Dealing with 11 Million Tons of Lithium Ion Battery Waste: Molten Salt Reprocessing.
Last edited Tue Oct 8, 2019, 06:38 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:
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:
The thermodynamics, reactions being viable when the Gibbs free energy, ?G, is below the zero line:
The caption:
A few more graphics:
The caption:
The caption:
The caption:
The caption:
Verification of the process is described:
From the conclusion of the paper:
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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