This intensive 1-day workshop will take place on Wed 6 Nov 2024 , 9:30-16:30 GMT at the IOM3, The Boilerhouse, Grantham location. The key topics include battery basics, sector specific applications, chronology of battery technology, technical deep dives, regulatory frameworks, resource management and techno-economics.
This course is relevant to anyone with an interest in overseeing operational efficiency, looking for eco-friendly solutions and identifying opportunities in green technology.
The course fee for this one-day programme based at The Boilerhouse in Grantham is £595 plus VAT at 20% where applicable. IOM3 members and subscribers to IOM3’s Business Partner Programme are entitled to a discount of 10% on the course fee. Fees includes CPD Certificate, lunch and refreshments
This presentation will highlight growth segments in the fine chemicals market and detail examples of published, non-confidential routes for large volume agrochemicals which use a precious metal catalyst. Precious metal refining challenges will be reviewed and strategic analysis of options for supply chain participants to provide efficient, competitive, and sustainable PGM supply chain products and services will be set out.
The presentation content showcases the Enabled Future Limited PGM Catalysts for Fine Chemicals Subscription Service which is available as an annual subscription divided into quarterly deliverables for Europe and North America. Custom geographies are available on request. The service covers the pharmaceutical, agrochemical, flavours & fragrances and food, personal care and other (FPCO) markets. Please contact us for subscription details.
Enabled Future Limited CEO, Dr Michelle Lynch, will be presenting at the Vehicle Electrification Expo due to take place at the Birmingham NEC on June 28th-29th, on the topic of ‘How to Ensure Sufficient Sustainable Metals Supply for Advanced Materials‘ which is one of several presentations in the session on “Understanding and Reducing the Environmental Impact of an EV from Raw Material to End of Life“. (Wed June 28th at 13.55 – 14.55).
She will also be chairing a panel discussion at the co-located Advanced Materials Show on “Moving Beyond the Easy Steps Towards Net Zero for Ceramics Manufacturing” on (Wed June 28th at 15:30-16:30). The panel of industry expert leaders will discuss options for the ceramics when it comes to meeting Net Zero, particularly relating to energy sources, with discussion of what can we can expect to happen in the coming 20 years, and what this means for ceramics manufacturers and end users.
Enabled Future Limited attended this excellent set of Expo/Conferences in 2022 and we look forward to attending them again this year.
‘They’re materials that are either solids or liquids and they play a role essentially, to get a chemical reaction to proceed at lower temperatures and pressures, and at a faster rate than if they weren’t there. They also have inherently green benefits, for instance, they increase the yield of the product. So a catalyst enables you to make chemicals at a lower cost and higher yield. They reduce waste and they also replace things like liquid acids and corrosive substances and less green substances.’
How do we reduce the criticality of finite resources?
‘What we need is a good plan for using those resources very pragmatically and essentially using as little of them as possible to begin with. And when you look at the fuel cell car – so I don’t know if you’ve ever seen the Toyota Mirai up close; fantastic vehicle made by Toyota – on the fuel cell, the original amount of platinum was around about 35 grammes. That’s too much. Platinum is a finite resource. You can dig more of it out of the ground, and we will, but then you’re increasing the criticality. So it’s very expensive to put that much PGM on a vehicle. So the amount on there now is 15 grammes. We need it to get down even further and if we can get down to five grammes, then you are then on a level with a diesel vehicle. So one of the ways that we deal with it essentially, is to thrift that metal down as much as possible. One of the second ways you’d have to deal with it is thinking about how you can get as much of that metal back.’
How many times can you recycle these metals? Is it endless?
‘So the metals, what you can collect and process, you should be aiming for at least 97%. But you have to be able to collect it. And that’s where some of the problems happen. For instance, an automotive catalyst, it shakes while you’re driving, and it shakes and it creates dust and some of that dust ends up on the road. So we lose a certain percentage of the metal there, you might lose a little bit in manufacturing, you might lose a little bit in refining. But one of the key things is being able to collect it, if you don’t collect it, if you dismantle the car and crush the car and incinerate it without taking the catalyst off, which can happen, then you don’t get the metal back.’
How are catalysts helping us on that journey towards carbon neutrality?
‘One of the things that people need to consider is just because something’s carbon neutral, or it fits with net zero doesn’t mean it was produced according to a circular economy approach. Because you can burn down every tree on the planet and be carbon neutral. But clearly burning down every tree on the planet wouldn’t involve any sustainability or circular economy. So we need to be quite cautious.’
When you capture the co2 emissions, what can you use that for?
‘Co2 gets used in electronics applications, it gets used inside greenhouses to make flowers and fruit and vegetables grow faster. It gets used if you’ve breakfast crumpets and little holes in the crumpets you blow co2 gas through the dough. And so you can just sell co2 actually. And in fact, there is a market for co2 such that we end up with shortages. So for instance, during the World Cups, we always end up with a shortage, we haven’t got enough co2 for your beer and carbonated drinks.’
How do we improve the performance of catalysts?
‘Catalysts are generally improved all the time. When we replace a catalyst, we don’t tend to just replace it because of its composition being unfavourable, we change it because it will produce more technically improved products and produce them more cheaply and produce them more sustainably. So every generation of catalysts that comes out is better than the previous ones, and achieves more from an ESG perspective.’
How do we move fast enough to continue to meet the needs of a growing population, without destroying the planet?
‘So for me, we really need to start moving towards a situation where we can eliminate as much of the waste upfront. And one of the things that we need at the top is renewable energy. So if you replace your fossil electricity to the plant with green electricity, and you replace fossil gas with for instance biogas, then your carbon footprint comes down a lot further. And if you got rid of your natural gas reactant, and you replaced it with just co2 and hydrogen, then you’re coming down even further.’
Do you think governments and global governing bodies, are doing enough?
‘It is a big, important issue that we need to get all of the main global leaders to agree on a strategy. And strategy has to be different for each country, because each country has different natural resources. So there isn’t one size fits all. But we still need, and I know that we have cop cop 26 or 27 where it’s at now, and we have climate goals, translated into nationally determined contributions NDCs. But there’s still this massive problem with not having a level playing field, you’ve got one major world country making products from coal. And it’s quite risky to try to decarbonize without a level playing field.’
What is the repair economy and how does that help with sustainability?
‘So I think that the resource management side is seeing some really exciting new models, one of which is the repair economy, where we’re having quite a few initiatives and companies involved in saying that we need to extend the life of products. And when you extend the life of products, you effectively displace the need for a brand new product. So if you can start repairing things, then you have some individual control over improving sustainability. And it’s a much better model than this one I mentioned earlier where we said, we can just have as many of this that we wanted, because it’s carbon neutral.’
Tribosonics, based in Sheffield, UK, is a transformational technology business taking its unique sensing technologies into uncharted and valuable territories, to deliver scale and impact. Tribosonics develops smart sensing technology that can monitor and measure asset performance in key industries such as polymers and plastics, nuclear, renewable energy, automotive and marine.
The Need for Sustainability 4.0 – The Share and Repair Economy.
The premise of a sustainable society is a highly complex one which requires many different solutions. There is a need for systems thinking on managing resources and consumption on a local, national and global scale. The media emphasis does however seem to have shifted to one of a predominantly “NetZero” ideology with only the carbon footprint of a product being considered, when in fact there are many other factors that need to be controlled i.e., non-CO2 air pollutants, land use, soil erosion, marine life, water usage, water pollution etc.
The Circularity Gap Report 2023, which was published in January points to disappointing results on circularity with the figure for global circularity now put at just 7.2% in 2023. More worryingly this figure has dropped from 9.1% in 2018 due to rising material extraction. (Circularity Gap, 2023)
The challenge is even more complex however, because the introduction of new technologies such as electric mobility and renewable power, necessitate the increased extraction of raw materials and metals because there is simply not enough above ground to meet growing demand and in fact forcing through premature recycling of high value add products such as lithium-ion batteries (LIB) would miss the opportunity for reuse in multiple additional lives resulting in an even worse lifecycle footprint for electric mobility. (Karomah, 2021). Recycling in the EV industry also does not necessarily reduce the amount of mined material required. As EV Recycling and Reuse expert Hans Eric Melin, CEO of Circular Energy Storage (CES) recently stated:
“Recycling is important and can be very profitable. It is also a great source of material. But to be recycled the materials first have to be mined. What hasn’t been mined can’t be recycled.” (Melin, 2023)
Therefore, we need to think about Sustainability in a different way. The trajectory can be viewed as a series of new paradigms (which add to rather than supersede, at least initially, previous ones), as shown in Figure 1.
Figure 1. The four sustainability paradigms
Of these above paradigms, only Sustainability 4.0 results in significant lowering of consumption of virgin manufactured goods. Note the difference in thinking – “virgin manufactured goods” vs. “virgin raw materials” because the recycled materials as noted in the Melin article referenced above in fact ends up on brand new consumer goods. “Contains recycled content” is a phrase we see often now, but the virgin manufacturing aspect is still present. Compare this to a repaired or “secondary good”. The entire raw material extraction, processing and manufacturing processes, not to mention transport are missed out, thereby making the reused goods far more sustainable.
Sustainability 4.0 (which is a term used in this context for the first time by Enabled Future Limited) is a quiet but growing revolution. Businesses are springing up everywhere which have a repair and share focus. Organisations which loan out goods from a library, e.g. Library of Things in London. (Library of Things, n.d.). Startups such as Team Repair which makes educational kits aimed at teaching young people to repair broken electronics. (Team Repair, n.d.) An exciting growing movement is that of Repair Cafes throughout the UK and elsewhere in Europe. (Repair Cafe, n.d.) There are now 2,635 Repair Cafés with an estimated 39,525 volunteers involved, repairing some 47,430 items per month including everything from laptops, to coffee makers and furniture. (Repair Cafe, n.d.) The societal benefits are clear – these Repair Café and LoT activities bring together local communities and help those in poverty to access goods that they might not otherwise be able to afford. Something much needed after the social isolation of the pandemic lockdowns and subsequent impact on mental health. A point to remember that all our green activities are aimed primarily at preserving both people and the planet – surely a Sustainability 4.0 metric should include our Quality of Life (QoL).
Figure 2. Fixing Workshops hosted by Team Repair during London Repair Week (Source: Team Repair)
Circularity Gap. (2023, January). The Circularity Gap Report 2023. Retrieved from Circularity Gap : https://www.circularity-gap.world/2023 Karomah, A. (2021, Nov 12). Reusing and Recycling Li-Ion Batteries. Retrieved from AZOM: https://www.azom.com/news.aspx?newsID=57297#:~:text=Based%20on%20the%20batteries%20chemistry,by%202%20to%206%20percent. Library of Things. (n.d.). Library of Things. Retrieved from Library of Things: https://www.libraryofthings.co.uk/ Melin, H. E. (2023, February). LinkedIn. Retrieved from LinkedIn: https://www.linkedin.com/feed/update/urn:li:activity:7034226512685887488/ Repair Cafe. (n.d.). Repair Cafe. Retrieved from Repair Cafe: https://www.repaircafe.org/en/ Team Repair. (n.d.). Team Repair. Retrieved from Team Repair: https://team.repair/
Approaches to Improving Manganese Circularity in Lithium Ion Batteries
Dr Michelle K. Lynch CChem FRSC, CEO, Enabled Future Limited
Snapshots of Battery Chemistries
The chemical formulations of cathode materials for lithium ion batteries (LIB) have changed over the last decade to meet the evolving needs of different applications. For instance, in electric vehicles (EVs) driving range, power performance, low temperature operation, battery life requirements and many other parameters have dictated the need for LIB technology improvements. One of the major trends in recent years was to reduce the amount of cobalt (Co) in LIB and to increase the amount of nickel (Ni). This had a two-fold benefit – reducing the demand for Co to a level where responsible supply could be managed and increasing the energy density of the battery by incorporating higher levels of Ni. However, as discussed in this month’s EnabledCircular feature, Ni prices have seen volatility and all time high prices over the last two years.
As a result of the market dynamics of Co and Ni, there is a desire to use more earth abundant metals in LIB and other rechargeable battery types. One way this can be achieved is by using higher levels of manganese (Mn) in place of the Ni. There are two main types of battery chemistry with predominantly Ni and Mn – the spinel-type lithium nickel manganese oxide (LNMO) and layered-oxide types (NMx) and high Mn NCM. Doping of lithium iron phosphate (LFP) to produce LMFP is another source of Mn demand.
The percentage by weight of Ni, Co and Mn in different battery chemistries are summarised in Figure 1 and Table 1. NB in this analysis, NCA and LFP are not included as they do not contain Mn. The trajectory of cathode chemistry development as discussed above moved from formulations with relatively high levels of cobalt e.g. NCM111 to those with higher nickel e.g. NCM811 and NCM955. To those unfamiliar with these codes, the numbering system corresponds to the relative amount of Ni, Co and Mn on a molar basis. The percentages in the chart and table refer to weight content of the pure cathode material powder prior to mixing with any coatings, binders or additives. The highest Ni content is seen in NCM955 (54 wt%) which contains only 3% Mn.
Figure 1. Metal Mass Content in LIB by Chemistry and Key High Mn LIB Innovators (Source: Enabled Future Limited)
Forecasted Manganese Demand
With most EV batteries coming onto the market expected to be high-nickel NCMs, it could be assumed that Mn would not have the level of supply criticality as do Ni and Co. However, this is not predicted to be the case. A recent analysis from Benchmark Mineral Intelligence indicates that for the NetZero scenario, Mn demand is set to rise by almost 600% between 2025 and 2040 with over 1.2 million tons of Mn required per annum by the end of that forecast period. Even more interesting, is that the largest portion of 2040 demand is expected to be for non-NCM Mn rich LIB chemistries. (Fleming, 2023) (See Figure 2 below). This has implications, not just for sourcing sufficient battery grade Mn to produce the batteries, but also for incorporating recycled content in those battery formulations in the near term and recycling them in the long term.
Table 1. Metal Mass Content in LIB by Chemistry (Source: Enabled Future Limited)
Figure 2. Manganese Demand Requirements for LIB (Fleming, 2023) republished with permission
Sources of Mn Supply
Manganese is supplied from primary mining operations. In total 20 million tons of Mn was mined in 2022 with South Africa being the largest producer (35%), followed by Gabon (22%) and the USA 16.5%. (USGS, 2023) There is no European country with a significant primary manganese mine supply – only Ukraine and Kazakhstan produce and this is from concentrates.
While the amount of Mn mined globally is much higher than that required for LIBs, there is currently insufficient capacity for producing enough high purity Mn (HPM) suitable for battery grade cathode material to meet future demand. Only 1% of the ore produced goes to HPM and most HPM is produced in China. The remainder is for steel ferroalloys (91%) and lower grades of electrolytic manganese and Mn sulphate (8%). (Fleming, 2023) In addition, while Mn is not part of the current draft of EU regulations for recycled content in LIB, the ESG goals of battery and EV OEMs may require it anyway. Therefore, there is a need to find secondary and sustainable sources of Mn for future LIB demand.
Figure 3 shows three different secondary sources of Mn – recycled LIB, other recycled batteries and sustainable mine sources along with their advantages and disadvantages. Considerations for these options are discussed in the proceeding sections of this article.
Figure 3. Sustainable Sources of Manganese and their Relative Advantages and Disadvantages
Manganese from Recycled Batteries
LIB cathodes need to have recycled content in line with the forthcoming EU Battery Passport regulations. (Popp, 2022) Although Mn is not included in these regulations currently, cell makers and EVs also require recycled content in LIBs to meet their ESG goals and this includes the Mn content – especially for Mn rich batteries. Therefore, cathode material producers in Europe are looking to source recycled content for their products. Recycled content is generated at metal refineries across all the key battery metals in the form of metal salts e.g. Ni, Co, Mn sulphates from so-called “black mass” generated from shredded waste batteries. These salts can also be recovered from treating other types of waste Mn e.g. non-LIB that contain Mn as well as scrap from metallurgical operations, catalysts and other industrial materials. The refiners then supply the cathode material producers with metal salts and solutions that have a % of recycled content mixed with virgin content.
One issue with this system is that the metal salts are generated from the output of central hydrometallurgical processing of both mixed waste streams and primary concentrates. Some cell OEMs would like a closed loop supply – whereby only their battery waste is put into the hydromet unit. However, this could only work for the largest companies, so that refineries could justify a separate line just for that OEM’s materials. This isn’t possible yet as there is not enough hydromet capacity in Europe and not enough waste batteries. However, this will change over time as that capacity comes online and waste battery levels rise. One challenge is that refining projects are only bankable if they have green electricity sources – so refiners are competing for “green-electrons”. Many new wind farms in Scandinavia are attracting battery metal refining capacity for this reason.
A second issue is the need to develop specifications for material provided from recyclers/refiners. For well-established battery chemistries such as NCM622 and NCM811, there are already well understood specifications. It should be noted that, according to leading industry contacts, the Mn coming back from recycled materials is not sufficient to be used in high-nickel NCM batteries – and it is not clear how those materials will be supplied. However recycled Mn may be good enough for LNMO. Currently for LNMO there is no long-term data on the battery performance in the end-use application and as yet, not a clear understanding therefore of the exact cathode specifications.
LNMO cathode material producers such as Topsoe in Denmark are working from the existing NCM811 specifications and learning how they should be tailored for LNMO through extensive R&D work on cathode materials containing recycled content.
Some impurities cause more trouble than others for LNMO. For instance, Co isn’t as bad as Fe – it doesn’t reduce performance, it simply doesn’t contribute to it. Whereas for Fe, which can cause self-discharge and shelf-life issues in cells, more specification development is required and testing in end-use applications. Other problem contaminants include Zn, Ca, Mg, P and F.
The pragmatic approach for producing recycled cathode materials is to start with the cheapest recycled salts available in the largest quantities. These are evaluated first and after that smaller and/or more expensive feeds are considered. The ideal is to have a constant supply of material within a range of specifications.
Recycled materials are unlikely to contribute enough to meet the rapidly growing demand for battery grade Mn. The batteries reaching their EoL over the next 10-20 years have only small quantities or no Mn at all i.e., nickel rich NCM, LCO and LFP. A second issue is that it might be difficult to keep recycled materials in Europe as cars have a habit of being sold outside the region – first going to East Europe, then South to Africa for instance. Once this happens it is unlikely that the batteries would be exported back. Attempts to force vehicle batteries to be kept and recycled in Europe are problematic from a sustainability perspective and as discussed in the EnabledMetals news insight, would do little to relieve the pressure on metal demand requirements given the growth in the battery industry.
Manganese from Sustainable Mine Sources
Production of metals from former working mines is another method to generate sustainable battery materials. Euro Manganese, headquartered in Vancouver, Canada is a producer of battery materials with a focus on producing sustainable battery grade manganese chemicals for the EV industry. Its project at Chvaletice, Czech Republic is aimed at large scale reprocessing of Mn from old mine tailings at a decommissioned mine site. The site is reportedly Europe’s largest Mn resource hosted in tailings and is a 25-year project looking to produce 50,000 tons per annum of high purity battery grade products. The output is intended to provide much needed material to plug the current and increasing Mn supply gap. The project involves no hard rock mining is cleaning up a site which is already polluted and produces Mn chemicals at around one-third the carbon footprint of industry incumbents, thereby contributing to the EU’s decarbonisation goals. (Votava, 2022)
In spite of the very positive outlook for Mn in LIB, it is not considered a desirable metal to collect and recycle from LIBs. In fact Mn is currently the last priority for a hydromet after Ni, Co and Li have been recovered. According to industry contacts, it costs as much to recycle Mn as it does Ni and Co combined. When it is recycled, most Mn is not purified back to the grade needed for most batteries i.e., NCM, NCA. The usual output is Mn hydroxide salts when the carbonates would be preferable.
Therefore, there is an industry need to take in a range of Mn-rich precipitates from different industries and process them centrally. According to Euro Manganese, this could be carried out at Chvaletice. Pyrometallurgical units have a Mn-containing slag which is in the form of oxides and silicates. This goes into construction materials currently. With some upgrading, industry contacts believe this could be viable for LNMO/LMFP battery chemistries.
As long the feeds don’t have too much Fe or F, they can be viable for upgrading – companies can also choose to do an extra upgrade themselves then send them for refining – this needs discussion and collaboration between the companies and the refiners. Blending of Mn salts from different recycled materials with purer feeds of Mn e.g., from the mine tailings can be a useful strategy although it needs to be demonstrated.
Patent Landscape for Manganese Recycling
There are relatively few patent publications for recycling manganese-rich batteries compared with NCM/NCA which is not surprising given their early phase of commercialisation. However selected patents and key details are provided for Mn recycling from LIB and other secondary sources in Table 2 below. Most of the patent literature comes from Chinese assignees and amongst those – key universities and institutes as well as the larger recycling companies with hydrometallurgical capacity i.e., GEM and Brunp.
Table 2. Selected Patents and Key Details for Mn Recovery from Waste Batteries and Other Secondary Sources (Source: Enabled Future Limited)
Enabled Future Limited provides ongoing analysis of patents related to the production and recycling of LIB for Mn rich formulations and these are available as a monthly download via subscription.
Key Takeaways
Cathodes with lower Ni/Co-Free chemistries are growing rapidly e.g., LNMO, NMx, LMFP
LNMO will be the largest user of Mn in batteries by 2040, even more than high nickel formulations
The need to meet demand for recycled materials in line with sustainability/ESG goals will require that much more secondary Mn is available
Recycled Mn is expensive to produce and could be detrimental to battery price competitiveness in the EU – there is a large need to bring down the price.
Sustainable mine sources can seriously help to bridge the supply gap – and projects such as Euro Manganese Chvaletice, Czech Republic are looking promising.
Much of the effort needed isn’t necessarily technical – it’s logistical and requires cooperation between different stakeholders.
There is a need to ensure that Mn doesn’t end up in landfill and is actually recycled – ESG practices ought to benefit the industry here.
There are opportunities – however we must be proactive and collaborative in order to realise them.
About The Author
Michelle Lynch is a PhD in Chemicals and Catalysis and is a Chartered Chemist and Fellow of the Royal Society of Chemistry (FRSC). Her 26 years of post-doctoral experience span catalyst R&D, catalyst and precious metals market research, patent analysis and consulting. She is currently the CEO and Owner of Enabled Future Limited (EFL). Prior to setting up EFL, Michelle worked with IHS (S&P Global), Nexant and Johnson Matthey. Michelle is a regular speaker at conferences, editor and contributor to industry magazines including the new Enabled Future magazine. Her publications have also appeared in the IHS Chemical Bulletin, IHS Quarterly, The Catalyst Review, Recycling & Waste World and The Catalyst Group subscriber reports. She lives and runs her consultancy in the West Midlands, UK.
Fleming, A. (2023). Manganese Panel. Benchmark Week (pp. 1-6). Benchmark Mineral Intelligence. Popp, D. (2022, December 9). Batteries: deal on new EU rules for design, production and waste treatment. Retrieved from Europarl: https://www.europarl.europa.eu/news/en/press-room/20221205IPR60614/batteries-deal-on-new-eu-rules-for-design-production-and-waste-treatment USGS. (2023). Manganese. Retrieved from USGS: https://pubs.usgs.gov/periodicals/mcs2023/mcs2023-manganese.pdf Votava, J. (2022, May 17-18). The Chvaletice Manganese Project. Retrieved from re-mine.eu: https://re-mine.eu/wp-content/uploads/2022/06/3_13_EMN-corporate-presentation_2022_05_18-_Conference-Micheleen_Belgium-combined-1.pdf
BR112019007821B1 : Method For Isomerization of a Feedstock Dehydration Non Linear Primary Alcohol in the Presence of Injection of Water and a Catalyst Comprising an Iron Type Crutcher MFS Or [FR3058415A1]
Applicants: FRENCH INSTITUTE OF PETROLEUM SA , TOTALENERGIES SE
1st Inventor: Sylyie Maury
This month’s catalyst patent is a granted publication in Brazil to the French Institute of Petroleum (IFPEN) and Total Energies SE. The work relates to production of olefins by alcohol dehydration over a zeolite catalyst. The first inventor on the patent is Dr Sylvie Maury from IFPEN, France. The patent comes from a French priority FR20160060803 published 08-Nov-2016. There are also French and US granted family members. The patent more specifically relates to the dehydration of iso-butanol to C4 olefins. The catalyst is prepared from a mixture of commercial NH4-ferrierite and silica binder(s) which are kneaded in an aqueous solution of triethylammonium TEAOH. The mixture is then extruded, dried, and calcined to give extrudates of 2-4 mm. Ferrierite is chosen because it has at least one channel with a ring of 8 oxygen atoms (8MR).
Catalyst testing is carried out in either a single or dual reactor with fixed beds operating in “down flow” mode. Water/iso-butanol feed is vapourised and passed over the catalyst bed at 8 bar/300-400°C. With 7% water added into the iso-butanol feed, the best results achieved were 97.8% olefin selectivity with a ratio of n-butenes/all butenes of 84.1% after 72 h at a conversion of 99%. The main by-product was iso-butyraldehyde. Further experiments were carried out with 30% water in the feed. When no water was added to the iso-butanol feed, a rapid deactivation of the catalyst was observed as shown in Figure 1 below.
Figure 1. Activity Testing of Ferrierite Catalysts for Iso-Butanol Conversion to C4-Olefins Example 2: 30% water; Example 3: 0% water
Electrode for fuel cell comprising non-platinum catalyst and graphene layered structure, and membrane-electrode assembly comprising same
Applicant: KOLON INC [KR] / WO 2023018126 A1
This patent application from Kolon refers to a non-platinum catalyst system from a PEM fuel cell. The electrode for a fuel cell of the present invention has a structure in which a catalyst layer and a graphene layer are stacked and alternately laminated, and the conductive polymer is intended to improve the catalyst efficiency by limiting the transition metal particle size.
The catalyst is prepared by mixing CNT as a carbon support, iron(III) phthalocyanine chloride as an Fe—N precursor (M—N precursor) in a mass ratio of 1:2. Then, dispersing in aniline a mass ratio of 2:1 using distilled water as a solvent, and drying at 60° C/8 h to obtain a solid powder. Then heat-treating at 800 ° C/3 h under N2. Then dispersing with Nafion PFSA ionomer, distilled water, and normal-propyl alcohol and spray drying with a graphene dispersion in the first nozzle and the catalyst dispersion in the second nozzle. The graphene layers is sprayed first onto a release material of FEP (Fluorinated Ethylene Propylene) to form a graphene layer, then the catalyst layer is sprayed onto the graphene layer. This process is continued until there are 100 layers. The spray drying is carried out with a mist size of 10 μm at an ultrasonic frequency of 180 kHz. The syringe pump flow rate was set at ~1 ml/min, a nozzle moving speed of 10 m/s, and an air pressure of 4 L/min.
A membrane-electrode assembly (MEA) was then prepared by applying the formed electrode layer as a cathode electrode part and a Pt/C electrocatalyst as an anode electrode part by thermally compressing the polymer electrolyte membrane (PEM).
Performance evaluation was performed under the conditions of a temperature of 65° C., air pressure of 100 kPa, RH of 100%, and a H2/air flow rate ratio of 1.5/2.0. The performance improved when the Fe-N precursor was changed to a Co-N precursor (Example 2) and even further when a Mn-N precursor (Example 3) was employed.
This work is of high importance because the use of scarce platinum group metals (PGM) raises the cost and potentially reduces the overall deployment possible of PEM fuel cells (and PEM electrolysers). The use of a dual spray nozzle simplifies the production method. It is interesting that Manganese (Mn) performed best because although the demand for high purity Mn including for lithium-ion batteries is increasing, the metal still has lower criticality than either Pt or Co.
