One of the biggest hurdles for the electrification of road traffic is the long charging time for lithium batteries in electric vehicles. A recent research report has now shown that charging time can be reduced to 10 minutes while the battery is being heated.
A lithium battery can power a 320-kilometer trip after only 10 minutes of charging − provided that its temperature is higher than 60 °C while charging.
Lithium batteries that use lithium ions to generate electricity are slowly charged at room temperature. It takes more than three hours to charge, as opposed to three minutes to tank a car.
A critical barrier to rapid charging is the lithium plating, which normally occurs at high charging rates and drastically affects the life and safety of the batteries. Researchers at Pennsylvania State University in University Park are introducing an asymmetrical temperature modulation method that charges a lithium battery at an elevated temperature of 60 °C.
High-speed charging typically encourages lithium to coat one of the battery electrodes (lithium plating). This will block the flow of energy and eventually make the battery unusable. To prevent lithium deposits on the anodes, the researchers limited the exposure time at 60 °C to only ~10 minutes per cycle.
The researchers used industrially available materials and minimized the capacity loss at 500 cycles to 20%. A battery charged at room temperature could only be charged quickly for 60 cycles before its electrode was plated.
The asymmetrical temperature between charging and discharging opens up a new way to improve the ion transport during charging and at the same time achieve a long service life.
For many decades it was generally believed that lithium batteries should not be operated at high temperatures due to accelerated material degradation. Contrary to this conventional wisdom, the researchers introduced a rapid charging process that charges a cell at 60 °C and discharges the cell at a cool temperature. In addition, charging at 60 °C reduces the battery cooling requirement by more than 12 times.
In battery applications, the discharge profiles depend on the end user, while the charging protocol is determined by the manufacturer and can therefore be specially designed and controlled. The quick-charging process presented here opens up a new way of designing electrochemical energy systems that can achieve high performance and a long service life at the same time.
At Frontis Energy we also think that the new simple charging process is a promising method. We are looking forward to the market launch of this new rapid charging method.
In our previous post we briefed you on the energy storage potential in the United Kingdom. With Brexit, Italy will become the third largest member state after Germany and France. With extensive mountain terrain in the north, Italy has long been dependent upon hydroelectric generation. Until the mid 1960s hydropower represented nearly all electricity production in Italy. The installed capacity of hydropower has been stagnant since the mid 1960s, with a rapid growth in fossil fuel based generation driving the overall share of hydropower fall from ~90% to 22% in 2014. A detailed breakdown of electricity sources in Italy is shown below.
Considerable effort has been made to transition Italy to a low carbon electricity sector. As of 2016, Italy had the 5th highest installed solar capacity in the world and the 2nd highest per capita solar capacity, behind only Germany. In addition to its impressive solar progress Italy ranks 6th worldwide in geothermal with 0.9 GW.
Italy’s solar growth was propelled by feed-in-tariffs that wer enacted in 2005. This provided residential PV owners with financial compensation for energy sold to the grid. However, the feed-in-tariff program ceased on 06 July 2014 after the €6.7 billion subsidy limit was reached.
Even with its impressive accomplishments in renewable energy, traditional thermal generation (natural gas) still account for ~60% of total electricity generation in Italy. How much effort will go into reducing this number is still unclear. Italy has committed to 18% renewables by 2020 and is nearly 70% of the way there already so there is little urgency on reducing fossil-based electricity from the perspective of meeting this target. However, Italy is heavily reliant on fossil fuel imports (Deloitte) and energy security requirements will likely continue to push the development of more domestic electricity sources like renewables.
Energy Storage Facilities
Italy is dominating the electro-chemical energy storage market in Europe. With over 6,000 GWh of planned and installed electro-chemical generating capacity (~84 MW installed capacity), Italy is far ahead of 2nd place UK. This is largely due to the massive SNAC project by TERNA (Italy’s TSO), a sodium-ion battery installation totaling nearly 35 MW over three phases. A breakdown of energy storage projects, by technology type can be seen below.
Italy is one of the top markets in the EU for energy storage and is primed for growth. The Italian TSO, TERNA, has been investigating selling energy storage as a service. In 2014 the AEEG, the electrical regulator under which TERNA operates, proposed that batteries should be treated as generation sources similar to cogeneration plants. Italy has always been a market completely dominated by a small number of big centralized utility companies and this trend is likely to continue when it comes to EES deployment. These companies have been focusing their efforts on battery technologies and are expected to continue down this path.
However, the private market could present great opportunity for P2G. The International Battery & Energy Storage Alliance have summarized the reality of Italy’s untapped energy storage market as follows: “With high solar output of 1,400 kWh/kWp, net residential electricity prices around 23 cent/kWh and currently no FIT, the Italian energy market is considered to be highly receptive for energy storage.”
Italy is now well-stocked with residential PV systems that can no longer collect subsidies. Combine this with the fact that the vast majority of homes in Italy burn natural gas imported from Russia, Libya and Algeria and it is clear that Italy presents a unique opportunity for P2G at a residential/community level. This is echoed by Energy Storage Update who in 2015 concluded that Italy was “one of the top four markets worldwide for PV-and-battery-based energy self-consumption.”
While it is unclear exactly how many residential PV systems there are in Italy, it was speculated in late 2015 that there were over 500,000 PV plants in Italy.
While the UK has been heavily dependent on carbon-intensive sources of electricity, in 2008 they committed to a 15% renewable energy target (by 2020) and 80% reduction in CO2 emissions (by 2050; Department of Energy & Climate Change). However, the UK has stated that they will miss the 15% renewable target for 2020, due to the lack of properly designed policy measures. There has been considerable pressure to transition to a low carbon market and with one-quarter of existing generating capacity (mainly coal and nuclear) expected to close by 2021; it is expected that growth in renewable energy will lead to more energy storage capacities.
The UK has made excellent progress on its short-term clean energy goals and there is optimism that this trend will continue. Large-scale development of low carbon generation technologies such as wind and solar is expected to continue.
Energy Storage Facilities
As of late 2016, there were 27 non-PHS EES plants representing 430 MW of installed capacity in the UK (Sandia National Laboratories). The UK’s energy storage portfolio is dominated by electro-chemical based technologies (primarily lead-acid and lithium-ion battery installations). This is shown below.
As was shown for Germany, only a very small fraction of EES facilities are dedicated to renewables capacity firming. The existing EES capacity is almost exclusively dedicated to critical transmission support (on-site power). While nearly all of the EES capacity under development is dedicated to bulk energy storage (electric energy time shift).
There is still considerable uncertainty around the growth of EES in the UK, and with such a small sample size it is difficult to infer any correlation from the data in the figure above. According to the previous UK government, however, being geographically isolated and a net importer of electricity, one would expect the UK to place a heavier focus on renewables capacity firming in the long-term.
Energy Storage Market Outlook
The UK is in the midst of a major restructuring of their electricity generating portfolio and the market under which these assets operate. With a large portion of the existing capacity due for retirement in the next 10-15 years, the UK faces challenges in meeting energy needs while balancing decarbonization efforts. As part of this, major investment is needed in all areas of the electrical grid, including energy storage.
In its Smart Power publication, the National Infrastructure Commission outlined that while the UK is being faced with challenges to cover aging infrastructure this represents an opportunity to build efficient and flexible energy infrastructure. The Commission stated that energy storage was one of the three key innovations for a “smart power revolution”.
Many other official government bodies have expressed similar thoughts regarding energy storage. In its Low carbon network infrastructure report, the Energy and Climate Change Committee stated that “storage technologies should be deployed at scale as soon as possible”, while urging the Government to eliminate the outdated and unfair regulations that have been handcuffing energy storage development in the UK (Garton and Grimwood).
In April 2016, the Government acknowledged concerns regarding the regulatory hurdles facing energy storage projects (primarily double-charging of network charges) and stated that they would begin working with the National Infrastructure Commission and ECCC to investigate the issue. While there may be regulatory hurdles hindering energy storage in the UK, the Government has shown commitment through funding. Since 2012, the government has contributed over £80 million to energy storage research. In addition to this, the Department of Energy and Climate Change have developed a new £20 million fund to help drive innovation in energy storage technologies.
Overall, the outlook for energy storage in the UK is positive. There is considerable pressure to begin developing energy storage facilities at scale from not only industry, but also many government bodies. Investors are ready as well. As stated by the National Infrastructure Commission: “businesses are already queuing up to invest”.
Simply put: regulatory hurdles are holding back growth in the UK energy storage market. With the Government making major strides in renewable energy development and being vocal about its commitment to making the UK a leader in energy storage technology, these regulatory hurdles will likely be relaxed and there should be considerable growth in the UK energy storage market in the near-term.
At this point, specific technology types and service uses have not been hypothesized in detail. However, with the UK being geographically isolated and a net importer of electricity, logic would suggest an emphasis on renewables capacity firming in the long-term to maximize domestic consumption of renewable energy. Rapidly decreasing costs in electro-chemical technologies, coupled with the fact that much of the existing gas-fired capacity will be reaching end of life by 2030 suggest that the UK EES market would not be ideal for P2G technologies.
In our last posts we introduced electrical energy storage (EES) and the EU market for EES. Now, we focus on some important EU members, beginning with Germany. The country’s electrical energy portfolio reflects its status among the most progressive countries in the world in terms of climate action. As of November 2016, Germany had produced ~35% of its 2016 electricity needs from renewable sources as outlined in the Figure below.
However, these numbers are somewhat skewed based on the fact that the electro-mechanical category is essentially two large capacity CAES plants. In reality, electro-chemical projects (mainly batteries) are much more prevalent and represent the vast majority of growth in the German storage market. There are currently 11 electro-chemical type energy storage projects under development in Germany and no electro-mechanical projects under development (see figure below).
Services Uses of Energy Storage
As outlined earlier, there are a multitude of service uses for EES technologies. Currently the existing EES fleet in Germany serves grid operations and stability applications (black start, electric supply capacity), and on-site power for critical transmission infrastructure. A breakdown of service uses in the German market is shown below.
Logic seems to indicate that with aggressive renewable energy targets, a nuclear phase-out, and increased emphasis on energy independence Germany will need to develop more EES capacity. However, many have conjectured that the lagging expansion of EES in the short and medium term will not pose a barrier to the Energiewende. In fact, some claim that EES will not be a necessity in the next 10-20 years. For example, even when Germany reaches its 2020 wind and solar targets (46 GW and 52 GW, respectively), these would generally not exceed 55 GW of supply and nearly all of this power will be consumed domestically in real-time. Thus, no significant support from EES would be required.
The German Institute for Economy Research echos these sentiments and argue that the grid flexibility needed with significant renewable energy capacity could be provided by more cost-effective options like flexible base-load power plants and better demand side management. Additionally, innovations in power-to-heat technologies which would use surplus wind and solar electricity to feed district heating systems present significant opportunity, while creating a new market of energy service companies.
While there is work being done, economically feasible production of P2G is currently not achievable due to limited excess electricity and low guaranteed capacity. This limited excess electricity, is an example of the effect of power exports discussed earlier. While there may not be a significant commercial market in the short-term, introduction of P2G for transport could act as an additional driver behind continued renewable energy development in Germany.
In our previous post of this blog series on Electrical Energy Storage in the EU we briefly introduced you to different technologies and their use cases. Here, we give you a short overview over the EU energy grid. Supplying approximately 2,500 TWh annually to 450 million customers across 24 countries, the synchronous interconnected system of Continental Europe (“the Grid”) is the largest interconnected power network in the world. The Grid is made up of transmission system operators (TSOs) from 24 countries stretching from Greece to the Iberic Peninsula in the south, Denmark and Poland in the north, and up to the black sea in the east. The European Network of Transmission System Operators (ENTSO-E) serves as the central agency tasked with promoting cooperation between the TSOs from the member countries in the Grid. The ENTSO-E, in essence, acts as the central TSO for Europe. With over 140 GW of installed wind and solar PV capacity, the EU trails behind only China in installed capacity. A breakdown of the individual contributions of EU member states is shown below in the figure above.
Energy Storage in the EU
For this study a number of European countries were selected for more detailed investigation into energy storage needs. These countries were selected based on a combination of existing market size, intentions for growth in non-dispatchable renewable energy and/or energy storage, and markets with a track record of innovation in the energy sector.
On a total capacity basis (installed and planned MW) the top three energy storage markets within the EU are: Italy, the UK, and Germany. These countries were selected on the basis of these existing market sizes.
Spain and Denmark were selected based on their large amounts of existing renewable energy capacity and − in the case of Denmark − the forecasted growth in renewable energy and energy storage capacity.
Each of the selected countries (Germany, UK, Italy, Spain, Denmark, Netherlands) are discussed in the proceeding sections, providing a more detailed overview outlining their current electricity portfolios and decarbonization efforts, current energy storage statistics, and a brief discussion on market outlook.
Electrical Energy Storage (EES) is the process of converting electrical energy from a power network into a form that can be stored for converting back to electricity when needed. EES enables electricity to be produced during times of either low demand, low generation cost, or during periods of peak renewable energy generation. This allows producers and transmission system operators (TSOs) the ability to leverage and balance the variance in supply/demand and generation costs by using stored electricity at times of high demand, high generation cost, and/or low generation capacity.
EES has many applications including renewables integration, ancillary services, and electrical grid support. This blog series aims to provide the reader with four aspects of EES:
An overview of the function and applications of EES technologies,
State-of-the-art breakdown of key EES markets in the European Union,
A discussion on the future of these EES markets, and
Applications (Service Uses) of EES.
Table: Some common service uses of EES technologies
Compressed Air Energy Storage (CAES)
Unlike any other commodities market, electricity-generating industries typically have little or no storage capabilities. Electricity must be used precisely when it is produced, with grid operators constantly balancing electrical supply and demand. With an ever-increasing market share of intermittent renewable energy sources the balancing act is becoming increasingly complex.
While EES is most often touted for its ability to help minimize supply fluctuations by storing electricity produced during periods of peak renewable energy generation, there are many other applications. EES is vital to the safe, reliable operation of the electricity grid by supporting key ancillary services and electrical grid reliability functions. This is often overlooked for the ability to help facilitate renewable energy integration. EES is applicable in all of the major areas of the electricity grid (generation, transmission & distribution, and end user services). A few of the most prevalent service uses are outlined in the Table above. Further explanation on service use/cases will be provide later in this blog, including comprehensive list of EES applications.
Electrical energy storage (EES) is not only a vital component in the reliable operation of modern electrical grids, but also a focal point of the global renewable energy transition. It has been often suggested that EES technologies could be the missing piece to eliminating the technical hurdles facing the implementation of intermittent renewable energy sources. In the following blog posts, selected EES markets within the European Union will be evaluated in detail.
With over 80 MW of installed wind and solar capacity, Germany is by far the leading EU nation in the renewable energy transition. However, experts have argued that Germany’s need for widespread industrial scale energy storage is unlikely to materialize in any significant quantity for up to 20-years. This is due to a number of factors. Germany’s geographic location and abundance of connections to neighbouring power grids makes exporting any electricity fluctuations relatively easy. Additionally, when Germany reaches its 2020 targets for wind and solar capacity (46 GW and 52 GW, respectively) the supply at a given time would generally not exceed 55 GW. Nearly all of this would be consumed domestically, with no/little need for storage.
When evaluating energy storage in the UK, a different story emerges. Being an isolated island nation there is considerably more focus on energy independence to go along with their low-carbon energy goals. However, the existing regulatory environment is cumbersome, and poses barriers significant enough to substantially inhibit the transition to a low-carbon energy sector – including EES. The UK government has acknowledged the existence of regulatory barriers and pledged to address them. As part of this effort, a restructuring of their power market to a capacity-based market is already underway. The outlook for EES in the UK is promising, there is considerable pressure from not only industry, but also the public and the government to continue developing EES facilities at industrial scale.
Italy, once heavily hydro-powered, has grown to rely on natural gas, coal, and oil for 50% of it’s electricity (gas representing 34% alone). The introduction of a solar FIT in 2005 lead to significant growth in the solar industry (Italy now ranks 2nd in per capita solar capacity globally) before the program ended in July 2014. In recent years there has been notable growth in electro-chemical EES capacity (~84 MW installed), primarily driven by a single large-scale project by TERNA, Italy’s transmission system operator (TSO). This capacity has made Italy the leader in EES capacity in the EU, however the market is to-date dominated by the large TSOs.
However, the combination of a reliance on imported natural gas, over 500,000 PV systems no longer collecting FIT premiums, and increasing electricity rates presents a unique market opportunity for residential power-to-gas in Italy.
Denmark is aggressively pursing a 100-percent renewable target for all sectors by 2050. While there is still no official roadmap policy on how they will get there, they have essentially narrowed it down to one of two scenario: a biomass-based scenario, or a wind + hydrogen based scenario. Under the hydrogen-based scenario there would be widespread investment to expand wind capacity and couple this capacity with hydrogen power-to-gas systems for bulk energy storage. With the Danish expertise and embodied investment in wind energy, one would expect that the future Danish energy system would be build around this strength, and hence require significant power-to-gas investment.
The renewable energy industry in Spain has completed stagnated due to retroactive policy changes and taxes on consumption of solar generated electricity introduced in 2015. The implementation of the Royal Decree 900/2015 on self-consumption has rendered PV systems unprofitable, and added additional fees and taxes for the use of EES devices. No evidence was found to suggest a market for energy storage will materialize in Spain in the near future.
The final country investigated was the Netherlands, which has been criticized by the EU for its lack of progress on renewable energy targets. With only 10% of Dutch electricity coming from renewable sources, there is currently little demand for large-scale EES. While the Netherlands may be lagging behind on renewable electricity targets, they have been a leader in EV penetration; a trend that will continue and see 1-million EVs on Dutch roads by 2025. In parallel with the EV growth, there has been a large surge in sub-100kW Li-ion installations for storing energy at electric vehicle (EV) charging stations. It is expected that these applications will continue to be the primary focus of EES in the Netherlands.
Similar to Italy, the Dutch rely heavily on natural gas for energy within their homes. This fact, coupled with an ever-increasing focus on energy independent and efficient houses could make the Netherlands a prime market for residential power-to-gas technologies.
Renewable energies, such as wind and solar energy are naturally intermittent. To balance their demand and supply, batteries of, for example, electric vehicles can be charged and act as an energy buffer for the power grid. Cars spend most of their time idle and could, at the same time, feed their electricity back into the grid. While this is still a dream of the future, commercialization of electric and hybrid vehicles is already creating a growing demand for long-lasting batteries, both for driving as well as grid buffering. Consequently, methods for evaluating the state of the battery will become increasingly important.
The long duration of battery health tests is a problem, hindering the rapid development of new batteries. Better battery life forcasting methods are therefore urgently needed but are extremely difficult to develop. Now, Severson and her colleagues report in the journal Nature Energy that machine learning can help to predict computer battery life by creating computer models. The published algorithms use data from early-stage charge and discharge cycles.
Normally, a figure of merit describes the health of a battery. It quantifies the ability of the battery to store energy relative to its original state. The health status is 100% when the battery is new and decreases with time. This is similar to the state of charge of a battery. Estimating the state of charge of a battery is, in turn, important to ensure safe and correct use. However, there is no consensus in the industry and science as to what exactly a battery’s health status is or how it should be determined.
The state of health of a battery reflects two signs of aging: progressive capacity decline and impedance increase (another measure of electrical resistance). Estimates of the state of charge of a battery must therefore take into account both the drop in capacity and the increase in impedance.
Lithium ion batteries, however, are complex systems in which both capacity fade and impedance increase are caused by multiple interacting processes. Most of these processes cannot be studied independently since they often occur in simultaneously. The state of health can therefore not be determined from a single direct measurement. Conventional health assessment methods include examining the interactions between the electrodes of a battery. Since such methods often intervene directly in the system “battery”, they make the battery useless, which is hardly desired.
A battery’s health status can also be determined in less invasive ways, for example using adaptive models and experimental techniques. Adaptive models learn from recorded battery performance data and adjust themselves. They are useful if system-specific battery information are not available. Such models are suitable for the diagnosis of aging processes. The main problem, however, is that they must be trained with experimental data before they can be used to determine the current capacity of a battery.
Severson and her colleagues have created a comprehensive data set that includes the performance data of 124 commercial lithium-ion batteries during their charge and discharge cycles. The authors used a variety of rapid charging conditions with identical discharge conditions. This method caused a change of the battery lives. The data covered a wide range of 150 to 2,300 cycles.
The researchers then used machine learning algorithms to analyze the data, creating models that can reliably predict battery life. After the first 100 cycles of each experimentally characterized battery their model already showed clear signs of a capacity fade. The best model could predict the lifetime of about 91% data sets studied in the study. Using the first five cycles, batteries could be classified into categories with short (<550 cycles) or long lifetimes.
The researchers’ work shows that data-driven modeling using machine learning allows forecasting the state of health of lithium-ion batteries. The models can identify aging processes that do not otherwise apparent in capacity data during early cycles. Accordingly, the new approach complements the previous predictive models. But at Frontis Energy, we also see the ability to combine generated data with models that predict the behavior of other complex dynamic systems.
As a loyal reader or loyal reader of our blog, you will certainly remember our previous publications on ammonia energy storage. There, we describe possible ways to extract ammonia from the air, as well as the recovery of its energy in the form of methane (patent pending WO2019/079908A1). Since global food production requires large amounts of ammonia fertilizers, technologies for extraction from air is already very mature. These technologies are essentially all based on the Haber-Bosch process, which was industrialized at the beginning of the last century. During this process, atmospheric nitrogen (N2) is reduced to ammonia (NH3). Despite the simplicity of the molecules involved, the cleavage of the strong nitrogen−nitrogen bonds in N2 and the resulting nitrogen−hydrogen bonds pose a major challenge for catalytic chemists. The reaction usually takes place under harsh conditions and requires a lot of energy, i.e. high reaction temperatures, high pressures and complicated combinations of reagents, which are also often expensive and energy-intensive to manufacture.
Now, a research group led by Yuya Ashida has published an article in the renowned journal Nature, in which they show that a samarium compound in aqueous solution combined with a molybdenum catalyst can form ammonia from atmospheric nitrogen. The work opens up new possibilities in the search for ways to ammonia synthesis under ambient conditions. Under such conditions, less energy is required to produce ammonia, resulting in higher energy efficiency for energy storage. In today’s Haber-Bosch process, air and hydrogen gas are combined via an iron catalyst. The resulting global ammonia production of this process ranges from 250 to 300 tonnes per minute, delivering fertilizers that provide nearly 60% of the world’s population (The Alchemy of Air, available at Amazon).
On industrial scale, ammonia is synthesized at temperatures that exceed 400°C and pressures of approximately 400 atmospheres. These conditions are often referred to as “harsh”. During the early days, these harsh conditions were difficult to control. Fatal accidents were not uncommon in the early years of the Haber-Bosch development. This has motivated many chemists to find “milder” alternatives. After all, this always meant searching for new catalysts to lower operating temperatures and pressures. The search for new catalysts would ultimately reduce capital investment in the construction of new fertilizer plants. Since ammonia synthesis is one of the largest producers of carbon dioxide, this would also reduce the associated emissions.
Like many other chemists before them, the authors have been inspired by nature. Nitrogenase enzymes carry out the biological conversion of atmospheric nitrogen into ammonia, a process called nitrogen fixation. On recent Earth, this process is the source of nitrogen atoms in amino acids and nucleotides, the elemental building blocks of life. In contrast to the Haber-Bosch process, nitrogenases do not use hydrogen gas as a source of hydrogen atoms. Instead, they transfer protons (hydrogen ions, H+) and electrons (e−) to each nitrogen atom to form N−H bonds. Although nitrogenases fix nitrogen at ambient temperature, they use eight protons and electrons per molecule N2. This is remarkable because the stoichiometry of the reaction requires only six each. This way, nitrogenases provide the necessary thermodynamic drive for nitrogen fixation. The excess of hydrogen equivalents means that nitrogenases have a high chemical overpotential. That is, they consume much more energy than would actually be needed for nitrogen fixation.
The now published reaction is not the first attempt to mimic the nitrogenase reaction. In the past, metal complexes were used with proton and electron sources to convert atmospheric nitrogen into ammonia. The same researchers have previously developed 8 molybdenum complexes that catalyze nitrogen fixation in this way. This produced 230 ammonia molecules per molybdenum complex. The associated overpotentials were significant at almost 1,300 kJ per mole nitrogen. In reality, however, the Haber-Bosch process is not so energy-intensive given the right catalyst is used.
The challenge for catalysis researchers is to combine the best biological and industrial approaches to nitrogen fixation so that the process proceeds at ambient temperatures and pressures. At the same time, the catalyst must reduce the chemical overpotential to such an extent that the construction of new fertilizer plants no longer requires such high capital investments. This is a major challenge as there is no combination of acids (which serve as a proton source) and reducing agents (the electron sources) available for the fixation at the thermodynamic level of hydrogen gas. This means that the mixture must be reactive enough to form N−H bonds at room temperature. In the now described pathway with molybdenum and samarium, the researchers have adopted a strategy in which the proton and electron sources are no longer used separately. This is a fundamentally new approach to catalytic ammonia synthesis. It makes use of a phenomenon known as coordination-induced bond weakening. In the proposed path, the phenomenon is based on the interaction of samarium diiodide (SmI2) and water.
Water is stable because of its strong oxygen-hydrogen bonds (O−H). However, when the oxygen atom in the water is coordinated with SmI2, it exposes its single electron pair and its O−H bonds are weakened. As a result, the resulting mixture becomes a readily available source of hydrogen atoms, protons and electrons, that is. The researchers around Yuya Ashida use this mixture with a molybdenum catalyst to fix nitrogen. SmI2-water mixtures are therefore particularly suitable for this type of catalysis. In them, a considerable coordination-induced bond weakening was previously measured, which was used inter alia for the production of carbon-hydrogen bonds.
The extension of this idea to catalytic ammonia synthesis is remarkable for two reasons. First, the molybdenum catalyst facilitates ammonia synthesis in aqueous solution. This is amazing because molybdenum complexes in water are usually degraded. Second, the use of coordination-induced bond weakening provides a new method for nitrogen fixation at ambient conditions. This also avoids the use of potentially hazardous combinations of proton and electron sources which are a fire hazard. The authors’ approach also works when ethylene glycol (HOCH2CH2OH) is used instead of water. Thus, the candidates for proton and electron sources are extended by an additional precursor.
Ashida and colleagues propose a catalytic cycle for their process in which the molybdenum catalyst initially coordinates to nitrogen and cleaves the N−N bond to form a molybdenum nitrido complex. This molybdenum nitrido complex contains the molybdenum-nitrogen triple bond. The SmI2-water mixture then delivers hydrogen atoms to this complex, eventually producing ammonia. The formation of N−H bonds with molybdenum nitrido complexes represents a significant thermodynamic challenge since the N−H bonds are also weakened by the molybdenum. Nevertheless, the disadvantages are offset by the reduction of the chemical overpotential. The SmI2 not only facilitates the transfer of hydrogen atoms, but also keeps the metal in a reduced form. This prevents undesired molybdenum oxide formation in aqueous solution.
The new process still has significant operational hurdles to overcome before it can be used on an industrial scale. For example, SmI2 is used in large quantities, which generates a lot of waste. The separation of ammonia from aqueous solutions is difficult in terms of energy consumption. However, if the process were used for energy storage in combination with our recovery method, the separation would be eliminated from the aqueous solution. Finally, there is still a chemical overpotential of about 600 kJ/mol. Future research should focus on finding alternatives to SmI2. These could be based, for example, on metals that occur more frequently than samarium and promote coordination-induced bond weakening as well. As Fritz Haber and Carl Bosch have experienced, the newly developed method will probably take some time for development before it becomes available on industrial scale.
At Frontis Energy we have spent much thought on how to recycle CO2. While high value products such as polymers for medical applications are more profitable, customer demand for such products is too low to recycle CO2 in volumes required to decarbonize our atmosphere to pre-industrial levels. Biofuel, for example from field crops or algae has long been thought to be the solution. Unfortunately, they require too much arable land. On top of their land use, biochemical pathways are too complex to understand by the human brain. Therefore, we propose a different way to quickly reach the target of decarbonizing our planet. The procedure begins with a desired target fuel and suggests a microbial consortium to produce this fuel. In a second step, the consortium will be examined in a bio-electrical system (BES).
Today’s atmospheric CO2 imbalance is a consequence of fossil carbon combustion. This reality requires quick and pragmatic solutions if further CO2 accumulation is to be prevented. Direct air capture of CO2 is moving closer to economic feasibility, avoiding the use of arable land to grow fuel crops. Producing combustible fuel from CO2 is the most promising intermediate solution because such fuel integrates seamlessly into existing urban infrastructure. Biofuels have been explored intensively in recent years, in particular within the emerging field of synthetic biology. However tempting the application of genetically modified organisms (GMOs) appears, non-GMO technology is easier and faster to implement as the required microbial strains already exist. Avoiding GMOs, CO2 can be used in BES to produce C1 fuels like methane and precursors like formic acid or syngas, as well as C1+ compounds like acetate, 2-oxybutyrate, butyrate, ethanol, and butanol. At the same time, BES integrate well into urban infrastructure without the need for arable land. However, except for methane, none of these fuels are readily combustible in their pure form. While electromethane is a commercially available alternative to fossil natural gas, its volumetric energy density of 40-80 MJ/m3 is lower than that of gasoline with 35-45 GJ/m3. This, the necessary technical modifications, and the psychological barrier of tanking a gaseous fuel make methane hard to sell to automobilists. To produce liquid fuel, carbon chains need to be elongated with alcohols or better, hydrocarbons as final products. To this end, syngas (CO + H2) is theoretically a viable option in the Fischer-Tropsch process. In reality, syngas precursors are either fossil fuels (e.g. coal, natural gas, methanol) or biomass. While the former is obviously not CO2-neutral, the latter competes for arable land. The direct conversion of CO2 and electrolytic H2 to C1+ fuels, in turn, is catalyzed out by electroactive microbes in the dark (see title figure), avoiding food crop competition for sun-lit land. Unfortunately, little research has been undertaken beyond proof of concept of few electroactive strains. In stark contrast, a plethora of metabolicstudies in non-BES is available. These studies often propose the use of GMOs or complex organic substrates as precursors. We propose to systematically identify metabolic strategies for liquid bio-electrically engineered fuel (BEEF) production. The fastest approach should start by screening metabolic databases using established methods of metabolic modeling, followed by high throughput hypothesis testing in BES. Since H2 is the intermediate in bio-electrosynthesis, the most efficient strategy is to focus on CO2 and H2 as direct precursors with as few intermediate steps as possible. Scalability and energy efficiency, economic feasibility that is, are pivotal elements.
Yeasts are among the microorganisms with the greatest potential for liquid biofuel production. Baker’s yeast, (Saccharomyces cerevisiae) is the most prominent example. While known for ethanol fermentation, yeasts also produce fusel oils such as butane, phenyl, and amyl derivate aldehydes and alcohols. Unlike ethanol, which is formed via sugar fermentation, fusel oil is synthesized in branched-off amino acid pathways followed by aldehyde reduction. Many enzymes involved in the reduction of aldehydes have been identified, with alcohol dehydrogenases being the most commonly observed. The corresponding reduction reactions require reduced NADH but it is not known whether H2 produced on cathodes of BES can be involved.
Clostridia, for example Clostridium acetobutylicum and C. carboxidivorans, can produce alcohols like butanol, isopropanol, hexanol, and ketones like acetone from complex substrates (starch, whey, cellulose, etc. ) or from syngas. Clostridialmetabolism has been clarified some time ago and is different from yeast. It does not necessarily require complex precursors for NAD+ reduction and it was shown that H2, CO, and cathodes can donate electrons for alcohol production. CO2 and H2 were used in a GMO clostridium to produce high titers of isobutanol. Typical representatives for acetate production from CO2 and H2 are C. ljungdahlii, C. aceticum, and Butyribacterium methylotrophicum. Sporomusa sphaeroides produces acetate in BES. Clostridia also dominated mixed culture BESs converting CO2 to butyrate. They are therefore prime targets for low cost biofuel production. Alcohols in clostridia are produced from acetyl-CoA. This reaction is reversible, allowing acetate to serve as substrate for biofuel production with extracellular energy supply. Then, energy conservation, ATP synthesis that is, can be achieved from ethanol electron bifurcation or H2 oxidation via respiration. While possible in anaerobic clostridia, it is hitherto unknown whether electron bifurcation or respiration are linked to alcohols or ketone synthesis.
Phototrophs like Botryococcus produce C1+ biofuels as well. They synthesize a number of different hydrocarbons including high value alkanes and alkenes as well as terpenes. However, high titers were achieved by only means of genetic engineering, which is economically not feasible in many countries due to regulatory constrains. Moreover, aldehyde dehydration/deformylation to alkanes or alkenes requires molecular oxygen to be present. Also the olefin pathway of Synechococcus depends on molecular oxygen with the cytochrome P450 involved in fatty acid decarboxylation. The presence of molecular oxygen affects BES performance due to immediate product degradation and unwanted cathodic oxygen reduction. In contrast, our own preliminary experiments (see title photo) and a corrosion experiment show that algae can live in the dark using electrons from a cathode. While the enzymes involved in the production of some algal biofuels are known (such as olefin and aldehyde deformylation), it is not known whether these pathways are connected to H2 utilization (perhaps via ferredoxins). Such a connection would be a promising indicator for the possibility of growing hydrocarbon producing cyanobacteria on cathodes of BES and should be examined in future research.
At Frontis Energy we believe that a number of other microorganisms show potential for BEEF production and these deserve further investigation. To avoid GMOs, BES compatible co-cultures must be identified via in silico metabolic reconstruction from existing databases. Possible inter-species intermediates are unknown but are prerequisite for successful BES operation. Finally, a techno-economical assessment of BEEF production, with and without carbon taxes, and compared with chemical methods, will direct future research.