Nickel reduction in EV batteries with NCM 217 cathode

Nickel reduction in EV batteries with NCM 217 cathode
Cathode evolution roadmap by BASF

Today most electric cars are powered by batteries with NCM cathodes, whose raw materials besides lithium include nickel, cobalt and manganese.

As you probably already know, for the last few years the goal has been to reduce the use of cobalt, which is rare and expensive. Nickel is being used to replace cobalt allowing more energy-dense and cheaper batteries.

  • NCM 111: cathode with a Ni:Co:Mn composition ratio of 1:1:1
  • NCM 424: cathode with a Ni:Co:Mn composition ratio of 4:2:4
  • NCM 523: cathode with a Ni:Co:Mn composition ratio of 5:2:3
  • NCM 622: cathode with a Ni:Co:Mn composition ratio of 6:2:2
  • NCM 712: cathode with a Ni:Co:Mn composition ratio of 7:1:2
  • NCM 811: cathode with a Ni:Co:Mn composition ratio of 8:1:1

 

However, the next important phase in the development of NCM batteries is to replace nickel with much more abundant and cheaper manganese.

To have an idea let’s see the average market price of these raw materials per ton.

  • Cobalt: 27.000 EUR/t
  • Nickel: 11.000 EUR/t
  • Manganese: 2.000 EUR/t

 

As you can see, regarding costs using manganese makes a lot more sense and for this reason BASF, world’s largest chemical producer expects to start producing cathode active materials for high manganese-content NCM 217 batteries already this year.

 

NCM Product Overview by BASF in November 4, 2014

 

With NCM 217 batteries the kWh cost for high-quantity buyers (automakers) is expected to be below 80 euros, which is similar to upcoming cobalt-free LFMP batteries. However, the volumetric energy density of NCM 217 batteries will be much higher (900-1.000 instead of 410-450 Wh/L).

For example the NCM 622 battery of the Hyundai Kona Electric has a total capacity of 67,5 kWh and is made with LGX E63 battery cells that have a volumetric energy density of 500 Wh/L. This means that with NCM 217 cells (1.000 Wh/L) we could double the battery capacity to 135 kWh and maintain the same volume. It would be enough to give the Hyundai Kona Electric a WLTP range superior to 900 km (559 miles)…

 

Battery evolution roadmap by Roland Berger

 

Anyway, while the cathode active materials might be available already this year, it doesn’t mean that battery cell makers will be using them immediately for mass production. Extensive testing is needed before mass production of EV batteries. Therefore, expect the phase 1 (cobalt reduction) to be completed with the introduction of NCMA cathodes in 2021/2022 and the start of phase 2 (nickel reduction) with NCM 217 cathodes one or two years later.

If we really want to know where NCM batteries are heading, we must consider what the world’s largest chemical producer is doing, instead of relying on constant press releases with claims too good to be true from likely scammers trying to lure investors.

 

 

More info:

https://catalysts.basf.com/products-and-industries/battery-materials/cathode-active-materials/ncm

https://fkg.se/wp-content/uploads/2019/05/8-BASF-Josef-R-Wuensch.pdf

https://www.energy.gov/sites/prod/files/2014/11/f19/Fetcenko%20-%20Industry%20Partners%20Panel_0.pdf

https://sci-hub.tw/https://link.springer.com/article/10.1007/s38314-018-0092-z

https://sci-hub.tw/https://www.sciencedirect.com/science/article/abs/pii/S0378775319306779

https://www.samsungsdi.com/column/technology/detail/55272.html

https://www.istc.illinois.edu/UserFiles/Servers/Server_427403/File/20111115.pdf

39 Comments
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Rodri
3 months ago

Thanks for another enlighting article. Did not know low nickel cathodes were a thing. About the last point you make I wonder if it possible that Tesla-Maxwell solid electrolyte is too far ahead into the future or even unreal or uneconomical at this point.

sola
3 months ago
Reply to  Rodri

Maxwell’s technology is not about the electrolyte but the electrode production process.

AFAIK instead of wet slurry coating and forced evaporation by furnaces they produce a kind of dry but malleable electrode material, fibrilize it and laminate it onto the collector.

Rodri
3 months ago
Reply to  sola

sola thanks for correcting my huge mistake. You are absolutely right. Maxwell tech is about producing electrodes without using liquid solvants for “manufacturing cost reduction, elimination of solvent toxicity, enabling the application of liquid sensitive battery chemistries and
enhancing cell performance”.

Dry Electrode Coating Technology
https://pdfs.semanticscholar.org/f5e8/82e125a1579b2b3cca88ed512c47fdcefcc0.pdf

3 months ago
Reply to  Rodri

Hi Rodri.

I don’t know what Tesla is going to unveil soon, but I wouldn’t be surprised if they finally ditch the cylindrical cells and go for prismatic in a CTP (cell to pack) battery pack. It’s just a matter of time, today cylindrical cells don’t make sense in EV batteries.

Gareth Claase
3 months ago
Reply to  Pedro Lima

Because, even with the same battery chemistry, that would increase energy density significantly?

3 months ago
Reply to  Gareth Claase

Yes, it would also make the battery pack simpler and quicker to assemble.

Benjamin
3 months ago

Very interesting article !

However isn’t it the Nickel proportion that gives high energy density ? How is it possible to get better result than 901 or 811 ? I’m a bit confused ;(

3 months ago
Reply to  Benjamin

What happens here is that manganese serves as a stabilizer and allows to increase the amount of lithium in the cathode, lithium is what gives you more capacity.
comment image

Benjamin
3 months ago
Reply to  Pedro Lima

Oh you’re right ! Is there an explanation why cell suppliers go for Ni-rich before Mn-rich ?

3 months ago
Reply to  Benjamin

Hi Benjamim.

“Historically, manganese-based cathodes have long been studied for their attractive cost and safety characteristics [1]. However, due to issues related to both surface and bulk instabilities, manganese-rich electrodes have yet to find substantial success in the high-energy lithium-ion battery market.”

https://sci-hub.se/10.1016/j.jpowsour.2019.226706

“Lithium-rich manganese-based cathode materials face severe challenges, like initial irreversible capacity
loss, poor cycling performance and rate capability, which seriously restrict their application in broader
fields. In this work, Li2WO4-coated Li [Li0.2Mn0.52Ni0.13Co0.13W0.02]O2 has been successfully prepared by the sol-gel method with a calcination process.
After coating with appropriate contents of Li2WO4, the materials display superior cycling performance and rate capability as well as low voltage decay. ”

https://sci-hub.se/https://www.sciencedirect.com/science/article/abs/pii/S0925838819332694

Mn-rich batteries were always extremely safe (thermally stable), however the poor life cycle – especially in high temperatures – was something that had to be solved. Just look at the degradation rates of the first generation 24 kWh LMO batteries of the Nissan LEAF or the GS Yuasa LEV50 battery cells initially used in the Mitsubishi i-MiEV.

Fortunately advancements have been made to reduce cathode’s corrosion in the electrolyte.

https://pushevs.com/2015/11/04/gs-yuasas-improved-cells-lev50-vs-lev50n/

Lars
3 months ago

Hi Pedro

What do you think about this:
https://www.newmobility.global/e-mobility/brighsuns-revolutionary-long-range-ev-batteries-enter-industrial-trials/

It is a different kind of chemistry and it is hard to know how really this breakthrough really is.

3 months ago
Reply to  Lars

Hi Lars. I’m very skeptical just by looking at the company’s name. Brighsun!? Really!?

Lars
3 months ago
Reply to  Pedro Lima

I don’t know if the name is a problem, it would maybe be better for a company that makes fusion reactors, but maybe the bright sun is a reference to when the battery burns? The bigger problem is maybe that it is a company that no one has heard of before that claims to have developed a wonder battery.

3 months ago
Reply to  Lars

BrightSun would be ok. But BrighSun just looks like their name has a spelling error, not great for credibility. It reminds me the kind of spelling errors we find in manuals written in ChinEnglish…

They should rename the company before looking for investors.

http://www.brighsun.com/En/NewsView.asp?ID=45

Freddy
3 months ago
Reply to  Pedro Lima

Strange indeed… specially because at the bottom of that webpage, there is an Australian co. (PTY) and address…. After checking address on GMaps, does not seem a place to find batteries for EV’s….

Marcel
3 months ago
Reply to  Freddy

Haha, yeah, street view on google maps shows a small convenience store at that address. Looks like a scammer site.

3 months ago
Reply to  Marcel

I also checked Google Street View and that convenience store looks like Apu’s Kwik-E-Mart from The Simpsons. Maybe they are already selling great Li-S batteries in Australia…

Anybody interested in a group buy?

Lars
3 months ago
Reply to  Pedro Lima

I have to admit I didn’t notice the spelling, yes now that I noticed the spelling I can see why you are sceptical.

Peter
3 months ago

The timelines are aggressive in this article. But anything is possible. The BASF chart may be more of
roadmap than a prediction.

Stefan
3 months ago

Pedro, great article as usual. Would you consider an article about cell balancing in EVs, what are the various solutions on the market, and what are the best practices for EV users e.g. how often we should try to charge with cell balancing. The information landscape in this regard is scarce and there is a lot of word of mouth. This would be a solid resource if you could do it.

3 months ago
Reply to  Stefan

Thanks Stefan.

I think that cell balancing is overrated. If it worked to prevent battery degradation the Nissan LEAF would have the lowest battery capacity loss, considering that most people always charge it to full and the cells are balanced at the top limit, since we can no longer limit charging to a variable percentage.

My advise would be to charge to 70-80 % on a daily basis if possible. The only area where a once a month full charge and discharge (where cells are balanced at the top and bottom voltage limits) might help is for the BMS estimate the remaining battery capacity more accurately.

Tom Houlden
3 months ago
Reply to  Pedro Lima

Without TMS, Leaf is the car I would MOST avoid fully charging!  I’d think many owners would also act on that, but maybe not, & almost certainly not on a lease with no plan to buy.   

Maybe more accurate to say balancing is good, but not good enough to compensate for no TMS, although eGolf seems okay without it.  Maybe VW group is really good with air-cooling from experience with all the classic Bugs, Busses, & 911s.  What do you guys think?   

My 2013 500e cells go about 20mv out of balance after a couple months, but at full charge they only balance within 6 or 7mV.   

As for capacity estimate, the Fiat’s % gauge eventually loses calibration, but the car stops driving when its GAUGE hits 0.00%, even if there’s really 10% or more capacity remaining!  Just driving til it shows 0% won’t reset it.  You need to then park by a charger with everything turned on* until the 12V warning comes on, indicating the HV batt is protecting itself from undervoltage, by stopping charging the 12V.   

A new forum member’s gauge was so far off that he gained nearly 20% range by doing that!   

* Lights, rear window/mirror heat, & vent fan are about all that still work at 0%.

Freddy
3 months ago
Reply to  Tom Houlden

I have a 2018 40kwh Leaf in Portugal (northern part), and usually in day-to-day commute I charge between 40/50% to 70%… Only really force 100% charge if I will really need that extra juice. Common sense on keeping Li-Ion in the better part of SOC to avoid premature degradation (altough on Leaf this will happen much faster than on other vehicles. Now almost 2 years and 42K Kms…all good (don’t have leafspy to check or worry 🙁 )

Tom Houlden
3 months ago
Reply to  Freddy

Good for you.  I do the same with my 500e, since it’s easy & should extend the already-great-seeming longevity.  Problem is, it’s not mainstream “common sense” yet, & it really isn’t intuitive, or similar to other common practices (you fill a gas tank, fridge, etc.).  I’m poor, so I research how to make things last.  Most people don’t.  I admit I take advantage of that when they ask “how long to charge” my 500e & I say “It’s like your cell phone: plug it in when you get home (or when you go to bed), & it’s done when you get up”.     

For the Fiat, that’s still pretty good, because just like sleep, it takes 8 hours to recharge the average daily use from a standard US outlet, so the car isn’t sitting long at 100%, & in fact it is factory-limited to only charge to about 85% of true full capacity (4.1V).  I don’t know what Leaf uses for top-end buffer, but of course it’s best to stay below its limit whenever possible.  Does anyone think/know if a big top-end buffer is how the eGolf avoids Leaf’s relatively inferior degradation?

Freddy
3 months ago
Reply to  Tom Houlden

Here in Europe, the leaf or the Renault Zoe were Kings due to their lower cost of purchase… I already knew limitations of the lack of tms.. I’m just counting on the 66% in 8 years warranty or 160k KMS… My average KMS is slightly above 20kkms… When car has 8 years it will either change battery under warranty, or most probably will become second car of the house…. The leaf believe does not have a big upper buffer, as at 100% doc I have no break Regen whatsoever… The 500e is quite nice.. there are some grey imports here in portugal as car was only sold in u.s.

Tom Houlden
3 months ago
Reply to  Freddy

LOL: I think Pedro here said the Zoe was King of degradation (worse than Leaf), but I also think fixed for newer model years. Ya, cheaper to make without TMS but more expensive for the customer long-term if battery replacement is needed.

I read that Leaf cheats, by basing the warranty on the DISPLAY, which they’ve programmed to give fake readings of 67% of original capacity & 161km range even when it’s really at 59% & will only take you 149km or so (didn’t do math but you get the point).    

Also, Fiat doesn’t use the top buffer EVER, even for regen.  There’s NO regen until you get below 98% or so, & even then it’s limited to very few kW until you get below 95 or 90 or something.  In other words, even if Leaf has a top buffer of 20% or more (to try to compensate for lack of TMS) it still could prevent regen from taking it into that buffer zone.   

Yes, the 500e is the deal of the century, so far, at $6k used here now, often with less than 30k miles, & full-on active TMS (A/C chilled when necessary) for Samsung SDI cells, & 100-mile mild-climate city range even with its built-in 15% top-end buffer.

Freddy
3 months ago
Reply to  Tom Houlden

Yeah, but new in Portugal there was no alternative to leaf for a family car in 2018. The ioniq costed +10keur, similar to egolf, the soul 30 was too small.. there were not many used cars – maybe i3 but only 4 seater and design wise… I saw in Europe today a 500kkms tesla S for around 30k Eur… Here, even now, used cars at decent prices, only leafs, Zoe’s and some i3s. I hope the leaf battery lasts at least the 8 years doing expected KMS to be our family car…after that we’ll think in the second ev to trade our 20 year old (now) 370kkms diesel that nowadays only runs like 2000kms year … Leaf is our 99% time car.

Tom Houlden
3 months ago
Reply to  Freddy

Glad you only use diesel 1%. Might want a 12v battery tender.

At only 40-70%, you’ll have the longest lasting Leaf on Earth! Only other thing you can do is try to stay as close as possible to 0C temperature & current, the latter mostly by driving/regenning a bit slower, but also when you can:

– Charge in shade, early morning, A/C garage or underground, no DCFC.

– Dress warm in winter, park in sun, use recirculate, preheat while charging, seat heat instead of cabin, bring giant hot Thermos. Dress cool in summer (wet shirt!), park in shade, big ice-cold Thermos, blast vent fan to avoid A/C, recirculate only when you need it colder inside than out.

Tom Houlden
3 months ago
Reply to  Tom Houlden

If Leaf Spy gives you the same accuracy of HV battery data as Fiat, you’re not missing a single thing! After 1 1/2 years of multiple geniuses on the forums working on it, we still haven’t found a way to determine battery health!

The most accurate reading we’ve found so far (full amp-hour capacity) is way off about 60% of the time, with over a tenth of the readings impossibly over 98% of new, even after up to 4 years & 50k km, & over 1/4 of readings with unbelievable 20% loss after as little as 4 years & 30k km, when nobody is reporting ANY measurable range loss!

Freddy
3 months ago
Reply to  Tom Houlden

It’s a problem to correctly read bms, and hey, even the bms has errors reading the batteries health… Ideally as far as I read is once a year since new make a deep charging/discharging/ charging and check amount of kwh entered the car… can this loss in health be compensated by the large upper buffer? That is being eaten by degradation?

Freddy
3 months ago
Reply to  Tom Houlden

Weather in northern seaside Portugal is very good for EVs, between 0 winter and 30/35 c max in summer. I usually baby the battery, but other days just drive like no tomorrow… Average consumption 13,5kwh/100kms.

3 months ago
Reply to  Tom Houlden

Hi Tom. Renault ZOE battery has always been fine, the electric car that had a battery degradation worse than the Nissan LEAF was the discontinued Renault Fluence ZE.

Tom Houlden
3 months ago
Reply to  Pedro Lima

Thanks for the correction.  At least I got the brand right! What do you think about my theories how eGolf avoids degradation? [big buffer(s), or superior air-cooling]    

Testing the input kWh from 0-to-full would have to be done after a recent gauge recalibration (above) & then a long cooling rest, before charging at the same ambient temperature as the entire duration last time.  You’d also need to check that the voltages at zero & full were the same or it could fool you by reducing buffers with age, to retain the same usable capacity before suddenly dropping rapidly once the buffers are gone.

Tom Houlden
3 months ago
Reply to  Tom Houlden

Another eGolf possibility is more heat tolerant battery chemistry.

3 months ago
Reply to  Tom Houlden

I think there are two reasons why the Volkswagen e-Golf battery has a better lifespan.

1. Larger buffer

Volkswagen e-Golf

Total battery capacity: 35,8 kWh
Usable battery capacity: 32 kWh (89 %)

Nissan LEAF 24 kWh

Total battery capacity: 23,4 kWh
Usable battery capacity: 22 kWh (94 %)

Nissan LEAF 30 kWh

Total battery capacity: 30 kWh
Usable battery capacity: 28 kWh (93 %)

Nissan LEAF 40kWh

Total battery capacity: 39,46 kWh
Usable battery capacity: 36 kWh (91 %)

2. Batteries with high power densities

The 37 Ah battery cells from Samsung SDI used in the Volkswagen e-Golf are in the PHEV2 format. They don’t have great energy density, however they are made to handle high charging/discharging rates without overheating.

Anyway, at least Nissan has been increasing the battery buffer by decreasing the usable capacity. Moreover, the fact that the battery has now more capacity allows it to work at lower C-rates, which also helps to reduce heat generation and degradation. I’m sure that the battery of the Nissan LEAF 40 kWh has a much lower degradation than previous versions.

Tom Houlden
3 months ago
Reply to  Pedro Lima

THANK YOU PEDRO! More capacity also allows the driver to add even larger buffers themselves.

Just for comparison to my water-cooled EV:

Fiat 500e

Total battery capacity: 24? kWh

Usable battery capacity: 22? kWh (92 % BUT it’s water-cooled, AND it only charges to 4.10 V on my OBD, which is supposedly about 85%, so these kWh numbers must be wrong)

Tom Houlden
3 months ago
Reply to  Pedro Lima

Thanks. A lot of interesting info at that first link, although I didn’t see anything at either one about voltage vs. % SOC. At the link below, about 4 pages down, a chart shows 4.1 V is 85-90%. Somewhere else that I can’t find right now showed 4.1 V as 85%.

It actually doesn’t matter to ME though, since I store mine at around 3,9 V in a cool garage, then only charge to about 4,0 V anyway, right before leaving, & return home with about 3,8 V.

However I am less & less concerned about it, after over 6.5 years & 40,000 km without any detectable range loss, or even reports of that from other owners with over double my mileage. I’m not pretending there is no loss at all, just that it’s probably well under 10%, & therefore can’t be differentiated from a bit of a headwind or change in ambient temp.

https://cleantechnica.com/2018/08/26/the-secret-life-of-an-ev-battery/

Tom Houlden
3 months ago
Reply to  Tom Houlden

Oops! It’s EIGHT pages down that link I attached by mistake, where they copied the chart from 4 pages down THIS link:

https://batteryuniversity.com/learn/article/how_to_prolong_lithium_based_batteries