Guest Speakers: Emma Kendrick, Martina Petranikova and Andreas Flegler
Moderator: Guinevere Giffin
Title: Perspectives in battery recycling
April 30th 2024
Agenda:
15:00-15:05 Intro BATTERY 2030+ Guinevere Giffin
15:05-15:35 Presentation “Advances in hydrometallurgical processing of Li-ion battery waste” Martina Petranikova
15:35-16:00 Presentation “Sustainable Routes to Recovery and Reuse of Battery Materials” Emma Kendrick
16:00- 16:25 Presentation “Design for Circularity Strategies to Enable Direct Recycling” Andreas Flegler
16:25-16:50 Panel discussion
16:50-17:00 Summary Guinevere Giffin
Emma Kendrick is chair of energy materials at the University of Birmingham and co-lead of the energy materials group. Her work focuses on sustainable battery design from cradle to cradle. Materials, manufacturing and recycling for lithium-ion, sodium-ion and novel cell technologies.
Martina Petranikova has over 15 years’ experience in the waste management of spent batteries of all chemistries including directive, collection systems, discharging, dismantling and material recycling. Development of chemical processes for recovery and reuse of valuable metals and non-metallic components. Experience in the optimization and scaling up of the developed chemical processes. Research project leadership and supervision. Manager of a pilot plant for metal separation and mechanical pre-treatment.
Andreas Flegler is the Head of the Fraunhofer R&D Center Electromobility Bavaria at Fraunhofer ISC, the head of the Process Technology group and heads a BMBF BattFutur Research Group. His work focuses on novel process development for lithium-ion batteries and direct recycling. In addition, his group is developing and implementing design for recycling strategies for future of lithium-ion batteries
Guinevere Giffin is currently the Scientific Head of the Fraunhofer R&D Center Electromobility Bavaria at Fraunhofer ISC and is doing her habilitation at the University of Würzburg. Her work focuses on the elucidation of structure-property-process relationships of materials and components for lithium-ion, sodium-ion and solid-state batteries, supercapacitors and during battery recycling
do you still see my screen yes y perfect thanks so I would like to welcome everyone to today’s excellent seminar this excellent seminar series is presented by battery 2030 plus um for those of you who don’t know battery 2030 plus uh it’s considered an essential part of the European battery ecosystem to invent sustainable batteries of the future um if you would like to know more about us and the initiative please go to the website um you can find it simply by searching in Google battery 2030 Plus in May the annual conference for battery 2030 plus will be held in groby on the 28th and 29th there are definitely still places open including for young scientists we always love to have young scientists present at our events um and so if you’re interested in coming and presenting uh a poster about your work at b2030 plus please submit your abstracts uh you can do so here by meet at uh www. meet b2030 plus. or over the QR code currently on the screen so the battery 2030 plus initiative has been organizing this EXC excellent seminar now uh for quite a while here you can see some of the people that have presented at the Excellence Seminar in the past and today we want to present or the topic of the Excellence Seminar is perspectives in battery recycling and we’re very lucky today to have three uh speakers who are going to give us different aspects about battery recycling particularly in Europe um the first speaker will be Martina petranova um the second will be Emma Kendrick and the third will be Andreas flea so we will open with Martina and she will be talking about advances in hydrometallurgical processing of lithium ion battery waste so Martina I hopefully can end sharing and then the floor is yours thank you very much I will share my screen can you see it yes but not in presentation mode yeah I think it’s coming let’s see okay what about now perfect yes good I hope you don’t mind I will switch also the camera because it’s a bit weird to see yourself and also to talk to the screen so thank you very much for inviting me to have this presentation and uh just to introduce myself I’m from chmer University of Technology which is in gothenberg in Sweden and our group has been working for over 15 or 16 years on the batter Recycling and um today okay so some difficulty to moved them okay good so today I will talk a little bit very shortly about the battery materials for those who are not that familiar with what we can find in lithium and batteries and then also very shortly about the motivation beh behind the recycling and then I will focus on the hydrological processing of the lithium ion batteries and then I will also share some research from Chalmer and this is uh know for uh majority of us that in European Union we are going to have a lot of battery producers and also uh car producing using electric uh or the batteries but what is important for us is for the European Union is that we have we don’t have the resources to actually make those batteries from so that’s why the recycling is so important especially for us and for those who are not that familiar with the the battery composition just to shortly that what we can find in lithium batteries is mostly transition metals so we either have lithium cobal oxide which is mostly in the small devices and then we have nickel lithium or lithium nickel manganese Cobalt oxide and then also these days lithium iron phosphate and then so the structure with aluminium and what was may be interesting to remember is that nowadays the effort is to decrease the content of cobalt for its price and also for its criticality but we have to keep in mind that if we are decreasing the amount of this valuable element in the waste then we are also decreasing the motivation for the recycling or incentives for the recycling for the companies to just keep in mind that if we are decreasing some valuable element in the waste then it’s not that interesting to recycle on the anod side what we have is mostly graphite and it’s mostly artificial graphite which is used in the butteries and us as um chemist who are using um chemical recycling we like graphite because graphite is very neutral material for the hydrological processing it’s very easily recovered and I will show you later where in each which Step so it’s a very good material but what is also considered to be used what is also used are different doping Elements which can be like Titanium or thin which then it’s also it complicates hydrological processing and for those who are developing the batteries it’s very important to remember that these kind of the elements if they enter the recycling uh streams then it’s quite difficult to get them out from them and then we also have electrolytes it’s mostly lithium salt and also some organic solvents usually I call these troublemakers in the recycling because it’s always a problem to to remove them and they also causing some problems in the hydrological processing if they stay within the waste and then what we should also remember is that inside we have a binder pbdf and then some current collectors which is metallic copper and metallic aluminium so what is the motivation for the recycling these days of course we are in European Union so we we have to obey the law so the first and main reason is that we have a battery regulation which requires us to achieve some efficiency in the battery recycling and it is focused on the transition metals and then also on the recovery of lithium so it’s set some values which we have to be able to reach in 2027 and then in 2031 it’s even higher which is quite challenging for the recycling processes and not only this but uh except that we have to achieve some recycling efficiencies then we also will have to or battery producers they will have to use some recycled material again in the production of the new batteries so that is also quite challenging these days another reason what why we should uh do the recycling is that we have to we have the materials and metals which are present in the lithium batteries they are also on the list of critical materials for the European Union and now recently it was even manganese which entered the the list and then also copper and nickel they are not critical raw materials but they are included as a strategic raw materials so quite a lot of elements and um yeah elements are in the batteries are also on these list so there’s another reason another reason is also of course profit for the recycling companies because what they do is that they can sell the metals and materials recovered from these batteries but then also in European Union we have extended producer responsibility which comes with a gate fees which these days they are from 0.5 to2 per kilogram of the battery some companies are even on the Zero because the material is available and then of course metals they are quite still valuable even lithium hydroxide the prices has been changing but by time but still it’s a very very able material in those batteries and then another reason is that we have to fulfill the demand so we have a quote from the recycler who says that recycling cannot provide enough uh supplies so we have to continue Mining and then from the minor or from the M primer producer of nickel we have that recycling is necessary because the primary sector or the the primary production of the metals cannot satisfy the demand for nickel for example so then to be able to have enough materials for the battery production we actually have to do the recycling so how it is actually done these days so for maybe many of you are familiar how this is done these days but in general we have two main roads so one is pomological Road where batteries are smelted together very often together with nickel metal hydrate batteries and what is recovered is iron nickel Cobalt and copper but it’s important to remember that this is recovered in the form of alloy which has to be then sent for for the chemical processing to separate these metals from each other usually what is lost is manganes aluminium electrolyte these days there are also efforts to recover lithium from the from these recycling streams but this is just in the beginning the main road which we can see is the mechanical pre treatment and then the Black Mass recovered from this mechanical treatment is sent to the chemical processing very often we can see and now it’s even like coming back is the use of thermal treatment to handle the electrolytes and also better separation of the active material from the foils and since I’m supposed to talk today about the hydrological processing they I would focus on the on the main steps which are used in the chemical processing and the first step which we start with is the leeching where you we usually recover all the metals we get them in the solution and then the next step what is used is to remove the impurities for us the main impurities are iron aluminium and copper if the mechanical pre treatment is effective then usually these are at very low concentration but usually we still have to remove them before we are going to process transition metals and very often what is used is either Solon extraction the process I will talk about that later a little bit or co-precipitation and then lithium is usually recovered as the last one there is also now an approach where transition metals are recovered before the impurities so as it is written there there are a lot of combinations and and versions of hydr mechanic or hydrochemical processing which can be used for the battery cycling and also a different combination of them is and is being used you will see later and since I always say that I’m a teacher so not everybody is familiar also so with this uh terms if I’m talking about some chemical terms so I will talk a little bit what the leeching is for those who are not familiar and the leeching is that we have our black mass which in this simple form we can consider that we have some Transit transition metal oxides we have maybe some Copper from the foil and then we use the acid we apply some th and also some temperature we mix it for some time and then what we get we dissolve these Metals into the solution and we call it that we get them in the ionic form and then we apply a filtration or the separation and then in this step we very easily recover graphite because graphite is not going to be dissolved in the leeching media which is usually acid or some basic or it can be inorganic or organic acid or deetic solvent also used these days and this is the point where we can get a very pure or we can recover the majority of the gra graphite usually the efficiency of the leeching is very high when it comes to the metal so we can get almost all the graphite in this solid form and then we get all the metals in the solution so usually this step is very effective these days another step which is used in the hydrological processing very often is a precipitation and mostly the point is to sort of like get this metal from ionic form back to the solid form so we can use different agents it’s very very often sodium hydroxide is being used but also for example for copper it’s very often some gas media and again we apply this media to the solution where we have our Metals the metal we want to remove uh precipitates and then again we use a simple filtration and then we can recover or remove this metal uh when it comes to the precipitation the efficiency is usually also quite high so we can remove from 999 98 to 99 of the impurities what is maybe good to remember that very often in this step we have some loss of the transition metals so that depends on the technique or how the process was effective but it can the loss can be from 5 to 10% so then after the removal of the impurities then we have our transition metals plus lithium in still in the solution but still if the process was wasn’t very effective or completely effective then we still have some small impurities in the solution another method which has been used quite often for the separation of the transition metals is Sol extraction because transition metals are very similar to each other it’s not easy to separate them with just with the precipitation so very often s extraction is used it’s a technique which is very old and being used in the primary production of metals and the main um principle is that we have organic molecules which are very selective and very often we use the molecules which we can sort of like trick which changing the pH so if we set a proper pH of the solution and mix this solution with the organic phase then we can get into this organic phase just the metal we want to recover so the principle is that we mix these organic molecules with our solution and then the metal we want to extract or we want to get usually gets into the organic phase and then they have the since it is organic molecule it has a different density from the equas so they get separated based on the different um density and then we wash these um organic molecules which contain mostly only the metal which we wanted to recover with some clean acid usually it’s acid and then we get the metal in the clean form what is very important especially for people who are working with LCA is to remember that these organic molecules are not consumable so they can be used for many years within the process so sometimes Solon extraction is seen as a very sort of like a chemical consuming process but it’s actually not because these molecules they can be used for some companies are using them for 10 or 30 years so it’s um they can be reused again and again for the separation of these elements usually we use um different organic molecules so for manganese it’s very often this commercial D to HBA and for Cobalt it can be sinx 272 and the Purity is actually very high because it’s very effective method and we can achieve battery gr Purity for these metals and also the recovery is very high and then usually lithium is just precipitated at the end because if we remove all the transition metals then in our solution we keep only lithium which and is precipitated and the the battery grade or the Purity is very high what is maybe important also to remember is that if we are talking about Solon extraction it’s usually not just only one step but there are several steps involved so we have some extraction of the metal then we can have some removal of the impurities from the organic molecules and then at the end we have this recovery which we calls tripping so it’s a several steps for each metal because for some companies the can this can be either too difficult or too expensive method to be used then also what is applied these days is just co-precipitation of the transition metals and then again lithium stays in the solution and um can be used but the Purity is slightly lower for the transition metals product so how it looks like for the future is that it is expected that uh the main sort of like approach which is going to be used in the recycling is actually mechanical prot treatment and then hydrology and uh it is sort of expected because uh if we look into the directive we are supposed to fulfill and Achieve these efficiencies in the chemical recycling or in the recycling of the lithium ion batteries then usually the hydrology provides this uh this ability to fulfill and also achieve the purities which we have to have for the battery production in nordics it is uh several companies and uh um all noral and foron they are using hydrological processing sta is using mechanical pre treatment and just since we are talking about or I mentioned that there are different ways how to do the recycling and use different techniques in a different combination this is for example the phoms approach where they’re also using chromatographic separation for the separation of their Metals so it’s again another technique used for the recycling so what we do at Chalmer uh since I’m supposed to talk about the hydrological processing but I wanted to just mention shortly that uh we are also focusing on the removal of the electrolyte and we are using super critical CO2 where we can remove the electroly a colleague of mine Dr bak ebin and his PhD students they are using super critical CO2 where they can very effectively remove the electrolyte and then also the binder which then helps us in the hydrological processing to get more pure material for the hydrological processing so if you’re interested in their results they have published several papers and they also or you can also contact them and when it comes to the group which is working on the recycling of um of the CH chemical recycling of the batteries we have developed to sort of like two roads the one the the gray one is this very traditional one which is quite noen where we use the leeching then removal of the impurities and then we go for the separation of the transition metals but we also wanted to focus on something shorter and maybe more feasible for the recycling companies and more easier so then the idea was to get the lithium first before all the other elements then remove the impurities and then keep together transition metals and then go for the synthesis of MC material from this mixture so we have we can skip all the s extraction or all the separation of the transition metals and with this one we cooperate with the University from Upsala and they are helping us to to make this nmc material so the first idea was to get the lithium first and the reason the main reason was that if we remember the directive it’s quite High also on the and it’s going to be increased on the recovery of lithium and usually what you don’t don’t see and don’t hear is that there is a loss of lithium throughout this traditional way of the recycling so some lithium is lost in the precipitation of the impurities and then also in the Solon extraction and then also this is related to quite a large generation of the waste so then the idea was to to recover this uh first before everything and what we did was that we did a tremal pre treatment because that’s also what we have been working on um for for many years and when we do the per thermal treatment the pyrolysis then we can transform this lithium from lithium oxides and also from salts in the form of lithium carbonate and lithium carbonate is leachable with the water so my PhD student did that but we sort of started or we stopped and the efficiencies and usually other efficiencies were approximately from 60 to 70% so there was some limit how much can be actually recovered with the current setup but what is positive about this approach was that the main elements which were Le was just lithium and then a little bit of aluminium and then we looked also at the product what we could recover and we recovered lithium carbonate it was mainly this and then a little bit of lithium fline because of course we have some fluorides in the system so then lithium will likely bound to the Florine as well and we are still working on this method and we would like to achieve much higher efficiencies but because we met this limit and it was actually confirmed at several universities in working in uh in Europe with this kind of the approach we all got to this sort of like a limit and these numbers so then another way was to use organic acids and my PhD student she started to work with the oxalic acid and did experimental design and tried to find the conditions where we could selectively recover lithium and what she has achieved was that she was able to recover 100% Almost 100% of uh lithium but also what was very interesting in this approach was that with this experimental design she also recovered 100% of aluminium so in one step we could recover all the lithium and then also all the aluminium which is the impurity in the system so then we could Skip One Step for the removal of the impurity and uh mostly what uh what as I said it was mostly lithium and then also aluminium and then rest stayed in The solid residue so it also very simple to then separate the solution from The solid residue then because lithium and aluminium acire different elements that is also that helps the separation so then she also tried evaporative crystallization and with the with the conditions she has been tested she very effectively also separated lithium from the aluminium it is also still the research which we have been uh working on and we will continue also using different uh different approaches to get the good separation of the lithium and aluminium but still like already with this step we have reached and we have separated all the lithium uh from the system while copper and transition metals stayed in the solid form what we have been also working on is uh mechanical activation of these of the Black Mass because uh as we all know there is also binder or glue which is used for the cathod materials on the aluminium foils and this glue can also affect the separation and then the contact of the leeching media with the with the material so we have tested mechanical activation with the High um high energy milling and what we could see when we were testing the base conditions that for the lithium and for the Cobalt the increase of the leing efficiency was from 5 to 10% % which is not much and it cannot sort of compensate for the energy need for this kind of theing but for aluminium it was also quite uh quite important and then uh or a little bit increase so that can be good and improve the removal of the impurities and maybe this like this is this that doesn’t look now very significant but in case of need for the even increased efficiencies in the recycling process this could be also one of the steps where the recycling efficiencies could be improved for the material recovery what we have been also working on a lot is together with nuon who is the producer of hydrogen peroxide is to look into the different consumption of hydrogen peroxide when it comes to the different nmc materials and what we also looked into was actually the way of dosing the hydrogen peroxide hydrogen peroxide is used to to leech all the Cobalt and transition metals because we need to change the oxidation state to to get it into the solution and one positive of this chemical is that um it doesn’t come with any other impurities so when it reacts in De composes to oxygen and to water so it’s a very clean chemical but it’s quite expensive chemical and it’s also its consumption should be optimized so we did the research on the optimization and then also on the defining the con assumption and we could see that um it’s uh mostly in the most of the cases it didn’t matter how we were dosing if we were dosing in the beginning of all the volume needed for the reaction or we were dosing throughout the experiment so at the end the consumption was very similar the only difference was for nmc 811 when the consumption or the effect on the manganese was slightly better if we multiplied the dosing what we also did the research on was this effect of Thal treatment then on the consumption of hydrogen peroxide and we have received industrial samples from different companies doing the recycling with different way and different thermal PR treatment and the yellow line it’s represents the pyrolysis which usually shows to be the best option as a thermal prot treatment red line is incineration green light green line is without any thermal pre treatment and blue is a mild thermal pretreatment and uh what we have seen is that if we use or the companies use pyrolysis then usually very small amount of hydrogen peroxide is actually needed for the reaction of the to achieve the complete recovery and then also it’s very fast when it comes to the pyrolysis if you look at the red lines then you can see that even though we dosed a lot of hydrogen peroxide for the samples which were incinerated it didn’t help that much to Cobalt and also to Nickel so incineration is really usually very bad option for the for the recycling of the batteries because if you achieve some temperature then you can form the phases which are not that leachable at these kind of the conditions so it can be harmful for the recycling of the batteries we have been also focusing a lot on the optimization of the th extraction and we did a lot of research on the manganese which this day days or previously we can see that a lot of recycling is done by its precipitation because it doesn’t have any value but maybe that now we can see that there is actually an increase interest from the industry to also recover manganes with the Solen extraction because again it got into this list of critical raw materials and uh it’s also needed for uh for the production of nmc material so with this method we can achieve very high Purity so we have optimized the process and developed the process where we achieved very high purities for the manganese recovered from the batteries we have been also working quite a bit on the recycling of uh lfp because we have been using organic acid and also deetic acids and inorganic acids unfortunately this research hasn’t been published yet so I cannot share what kind of the organic acid we have been using and also what kind of the deputati acid uh solvents or inorganic but what is interesting here to see that with Organic acid we used we actually achieve very nice separation of the lithium and iron throughout the time so that can be one way how the lithium could be selectively recovered from the system and then also to achieve that the iron and um phosphorus will stay in the solution with the deetic uh solvent it actually the separation or selectivity wasn’t that well but still we are working on this research and then when it comes to inorganic acid what is quite interesting to see is that there is different kinetics of these element so if we if the if the leeching process is very short then we can get lithium the majority of the lithium very quickly while the iron and phosphorus stays still in the solid phase we have been also working on the recycling of the graphite and there is a lot of research where uh there is an attemp to do the Regeneration of the graphite but our approach is to do the graphine from this kind of the material because it’s quite substantial material generated uh in this process and we have been able to make uh the graphine out of this material but still this process and project is uh still continues so thank you very much for your attention and if you are interested in our work you can find us on the [Music] Linkin so thank you very much Martina for the viewers um please put your questions down in the uh Q&A box below we will come back to all of these questions at the very end when we have the panel discussion with our three speakers and so next I would like to introduce Emma Kendrick and she will present uh sustainable roots to recovery and reuse of battery materials so thanks Emma the floor is yours hi thanks Gwen um so I’m going to talk a little bit today about what we’re looking at to recover some of those battery materials and then looking at directly reusing them um into a battery if we um think about sustainability um we need to think about it holistically so where the materials come from as Martina’s already explained some of these are on a critical material list um there’s a security of the supply that we need to think about um also how much of those materials um are actually recycled but then how do we use them to make those materials um how are those materials transformed into electrodes into the cell the cell in life and ultimately reclaiming those materials at end of life to to kind of complete that um circular economy picture of use and the things that we’re really interested in are trying to reduce the energy inputs um and the environmental impact of all of these parts of the value chain for for these uh lithium battery systems and potentially other uh battery technologies as well um the bit that I’m going to talk about today is um recovery of those materials Martina’s already spoken of how we can recover them and then use them as a secondary or to remanufacture but is there a group that we can short Loop uh potentially um so this is the list of critical materials and just to highlight the number of materials that are used in batteries on this list there’s a huge number of materials um you can notice also at the bottom which is interesting um the Niel down here um and copper which are not actually in the critical uh quarter but are called critical because um they’re strategic materials so really important in terms of the technologies that they’re used for and then I’ve just highlighted a couple that aren’t sulfur and iron um all of these CR critical materials are are assessed by a supply risk and an economic importance and incorporated into that calculation is looking at where the materials come from the governance of those um countries that they come from where they’re refined and also looking at the recycling input rate as well so the point being if we can recycle more actually the criticality can be reduced and so it’s not a static number is is a number that we can influence uh through recycling I mean there’s other things that we can look at as well to reduce the use of these critical materials so we could substitute so for example lithium we can substitute for things like sodium recycling as I said is really important but also reusing some of those recycled materials and repurposing them in potentially other Technologies we can do a quick assessment and I just wanted to highlight some of the value against the criticality um between different cathode materials from different types of technology so I’ve got lithium cathodes here um and then sodium ion on the bottom and as you can imagine just because we’re substituting lithium for sodium actually the value of these materials reduce significantly because lithium is quite a a relatively high cost um material and also reducing the content of lithum improves the the criticality in some cases but not all cases because we’re still using nickel and manganese in some of these uh materials and if we particularly look at the value of these materials remembering that the cost associated with recycling we do need to consider then um what I’ve done here is plotted some of the lithium uh primary materials against some of the lithium secondary materials that we may be recovering so we have spodine here which is a a lithium or um and in Europe we we get that um mainly from uh the spyine rock is mainly from Australia in Europe most of our lithium actually comes from um Chile which is from from lithium brins but if we look at the lithium content in spaming compared to the lithium content in some of our battery materials our battery materials per kilogram or metric ton actually contain significantly more quantity or value um compare compared to our primary materials petalite is a clay which also is a primary material and even some of our even very low cost materials like lithium phosphates and our lithium manganese spel these still contain a a good quantity of lithium in comparison to osine rock so it it kind of makes sense that we should look at recovering lithium from our secondary ORS as well as our primary ORS I mean in addition the the value of our transition metals are significantly larger so Cobalt and nickel have a very high value and so it it is economically viable to recover some of these high value materials if we move however to to lithium phosphate as you can see we’re competing with the primary ORS but moving to some of the sodium systems actually the value can be quite low and we do need to consider how we do this recycling to retain some value rather than it being just a metallic value from the composition of our cathodes um in these materials um in essence short looping that recycling so rather than taking it from a recyclate using it as a secondary uh raw uh primary or or secondary oil can we just take it from the recycled material straight to an active material called um recycling a direct recycling um and if we look at some of the values of these materials either as a recycled um recyclate or a recovered or a actual material that’s used in batteries you can see there’s a big difference and this is because um people are still looking at the value of the black mass or the recovered cathode materials is only the metallic value uh contained within that material if can retain some of that value being the actual active material um that would be beneficial for some of these low cost uh and low value materials for example so these are the typical um recycling roots that are possible we can take it through a param metalogical process recover the the metals as an alloy and the lithium aluminium manganese in a light fraction or a slag which we can recover from from that or we can as Martino has already spoken about do some hydrometallurgical processes to recover the salts and then uh remanufacture the active material components from this or we can directly recover the active material components and try and reprocess them back into an electrode and back into a cell and this is very much what we’re trying to do in a lot of our work so we have several roots to trying to reclaim these materials and these are just some examples so we’ve got um the particular called processes shredding um and this is actually a gen one Nissan Leaf cell being put through our Shredder in the safety chamber out the back of our uh University here um this tends to mix all our very highly engineered cell components together which we then subsequently have to try and um pull out again um or we can do some disassembly and and the top shows uh one of our researchers in a lab under a fum Hood I might add doing some uh disassembly very carefully of some uh cells to try and separate out the anodes and cathod so that we get less impurities in our uh streams for then reprocessing whilst we’re also looking at trying to automate this um and in the video um below you saw some automation of trying to identify the cathode the anode and the separating material so that we can separate them out again to try and look at creating Pur materials waist stream so we can um reuse some of these materials with as little processing as possible um and so what we have done is look at the the disassembly and the shredding process first of all we’ll we’ll take the shredding process we go through a drying step to recover the electrolyte and then an electrostatic uh process from The Shred which then ionizes the uh feed stock the separator sticks to a drum and we can just brush off the separator as a non-conductive material um and then keep the conductive material separate what we do with this and this is kind um kind of the example of the the separator that we get from this process it there’s a little bit of contamination um it’s it’s rather low in Mass because separator is low in Mass but we can separate it it’s about 97% efficiency from this method um after electrostatic process we take it through a magnetic um electrode separation process and here we use um a rare earth magnet on a belt and we can exploit the active material properties to separate out the magnetic materials from the magnet gentic materials and what we do here because the cathode materials tend to be paramagnetic we can actually use that and as long as they’re stuck to the current collector we can separate out the aluminium uh coated uh part and the copper coated Parts with the um um of the electrodes so here’s just some examples of the aluminium coated which have been separated because we’ve exploited the in this case the nmc properties and here the graphite which is nonp paramagnetic um which is stuck to the current collector be can be separated out as the non-magnetic material so we need to take it from these um kind of large pieces of coating to then produce powder um and we have a couple of processes to do that we can use ultrasound lamination um and then filtration um and we can uh produce the the powdered Black Mass um separating it now into a cathodic black mass and an anodic Black Mass so mainly graphite in the an anodes and mainly the cathode material in the cathode whether it’s lithium ion phosphate um or nmc U we’ve got some examples of taking this um using nmc materials which is a Gen 2 Nissan Leaf where we’ve um disassembled a module we’ve taken out the the P es and then we’ve put this through a shredding process we’ve also compared a quality control reject which is of the straight from the manufacturing line where the cells have been rejected from a quality control process and also an end of life uh from the module now interestingly in this case the quality control rejects uh were not filled um they were open and they’re a few years um old which meant that the the delamination was rather difficult and everything had kind of stuck together the aluminium had basically corroded within the cell which meant the only way that we could recover that rather than using another an ultrasound method was actually to dissolve out the aluminium which is obviously not really wanted because ideally what we do is recover the aluminium as metal so that we can recycle that directly again rather than having to dissolve it out and then using enormous amounts of energy to remanufacture um aluminum but this just goes to show that we actually need to be careful how we handle our waste as well even from our processing because chemical reactions just continuously happen and so we need to know um state of health of the cell after uh use but also after it’s being shredded or dissembled or or dismantled so we know what processes we can use and for um recovering of these materials um in this case we were able to recover quite nice uh pieces of the cathodes grounded up into a powder and then analyze the quantity of elements in here in this case we actually had very pure samples with very little aluminium or uh copper impurities um and by a simple reiation process just using a lithium Source such as lithium hydroxide or lithium carbonate could actually re lithate this 532 material um from what was the QC rejected and the end of life um after delamination we lost a bit of lithium uh we could reinsert these into the materials and actually both of them showed some pretty decent um specific capacities reversibilities um and cycle life um as you can see from this still need some work on on trying to improve the lamination process uh however one of the issues that we do have is the binder um this just shows you that we have pbdf in this binder both QC reject and the end of life and using the sodium hydroxide we can remove some of that uh sodium hydroxide actually attacks the the pvdf um in a hydrothermal process and then when we uh fire it that pvdf does uh is removed it does cause some issues in terms of particle size as well because all the particles are stuck together obviously um they they weaken through the hydrothermal process or or the the sodium hydroxide and once fired we we get a pretty decent uh particle size distribution which is relatively similar to what we uh would expect um from a a pristine material but pvdf is a problem we burn it off it means we’re producing HF which also has been shown to delate some of these materials if there’s a large quantity um around so ideally what we’d want is something not pvdf that would be removed much more easily and we can see this as an example in a lithium phosphate cell this is a cal lithium ion phosphate um in this case we’ve separated it and we just used a simple water method to uh delaminate the material we can soak it in water um heat it to to about 40 degrees and it delaminates relatively easily and you can see the the aluminium foil here being left behind rather than being dissolved by sodium hydroxide and we can create a very high uh Purity material stream for this and this is the uh black mass that we obtain um it still has its binder some of its binder in as you can see which is CMC and sp sp are but what we can do is take that directly and re lithiate it again uh using lithium hydroxide or lithium carbonate um and what you see here is the recovered lithium ion phosphate which has about 10% ion phosphate which we’ve measured from both mosow and um reement on xrd and then relating it we can recover and REM manufacture the lithium phosphate um we get um some capacit back but the quantity of carbon that we end up with in the system is actually quite high and we need to kind of look to try and improve or reduce the level of residual carbon um from this carbothermal process that we’ve used to remanufacture uh the lithium phosphate um but it’s but it’s a good start and it shows that waterbased binders um are an efficient way of removing some of the issues associated with pbdf binders that only dissolved things like nalone or n nmp uh in this process we got 90% 97% recovery of or lithum phosphate from the cell um which is quite a b achievement but we’re still trying to reduce some of the waste that get that we produce from these processes um and what we’ve uh developed as part of um the simple project for sodium projects is to try and reduce the waste that’s associated with these delamination processes and we’ve developed what’s called an ice stripping method um what you see here is someone spraying some water on electrodes um it’s placed onto a cold plate or in this case an ice cream maker and the electrode sticks to the surface and we can simply uh peel off the electrodes leaving uh very little axd material left behind on it and a in a quite a pure aluminium um oil um and in this process we use very little water indeed um initially we’d pour water on we’d lay on the electrode and we’ pull it off just by spraying the water on um we can reduce the time that it takes to freeze quite significantly to about 10 seconds which means we can start to think about incorporating this in potentially a real toore or inline uh process for for delamination um and it’s it’s quite a simple method what happens is the water um goes into the electrode structure the porous electrode structure it freezes because the um heat transfer is so quick in in those thin electrodes you can take the heat out the electrode sticks to the surface very quickly um and then the adhesion to the surface of the um the cold plate is so much greater than that to the adhesion of the current collector that we can simply just peel it off um we can wet the water uh wet the surface in about 5 Seconds depending upon what the electrode is and then it it freezes in about about 4 seconds as you can see from some of these measurements that we’ve done um so using this we’ve tried to look at Reclamation and reuse of some sodium ion samples as well this is some hard carbon um these are carbon elect CES that um we’ve made with CMC spr uh We’ve recovered this and then tried to remove the binder by a pyrolysis method where we’ve heated it from between um 200 up to 500 to decompose the binder compounds in there and you can see that as pristine um particle size um is about 10 microns and when you start to uh when the binder is still present you have a much larger glomeration of about 100 microns in this case even after grinding but we do get some uh much better particle size when we decompose the CMC and the spr about 300 degre C it doesn’t decompose the um s spr fully but it does um kind of denature the CMC somewhat and looking at this we can start to think about reusing it this is the high carbon in a uh half cell we’ve got some good cycle life of the pristine which is in the blue um and the reclaimed the 300 are cycling pretty well in fact the 300 is as good as our pristine whereas we go up in higher in temperature we end up with a much higher surface area we also get higher F cycle loss and also lower uh capacity um when we IP sticking this into a full cell we get um from the directly recovered we can actually disperse this back into an ink again and recat it uh as and it performs almost exactly the same as the pristine um if not slightly better whereas the 300 heated we get a hyos cycle loss so a lower overall capacity in a full cell but it’s is cycling um quite well and then moving on to end of life using the same methods we can still reclaim our electric materials use the same ice stripping method we heat it again to 300° um and we’ve uh attempted to use it directly at end of life and we get uh in a Hell similar results it Cycles okay similar to what we would expect this material but when we put it into a full cell our our 300° heated actually performs quite well we get a a higher first cycle loss but we get um a good capacity retention with this material so again showing that we can start to think about Recycling and reusing both scrap and end of life materials uh directly from the Reclamation processes using um only a little bit of further uh treatment we we’re continuing to look at this further and this is a a project called Revitalize which is headed by Mt andu um which we’re looking at some of the separation and direct recycling of um different lithium and sodium ey materials so just to summarize um improving the cycling rates will reduce the criticality by improving Supply risk we’ve shown that we can use electrostatic and magnetic separation with large pieces of current collectors to reduce impurity levels in our uh black mass that we reclaim for direct recycling some of our issues are still about the binder we need to really think about what binder we’re using if we can use different binders and are there some better ways of negating the binder in these black masses um we’ve also shown that ice stripping can be used for delamination it has a lot less waste associated with it and because it’s so quick energy as well for delamination and we can use this uh both of these processes to show that we can start to direct recycle things like nmc 532 lfp and hard carbon have been shown here as an examples I’d like to thank um the group um these people listed here are the people that have done most of the work that I I’ve spoken about today uh and the funding sources and thank you for your attention thank you very much so as I mentioned before we will take the questions at the end and so for our last presentation of the day before we move into the questions and the panel discussion I would like to introduce Andreas flea and he will present design for circularity strategies to enable direct recycling so Andy the floor is yours so thank you very much quen can you hear me and can you see the slides yes to both okay perfect so in my talk I will focus on um the design for recycling to enable the direct recycling approach so we’ve learned in the in the last two talks a lot of the importance of battery recycling and also very uh very interesting approaches also for the direct Recycling and in this talks I wanted to show you some results and also some Concepts to enable it via a design for circularity for future batteries um first of all I want to introduce uh shortly my my group here in wburg he um 35 people work on different um topics of battery research mainly on the lithium ion batteries also on sodium ion batteries and solid state batteries and five years ago we started with the direct recycling approach and now we look also for um the design for circularity for future batteries so we’ve heard a lot of the different recycling um methods so the pyrology the hydrology and the direct recycling approach and when we look um at the different waist streams we have here uh we there’s the question uh for which um recycling um method um or which recycling stream is best for the recycling method and we try here a small selection so when you look at the the small batteries in the 3C sector so in Mobile phones or laptops or something like that there we have a lot of different chemistries and here we we have to use the the the pyrology because we have no no knowledge about the cell chemistry for the larger batteries in EV or in stationary batteries we have the knowledge and here we can go with the hydro processes and at the moment for the production scrap uh it the direct recycling approach can be done but uh we will get a lot of uh a lot of a high number of um new batteries with the or lfp batteries with a low material value and for this we have at the moment no profitable uh recycling processes now the battery regulation from the European commission came and regulates um the material recovery and also the recycl content in the new batteries and also the battery passport and with this battery passport we will get more knowledge regarding the cell chemistry and we can shift the the different waist streams to other um recycling processes but there we have also the problem for the um nonv valuable materials like the lfp materials or also the sodium ion batteries and here we have to look into the into the design of the batteries to uh designed them in this way to recycle it more easily and with this Vision um we can shift also this um way streams to um more efficient um recycling processes like the hydro process or the direct recycling approach and um to summ it a little bit up what are the challenges for the for to implement the direct recycling approach is so we have a lot of different um different cell types different layouts we don’t know what is inside the cells then we have a lot of um mixtures in the in the black mass and all some some impurities through the shredding process and so on then the recover recovery of the electrolyte is a big issue and we have a very it’s very hard or complex to automat automatize the the cell opening of such different layouts and also a topic is um how can we upgrade older cell chemistries like the nmc111 to newer ones like the MMC 811 but the potentials of the direct recycling approach is very high so we can get the active materials as in as its structure back so we have the nmc or the lfb in this structure we have very high um recovery rates and green processes so here we can use water-based processes which we have heard um at Emma talk and it’s also profitable for the and low valuable active materials like lfp and sodium ion which are increasing numbers come on the market and also we can recover the other battery components so also the carbon blacks the graphite electrolyte the current collectors and the casing in a high Purity and the R9 framework which is shown here is um it provides so some 10 strategies um for um for um for um for a design for circularity and we see that at the end of the battery life we end up at a recycling or recover strategy so this is only to uh prevent uh waste so here we only get energy or elements back but when we want to increase the circularity we have to look at the first stage in the design and Manufacturing stage so here the rethinking or the rethinking is one of the key to think how we can design the batteries in other way to come into F strategies in the operational use so perhaps the R5 the refurbishment or the R6 the remanufacturing here we want to use the active materials in its function back so we have to look at this design phase and this uh can be also a unique selling point for the European battery industry to look in this kind of Circ poity now I want to show you some approaches what we’ve we’ve doing at frover ISC um so we look at different topics of the uh around the circle so we start with the um design for circularity in the cell production then the cell sorting here we are focusing on integration of marker particles as a identifier with a battery passport then we look at a disassembly of stateof yart cells and also for future cells then um we separate cathodes anodes uh separator and the casing um and then we go to the coating Detachment for anodes and cathodes um the binda deactivation which is very key Topic in this uh in this recycling process then the separation of the active materials so separate the active materials from the carbon black um then the the Regeneration and upgrading and then we close the loop and use the materials again in this talk I will focus on this on this process um steps and I start with the design the design for circularity in the cell production um before I start um we have in this process we we can uh bring the way stream into this process the the production scrap uh wi the coding Detachment and the end of life cells um and the in the beginning and what we get out in the in the cell disassembly step we get out electrolyte separator and casing in the coating Detachment the um the current collectors aluminum and copper foils then the binder in the deactivation and in the separation of the active materials we can get the carbon black back and then the anode and cathode materials after the Regeneration so um for the cell production we focusing on the acreas processing for for cathodes and here we need a surface coating and the tailoring of binders and also the integration of functional additives first the the acous cell production here we see it as a design for circularity H we have a lot of advantages um so we eliminate the nmp and also the fluorinated pbdf binder and we don’t need a solvent y system in the production anymore um this have a lot of challenges with it brings with it and we have a degradation of the the cathod active materials with a high nickel content so we have a leeching of lithium so exchange with lithium and protons and also the pH value increases and we get an aluminum corrosion of the current collector to Brand it or uh we we we have we looked at at the content of water so how many water if how many water uh affects the the leeching process so we start with a ratio of one to one that’s like a aquous processing like in the in the aquous processing step and we see that we have a lot of leeching and when we increase the amount we see that we get in a we we reach a saturated um uh phase so at a water-based recycling process we have um a saturated region and we see that we have a lot of um a lot of uh Coatings like carbonates are on the active materials and this gives a poor performance in electrochemical Behavior so to prevent this issue we coat the active material with an phosphate based coating here we use the method of a spray trying and with this uh waterbased we can use water ass solvent and also a water soluble binder like CMC this we incorporated in the in the in the electrodes and processed um nmc 811 Co cathodes by a ro to- roll process and buil Pou shells with uh with a capacity of three amp hours and um measured them over 45 cycles and we see that with with the coating with this phosphate coating we can increase the discharge capacity of around 10% and this uh this um this water-based processes will be a very uh Advantage ad is a very high advantage in the recycling step later on then also the binders is a key Topic in in the recycling in the direct recycling so here we you we can we we looked at the um the different CMC species so here we looked at different degrees of substitutions of the carox side carboxy um groups and we see that a higher degree of substitution um is a better solubility in in the polar solvent so we have a better distribution um in the in the in the electrode and get better electrochemical um performances and also this higher degree of substitution uh is um very good at the recycling process when we put the electrodes into water um without steering or something like that so we um we get a Detachment of this electrode with a higher degree of substitution so this is uh in our opinion a a huge research area to develop new binders which can be uh easily recycled and extracted out of the recycling step then here a concept of a new project it’s called the ATB project um here we integrate additives uh which can be triggered so we integrate them in three different um areas of a pouch cell one in the ceiling of the casing then between the the interface current collector and electrolyte and then we integrate it also in the electrodes um between active materials and additives like carbon black and binders as um trigger materials we use inductive heatable particles combined with blowing agents different surfectants and Coatings and later on in the in the um in the recycling step we activate these triggers via perhaps the magnetic field or temperature or pH changes and then we can easily recycle these um these components um results I cannot show today uh but uh we will publish the results um soon and the next step is the the Sorting U here we uh we use magnetic particles as identifier and we work also on an automating um battery sorting process um the magnetic particles was the research of the magnetic particle particles are done at the fhu in um in aangan um they use iron oxide nanop particles bring them together as a system and create their um different IDs so the magnetic particles are like a barcode or QR code they have a unique um signal and we can detect them via a spectroscopy the magnetic particle spectroscopy and the big advantage of this magnetic particles is that we can integrate it in the bulk of the cell and it’s not visible and we can also use it as a counter fight protection protection so so um in the first step we integrated it in three different areas of the cell so one in the ceiling uh then we mix it in the cathode um in the cathod in the electrolyte layer and also bring it uh on the inside the separ at the separator and for all three cases uh we we can detect the particles and detect the signals and in the next step we integrate different um uh different marker particles for different cell chemistries with this particles we can integrate in these different steps in our um Electro in our cell manufacturing step uh so we can integrate it in the in the coating of the electro electrodes in the stacking or in the packaging and we can directly integrate them in our data space so we have a we have digitalized our our our cell production and here we can integrate this marker particle which have the the the ident which are the identifier that that the identifier in the cell which give an access to the battery passport in The Next Step uh we look at the cell disassembly in the cell disassembly we look at the one hand uh for the opening of um pouch cell so the contactless opening here we use a inductive method we uh Focus the inductive field on the the ceiling and and open it um via melting the the polymers and here we have to focus that we have a a spot and don’t burn the the electrolyte the the flamable electrolyte with this approach you can open contactless uh the the pouch cells and separate uh cathode and anodes and separator from each other um we want to auto size the the opening of um the Prismatic cells here we work in a European project called reuse since the beginning of this year so at front of IC we built up a set up a robot which open the cells and separate um cathodes anodes separator electrolyte and casing this we buil in a in a glove box and use um the Prismatic cells from the cell um manufacturers Mor batteries and 11 um for the coating Detachment um here we use different methods one is uh together with a partner from Germany with impulse Tech or re and re elements here we use the electric Hy electric hydraulic fragmentation that we have a reactor which is filled with water we can put inside the cells or also a production scrap or only aged cathodes or anodes then we have um shock waves and open the cells then in the first step we receive the Circ casing then uh the separator and the the foils and then we have the Dem the delamination of the different um active the of the electrode coding and can see uh different fractions when you look at detail at detail and the different fractions we see at the the low the smallest fraction we have a graphite Rich fraction so the graphite was distributed very well in the water with this shock waves and in the in the in the um seing Step 250 microns to one millimeter we see a larger um particles this is the the lfp rich um fraction so with this method we can uh we can separate or we can concentrate cathode and anode Black Mass for further steps and then we work also for different chemical and physical detachments um here we use different um different solvents with different temperatures and uh for the physical method we also use some different um approaches um which is which um which uh the the results are not published yet so I cannot go into detail but we see it’s a very strong dependence on the binder type and we also work on the scaling of these Technologies um then the bind um DET extraction I don’t want to go into detail but I want to um say also like Emma said um that it’s a key topic to um to extract or deactivate the binder that we have single particles to go further with them with further processes for the separation of the active materials we use a s send Refuge technology it’s a semicontinuous send refuge and we pump in the Black Mass so in this case it’s a lfp black mass with carbon black um the the centri cylinder rotates and the the particles with higher density or higher particle size um end up in the centrifuge and the smaller one goes into the centrate and when you adjust the process parameters you can um you can um earn the active materials in the centrifuge and the the carbon black will go into the centrate um this is a semicontinuous process so when the centrifug is filled we have to um stop the stop it and earn the particles and uh to prevent this we uh build up a automated um process for this so we use a robot which can uh um which can uh bring the cylinder into the centrifuge and then in a cleaning section which is out which runs automatically and so we can uh we can use this or we can transfer this process from a semicontinuous or from sem continuous to a quasy continuous process um what we see with the centrifuge type we cannot um um recover um uh materials with a higher density or with a higher particle size for this we um um we developed an with our partner sepa a new um centrifuge type it’s a Trum centrifuge and with this we can separate graphite materials from blackm and also nmc materials and you can see in the sem images that we can um we can earn here a very a cite with a very high Purity in a high amount and we have a lot of aquous processes so we have a lot of process water and when we want to check if which materials are inside this um this process water and uh looking for methods how we can um put out the the valuable materials out of this processed water or to clean it we have um in a project called idy with the partner pure devices we um we developed a a setup where we can measure lithium Florine and aluminium in Black Mass or in processed water and the big Advantage is that is uh the measuring time is around one to five minutes it’s via an NMR technology and we get out the information how what is the concentration of these elements in the in the water and this we have successfully qualified with the ICP and it’s very um we get a very good compatibility with the ICP and for the Regeneration process I don’t want to go into detail here we have a lot uh of other um activities and with this I want to uh conclude my talk so um for us it’s a a the conclusion is that we need some regulatory Frameworks um to to to look all to give standards for the design that you get an acceptance from the industry to to to use this design standards and um we have only when we implement this design for circularity strategies um it’s profitable for the lowcost chemistry like lfp and sodium ion batteries and yeah the battery sector could be a role model uh for other Industries to gradually from a linear to a circular economy and with this I want to thank um for your attention and also I want to thank my group and also the project partners and the uh the funding from the European commission and also from the bmbf thank you thank you very much Andy so this is then the end of the formal part of our battery 2030 Plus excellent seminar and