitrogen, but it could pose a problem.



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[*] posted on 29-7-2018 at 23:40


Quote: Originally posted by Abromination  
I preferably would but I dont have access to any right now. Ive decided that most of the oxidation on the bottom is from when I was unwraping it from the other stufd (the carbon disulfide got real damn hot) and some from air bubbles that got stuck underneath the lithium when I put it under the mineral oil. Also, is it possible that the air in the jar could completely react with the exposed lithium and pull a vacuum in the jar? It wouldnt be a full vacuum because of other non reactive stuff like nitrogen, but it could pose a problem.


Keep in mind that lithium is the only alkali metal that also reacts with nitrogen, so it cannot be considered inert in this instance. TBH the best way to store the lithium would be in the cells it comes in, and only extracting it when needed. Here is a way to get out all the lithium in under a minute:

The batteries has a small indent that goes all the way around near the positive terminal. Using a pair of garden shears (regular scissors might work as well), cut off the positive cap in one swift move. The core will be exposed at this point. Next, use a pair of needle nose pliers to grip the center of the rolled of core and pull hard. The layers will telescope out and with enough pulling come free entirely. Separate out the lithium from the other layers, and you're done! No mess, no fuss. (Keep in mine that you will likely short out the battery once you cut off the top, and you can feel it getting warm, but this is perfectly alright as long as you act reasonably quickly. I estimate you have around 5 minutes before the casing gets too hot to hold and you are better chucking it out the door.)
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[*] posted on 30-7-2018 at 07:29
Lithium shelf life


This thread reminded me that I have a part box (20 cells remaining) of Energizer +123 cells, CR17345.
Each cell has a date code 03-2020
The label on the box reads:-
Date of manufacture : February 2011
Not to be stored beyond : February 2017 (which is why I have them)

I have two simple questions :D

What liquid can be used to store lithium ?
(I don't understand toluene - the lithium should float ?)

Given that the cells are not new,
which is more likely to be a 'better' source of lithium as time goes bye,
future removal from un-modified cells, or immediate removal and storage

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[*] posted on 30-7-2018 at 08:14


Most oils that do not saponify (spelt that wrong) on contact with lithium. It is very common to store it under minneral oil (although it floats because lithium is way less dense) but it will sink under toluene, which is not reactive with alkali metals and just a better choice. Just be aware of its flammability.

The newer the batteries, the higher quality the lithium will be. But, since you have so many it would probably be worth extracting the lithium. Jusy be aware that it is extremely difficult and time consuming. I imagine that after a while you would get the hang of it. Wear gloves and goggles and work outside or in a fume hood as the fumes are really bad. If the battery shorts chuck it outside and atay away until it cools. It could easily explode. Immediately once removal put the lithium under mineral oil or toluene and make sure if you use mineral oil to deoxygenate it under a vacuum.




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[*] posted on 30-7-2018 at 09:31


https://www.ebay.com/itm/10g-High-Purity-99-9-Pure-Lithium-L...

10 g high purity Li free shipping.....$7.69

Just sayin'







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[*] posted on 30-7-2018 at 11:10


Quote: Originally posted by Dan Vizine  
https://www.ebay.com/itm/10g-High-Purity-99-9-Pure-Lithium-L...

10 g high purity Li free shipping.....$7.69

Just sayin'




There certainly is a place for buying, but if you are like me and have a bit of time and enough old batteries its worth your time. 7.69 is the price of a good pyrex flourence flask I bought a few weeks ago. Plus, we all know how buying elements of off of ebay can go...




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[*] posted on 31-7-2018 at 10:59


Quote: Originally posted by Abromination  
Most oils that do not saponify (spelt that wrong) on contact with lithium. It is very common to store it under minneral oil (although it floats because lithium is way less dense) but it will sink under toluene, which is not reactive with alkali metals and just a better choice. Just be aware of its flammability.

The newer the batteries, the higher quality the lithium will be. But, since you have so many it would probably be worth extracting the lithium. Jusy be aware that it is extremely difficult and time consuming. I imagine that after a while you would get the hang of it. Wear gloves and goggles and work outside or in a fume hood as the fumes are really bad. If the battery shorts chuck it outside and atay away until it cools. It could easily explode. Immediately once removal put the lithium under mineral oil or toluene and make sure if you use mineral oil to deoxygenate it under a vacuum.


I have to smile at this post, thank you for that. Looking at the first post in this thread tells me you have advanced much. Congrats
I may actually use some of your advice.
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[*] posted on 3-8-2018 at 17:32


Quote: Originally posted by morganbw  
Quote: Originally posted by Abromination  
Most oils that do not saponify (spelt that wrong) on contact with lithium. It is very common to store it under minneral oil (although it floats because lithium is way less dense) but it will sink under toluene, which is not reactive with alkali metals and just a better choice. Just be aware of its flammability.

The newer the batteries, the higher quality the lithium will be. But, since you have so many it would probably be worth extracting the lithium. Jusy be aware that it is extremely difficult and time consuming. I imagine that after a while you would get the hang of it. Wear gloves and goggles and work outside or in a fume hood as the fumes are really bad. If the battery shorts chuck it outside and atay away until it cools. It could easily explode. Immediately once removal put the lithium under mineral oil or toluene and make sure if you use mineral oil to deoxygenate it under a vacuum.


I have to smile at this post, thank you for that. Looking at the first post in this thread tells me you have advanced much. Congrats
I may actually use some of your advice.


Thank you. I feel like I do often. It was more the batteries that were troubling me than the lithium itself as I have worked with it before but with larger quantities I have certainly learned more.

Also do be very careful with the toluene as a toluene and lithium fire could be catastrophic for your lab (or you). NileRed demonstrated this with potassium.




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[*] posted on 4-8-2018 at 06:59


Quote: Originally posted by Abromination  
It is very common to store it under minneral oil (although it floats because lithium is way less dense) but it will sink under toluene, which is not reactive with alkali metals and just a better choice.


Density of lithium: 0.534 g/cm3
Density of toluene: 0.87 g/cm3

Lithium will float in toluene. To my knowledge, there is no solvent inert to lithium that it will not float in.
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[*] posted on 4-8-2018 at 13:10


I could swear I've read somewhere else that lithium floats on toluene. But after double checking those numbers I see that you're 100% right, MrHome Scientist. I guess that's just one of the misinformation that's floating around. No pun intended.



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[*] posted on 4-8-2018 at 20:48


Also, mineral oil can have a small (but not insignificant) amount of moisture which will also of course react with Li. Better than a vacuum is a vacuum with heat and stirring (120°C should work). Or you could place it in an evaporating dish in an oven @ 200-225°C for a few hours. Be careful because mineral oil is flammable at this temp.

Quote: Originally posted by MrHomeScientist  
To my knowledge, there is no solvent inert to lithium that it will not float in.


Paraffin wax, petroleum "jelly".

[Edited on 8-5-2018 by happyfooddance]
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[*] posted on 5-8-2018 at 17:13


Paraffin wax's density is about 0.9 g/cm3, so it would still float if it were liquid. It's solid at room temperature, though, so that's kind of a different situation. Perhaps I should have said 'liquid', but I figured 'solvent' covered that.
You could also store it under an inert gas, of course, which is what I do with mine (under argon).
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[*] posted on 5-8-2018 at 17:52


"Solvent" also covers things that are solid at room temperature, like paraffin wax. Sometimes I have to warm my acetic acid to get it out of the bottle in the winter, I still think of it as a solvent.
Even things that are gas at room temperature are commonly used as solvents (CO2, NH3, and countless others). I have no idea why you would think parrafin wax would be excluded from being considered a solvent because of its melting point. Tert-butanol, anyone?

Also, if someone can't figure out how to manipulate the melting point of paraffin to get their lithium to stay under the surface, they probably shouldn't be playing with lithium anyway, for their safety.

[Edited on 8-6-2018 by happyfooddance]
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[*] posted on 6-8-2018 at 03:13


Err, paraffin wax a solvent ?

It's an interesting idea but then how do you clean your lithium from the paraffin ?
I dont doubt it can be done, just unsure how messy and efficient it'll be.
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[*] posted on 6-8-2018 at 07:05


Quote: Originally posted by Herr Haber  
Err, paraffin wax a solvent ?

It's an interesting idea but then how do you clean your lithium from the paraffin ?
I dont doubt it can be done, just unsure how messy and efficient it'll be.


Rinse it in warm xylene. You can use a small brush to get the nooks and crannies as well as any oxidation layer.

I still don't know why anyone is shocked at the idea of wax as a solvent...
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[*] posted on 8-8-2018 at 20:40


Quote: Originally posted by Herr Haber  
Err, paraffin wax a solvent ?

Of course parrafin wax can be used as a solvent, it is used as one industrialy. Not a bad idea for storing lithium, as the lithium could be pushed under the hot liquid parrafin and the parrifin would hold it under when it solidifies . Just be careful not to light your lithium on fire.




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[*] posted on 8-8-2018 at 21:22


lithium extraction i did the same as the OP a couple years ago also some button cells have lithium metal knife cuts like clay. The botton cells can even be opened with nail clipers and much easier to open especially if you would rather work on small scale

[Edited on 9-8-2018 by symboom]




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[*] posted on 9-8-2018 at 02:27


Why are the Energizer Li cells 1.8V? Most (all?) other Li cells are right around 3V.
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[*] posted on 9-8-2018 at 02:32


Quote: Originally posted by Herr Haber  
Err, paraffin wax a solvent ?

It's an interesting idea but then how do you clean your lithium from the paraffin ?
I dont doubt it can be done, just unsure how messy and efficient it'll be.


In British English sometimes kerosene is called "paraffin" and Americans confuse this for the wax. I'm almost certain this is what's meant by keeping Li in paraffin.
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