Zinc-air batteries as an alternative to lithium-ion: study
ecu.edu.au
ecu.edu.au
Each 2 kilos of elemental zinc that can be oxidized to release electricity requires 1 kilo of oxygen to be brought into the reaction. So it's efficient in some ways since you don't have to supply the oxidant as part of the battery package. But it takes a lot of cubic feet of oxygen to make a kilo, it's not easy to get that many grams of oxygen into the eletcrolyte very fast, and air is only about 21 percent oxygen. So it takes way more kilos of air than it does zinc.
Rechargeable or not, for very high current duty you may just need pure oxygen and it may be better under pressure, or perhaps compressed air might up the current capacity in a worthwhile way.
Interestingly, in some industrial oxygen measuring devices the sensor itself is a zinc-air "battery" consisting of a thin film of teflon (which is somewhat porous to oxygen) streched across the only exposed face of an electrolyte-moistened metallic zinc electrode, surrounded by a reserve of gel electrolyte that replenishes as it creeps into the layer between the zinc and the teflon film. At nominal 21 percent ambient oxygen content a steady current is produced from the rate of oxygen diffusing through the film making contact with the zinc, measured by a meter, and calibrated to display 21. In reduced oxygen atmospheres the minuscule oxygen directly in contact with the zinc is rapidly depleted and the meter declines accordingly into the "unsafe" region.
The amount of gas released can be controlled with the current through the cell. Very interesting technology!
oxygen un air: 21%
1kg/1.429g/L~=700L of oxygen/21%~=3.332m³ of air (~=118 cubic feet)
"Herein, we report a nanocomposite based on ternary CoNiFe-layered double hydroxides (LDH) and cobalt coordinated and N-doped porous carbon (Co-N-C) network"
So it contains Nickel and Cobalt.
Lithium has an efficient (enough for cars and stationary storage), durable (> 5000 cycles to 80% SoC) and mass produced battery chemistry: LFP (Li-Fe-P), with no controversial mineral like Cobalt.
Why? Lifespan is basically irrelevant even without considering that battery technology continues to rapidly improve: the thing that matters is the cost of upkeep.
> in harsh very hot/very cold weather conditions.
They don't have to be capable of being placed in every single possible location: the whole point of the power grid is that generation doesn't have to be colocated with consumption. But even if they did, EVs have the same constraints, except you can't design an EV to be permanently in the shade.
> They also need to be much cheaper per kW/h than current lithium ion tech.
This depends on what they're competing against. Even current batteries are cost-competitive in some scenarios (i.e. ones where you can't do pumped-storage hydroelectric, either because you don't have water to pump or it'll take too long to build).
Yes, but I'm looking at this through the lens of where I live. My country has 40 times less GDP per capita than the US, and electricity has to be (and currently is) very cheap for people to afford it. Also, my country is very hot in summer and can be very cold in winter. It is a dry Central Asian region with up to 45-47C in summer and -10C in winter. Also, we had -27C last January which was a record cold and was a disaster.
Here we have very good conditions for solar. Solar has become very cheap, and we are building several 100-400 MWh plants with more of them coming in the near future. But multi GWh battery storages for solar plants will cost billions. If we need to replace it in 5-10 years, this is not viable for us. But 30+ years or at least 25+ years is definitely worth looking at.
Or, even if the life span is 10 years, it needs to be 3x cheaper per MWh storage than 30+ year option. But in that case, we'll have 3x more stuff to get rid of/recycle/pollute the environment.
Obviously li-ion doesn’t need to get cheaper to be used for grid storage. It’s used profitably for that purpose today. What kind of grid storage are you talking about?
Li-ion is already excellent for frequency regulation and short term energy storage. Li-ion has never and will never be a solution for long term seasonal storage. Then you’ll want pumped hydro or other gravity based storage, flow batteries, thermal storage, liquid air battery, etc.
I think liquid metal batteries might outcompete li-ion in the end. And they do probably have 30 year lifespans with little to no maintenance. But it’ll be the cost and rapid scalability that’s the critical factor.
The perfect is the enemy of the good enough. Many things deploy at scale before true economies of scale are reached.
No, not at all. They can be adequately shielded from the elements, they don't need to last so incredibly long, and even currently priced Li/ion batteries make economical sense today in given scenarios.
What's your rationale for these criteria?
And while solar has become cheap enough that our utilities are starting implementing it, the storage is still too expensive if you want GWh scale storage. It can literally cost billions, and considering we may need to replace it in like 5-10 years, it is not a viable solution for us. We just can’t afford it.
I'm actually kind of surprised/disturbed they aren't used in consumer gadgets a lot, since they are affordable in small sizes and the battery is the main thing to wear out on a lot of products.
I just wanted to make that clarification in case anyone who isn't familiar with LFP is misled into thinking that LFP-based cars would have a range of like 30 miles.
While it’s not perfect, the collective harm of cobalt is a firecracker vs the supernova that is oil.
A cobalt mine can’t fail and poison the entire Gulf of Mexico. Anyone who addresses the “controversy” of cobalt without proportionally addressing oil is a fraud.
I mean the Congo has been a mess my entire life, but it’s still a poor trade.
https://www.eenews.net/articles/biden-is-scrambling-for-mine...
Yes, oil extraction, processing, and consumption is also horrible. So what? The comment was on Li-Fe-P vs. CoNiFe battery technologies.
Seems like you are just projecting and are coming off as a disingenuous with the what-about-ism.
They aren't evenly that closely related other than being resources, so why even link the two?
Seems like your response may have been fraudulent
Cobalt and nickel are basically used by auto manufacturers to make luxury supercars with slightly more range than they would have otherwise. They're also a convenient excuse not to make more EVs. "Sorry, cobalt is just too expensive, and we can't get enough of it to make as many EVs as we need. I guess we'll just keep making ICE vehicles." If you want to make a million cars, cobalt/nickel based batteries are maybe acceptable. If you want to make a billion cars (which is the scale on which EVs are going to need to be made), they're not a realistic option. The best battery technology for that right now is LFP. Some companies (CATL for instance) are working on sodium ion, to reduce the lithium dependency.
(As other comments have noted: the cobalt in these new batteries is used in a catalyst, so presumably they'd need a lot less of it than in a conventional lithium ion battery, which would be a good thing.)
All mining is harmful, that's kind of a given. Drilling too.
The modern world does not come out of thin air.
If I understand correctly, nickel is often a side-product of copper mining.
LFP batteries don't use nickel or cobalt. That's a good thing. Iron mining has downsides too, but it's far more abundant. We have no realistic way to mine enough cobalt and nickel to make a billion cars (or an equivalent amount of grid storage, or whatever it is we want to use batteries for) using current nickel/cobalt based lithium ion battery technology. We might not have enough lithium for that either, so maybe that will be the bottleneck on LFP production. But dealing with one resource constraint is easier than dealing with three, and if nothing else works we can extract lithium from sea water.
We use nickel and cobalt in EV batteries so that rich and upper middle class people can have 20% more range, at the expense of worse longevity, increased fire risk, and requiring more expensive minerals. If we're going to phase out internal combustion cars entirely, that means they need to be affordable to everyone who would have bought a fossil fuel car. That means using cheap components that can be produced at massive scales.
For awhile non-Chinese manufacturers were kind of stuck due to an issue of patents, but the main ones on LFP expired a little while ago, and we're starting to see LFP factories being built that aren't in China.
Not scarce. It's the 5th most common element on this planet and there are enough reserve/deposits out there - it's just that they need to be mined which is a multiyear undertaking (and polluting like all mining). And nickel is no more expensive than lithium. The price of lithium at the current market rate is higher than that of nickel, which makes LFP more expensive per Wh/kg.
>> LFP batteries don't use nickel or cobalt. That's a good thing. Iron mining has downsides too, but it's far more abundant. <<
LFP has a lot of shortcomings, and to name a few, in the context of this discussion:
1. LFP is a lithium-ion battery. Due to its low energy density, it requires a lot more lithium to achieve the same Wh as NCM8/9/A. That which in turn makes LFP more expensive when the prices of lithium is higher than that of nickel.
2. cost of LFP recycling is also much higher than that of NCM/A counterparts for two reasons: higher processing cost of the cathodes and lack of valuable metals recovered[1].
[1] Financial viability of electric vehicle lithium-ion battery recycling, https://www.sciencedirect.com/science/article/pii/S258900422...
>> We have no realistic way to mine enough cobalt and nickel to make a billion cars ..., <<
Why so much FUD? Are you a mainlander Chinese, or perhaps a Tesla fanboi?
>> We use nickel and cobalt in EV batteries so that rich and upper middle class people can have 20% more range <<
First, the industry trend is to minimize the use of cobalt -- the cutting edge high-nickel NCM8/9 batteries, which is already widely adopted in popular EVs such as the Ioniq5/F-150/EV6/etc, contain less than 10% and 5% of cobalt, respectively and they also have much higher energy density due to higher nickel content. There are also ultra-nickel lithium-ion batteries without any cobalt, NMX, already developed and would be available in a couple of years.
And no worries, when the South Korean battery trios bring up 300+GWh NCM8/9+/A battery production online around 2025-2026 in the US, LFP would lose much of price competitiveness, so your class dividing rhetoric isn't going to win much vote. GM already reported that their battery cost would drop to $87/Wh in 18 months (back in Feb 2023). The Chevy Bolts are already under $20K and made with NCMs batteries. But nice try though.
Now, we use NCM/A batteries b/c, in moving vehicles, the energy/weight ratio matters quite a bit. LFP's low energy density, weight and lower tolerance for high C made it unsuitable for EVs, but in other applications, such as stationary energy storage system (aka, ESS), until China spiked it up for EVs application not to long ago - which in turn came with a number of compromises. LFPs are still limited to mostly entry-level, low-range EVs under ~250 miles range (60KWh), but, beyond that, there are significant technical baggages and risks (and unknowns), for instance:
* LFP EVs must be charged to 100% full to recalibrate the BMS frequently to avoid misreading SOC/range, and, as we recently discovered, that in turn accelerates battery degradation. The short-term data we have from Tessie (via CleanWatt) -- also seems to be corroborated by Recurrent's battery life study -- reveal that LFPs in fact degrade twice as fast as non-LFP to 10% range loss, or 90% SOH in Tesla EVs[2].
* BYD likewise has dozens of fires every year with their trademarked blade LFP in PHEVs operating at 5+C.
The physical size of the Cobalt complex in the cathode is quite different from the "lithiated" vs "unlithiated" states so in the extremes Lithium batteries with cobalt "puff up": they get physically larger. This can physically crush its neighbor which can also lead to a chain reaction.
LiFePO4 doesn't have either of these problems. Its physical size is very similar in the lithiated/unlithiated states so these batteries don't puff up or expand. They don't have thermal coefficient problems. And when severely abused the Iron-Oxygen bond is much stronger so they don't feed any potential fire with fresh oxidizer. The only real downside to ditching Cobalt is the lower density of LiFePO4... but for many applications that doesn't matter or is worth the tradeoff.
tl;dr: you can over-volt, over-charge, over-discharge, puncture, smash, and/or heat a Lithium Iron Phosphate battery. It will both tolerate way more abuse without being ruined and in no case will it start a runaway reaction that sets the entire battery bank on fire. Lithium batteries with any Cobalt chemistry are way less likely to survive such abuse and way way way more likely to start a runaway fire chain reaction, resulting in a lithium fire.
The quantity of cobalt used in the lithium batteries that contain cobalt is proportional with the energy stored in the battery.
The quantity of catalyst used in a battery, i.e. of cobalt and nickel in this case, is proportional with the maximum current through the battery, i.e. with the maximum power of the battery, not with the energy that can be stored in it.
Normally the quantity of cobalt used in a catalyst should be much less than what is needed in a lithium battery with cobalt.
That said its early days here. I keep hoping flow batteries would happen but they too have their challenges (who wouldn't want to "recharge" at a station where you just swap out your electrolyte and go on your way?)
https://www.silanano.com/our-solutions/titan-silicon-anode
The only public uses I can share is the WHOOP 4.0 band and in Mercedes-Benz G-class EVs coming 2025.
I remember friends telling that gallium nitride was the future a few years ago. 2022 came and went and *poof* I haven't heard a peep out of any tech trade resources (magazines, podcasts, blogs, etc) since then about it
Like you said, these technologies came out when tons of flash and circumstance and within a few months get memory holed out of existence.
Even graphene has a lot of real-world applications that are far removed from the sci-fi marketing of speculators, but offer a great advance over past technology.
Turns out they got some industrial customers for their battery cells in some demanding niche. Since they didn’t need to attract investors anymore, and I guess they had enough customers to fill the capacity they had in that period, they had no reason to publicise their activities.
Now they’re out there again with interviews and such. I suppose they’re looking to scale up.
Feels like there’s a lot of companies like that these days. Ones that you might heard about as a breakthrough 5-10 years ago and then nothing.. while they’re busy using the investments they got figuring out manufacturing at scale. That’s just the time it takes. Many of them now seem to have pilot/demonstration manufacturing plants up and running now.
In another 3-6 years I think we’ll start to see several of these chemistries in consumer products.
And the article (if you can call a paragraph an article) is about rechargable batteries.
So I'm not going to get excited until there is an actual product which may well be many years away. So there is nothing to 'move over' just yet.
Big sloppy batteries have wider safety margins and uninspiring performance. The safety margins and avoiding toxicity in manufacturing can eat up gobs of the “potential” for a battery chemistry. For years or indefinitely.
Gasoline is ~100X energy dense compared to Li-ion batteries.
It’s fundamentally very hard for batteries to come anywhere close to hydrocarbon fuels.
One is pushing electrons around with anode/cathode, while hydrocarbon fuels are breaking the chemical bonds to release energy.
Intense electron gradient is pretty hard to achieve per unit mass. Electrons love their protons.
I see I was confusing Wh/kg with MJ/kg. Zinc-air could reach 5. Still down there.
Dear battery technology claimant, Thank you for your submission of proposed new revolutionary battery technology. Your new technology claims to be superior to existing lithium-ion technology and is just around the corner from taking over the world. Unfortunately your technology will likely fail, because:
[ ] it is impractical to manufacture at scale.
[ ] it will be too expensive for users.
[ ] it suffers from too few recharge cycles.
[ ] it is incapable of delivering current at sufficient levels.
[ ] it lacks thermal stability at low or high temperatures.
[ ] it lacks the energy density to make it sufficiently portable.
[ ] it has too short of a lifetime.
[ ] its charge rate is too slow.
[ ] its materials are too toxic.
[ ] it is too likely to catch fire or explode.
[ ] it is too minimal of a step forward for anybody to care.
[ ] this was already done 20 years ago and didn't work then.
[ ] by the time it ships li-ion advances will match it.
So your full list is required to be a replacement for mobile devices and/or EVs, but a couple of them could be removed for the case of grid scale storage.
Generally agree though that almost all "revolutionary replacement" batteries have critical flaws that make them inferior to Li-ion
This is the selling point of iron-air batteries, which discharge over the course of a hundred hours, but are a tenth the cost of lithium-ion. The first iron-air factory is supposed to be operational in 2025.
If you mean self-discharge, and the importance of that being low, yeah, that might become a factor to keep an eye on once we reach capacities to solve seasonal cycles. But even then it's nothing more than another element in what makes up the total charge/discharge efficiency.
The best long term grid storage is probably still electrolyzed hydrogen pumped into a cavern underground. ~50% round trip efficiency but very high energy density at relatively low cost.
You may have been confused by stories misleadingly touting these kinds of batteries as "alternatives to" lithium ion batteries. They're all subtypes of lithium ion battery.
There's a good overview article here covering various subtypes of lithium ion batteries:
https://batteryuniversity.com/article/bu-205-types-of-lithiu...
You may have been confused but John B. Goodenough didn't work on lithium iron phosphate, they are a completely different chemistry.
You may have been confused by the lithium in the name, but that doesn't mean they are the same.
It's the like the new publishing executive who reportedly ordered the peons to "just publish the best-sellers" from now on.
If you know of some way to invent a superior new battery technology without doing a lot of research and development (with the inevitable dead-ends), you should probably be off doing that.
See also: the people who post a snarky "in mice" comment on every new medical development.
[x] it suffers from too few recharge cycles.
[x] it lacks thermal stability at low or high temperatures.
[x] it is too likely to catch fire or explode.
at least, right?
[x] it is incapable of delivering current at sufficient levels.
"High power density" in the paper means 220 milliwatts per square centimeter. That's higher than other air-breathing cathodes, but it's still basically nothing compared to a solid cathode.
[x] clogs up with carbonates when the electrolyte is exposed to air
Edit:
Your proposed replacement for stone tools, "steel", is impractical because:
[ ] it's not as sharp
[ ] it rusts
[ ] it's more expensive
[ ] it requires a much more complex fabrication process
I'm not entirely sure if a stone axe is sharper or not, but a steel one will last much longer – a metal one may corrode, but a stone one will chip easily (whether it's sharp or not is unimportant as such; you don't make an axe to be sharp, you make an axe to cut down a tree – one reason steel axes work better is that they're smaller: for bigger trees you will have to cut less).
There's a reason why people started using steel, and why archaeologists find discarded broken stone tools all over the place.
Seems like there ought to be a market... every electrical system in the world would be much better off with gobs of storage.
But there isn't... because...
Electrical markets are very highly regulated. The barriers to market entry are astronomical and quite frankly uninvestable.
When I was active in the space, no utility would even think of buying a piece of new hardware unless the design had a 7 year track record in actual on grid operation for a respected utility. Not quite a pure circular fallacy, but darn close.
There are a lot of good technologies out there that really do work.
But they can't attracted funding to scale because they simply can't reliably access the market.
The grid scale energy storage problem is social, not a technical.
Texas (ERCOT) is by far the easiest electrical market to enter. It is also one of the highest volatility markets which is also good for storage.
But the barriers to entry are still way too high to call it anything like an open market.
To be sure, traditionally there are somewhat good reasons to have high barriers to entry into electrical markets.
But in the context of climate change, those reasons seem more like tradition than real reasons.
https://iceberg-research.com/2021/01/14/eos-energy-fake-cust...
Gelion has a Zn-Br with a higher but not great Coulombic efficiency (87%), though they still have a questionable near-term demand outlook. No company AFAIK is commercializing Zn-air due to the severe power density issues.
But https://en.wikipedia.org/wiki/John_B._Goodenough says that someone else did that.
Am I missing something or is that claim in the article incorrect. ECO or mr. Azhar are also not mentioned at all on the wikipedia page about Lithium-Ion.
I wonder if that was an accident or if this was worded that way on purpose to trick the reader.
There's probably some intermediate draft version where it all made sense and perhaps each of the changes that led from there to the eventual outcome appear perfectly sensible when looked at from the right angle. But none of that will make the end result any better.
Also, while I generally agree on sounding the "divest from China, Russia and other enemy nations" bullhorn, with Australia and Canada there are close allies of ours among suppliers [1] and Chile and Argentinia may not be allies but at least neutral so we can broker deals with them.
The problem is more in the refinement of said lithium and the manufacture of batteries. For environmental and cost reasons, most countries were OK with having that shit done in China, but nowadays there's serious capability built up in the US and EU.
[1] https://www.statista.com/statistics/268790/countries-with-th...
[2] https://pubs.rsc.org/en/content/articlelanding/2019/em/c8em0...
The only metals that are abundant in sea water, due to the high solubility of their compounds, are the alkali metals and the alkaline-earth metals, more precisely the eight metals lithium, sodium, potassium, rubidium, magnesium, calcium, strontium and barium. (beryllium is not an alkaline-earth metal, despite the fact that most chemistry manuals group it with the alkaline-earth metals, because it is believed that simple minds will easier remember simplified classifications, even if they are only approximately true, while cesium is extremely rare and, due to that, it remains rare in sea water too)
For any of these 8 metals, it can be profitable to extract them from sea water, where they exist in huge quantities. For the other metals, which are present only in tiny quantities in sea water, it is likely that the great amount of energy needed to separate them from sea water makes their extraction not worthwhile.
Bromine is even more abundant than lithium in the ocean, but we don't extract it from the ocean; most of the world's bromine comes from the Dead Sea, and despite the location the supplies of Br is considered secure and the price is low. Processing large quantities of seawater is annoying, even though the energy cost in principle is attainable.
Magnesium can also be extracted from seawater.
https://oceanservice.noaa.gov/facts/whysalty.html
Since there is no outflow for these minerals the ocean has become salty over time.
I wish people would stop trying to paint the energy future along these lines.
It's a fossil fuel rip-it-and-ship-it mindset from the past bolted onto the future and it's often propagated by people who an $$ interest in keeping things the way things are, or are trying to pump some new temporary get-rich-scheme ("harvest lithium from abandoned oil wells!" "buy these penny lithium stocks" etc)
Funny thing is: laws like EU's one that demands all new cars be electric by 2035 will lead to lithium shortages, which means Lithium batteries will become much more expensive in the next few decades.
This was a while back -- possibly they've been supplanted by some lithium based technology by now.
"Zinc–air batteries cannot be used in a sealed battery holder since some air must come in; the oxygen in 1 liter of air is required for every ampere-hour of capacity used."
More complex details on the wikipedia article ofc.
From the article there. They cover that rechargeable zinc-air batteries exist and that is what this is focused on.