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Tue Oct 8, 2019, 04:38 PM

Dealing with 11 Million Tons of Lithium Ion Battery Waste: Molten Salt Reprocessing.

Last edited Tue Oct 8, 2019, 05:38 PM - Edit history (1)

The paper I'll discuss in this post is this one: Low-Temperature Molten-Salt-Assisted Recovery of Valuable Metals from Spent Lithium-Ion Batteries (Renjie Chen et al, ACS Sustainable Chem. Eng. 2019, 7, 19, 16144-16150)

There is, in the United States, about 75,000 tons of used nuclear fuels, generated in the United States, with 100% of the materials therein being valuable and recoverable. All of this material, called "nuclear waste" by people who have never opened a science book in their lives but nevertheless like to assert their ignorance loudly - as in the idiotic comment "Nobody knows what to do with 'Nuclear Waste'" - is located in about 100 locations, where it has been spectacularly successful at not harming a single soul.

If one doesn't know what to do with so called "nuclear waste," it's not like one is even remotely qualified to understand anything about nuclear energy because it is obvious that one has not opened a reputable science book in one's life. One's ignorance it obvious in this case, but it's not like, in Trumpian times, people are unwilling to make sweeping generalizations and pronouncements on subjects about which they know nothing.

Irrespective of the ignorance of anti-nukes, it is a shame to let these valuable materials, the only materials with high enough energy density to displace dangerous fossil fuels, go to waste, and I have spent about 30 years studying their chemistry, coming to the conclusion that the ideal way to recover the valuable materials therein is via the use of molten salts in various ways.

There are, by the way, as has been discovered in my lifetime, potentially an infinite number of such salts, and they can be finely tuned for any purpose one wishes.

By contrast to used nuclear fuel, electronic waste is widely distributed; its toxicology is not understood by the people who use it, including scientifically illiterate anti-nukes who run their computers parading their ignorance, without a care in the world about what will become of the electronic waste in their computers, their electric cars, their solar cells, their inverters, and the television sets in front of which they evidently rot their little brains. Electronic waste is not only widely distributed; it is massive and growing rapidly in volume, because of the dangerous conceit that so called "renewable energy" is "green" and "sustainable," neither of which is true.

The lithium ion battery was discovered in 1980 According to the paper I'll discuss shortly, by 2030 the total mass of lithium batteries that have been transformed into potential landfill will be 11 million tons. (I'll bold this statement in the excerpt of the paper's introduction below.) This means that each year, on average, since their discovery, 282,000 tons of waste batteries are taken out of use, about 370% of the mass of nuclear fuel accumulated over half a century.

It is only going to get worse with the bizarre popularity of electric cars, which dumb anti-nukes, with their Trumpian contempt for reality, imagine are all fueled by solar cells and wind turbines, even though solar cells and wind turbines, despite the expenditure of trillions of dollars on them have only resulted in climate change accelerating, not decelerating, since a growing[ proportion of the electricity on this planet is generated by dangerous fossil fuels, not so called "renewable energy."

It is difficult to recycle distributed stuff, and of course, it takes energy even if one can find an electronic waste recycling center, to drive to it, never mind the energy required to ship it to some third world country where the toxic materials therein will be less subject to health scruples. Inevitably, much electronic waste ends up in landfills, where it is forgotten, at least until the health effects begin to appear.

From the paper:

Lithium-ion batteries (LIBs) have emerged as a remarkable power source for consumer electronics, electric and hybrid electric vehicles, and large-scale energy storage, owing to their high energy and power density.(1−3) The fast-growing electric-vehicle market has strongly boosted the application of LIBs, resulting in the inevitable generation of a large amount of spent LIBs each year. It is estimated that the mass of discarded LIBs will exceed 11 million tons by 2030.(4) Discarded LIBs have the dual attributes of a resource and an environmental hazard: On the one hand, they are rich in valuable metals, such as lithium and cobalt; on the other hand, they contain organic substances harmful to the environment. Recycling of discarded LIBs will not only address the problem of resource shortages but will also avoid environmental pollution.(5)

State-of-the-art techniques for recycling of spent LIBs have been reviewed in several studies.(2,6−10) Generally speaking, existing recovery strategies can be divided into pyrometallurgical, direct generation, and hydrometallurgical processes. Pyrometallurgical processes are usually undertaken at high temperature, resulting in relatively high energy consumption.(11−13) The alloyed product and residue require further processing to obtain high-purity products.(14) Direct generation has stringent requirements for the purity of the feed and is not appropriate for recycling materials containing large amounts of impurities.(15) In contrast, hydrometallurgical methods have obvious advantages, including high recovery efficiency of valuable metals, mild reaction conditions, and environmentally friendly conditions. These advantages make hydrometallurgical methods a preferable and promising approach for disposing of spent LIBs; however, the inorganic(16−19) and organic(14,20−22) acids used in hydrometallurgical processing may cause secondary pollution, such as acidic waste waters and production of toxic gases (Cl2, SO3, and NOx) during the leaching process, which are threats to the environment. Therefore, developing a method to reduce acid consumption, decrease the emissions of the secondary pollution, and increase recovery efficiencies of metals is critical. A salt-assisted calcination method has recently been proposed that avoids the above issues and increases recycling efficiency.(23)

Salt-assisted calcination has become widely used as a metal-recovery method for waste materials due to its high reactivity, high volatility, low melting point, and high solubilities of salts.(23−30) In addition, the solid salt agents used are generally environmentally friendly, and the process has simple operation and low-cost equipment.(28) For example, Liu et al.(31) reported a vacuum chlorinating process for simultaneous sulfur fixation and lead recovery from spent lead-acid batteries using calcium chloride (CaCl2) and silicon dioxide (SiO2) as reagents. Dang et al.(23) proposed a chlorination roasting method to recycle lithium from a pyrometallurgical slag using three chlorine donors; namely, NaCl, AlCl3, and CaCl2. These findings showed that it is possible to recover metals through salt-assisted roasting, but the reaction temperature of these solid salt fluxing agents is quite high.

In this work, we developed a combination of low-temperature ammonium salt roasting and water leaching to efficiently and environmentally recover valuable metals from spent LIBs. NH4Cl, a nontoxic and noncorrosive solid chlorinating agent, can be decomposed to NH3 and HCl gases above 230 °C; (32) the introduction of NH4Cl as a chlorinating agent into the calcination process can therefore destroy the crystal structure of LiCoO2 and enable precipitation of Li and Co. Owing to the high solubilities of the chloride salts, the metals are recovered by water leaching after chlorination. The effects of various parameters on recovery efficiencies of Co and Li, including calcination temperature, time, and mass ratio of LiCoO2 to NH4Cl, were systematically investigated. The mechanism underlying the low-temperature molten-salt-assisted recovery process is discussed in detail. The method was proven by efficiently recovering valuable metals from LiMn2O4 and LiCo1/3Mn1/3Ni1/3O2 spent LIBs. This study presents an environmentally friendly and efficient method for recovery of metals from mixed cathode materials of spent LIBs.


I have bolded the information described above. Reference 4 is here: Burgeoning Prospects of Spent Lithium-Ion Batteries in Multifarious Applications (.Natarajan, S.; Aravindan, V. Burgeoning Prospects of Spent Lithium-Ion Batteries in Multifarious Applications. Adv. Energy Mater. 2018, 8 (33), 1802303– 1802319)

One can question, if one wishes, how environmentally "friendly" a process requiring a temperature of 230 °C really is, there is certainly no efficient and scalable way to do this with so called "renewable energy" on which all our battery worshipping types have bet the planetary atmosphere, a bet we are losing at great cost to all future generations.

No matter. I personally believe that to the extent that we can close material cycles, not just for nuclear fuels but for everything, not limited to carbon either, the less odious we will appear in history, although, as I often say, history already will not forgive us, nor should it. I own lithium batteries, and to the extent the materials in them can be recovered, so much the better, fewer modern day African children will need to dig cobalt for example.

Here are the chemical reactions and the equations for thermodynamic values in this process:

















Note that one of these reactions is the oxidation of ammonia to nitrogen gas using chlorine gas. Almost all of the world's ammonia is produced from hydrogen produced using dangerous natural gas, although one could have read over the last five decades or so, and can still read, lots of increasingly delusional claims that hydrogen "could" be produced by so called "renewable energy." After half a century of such rhetoric, almost none of it is.

The oxidation of ammonia by chlorine is thus an energy penalty reaction.

Before touching figure two which graphically obviates the thermodynamic penalties for recycling these putative energy storage devices, let me offer the cartoon of the "flowsheet" which is nice art:



The caption:

Figure 1. Flowsheet of the proposed recycling.


The thermodynamics, reactions being viable when the Gibbs free energy, ΔG, is below the zero line:




The caption:

Figure 2. Relationship between ΔG and temperature for different reactions.


A few more graphics:



The caption:

Figure 3. Effects of (a) temperature, (b) LiCoO2/NH4Cl mass ratio, and (c) roasting time on the leaching efficiency of Li and Co.




The caption:

Figure 5. Possible reaction pathway of the cotreatment process and SEM patterns of different stages: (a) NH4Cl, (b) LiCoO2, (c) mixed raw materials, and (d) sample after roasting.




The caption:

Figure 6. XRD pattern of recycled CoC2O4·2H2O and Li2CO3.





The caption:

Figure 7. Leaching efficiency of different samples.


Verification of the process is described:

Based on the above discussions, Li and Co can be recovered as chlorides from LiCoO2 powders by roasting with NH4Cl. To verify the feasibility of recovering these metals from other LIBs, wastes from LiMn2O4 and LiCo1/3Mn1/3Ni1/3O2 batteries were also examined. Spent cathode materials were prepared using the pretreatment process described above. Similar to the LiCoO2 material, LiMn2O4 and LiCo1/3Mn1/3Ni1/3O2 materials are metal oxides. The crystal structures of LiMn2O4 and LiCo1/3Mn1/3Ni1/3O2 are spinel and layered, respectively. The main metal element ingredients of waste LiMn2O4 and LiCo1/3Mn1/3Ni1/3O2 materials are shown in Table S1. The waste cathode powders were then completely reacted with NH4Cl by roasting under optimized calcination conditions. The metal elements were recovered by water leaching. Using this process, 97.99% Li and 95.27% Co were recovered from the spent LiMn2O4 material, while the leaching efficiencies of Li, Ni, Co, and Mn reached 94.95%, 92.87%, 91.59%, and 90.91%, respectively, from the spent LiCo1/3Mn1/3Ni1/3O2 battery material (Figure 7). After leaching, Ni2+, Co2+, and Mn2+ in the leachate can also be recovered and separated from lithium by the coprecipitation method. The coprecipitation reaction can use oxalic acid, sodium hydroxide and ammonia–water, and sodium carbonate as the precipitating reagents.(42−45)


From the conclusion of the paper:

A closed-loop and environmentally friendly process, including salt roasting, water leaching, and precipitation, was developed to recover valuable metals from spent LIBs. Using hydrogen chloride gas produced by the decomposition of NH4Cl as an acid source, Li and Co were released from LiCoO2. The optimal calcination conditions for the recycling process were 350 °C, a mass ratio of LiCoO2/NH4Cl 1:2, and a 20 min reaction time. Leaching efficiencies of Li and Co were 99.18% and 99.3%, respectively, using water leaching at a solid–liquid ratio of 100 g/L. Based on thermodynamic analysis and characterization conducted by XRD and XPS, a reaction mechanism was proposed. More than 90% of the Li and Co from spent LiNi1/3Co1/3Mn1/3O2 and LiMn2O4 cathode materials could be recovered by this novel process. In summary, this study presents a promising technology for metal recovery from spent LIBs.


There is very little discussion of the electrolytes and what to do with them in this paper, but no matter. This process seems fairly sustainable with the use of clean heat, readily accessible with nuclear energy.

To the extent we can close materials cycles, even given the logistics and energy requirements of recovering distributed materials, the better we can do at ameliorating the contempt in which history will hold us.

Have a nice evening.

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Reply Dealing with 11 Million Tons of Lithium Ion Battery Waste: Molten Salt Reprocessing. (Original post)
NNadir Oct 8 OP
Mopar151 Oct 8 #1
NNadir Oct 8 #2
Mopar151 Oct 9 #3
NNadir Oct 9 #4
Outlaw Star Oct 14 #5
NNadir Oct 14 #6
Outlaw Star Oct 15 #7

Response to NNadir (Original post)

Tue Oct 8, 2019, 07:51 PM

1. If nuclear waste is valuable

And reprocessible, 100%? Shoot......What are you waiting for? The Hanford Reservaton awaits!

Last I knew, fuel reprocessing had been tried commercially, and failed. IIRC, the test plant is awaiting decontamination or burial. No easy answers... I know a couple of smart guys who were making bank on the Rocky Flats cleanup, stripping off the surface layers of concrete + steel contaminated by weapons manufacturing.

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Response to Mopar151 (Reply #1)

Tue Oct 8, 2019, 08:43 PM

2. What am I waiting for? How about some common sense.

Seven million people die each year from dangerous fossil fuel and dangerous biomass combustion waste.

I'm waiting for a race of people who care more about that fact than their idiot terror of radioactive atoms.

You know, it's interesting how many people are stuck in the 1950's, thinking that what applied then applies now. I note that all these "unbelievable tragedies" at reprocessing plants haven't killed very many people, although people with no science background whatsoever obsess about them, less so when an oil refinery blows up, or an oil well blows out, say, in the Gulf of Mexico, killing people.

Selective attention? Moral indifference?

How is the clean up of the Gulf of Mexico going. Know any smart guys making bank scraping asphaltenes and tars off the floor of the Gulf?

There was actually an idiot here, now on my ignore list, who claimed that the collapse of a tunnel at Hanford was an unbelievable tragedy, and the deaths of seven million people in 2018, soon to be matched in 2019 from air pollution, um, wasn't.

Here is the most recent full report from the Global Burden of Disease Report, a survey of all causes of death and disability from environmental and lifestyle risks: Global, regional, and national comparative risk assessment of 79 behavioural, environmental and occupational, and metabolic risks or clusters of risks, 1990–2015: a systematic analysis for the Global Burden of Disease Study 2015 (Lancet 2016; 388: 1659–724) One can easily locate in this open sourced document compiled by an international consortium of medical and scientific professionals how many people die from causes related to air pollution, particulates, ozone, etc.

Why don't you commiserate with the tunnel asshole to find out how many people died from exposure to Hanford?

People make a lot of money on nuclear clean ups to save zero lives because there are a lot of very, very, very, very stupid people who live in dire fear of radioactivity, even though they would die without radioactivity in their bodies, since potassium is an essential atom and it contains radioactive potassium-40 naturally.

There is 750 tons of plutonium roughly in US nuclear fuel. World energy demand is currently about 578 exajoules per year. In order to meet the world energy demand, thus eliminating every coal mine, every oil well, every gas fracking field, every fucking wind turbine industrial park set up in pristine wildernesses to satisfy shit for brains people, every damn dam, and every piece of future electronic waste in the solar industry, it would be required to fission about 230 grams of plutonium per second. In a "breed and burn" reactor of which several types have been designed, this would enable humanity to live for centuries with uranium already mined.

his would save 70 million lives lost every decade to air pollution, and eliminate the accumulation of the dangerous fossil fuel waste carbon dioxide that is destroying the whole fucking planet while airheads prattle on about Hanford.

By contrast with 230 grams of plutonium persecond, at 35 billion tons of the dangerous fossil fuel waste carbon dioxide being dumped each year while airheads prattle on about Hanford, the dumping amounts to about 1100 tons per second.

I have, I confess, never met an anti-nuke who could grasp simple numbers and do simple calculations though.

If someone can't grasp that obvious environmental advantage of those mass ratios, I really, really, really, can't help them, since they are way beyond the possibility of becoming educated human beings.

Does that answer your question?

No?

I couldn't fucking care less about whether or not it does, but I am concerned about the 19,000 people who will die today because anti-nukes have their heads up their asses and have never, in their overly long lives, opened a fucking science book or a scientific paper.

Recently, thinking of the airhead who was having a panic attack because an old train tunnel containing some abandoned chemical reactors with trace plutonium on the walls collapsed, I wrote the following:

One of the interesting facets if one is to ponder this quality of thinking, which is Trumpian the depth of its delusion and the inherent gaslit (literally) lies such thinking involves, is the amusing fact that it is easy to insert one's head very far up one's ass if one's brains are soft, small, and largely empty.


That about sums it up.

In the ten minutes it took to write this post, 13 or 14 people died from air pollution. How many people died at Hanford from radiation in the last ten years again?

Ignorance kills people.

History will not forgive us, nor should it.

Have a nice day.

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Response to NNadir (Original post)

Wed Oct 9, 2019, 06:34 AM

3. How many tons of HOT steel are there, in the world?

Or irradiated concrete? How much would we have, in 50 years, if we build a new generation of uranium fission reactors to replace renewables?

Are there any commercial entities capable of building them safely, and operating them economically and safely?

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Response to Mopar151 (Reply #3)

Wed Oct 9, 2019, 09:59 AM

4. How many people have died from "hot steel?"

Anything like the 19,000 people who will die today from air pollution?

The bizarre radiation paranoia of antinukes would be amusing if it didn't kill people but it does.

Nuclear energy need not be perfectly without risk in the minds of every obsessive fool lacking a shred of scientific training to be infinitely superior to everything else. It only needs to be superior to everything else.

We could save millions of lives if we had more hot steel. The existence of iron plutonium eutectics makes hot steel particularly interesting, but in order to discuss this, one would need to have more scientific knowledge than can be found in comic books.

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Response to NNadir (Original post)

Mon Oct 14, 2019, 02:38 PM

5. This is good news

Very interesting and promising.Thanks for this. Its a shame you so often put a bunch of posturing and condescending statements in the beginning of your intriguing articles. I'm sure more people would read them if you didn't do that.

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Response to Outlaw Star (Reply #5)

Mon Oct 14, 2019, 03:05 PM

6. Understood, but frankly...

...the way I see it is that pure science is generally treated with condescension and posturing.

I see it every time I read the newspaper.

Were it not so would we really be experiencing climate change?

Would we chasing like mad women and mad men after things that don't work to address climate change and insisting that future generations will do what we can't do ourselves, this with a destroyed environmental infrastructure and depleted resources?

Would we still be carrying on about Fukushima while 19,000 people die every day from air pollution?

Is there some reason that I am not permitted to not be angered about this state of affairs?

I'm too old to believe that what I say will matter, but as I approach the end of my life facing sons and the members of their generation who will need to live with what we have done, to the extent that anything I have said or done survives, which is unlikely, I want it said that at least someone had the decency to be ashamed and angered.

I'm not interested in readership so much as I am interested in truth, in particular, moral truth.

Thanks for your advice though, even if I decline to take it.

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Response to NNadir (Reply #6)

Tue Oct 15, 2019, 07:44 AM

7. well...

I think even if science were better respected and understood we would still be in this mess because I see it as the inevitable result of the success of fossil fuels. Also i expect Extend & Pretend to be the order of the day until it simply falls apart, and I sometimes find myself angry about it as well. You are far from alone in the shame and anger, but more people choose to hide it than admit it. I am fairly young so I will likely have to deal with the consequences of our carelessness for several more decades, but it's ok.

Some of us understand that humans are just another creature that sometimes overreaches it's limits and gets put back into it's place. We aren't angry with the previous generations because we understand we would have likely done much the same in those circumstances. So I think what I'm trying to say here is don't blame yourself too much. We all make mistakes, sometimes on a global scale.

In any case I look forward to your future posts!

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