Scrap Science - 2022-01-03
Since I've been collecting dead lithium ion phone batteries over the last few years, the time has come to try to extract the lithium from them. I've collected over 160 Wh worth of battery capacity over that time, which should contain at least 12g of lithium content overall Initially, we extract the electrode materials and attempt to dissolve them in nitric acid, for the purpose of decomposing these nitrate salts later on, but things don't quite go as planned for any stage of the extraction. In the end, the only thing we obtain is decomposed electrode materials, which we'll have to extract the lithium from in a future video by a different method.
It's not a failure, now we know two ways that don't work.
Thank you for your effort.
With a name like yours, I was not expecting you to throw out the copper bits.
Thank you for sharing your efforts with us and, being frank about the results.
Distract yourself from this for a while, it will all come together when you make a fresh start. 👍
you are a legend mate. thanks for taking us on this journey with you no matter the result
You should try out oxalic acid to form lithium oxalate from solution. I normally use oxalate acid salts and use ethanol or or other organic solvents to selectively precipitate products. I haven't extracted lithium in a while, but I typically get good results going the oxalate salt route.
Ohh mate! Disappointing results, but still an awesome project to watch!! Keen to see where you go with this in the future. Don't give up!!
I tried this a couple months back with some cheap lipo batteries from a broken drill battery, different route, but with similar results. I'd dissolved all the mess into concentrated HCl, filtered, and precipitated out the metals with oxalic acid. I didn't have the issue Ex and Ire had with having to add oxalic as a salt, but then when it came to dropping the lithium out with carbonate I got absolutely nothing. In any case I was mostly after the cobalt anyway, so I just burnt off the oxalate and dissolved the oxides into sulfuric. to seperate the nickel out I got the cobalt into a +3 oxalate complex and the nickel fell out. But i think there was a bunch of other mess left over in there as after I oxidised the cobalt again and turned it into a sulfate the red solution grew green crystals. I can only assume there must have been some iron contamination, likely from incinerating it in a stainless steel pot.
Anyways blah blah, this video series has got me excited in that project and I'm considering trying it again taking some lessons learned from your series and thoisoi's video on the topic. But it is kinda fun chopping apart other peoples methods and trying your own. And rewarding when it works!!
As far as I can tell, pretty much everyone seems to get disappointing results with this extraction, so my hopes aren't particularly high here. It's good to hear other people's experiences in this area as well, so thanks for that!
At the very end of the extraction, I do have plans to separate the cobalt from the rest of the transition metals. I like your cobalt/nickel extraction method here too, maybe I'll have to look into that one.
@Scrap Science ooof, i just got back from a short walk where i managed to collect 46 old iphone batteries, totalling 80605MaH. From some calcs it looks like there should be around 24.2g of lithium, or 257.6g if i can get it as a carbonate!! this video really made me wanna try it again haha.
Not a success perhaps buy not a fail, just one of the steps toward success, love your work mate
Nitric acid
those plastics membrane layers from those batteries.
Please tell me you kept those because those make really good membranes for other electrochemistry and they replace flower pots for it.
Interesting, I always assumed the separators were some kind of lithium ion selective membrane, and that they were useless for other processes. I had no idea they were just microporous diaphragms.
Yeah, I've still got all of them, I'll be sure to hold on to them for later use.
@Scrap Science some of them are useless like that but not all. you would have to test them individually because either they use a lithium ion selective membrane or a general cation exchange resin which is better than a porous diaphragm.
These are not porous diaphragms but are similar to my PVA-Citrate membranes but are better because they are selective and nonporous.
A selective cation exchange membrane will not let solution to pass but sodium ions and the like can pass through which means you get better yield in membrane processes.
This was very interesting and made me wonder about extracting lithium from lithium grease.
Lithium will be well incorporated into that mineral mass you formed after fusing, that is after all the favoured discharged state and very stable (e.g lithium cobalt oxide). It's not present as lithium oxide, rather lithium minerals, so won't just selectively dissolve out in high yield. A little probably dissolved as lithium aluminate, but most of it probably still locked away in that matrix of fused product.
+Scrap Science The nitric acid method actually works. You just need to add some hydrogen peroxide to convert the cobalt in the electrode from +3 to +2.
Even though you were not successful, it was great to watch too see the outcome
How many grams of cobalt can be obtained in a large battery?
There will be no lithium oxide , you start with pretty much pure lithium when you open battery then it starts reacting with air and those tapes get hot, then lithium oxide will react with water and carbon dioxide form air making lithium carbonate which is weakly soluble and very stable thermally. I think you could recover lithium with something like citric or acetic acid bit to have something useful it has to be converted into lithium hydroxide somehow and that is pretty hard to do.
Why tf I doesnt this have more likes
Hello, if we assume that the lithium battery has undergone some kind of dehydration, what is the solution that is added to it..because it is known that it does not receive water, otherwise a catastrophe will occur
Thank you for the video! Should we call this hydrometallurgy process? In general, it seems no much different compared to high voltage lithium ion battery from electric vehicle. What do you think?
what volt do they need to be before opening them
If nitric acid supply is inadequate because of aluminium excess, could you get rid of the aluminium first, by dissolving the whole lot is sodium hydroxide solution? Then the Al could be decanted as sodium aluminate solution; I presume (but am not certain!) that the lithium salts would remain behind...
Yep, that was one of the plans to get rid of the aluminium. However, I decided against it in this case so that we wouldn't be adding sodium ions to the process at any point. I'm desperately trying to avoid sodium contamination since it will easily dominate our flame tests in the future.
Technically, I could have used potassium hydroxide I suppose (potassium contamination is much less of an issue), but I didn't think of that at the time sadly.
Scrap Science: "the copper... [is] pretty much useless." 🤣🤣🤣
lithium oxide reacts with aluminium oxide at temperatures between 400 and 1000C to give lithium alluminate (that should be an insoluble compound) so maybe that's why you don't have any lithium in your leaching solution
I get that pain of needing to step back and regroup elsewhere. Just had a possibility preventable die off of some novel project plants after the same "Yep, this'll do the trick!" It's the few I thought I brought back that aggravate the most.
Remember to wash your lithium in water as dirt residue can stick to the metals surface 😃
Video Idea !! - can potassium hydroxide be extracted from regular AA Alkaline batteries and then be used to build an Alkaline Fuel Cell ? which also uses potassium hydroxide as the electrolyte.
"Im a very optimistic guy... but he makin meth"
I would think a trip through a ball mill before you try dissolving the lithium would increase your yield. Or at least drop the processing time
The easiest way to get the lithium out is to fully discharge the batteries, then shed the guts and treat with carbonic acid soda water under pressure. The bicarbonate of lithium is extremely soluble. All the other metals are insouble in carbonic acid. The aluminum side is generally the anode and is pretty worthless. The copper foil side has the goodies in it generally cobalt and nickel oxide. Sometimes the batteries have nickel plated alumium as the cathode side collector. The easiest way to get the metals out is to process with a strong alkali to disolve the aluminum and a strong acid to free the metals. ❤
Winning attitude
It's not a failure, it's just an alternative version of success. You mentioned that the black mass has graphite in it, have you considered just burning that out? Get the furnace up to high temperature and pump through oxygen. You'd certainly be sure that everything was oxides then but I doubt they would be simple elemental oxides. Good luck.
consider adding a ball mill to your lab :) Great Effort though.
You could use HCl (or acetic acid) with H2O2 (in a well ventilated area) some times it worked for me in such situations.
what is the purpose of H2O2? there is nothing to oxidize there
@deltaxcd The H2O2 is used to oxidise all metals to their highest oxidation state and in some cases to the oxide form because some metals like zink, lead and some inorganic salts are insoluble in HCl or organic acids.
The H2O2 with HCl also produce some Cl radicals and Cl2 gas which is quite corrosive to most metals.
@MrMidnightI've done many of these electrode dissolutions and so long as you don't mind the Chlorine gas that comes off, you do not need any H202 at all. HCl will straight up completely dissolve the Aluminum foil electrode giving off H2 gas and heat from the Aluminum and CL2 gas for any cobalt in the higher than +2 oxidation state. The leftover black bits are carbon/graphite + PVDF. Everything else should be in solution and probably a little bit of chlorinated hydrocarbons. Where the H2O2 comes in handy is if you use sulfuric acid as this does not have the ability to reduce and will not dissolve the cobalt in the higher oxidation states without H2O2 being added.
Another tip I've found is that you don't need nitric acid to dissolve the copper electrode. Just take some KNO3 or NaNO3, mix in some HCl toss in the copper foil, add some heat (you don't need much heat here as a warm summer day in direct sun will get this going vigorously) and that will make quick work of the copper foil. This method takes some finesse...if too much copper added, some of the Copper(II) (green solution) will reduce to Copper (I) (solution turns brown). Just add some more HCl + Nitrates to get it back to Copper (II). While this does make some NO2 gas, I find that it isn't that much (and nowhere near the amount of NO2 that nitric acid + copper produce) and the reaction is mostly happening via the NOCl route (Nitrosyl Chloride). NOCl reduces to NO2 + metal chloride and so long as there is excess HCl present, the NO2 will stay dissolved and reform Nitrosyl Chloride (2NO2 + 4 HCl → 2NOCl + 2H2O + Cl2). If you don't let the reaction proceed too fast, even the Cl2 will stay dissolved and reduce copper directly with very little net gassing.
In the last sentence, I meant to say "oxidize copper" not "reduce".
Still wished you used electrochemistry... maybe in part 2 you can precipitate cobalt and whatnot as well just to have around! idk im looking forward to part 2 anyways!
Don't worry, electrochemistry will play a big role in part 2. And yes, if we're able to precipitate the manganese/cobalt/nickel in reasonable quantities, I'll definitely keep some around. While I don't think we'll be able to separate the cobalt and nickel from each other in that video, I'm thinking I might make a third video for selectively extracting the cobalt.
@Scrap Science Sounds good, can't wait!!!! Well I can I just don't want to :)
Maybe dissolving the metals in aqua regia would have worked. It's also more efficient on HNO3 use since 3 out of 4 parts are cheap HCl anyways. After that, a good old hydroxide participation, followed by adding sulfide/bisulfide in any form should definitely percipitate all transition metals. You just gotta be careful and not add too much OH-, because the participates of some metals such as Nickel can redissolve as complexes in case of an excess. Lastly, reducing the volume of the filtrate, followed by adding carbonate while the solution is still warm, should yield the lithium.
I tried something along those lines in part two of this video series, though I used a different acid and an odd source of hydroxide for the hydroxide precipitation. Still didn't work in extracting lithium, but I was eventually able to isolate the cobalt and nickel from the original mass.
Wouldn't the Aluminum dissolve in a highly base solution? Or does it only dissolve in sodium hydroxide solution?
That's true - at least, I think. Any strongly dissociating hydroxide should dissolve aluminium to some extent. That would explain what's left in solution (and what I subjected to a flame test), but still leaves the question of what made the solution basic in the first place... If it were lithium, it should still have dropped out with carbonate.
Your guess is as good as mine here.
At least you tried
Why you cant boil of the water of the hydroxide and then decompose the hydroxide to lithium oxide by further heating? I understand thats what happens around 950c
I mean, we could. But since we didn't have any major quantities of lithium in solution, it wouldn't have been useful. If we did dissolve significant lithium, our carbonate precipitation would have done the job anyway.
Alumina is soluble in alkaline solutions, that is maybe the white fluffy precipitate you saw when you neutralised (i.e. aluminium hydroxide).
Yeah that was my thinking, the precipitate looked very much like aluminium hydroxide (that was one of the main reasons I thought it wasn't lithium).
I started to do this once, I still have the liquid. I dissolved the aluminium with 8% cleaning vinegar stirring it at around 60C. 10 batteries took around 6 hours and a liter of vinegar to dissolve most of it. I left it for a few days and it all dissolved. I never went any father. Maybe that can help
ok I look at my videos, I dissolved the aluminium with 30% acetic acid stirring it at around 60C, 10 batteries. 1 liter of 8% cleaning vinegar I dissolved one tablet battery
I think you should be keeping nitric acid in amber reagent bottle. Distilling potassium nitrate and sodium bisulphate is fast way of making red fuming nitric acid shouldn't take all day to do a few runs of that plus you can dilute it
Don't worry, I keep my nitric acid container wrapped in aluminium foil and out of the light when I'm not using it.
The potassium nitrate/sodium bisulfate method is actually how I made this nitric acid, and it did take me a full day to make 150 mL of the stuff (which was the combined total of six batches). I'm afraid I just don't have the glassware necessary to run the reaction on a large scale yet.
I feel sorry for the copper electrodes.... you called copper "useless"!!! :(
I might be wrong, my only education on this is an honors chemistry class.
So i understand that Li is above K on the activity series, and therefore a reaction with KCO3 will occur. But LiCO3 is still soluble. So it will not precipitate. It appears as if you were confused why it didn’t, but I thought it was commonly known that alkali metal compounds are soluble. Was there another point to this?
A couple of things here:
First, the activity series only applies to single displacement reactions. In this case, we're doing a double displacement reaction between potassium carbonate and the lithium hydroxide we were expecting to be in solution, so it's completely irrelevant to think of things in terms of the activity series.
Next, lithium carbonate is actually barely soluble in water. At boiling temperatures, less than 1 gram can dissolve in 100 mL. We were expecting a possible yield of over 60 grams, so the salt should definitely have precipitated if lithium were present in solution. In fact, this is a very common method for extracting lithium from its solutions.
Hope that helps!
Lithium carbonate is very soluble and bicarbonate is extremely soluble. He attempted common ion effect but for carbonate it is tricky to do. Generally you need a highly ionizing ion like sulfate or chloride, but it isn't gonna work with lithium because LiCl and Li2SO4 are more soluble than the Na and K salts. Easiest way to grab Li is to treat with carbonic acid and leach it with a soxlet type setup then dry it.
Leaching with 2 M sulfuric acid with the addition of 5% H2O2 (v/v) at a pulp density of 100 g/L and 75 °C result in the recovery of 99.1% lithium and 70.0% cobalt in 60 min. H2O2 in sulfuric acid solution acts as an effective reducing agent, which enhance the percentage leaching of metals.
From which time H2O2 can be "reducing" agent?
Where are you located? I has some if you're close.
Tasmania's the one. Thanks for the offer, but I'd be surprised if we're nearby.
@Scrap Science ok no I'm in Brisbane
Well I'm going to get straight to the point. Is there any money to be made recycling these batteries like this and if there is,is it worth the effort and cost of the chemicals used?
As it stands, the process I've used is many times more expensive than the materials that are extracted. It's possible it could be made profitable with some serious simplification and free electricity, but there's a lot of work involved in trying that.
@@ScrapScience what about the larger batteries? Like tool batteries and bigger? I saw another video where the guy took the lithium out of a AA battery. Would the larger types be more easily removed?
@@ScrapScience also, is there a way to store and keep the exposed lithium from igniting or blowing up?
Larger batteries will work in exactly the same way, you'll just have to work on a larger scale. Things might be easier to extract, but you're still working with processes that are more expensive than the products you get.
As for lithium AA batteries, these are a completely different type of lithium battery, hence why they contain lithium metal itself. Rechargable lithium ion batteries (i.e., pretty much all of the lithium batteries excluding the AA ones) only contain lithium ions, heavily incorperated in a matrix of metal oxides, hence why we need complex processes to extract it.
If you do manage to get lithium metal, storing it under mineral oil is normally the best option to protect it from the air. Since it floats, you may need to push it down into the oil with some cotton or something.
@@ScrapScience ok. So any battery that says ion is going to be expensive and a hassle to remove the lithium? Do you know what batteries have the metal sheets?
Watch extractions and ire's video. You need to check.
The polymer membranes probably contain dissolved lithium too
Yeah, I've watched it a few times lately. Since he was only capable of getting a 2% yield with that method, it's not the route we're going to be following. The point is to try something different here.
And yes, the membranes probably have a bit of lithium in them, but the quantity should be extremely small compared to the oxide mixture, and the process of extracting it is much more difficult. A better chemist might give it a go, but making the extra effort for a tiny increase in yield isn't something I'm prepared to do.
reacting a solution of aluminium forms aluminium carbonate which decomposes into aluminium oxide
this aluminium oxide should be difficult to dissolve in an acid, where the lithium should be more easy to dissolve in an acid
Why not test the black oxide mass with pH paper after washing it five times? "If it's still basic it still contains lithium.
Hi, im dongwoo I think you have to wear gloves because HCl very dangerous.
Using a furnace i think you had destroyed the lithium you should have separated the lithium from aluminum foil and then leach the metal from that cathode matrial and then precipitate
Why would the furnace destroy the lithium? And how are you suggesting to separate the lithium from the aluminium?
The lithium in these electrodes is not in the form of metal - it is in the form of lithium cobalt oxide, where the lithium is present as ions, and is impossible to separate mechanically from the surrounding material.
@@ScrapScience Hi thanks for your reply during the heating in furnace lithium accumulate in the slag but i have some queries when you have melted the whole cathode and then cold it what happend to oxide and why you used water to extract lithium not any acid. I'll be very grateful if i can establish a proper contact with you. I m a researcher and i need a good discussion with you. I hope you will understand
You may have extracted beryllium
I sure hope not, that would be extremely concerning.
It would be very odd to have any traces of beryllium in a battery anyway, so I think I'm safe there.
@firstmkb - 2022-01-19
Enjoyed watching your process, and looking forward to the next installment - whenever you’re up for it.