First of all, sorry for the weird audio in this video. I ended up having to re-do a voiceover for the first part, and was quite unwell when I recorded the middle section. You might notice some parts where the audio doesn't quite match the video, or other issues with sound. Regardless, please enjoy!
Wow, this really needs a bigger cathode! Putting that much current through a tiny little cathode is really inefficient. If you want good metal plating, with reasonable coulombic efficiency, the cathode needs to run at less than 50mA per square cm. 1.5A over the 5cm2 or so you’ve got there works out at more like 300mA / cm2. 6x too high! Most of the current will be splitting water and making your cathode very basic, which really slows it down and wastes electrons.
This is something I've been looking at doing with my lithium battery collection. Do you think it is possible that only one metal is plating due to the voltage used? I have read that electrowinnowing can plate out one metal at a time if you target the voltage needed and then step up the voltage for the next metal. I haven't tried this yet. A note on dendrite formation; from experience, this tends to form from a few different factors. Some will form because the metal is cleanest at the points where it has been freshly cut, having any passivating or oxide layers removed so current will want to go to the path of least resistance. A clean of the cathode will help with this. The second point is that from everything I have read, low current densities on the surface area of the cathode leads to a much more uniform coat of plated metal. I've seen this a few times as well but I suppose that you are only looking for extraction and not plating and purifying.
While it's generally possible to selectively plate out metals from solution, the reduction potentials of cobalt and nickel are so close together that this is virtually impossible unless you can influence overpotentials in some way. With metals exhibiting a higher difference in reduction potential (like copper and zinc), this is much more achievable. And yes, low current densities generally give a better metal coat, but we're more interested in minimising the parasitic hydrogen formation to maintain an acceptable efficiency. For this, it's generally better to use a higher current density. In proper plating experiments, hydrogen should not be an issue as it is here.
If you dont mind sharing, where did you get your platinum electrode? Trying to find one that doesn't empty the wallet and is of usable quality can be a bit of a gamble
I'm afraid the place I got my electrode from doesn't exist anymore. I've been looking around, but I can't actually guarantee the authenticity of any sellers right now.
Not that I expect you to try the lithium again, but if you do, look into Royal Water. It was/is a method of dissolving gold and platinum solids in hydrochloric acid and nitric acid. I can't recall the ratio off-hand, but memory is telling me 4:1 hcl to nitric. Extraction you can either distill off the acids (not my favorite way, but it works better under vacuum) or run it through an adequately sized aluminum silicate filter; I've not tried the latter but I have some on order to try with another process I'm working on. Gold isn't too surprising, but if it works for platinum, lithium ought to be a breeze.
Sulfuric acid will cause cobalt sulfate to precipitate due to common ion effect. You may have better luck using hcl as your acid. An easier way to get your cobalt free would be to mechanically separate the cobalt layer from the battery, then wash the black stuff in vinegar to remove the lithium. Next heat it to burn off the carbon. Then use a termite reaction to convert to the metal. They usually use copper 1 oxide mixed in with the cobalt oxide
Do you think using a claypot membrane would have made the process more efficient? Maybe place the undisolved hydroxides in with sulfuric acids snd the platnum anode and the cathode inside a clay pot. I'm thinking the pot will tend to keep more of the sulfuric in the anodic container jeeping it in a higher concentration to better react with and dissolve the undisolved hydroxides, while the metals will tend to hang out in the cathodic chamber and better plate rather than participate in side reactions with the sulfur that lower the overall efficiency.
The process would definitely be more efficient from a Faradaic standpoint. Everything you've said here is correct. However, there are two problems I've found with doing it like this. First of all, we completely lose the pH buffering capability in the cathode compartment. By separating the half-cells, the cathode chamber would steadily become more basic as electrolysis progresses, quickly reaching a basicity high enough to make transition metals insoluble. We need to maintain a neutral pH, which proves to be quite difficult with this type of setup. Other than that, introducing a diaphragm increases resistance considerably. This normally wouldn't be much of a problem, but the plating reaction seems to necessitate a high current density, which would become significantly more difficult with increased resistance.
@@ScrapScience cathodic chamber ph, and transition metal insolubility. 1) What falls out? 2) Does plating continue? 3) If plating continues then as the metals in solution are depleted would those that fell out go back into solution?
When the pH decreases, transition metal hydroxides fall out of solution. This is just a function of hydroxide ions being generated on the cathode during parasitic hydrogen evolution. In theory, plating could continue for a little while, but as hydroxide ions keep getting generated, the soluble transition metals will continue to be depleted and won't redissolve unless acid is added. In reality, it's even worse than this, because the insoluble hydroxide precipitate actually forms over the surface of the cathode, blocking current flow. I've encountered this quite a few times with my experiments in electroplating manganese.
@@ScrapScience pretty inefficient but I'm still surprised that running it for days was that cheap.great video sorry the experiment didn't work out as intended.keep it up!
@@ScrapScience... Interesting you say that. 😂 It is like for well over 10 years all those scrappers trying to save all the gold and silver composites (such as pins and platings) for their planned future projects. Even in a $200+ electronic device or computer they only recover like 75 cents in silver and $1-2 in gold using time and resources of $10+ completely outweighing what they'll gain in saving those component composites. That is why Lithium battery manufacturers haven't engineer designed for ease in recycling Nickel, Cobalt and Lithium because no recycling manufacturing company has made it a profitable venture ever. Yes it is possible to repair and replace dead Li automotive electric battery components but the remaining components aren't new and will create a cascading failure of repaired and reconstituted replacement batteries (of less shelf lives). Engineers understand that with no viable profitable recycling of raw materials Li, Ni, Co and whatever else plus no viable restore of used batteries cells matrices ... Ten years (more on restored and reconstructed and fixed damaged cells) is the lifespan engineered before new raw elements are needed from mines again here. This is no green earth reality right now in the sciences.
@@ScrapScience I was training for 3 months in metal plating company they were using metal salt and inert anode for copper chrome and gold but they used nickel anode for nickel . Because of that I said it maybe didn't work. And this guy tryed too but he failed checke 3:37 in his video ruclips.net/video/8DZvgP2eu4U/видео.html
That reaction is a little too dangerous for my current skill in chemistry. If I do get around to trying it (which I would definitely like to at some point), it won't be for quite some time.
Hey, I'm enjoying your videos. It's great to learn about an aspect of chemistry that I know virtually nothing about. Quick question. Is there an electrolytic reaction that produces nitrogen and oxygen, and isn't horribly toxic? I think that could be useful in more than one way. Thanks! As a side note, I think your perseverance in the attempted lithium extraction was pretty good.
As an aside, it just occurred to me that I don't of any compounds containing both nitrogen and oxygen that aren't a bit... Explody. Keeping in mind, with my general ignorance of chemistry, there may be an entire world of non explosive nitrogen and oxygen compounds out there.
I can't think of any individual electrolytic reactions which generate both nitrogen and oxygen. Oxygen is an easy one, but the activation energy usually involved in making elemental nitrogen means that there really aren't many electrolytic processes that make it in reasonable quantities. While there are a great deal of benign compounds that contain both O and N, (cyanates, for example), electrochemistry with them is a little weird.
The idea was to avoid sodium contamination when we were trying to get the lithium. Additionally, the calcium ion isn't very soluble under these conditions, so it's an easy way to precipitate the transition metals without putting any extra ions in solution unnecessarily.
Yeah definitely. I’m never going to suggest this process as a reasonable way to obtain cobalt. Of course, the point of the project is more for fun than for practicality though.
@@ScrapScience I was a battery test engineer, so I was trying to think of business ideas I could start in my backyard. Thank you for these experiments showing that I would need pallets and pallets of out-of-service used lithiums to recycle and convert into raw materials, and at that point it's a major capital venture. I see why companies out there are trying to figure out how to safely re-deploy used lithium battery cells, key-word "safely".
I'm sorry to be That Guy, but when I saw you'd decided to take perfectly good lithium metal, dissolve it, and try to get it back out, I screamed "don't do it," at my computer. The lesson: electrochemistry is the thing you try after you've exhausted all the other options. At the most fundamental level, the reason it comes last has to do with the Faraday constant. A mole is a quantity 6 orders of magnitude bigger than a coulomb, so you can expect to spend a hundred thousand times as much effort by pushing things around in coulomb quantities as you would doing more ordinary chemistry.
We never started with 'perfectly good lithium metal' though... Lithium ion batteries do not contain metallic lithium. They contain lithium oxide which is finely incorporated into a transition metal oxide structure. Simply extracting lithium by peeling the batteries apart is impossible, and instead requires extensive chemical extraction. That's what we're doing here. The reason we're using electrolysis to try to extract the transition metals is because it's a very effective way of doing so which doesn't involve adding any extra ions to solution. This simplifies any lithium extraction we may want to do later on. Simply precipitating them with hydroxide would inevitably introduce other cations to the mix. I'm pretty patient, and I'm perfectly happy to leave an electrochemical reaction going for a month or two if it works.
First of all, sorry for the weird audio in this video. I ended up having to re-do a voiceover for the first part, and was quite unwell when I recorded the middle section. You might notice some parts where the audio doesn't quite match the video, or other issues with sound.
Regardless, please enjoy!
as a researcher on Li ion battery recycling, I am really impressed with the depth of knowledge you have to design your experiments.
Happy to see a successful process, but I wonder how long will it take to complete.
Wow, this really needs a bigger cathode! Putting that much current through a tiny little cathode is really inefficient. If you want good metal plating, with reasonable coulombic efficiency, the cathode needs to run at less than 50mA per square cm. 1.5A over the 5cm2 or so you’ve got there works out at more like 300mA / cm2. 6x too high! Most of the current will be splitting water and making your cathode very basic, which really slows it down and wastes electrons.
Would adding a magnet to your electrode help to stop the dendrites from getting so long then dropping off?
Can't believe I didn't think of that! Yes, I'd believe so.
@@ScrapScience I was going to suggest that too.
This is something I've been looking at doing with my lithium battery collection. Do you think it is possible that only one metal is plating due to the voltage used? I have read that electrowinnowing can plate out one metal at a time if you target the voltage needed and then step up the voltage for the next metal. I haven't tried this yet. A note on dendrite formation; from experience, this tends to form from a few different factors. Some will form because the metal is cleanest at the points where it has been freshly cut, having any passivating or oxide layers removed so current will want to go to the path of least resistance. A clean of the cathode will help with this. The second point is that from everything I have read, low current densities on the surface area of the cathode leads to a much more uniform coat of plated metal. I've seen this a few times as well but I suppose that you are only looking for extraction and not plating and purifying.
While it's generally possible to selectively plate out metals from solution, the reduction potentials of cobalt and nickel are so close together that this is virtually impossible unless you can influence overpotentials in some way. With metals exhibiting a higher difference in reduction potential (like copper and zinc), this is much more achievable.
And yes, low current densities generally give a better metal coat, but we're more interested in minimising the parasitic hydrogen formation to maintain an acceptable efficiency. For this, it's generally better to use a higher current density. In proper plating experiments, hydrogen should not be an issue as it is here.
7:59 @@ScrapScience
My bro Harry is back finally with new video
If you dont mind sharing, where did you get your platinum electrode? Trying to find one that doesn't empty the wallet and is of usable quality can be a bit of a gamble
I'm afraid the place I got my electrode from doesn't exist anymore. I've been looking around, but I can't actually guarantee the authenticity of any sellers right now.
very good job, really you're a genius... maybe if you put a magnet out the glass help to keep metal separated of the hidroxid presipitates
The slightly pink color of your starting precipitate is due to cobalt chloride?
Cobalt hydroxide, but yes the cobalt is giving it the colour.
Not that I expect you to try the lithium again, but if you do, look into Royal Water. It was/is a method of dissolving gold and platinum solids in hydrochloric acid and nitric acid. I can't recall the ratio off-hand, but memory is telling me 4:1 hcl to nitric. Extraction you can either distill off the acids (not my favorite way, but it works better under vacuum) or run it through an adequately sized aluminum silicate filter; I've not tried the latter but I have some on order to try with another process I'm working on. Gold isn't too surprising, but if it works for platinum, lithium ought to be a breeze.
Sulfuric acid will cause cobalt sulfate to precipitate due to common ion effect. You may have better luck using hcl as your acid. An easier way to get your cobalt free would be to mechanically separate the cobalt layer from the battery, then wash the black stuff in vinegar to remove the lithium. Next heat it to burn off the carbon. Then use a termite reaction to convert to the metal. They usually use copper 1 oxide mixed in with the cobalt oxide
I've recently found your channel and i love your content keep it going :)
Where can you get platinum electrodes from in Australia? Or was it ebay?
I got mine online from electrodesupply.com/
Though they seem to be out of platinum electrodes at this time.
@@ScrapScience Thank you!
Did you get the power supply from Jaycar?
I was going to, but power supplies online are genuinely three times cheaper for twice the power. I just got it off Ebay.
Why do I get suggested this, but if I go to your channel I can't find this video?
That's very odd. Maybe I've got some strange setting making it hidden.
It should be my fourth most recent video right now. Does it not show up at all?
Do you think using a claypot membrane would have made the process more efficient?
Maybe place the undisolved hydroxides in with sulfuric acids snd the platnum anode and the cathode inside a clay pot. I'm thinking the pot will tend to keep more of the sulfuric in the anodic container jeeping it in a higher concentration to better react with and dissolve the undisolved hydroxides, while the metals will tend to hang out in the cathodic chamber and better plate rather than participate in side reactions with the sulfur that lower the overall efficiency.
The process would definitely be more efficient from a Faradaic standpoint. Everything you've said here is correct. However, there are two problems I've found with doing it like this.
First of all, we completely lose the pH buffering capability in the cathode compartment. By separating the half-cells, the cathode chamber would steadily become more basic as electrolysis progresses, quickly reaching a basicity high enough to make transition metals insoluble. We need to maintain a neutral pH, which proves to be quite difficult with this type of setup.
Other than that, introducing a diaphragm increases resistance considerably. This normally wouldn't be much of a problem, but the plating reaction seems to necessitate a high current density, which would become significantly more difficult with increased resistance.
@@ScrapScience cathodic chamber ph, and transition metal insolubility.
1) What falls out?
2) Does plating continue?
3) If plating continues then as the metals in solution are depleted would those that fell out go back into solution?
When the pH decreases, transition metal hydroxides fall out of solution. This is just a function of hydroxide ions being generated on the cathode during parasitic hydrogen evolution.
In theory, plating could continue for a little while, but as hydroxide ions keep getting generated, the soluble transition metals will continue to be depleted and won't redissolve unless acid is added. In reality, it's even worse than this, because the insoluble hydroxide precipitate actually forms over the surface of the cathode, blocking current flow. I've encountered this quite a few times with my experiments in electroplating manganese.
@@ScrapScience I can see where the hydroxides crystalize on the cathode represent a serous problem when trying to make the metal.
Which white magnetic oil contain low radiation
Good to see something came from all your efforts.i wonder if it would be cheaper than the electric bill to just buy the cobalt
Haha, well the electricity cost me about $1.50, and the extracted cobalt is worth around $0.75, so feel free to do the maths...
@@ScrapScience pretty inefficient but I'm still surprised that running it for days was that cheap.great video sorry the experiment didn't work out as intended.keep it up!
@@ScrapScience... Interesting you say that. 😂 It is like for well over 10 years all those scrappers trying to save all the gold and silver composites (such as pins and platings) for their planned future projects. Even in a $200+ electronic device or computer they only recover like 75 cents in silver and $1-2 in gold using time and resources of $10+ completely outweighing what they'll gain in saving those component composites. That is why Lithium battery manufacturers haven't engineer designed for ease in recycling Nickel, Cobalt and Lithium because no recycling manufacturing company has made it a profitable venture ever. Yes it is possible to repair and replace dead Li automotive electric battery components but the remaining components aren't new and will create a cascading failure of repaired and reconstituted replacement batteries (of less shelf lives). Engineers understand that with no viable profitable recycling of raw materials Li, Ni, Co and whatever else plus no viable restore of used batteries cells matrices ... Ten years (more on restored and reconstructed and fixed damaged cells) is the lifespan engineered before new raw elements are needed from mines again here. This is no green earth reality right now in the sciences.
Great vid
I think you might recoved Cobalt only. Because Nickel usually doesn't fall out with this method . But I could be wrong.
Why wouldn't nickel plate out like this?
@@ScrapScience I was training for 3 months in metal plating company they were using metal salt and inert anode for copper chrome and gold but they used nickel anode for nickel . Because of that I said it maybe didn't work. And this guy tryed too but he failed checke 3:37 in his video ruclips.net/video/8DZvgP2eu4U/видео.html
Can you teach how to make cloride acid by mixing directly cloride gas with hidrogeno gas?
That reaction is a little too dangerous for my current skill in chemistry. If I do get around to trying it (which I would definitely like to at some point), it won't be for quite some time.
Hey, I'm enjoying your videos. It's great to learn about an aspect of chemistry that I know virtually nothing about. Quick question. Is there an electrolytic reaction that produces nitrogen and oxygen, and isn't horribly toxic? I think that could be useful in more than one way. Thanks! As a side note, I think your perseverance in the attempted lithium extraction was pretty good.
As an aside, it just occurred to me that I don't of any compounds containing both nitrogen and oxygen that aren't a bit... Explody. Keeping in mind, with my general ignorance of chemistry, there may be an entire world of non explosive nitrogen and oxygen compounds out there.
I can't think of any individual electrolytic reactions which generate both nitrogen and oxygen. Oxygen is an easy one, but the activation energy usually involved in making elemental nitrogen means that there really aren't many electrolytic processes that make it in reasonable quantities.
While there are a great deal of benign compounds that contain both O and N, (cyanates, for example), electrochemistry with them is a little weird.
@@ScrapScience gotcha, thanks! There goes my permanently submerged submarine idea 😁 back to the drawing board.
05:54 Wow, 17.4 Watts and it makes so much noise with the fans already? :o
Good idea but how to take cobalt out niken 😮
All covered in part 4. It’s a bit involved, but doable.
It takes much less time if you neutralize extra acid.
I'm preety sure that metal you got is mostly or purely cobalt
Yep, there's very minimal nickel contamination. It's definitely there though, and I'd still like to get rid of it at some point.
Enjoyed the video
Your next video should be on extracting potassium metal by electrolysis
I am waiting for that video
I can guarantee that I'll be giving that a go at some point. Not for a little while though. There are a few videos I'm planning to make first.
how about doing batteries diy, primary mechanical reloadable fuel cells, try CuSO4 + dilute H2SO4 water with graphite/iron pair, should be very nice
Why CaO and not NaOH?
The idea was to avoid sodium contamination when we were trying to get the lithium. Additionally, the calcium ion isn't very soluble under these conditions, so it's an easy way to precipitate the transition metals without putting any extra ions in solution unnecessarily.
Cobalt goes for $15/lb, seems like it would be easier to just go buy it than to extract it =)
Yeah definitely. I’m never going to suggest this process as a reasonable way to obtain cobalt.
Of course, the point of the project is more for fun than for practicality though.
@@ScrapScience I was a battery test engineer, so I was trying to think of business ideas I could start in my backyard. Thank you for these experiments showing that I would need pallets and pallets of out-of-service used lithiums to recycle and convert into raw materials, and at that point it's a major capital venture.
I see why companies out there are trying to figure out how to safely re-deploy used lithium battery cells, key-word "safely".
this is a certified behjy moment
this isn't the easyest thing to do but lets have a go - wise words
Hi!
I'm sorry to be That Guy, but when I saw you'd decided to take perfectly good lithium metal, dissolve it, and try to get it back out, I screamed "don't do it," at my computer.
The lesson: electrochemistry is the thing you try after you've exhausted all the other options. At the most fundamental level, the reason it comes last has to do with the Faraday constant. A mole is a quantity 6 orders of magnitude bigger than a coulomb, so you can expect to spend a hundred thousand times as much effort by pushing things around in coulomb quantities as you would doing more ordinary chemistry.
We never started with 'perfectly good lithium metal' though...
Lithium ion batteries do not contain metallic lithium. They contain lithium oxide which is finely incorporated into a transition metal oxide structure. Simply extracting lithium by peeling the batteries apart is impossible, and instead requires extensive chemical extraction. That's what we're doing here.
The reason we're using electrolysis to try to extract the transition metals is because it's a very effective way of doing so which doesn't involve adding any extra ions to solution. This simplifies any lithium extraction we may want to do later on. Simply precipitating them with hydroxide would inevitably introduce other cations to the mix. I'm pretty patient, and I'm perfectly happy to leave an electrochemical reaction going for a month or two if it works.
😂
Cobalt is radio activity
Only the cobalt that comes out of a nuclear reactor, not this stuff.
You're listening to Radio Cobalt! All of metal's greatest hits!
Call sreetips