Recycling Lithium Ion Batteries

One of the biggest contributors to greenhouse warming is transport, and the solution that seems to be advocated is to switch to electric vehicles as they do not release CO2, and the usual option is to use the lithium ion battery A problem that I highlighted in a previous blog is we don’t have enough cobalt, and we run out of a lot of other things if we do not recycle. A recent review in Nature (https://doi.org/10.1038/s41586-019-1682-5)   covered recycling and the following depends on that review. The number of vehicles in the world is estimated to reach 2 billion by 2035 and if all are powered by lithium ion batteries the total pack wastes would be 500 million tonnes, and occupy a billion cubic meters. Since the batteries last about nine years, we eventually get drowned in dead batteries, unless we recycle. Also, dead lithium ion batteries are a fire hazard. 

There are two initial approaches, assuming we get the batteries cleanly out of the vehicle. One is to crush the whole and burn off the graphite, plastics, electrolyte, etc, which gives an alloy of Co, Cu, Fe and Ni, together with a slag that contains aluminium and manganese oxides, and some lithium carbonate. This loses over half the mass of the batteries and contributes to more greenhouse warming, which was what we were trying to avoid. Much of the lithium is often lost this way to, and finally, we generate a certain amount of hydrogen fluoride, a very toxic gas. The problem then is to find a use for an alloy of unknown composition. Alternatively, the alloy can be treated with chlorine, or acid, to dissolve it and get the salts of the elements.

The alternative is to disassemble the batteries, and some remaining electricity can be salvaged. It is imperative to avoid short-circuiting the pack, to prevent thermal runaway, which produces hydrofluoric acid and carcinogenic materials, while fire is a continual hazard. A further complication is that total discharge is not desirable because copper can dissolve into the electrolyte, contaminating the materials that could be recycled. There is a further problem that bedevils recycling and arises from free market economics: different manufacturers offer different batteries with different physical configurations, cell types and even different chemistries. Some cells have planar electrodes, others are tightly coiled and there are about five basic types of chemistries used. All have lithium, but additionally: cobalt oxide, iron phosphorus oxide, manganese oxide, nickel/cobalt.aluminium oxide, then there are a variety of cell manufacturers that use oxides of lithium/manganese/cobalt in various mixes. 

Disassembling starts with removing and the wiring, bus bars, and miscellaneous external electronics without short-circuiting the battery, and this gets you to the modules. These may have sealants that are difficult to remove, and then you may find the cells inside stuck together with adhesive, the components may be soldered, and we cannot guarantee zero charge. Then if you get to the cell, clean separation of the cathode, anode, and electrolyte may be difficult, we might encounter nanoparticles which provide a real health risk, the electrolyte may generate hydrogen fluoride and the actual chemistry of the cell may be unclear. The metals in principle available for recycling are cobalt, nickel, lithium, manganese and aluminium, and there is also graphite.

Suppose we try to automate? Automation requires a precisely structured environment, in which the robot makes a pre-programmed repetitive action. In principle, machine sorting would be possible if the batteries had some sort of label that would specify precisely what it was. Reading and directing to a suitable processing stream would be simple, but as yet there are no such labels, which, perforce, must be readable at end of life. It would help recycling if there were some standardised designs, but good luck trying to get that in a market economy. If you opt for manual disssembling, this is very laboour intensive and not a particularly healthy occupation.

If the various parts were separated, metal recovery can be carried out chemically, usually by treating the parts with sulphuric acid and hydrogen peroxide. The next part is to try to separate them, and how you go about that depends on what you think the mixture is. Essentially, you wish to precipitate one material and leave the others, or maybe precipitate two. Perhaps easier is to try to reform the most complex cathode by taking a mix of Ni, Mn, and Co that has been recovered as hydroxides, analysing it and making up what is deficient with new material, then heat treating to make the desired cathode material. This assumes you have physically separated the anodes and cathodes previously.

If the cathodes and anodes have been recovered, in principle they can be directly recycled to make new anodes and cathodes, however the old chemistry is retained. Cathode strips are soaked in N-methylpyrrolidine (NMP) then ultrasonicated to make the powder to be used to reformulate a cathode. Here, it is important that only one type is used, and it means new improved versions are not made. This works best when the state of the battery before recycling was good. Direct recycling is less likely to work for batteries that are old and of unknown provenance. NMP is a rather expensive solvent and somewhat toxic. Direct recycling is the most complicated process.

The real problem is costs. As we reduce the cobalt content, we reduce the value of the metals. Direct recycling may seem good, but if it results in an inferior product, who will buy it? Every step in a process incurs costs, and also produces is own waste stream, including a high level of greenhouse gases. If we accept the Nature review, 2% of the world’s cars would eventually represent a stream of waste that would encircle the planet so we have to do something, but the value of the metals in a lithium ion battery is less than 10% of the cost of the battery, and with all the toxic components, the environmental cost of such electric vehicles is far greater than people think. All the steps generate their own waste streams that have to be dealt with, and most steps would generate their own greenhouse gases. The problem with recycling is that since it usually makes products of inferior quality because of the cost of separating out all the “foreign” material, economics means that in a market economy, only a modest fraction actually gets recycled.

Non-Battery Powered Electric Vehicles

If vehicles always drive on a given route, power can be provided externally. Trams and trains have done this for a long time, and it is also possible to embed an electric power source into roads and power vehicles by induction. My personal view is commercial interests will make this latter option rather untenable. So while external power canreplace quite a bit of fossil fuel consumption, self-contained portable sources are required.

In the previous posts, I have argued that transport cannot be totally filled by battery powered electric vehicles because there is insufficient material available to make the batteries, and it will not be very economically viable to own a recharging site for long distance driving. The obvious alternative is the fuel cell. The battery works by supplying electricity that separates ions and converts them to a form that can recombine the ions later, and hence supply electricity. The alternative is to simply provide the materials that will generate the ions and make the electricity. This is the fuel cell, and effectively you burn something, but instead of making heat, you generate electric current. The simplest such fuel cells include the conversion of hydrogen with air to water. To run this sort of vehicle, you would refill your hydrogen tank in much the same way you refill a CNG powered car with methane. There are various arguments about how safe that is. If you have ever worked with hydrogen, you will know it leaks faster than any other gas, and it explodes with a wide range of air mixtures, but on the other hand it also diffuses away faster. Since the product is water (also a greenhouse gas, but one that is quickly cycled away, thanks to rain, etc) this seems to solve everything. Once again, the range would not be very large because cylinders can only hold so much gas. On the other hand, work has been going on to lock the hydrogen into another form. One such form is ammonia. You could actually run a spark ignition motor on ammonia (but not what you buy at a store, which is 2 – 5% ammonia in water), but it also has considerable potential for a fuel cell. However, someone would still have to develop the fuel cell. The problem here is that fuel cells need a lot more work before they are satisfactory, and while the fuel refilling could be like the current service station, there may be serious compatibility problems and big changes would be required to suppliers’ stations.

Another problem is the fuel still has to be made. Hydrogen can be made by electrolysing water, but you are back to the electricity requirements noted for batteries. The other way we get hydrogen is to steam reform oil (or natural gas) and we are back to the same problem of making CO2. There is, of course, no problem if we have nuclear energy, but otherwise the energy issues of the previous post apply, and we may need even more electricity because with an additional intermediate, we have to allow for inefficiencies.

As it happens, hydrogen will also run spark ignition engines. As a fuel, it has problems, including a rather high air to fuel ratio (a minimum of 34/1, although because it runs well lean, it can be as high as 180/1) and because hydrogen is a gas, it occupies more volume prior to ignition. High-pressure fuel injection can overcome this. However there is also the danger of pre-ignition or backfires if there are hot spots. Another problem might include hydrogen getting by the rings into the crankcase, where ignition, if it were to occur, could be a real problem. My personal view is, if you are going to use hydrogen you are better off using it for a fuel cell, mainly because it is over three times more efficient, and in theory could approach five times more efficient. You should aim to get the most work out of your hydrogen.

A range of other fuel cells are potentially available, most of them “burning” metal in air to make the electricity. This has a big advantage because air is available everywhere so you do not need to compress it. In my novel Red Gold, set on Mars, I suggested an aluminium chlorine fuel cell. The reason for this was: there is no significant free oxygen in the thin Martian atmosphere; the method I suggested for refining metals, etc. would make a lot of aluminium and chlorine anyway; chlorine happens to be a liquid at Martian temperatures so no pressure vessels would be required; aluminium/air would not work because aluminium forms an oxide surface that stops it from oxidising, but no such protection is present with chlorine; aluminium gives up three electrons (lithium only 1) so it is theoretically more energy dense; finally, aluminium ions move very sluggishly in oxygenated solutions, but not so if chlorine is the underpinning negative ion. That, of course, would not be appropriate for Earth as the last thing you want would be chlorine escaping.

This leaves us with a problem. In principle, fuel cells can ease the battery problem, especially for heavy equipment, but a lot of work has to be done to ensure it is potentially a solution. Then you have to decide on what sort of fuel cells, which in turn depends on how you are going to make the fuel. We have to balance convenience for the user with convenience for the supplier. We would like to make the fewest changes possible, but that may not be possible. One advantage of the fuel cell is that the materials limitations noted for batteries probably do not apply to fuel cells, but that may be simply because we have not developed the cells properly yet, so we have yet to find the limitations. The simplest approach is to embark on research and development programs to solve this problem. It was quite remarkable how quickly nuclear bombs were developed once we got started. We could solve the technical problems, given urgency to be accepted by the politicians. But they do not seem to want to solve this now. There is no easy answer here.

Voting: a right or an obligation?

Nobody can predict the future, but I think you can make reasonable guesses about some aspects of it based on applying logic to current evidence. An example might be, eventually, if we keep expanding our use of fossil oil, there will come a time when production cannot match needs. After all, we are using oil that was formed tens of millions of years ago, and even if nature is still making it, it is doing so too slowly to be of any further use to us. We do not know how much is there, so we do not know when the shortage will bite, but we know it will sooner or alter. In logic, our choices would appear to include (a) find an alternative source of energy, (b) find an alternative means of making products similar to what is made from oil, e.g. biofuels, (c) find an alternative means of propelling vehicles, e.g. electric vehicles, (d) transport fewer things and more slowly, e.g. walk to work, use wind-powered ships. There are probably others, but that is not the issue. What is obvious, at least to me, is that at some time in the future, those in power will have to make some very difficult decisions that will affect everyone’s future. The question is, how will they decide? And how will the decision makers be chosen? In a democracy, the voters select the decision-makers, but what happens if the election is based on little more than attractiveness on TV?

 What bothers me is that only too many people are not interested in thinking, but in our democracy, they have equal influence. As an example, check out some of the debates on evolution. Some people seem to believe asserting evolution is a challenge to their belief in God. Their thinking then goes, God is, therefore evolution is not. This is just silly logic. There is absolutely no connection between whether God or evolution, or both, are true. Einstein was amongst one of the greatest scientists of all times and he happily accepted evolution, and he believed strongly in God. The issue lies in the failure of many to accept and analyze the facts through logic. Strictly speaking, it hardly matters whether everybody properly consider evolution, but it matters if people stop logically analyzing the facts when forming policy upon which millions of lives depend. Should not everybody who wants to vote accept the responsibility of thinking about the issues?

 The question then is, what can be done about this? When I was writing the trilogy of futuristic novels, starting with A Face on Cydonia, I needed a new form of government to get around this problem. What I proposed was that many countries formed a Federation, they retained their national governments, but the Federation Government had members appointed partly by election from sections of the community, but all candidates had to be approved as capable of doing the job for which they were standing. Their role was to determine whether a given policy was workable, and to show what the consequences of implementation would be, and to prevent anything that would give consequences outside those considered “acceptable”. People standing for power had to announce in advance essentially what they were going to do, although of course there was always flexibility for reasonably unforeseen circumstances. The novels, of course, are not intended as a political treatise, but merely to provide some rules that the characters must follow.

 What I was trying to do, though, is to suggest that decisions have to be made based on analysis of the situation, and based on the facts. The stories are based on the obvious problem: people do not necessarily follow the rules. Nevertheless, I feel that it is important that governments behave logically. I am sure that with climate change, debt, decreasing availability of easy resources and an increasing population, some difficult decisions will need to be taken. If we get it right, future generations will be secure, but if we do not, then we are in trouble. My argument is that the time to start thinking about these problems is now. Do you agree?