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Energy storage in the European Union

Grid integration of renewables

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.

While still lagging behind the rest of the EU in terms of decarbonization efforts and having a small portion of their energy from renewable sources, the Netherlands were also selected for further investigation.

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.

Pumped Hydro Storage

With over 183 GW of installed capacity worldwide, pumped hydro storage is the most widely implemented and most established form of energy storage in the world. Due its extensive market penetration, technology maturity, and the fact that this blog is aimed at emerging new storage technologies, the data presented in the following posts excludes this technology.

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Electrical energy storage

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:

  1. An overview of the function and applications of EES technologies,
  2. State-of-the-art breakdown of key EES markets in the European Union,
  3. A discussion on the future of these EES markets, and
  4. Applications (Service Uses) of EES.

Table: Some common service uses of EES technologies

Storage Category

Storage Technology

Pumped Hydro

Open Loop

Closed Loop

Electro-chemical

Batteries

Flow Batteries

Capacitors

Thermal Storage

 

Molten Salts

Heat

Ice

Chilled Water

Electro-mechanical

Compressed Air Energy Storage

Flywheel

Gravitational Storage

Hydrogen Storage

 

Fuel Cells

H2 Storage

Power-to-Gas

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.

Area

Service
Use/Case

Discharge
Duration in h

Capacity
in MW

Examples

Generation

Bulk
Storage

4
– 6

1
– 500

PHS,
CAES, Batteries

Contingency

1
– 2

1
– 500

PHS,
CAES, Batteries

Black
Start

NA

NA

Batteries

Renewables
Firming

2
– 4

1
– 500

PHS,
CAES, Batteries

Transmission
& Distribution

Frequency
& Voltage Support

0.25
– 1

1
– 10

Flywheels,
Capacitors

Transmission
Support

2
– 5 sec

10
– 100

Flywheels,
Capacitors

On-site
Power

8
– 16

1.5
kW – 5 kW

Batteries

Asset
Deferral

3
– 6

0.25
– 5

Batteries

End
User Services

Energy
Management

4
– 6

1
kW – 1 MW

Residential
storage

(Jon Martin, 2019)

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EU market summary for energy storage

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.

Read more about electrical energy storage here.

Jon Martin, 2019

(Photo: NASA)

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Machine learning makes smarter batteries

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.

Experimental techniques are used to evaluate certain physical processes and failure mechanisms. This allows the rate of future capacity loss to be estimated. Unfortunately, these methods can not detect any intermittent errors. Alternative techniques use the rate of voltage or capacitance change (rather than raw voltage and current data). In order to accelerate the development of battery technology, further methods need to be found which can accurately predict the life of the batteries.

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.

(Photo: Wikipedia)

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Ammonia energy storage #3

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).

Comparison of different approaches to produce ammonia. Top: In the industrial Haber-Bosch synthesis of ammonia (NH3), nitrogen gas (N2) reacts with hydrogen molecules (H2), typically in the presence of an iron catalyst. The process requires high temperatures and pressures, but is thermodynamically ideal because only little energy is wasted on side reactions. Center: Nitrogenase enzymes catalyze the reaction of six-electron (e) nitrogen and six protons (H+) under ambient conditions to form ammonia. However, two additional electrons and protons form one molecule of H2. The conversion of ATP (the biological energy “currency”) into ADP drives the reaction. This reaction has a high chemical overpotential. It consumes much more energy than is needed for the actual ammonia forming reaction. Bottom: In the new reaction proposed by Ashida and colleagues, a mixture of water and samarium diiodide (SmI2) is converted to ammonia using nitrogen under ambient conditions and in the presence of a molybdenum catalyst. SmI2 weakens the O−H bonds of the water and generates the hydrogen atoms, which then react with atmospheric nitrogen.

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.

(Photo: Wikipedia)

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Producing liquid bio-electrically engineered fuels from CO2

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).

CO2 can be used for liquid fuel production via multiple pathways. The end product, long-chain alcohols, can be used either directly as fuel or reduced to hydrocarbons. Shown are examples of high level BEEF pathways using CO2 and electricity as input and methane, acetate, or butanol as output. Subsequent processes are 1, aerobic methane oxida­tion, 2, direct use of methane, 3 heterotrophic phototrophs, 4, acetone-butanol fermentation, 5, heterotrophs, 6, butanol di­rect use, 7, further processing by yeasts

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 metabolic studies 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.

First, an electrotrophic acetogen produces acetate, which then used by heterotrophic algae in a consecutive step.

The biggest obstacle for BEEF production is lacking knowledge about pathways that use CO2 and electrolytic H2. This gap exists despite metabolic data­bases like KEGG and more recently KBase, making metabolic design and adequate BEEF strain selection a guessing game rather than an educated ap­proach. Nonetheless, metabolic tools were used to model fuel pro­duction in single cell yeasts and various prokaryotes. In spite of their shortcomings, metabolic data­bases were also employed to model species interactions, for example in a photo-het­erotroph consor­tium using software like ModelSEED / KBase (http://mod­elseed.org/), RAVEN / KEGG and COBRA. A first sys­tematic at­tempt for BEEF cul­tures produci­ng acetate demonstrated the usability of KBase for BES. This research was a bottom-up study which mapped ex­isting genomes onto existing BEEF consor­tia. The same tool can also be em­ployed in a top-down ap­proach, starting with the desired fuel to find the re­quired or­ganisms. Some possi­ble BEEF organisms are the following.

Possible pathways for BEEF production involving Clostridium, 3, or heterotrophic phototrophs, 7, further processing by yeasts

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. Clostridial me­tabolism 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.

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Ammonia energy storage #2

Recently, we reported on plans by Australian entrepreneurs and their government to use ammonia (NH3) to store excess wind energy. We proposed converting ammonia and CO2 from wastewater into methane gas (CH4), because it is more stable and easier to transport. The procedure follows the chemical equation:

8 NH3 + 3 CO2 → 4 N2 + 3 CH4 + 6 H2O

Now we have published a scientific article in the online magazine Frontiers in Energy Research where we show that the process is thermodynamically possible and does indeed occur. Methanogenic microbes in anaerobic digester sludge remove the hydrogen (H2) formed by electrolysis from the reaction equilibrium. As a result, the redox potentials of the oxidative (N2/NH3) and the reductive (CO2/CH4) half-reactions come so close that the process becomes spontaneous. It requires a catalyst in the form of wastewater microbes.

Pourbaix diagram of ammonium oxidation, hydrogen formation and CO2 reduction. At pH 7 and higher, the oxidation of ammonium coupled to methanogenesis becomes thermodynamically possible.

To prove our idea, we first searched for the right microbes that could carry out ammonia oxidation. For our experiments in microbial electrolysis cells we used microorganisms from sediments of the Atlantic Ocean off Namibia as starter cultures. Marine sediments are particularly suitable because they are relatively rich in ammonia, free from oxygen (O2) and contain less organic carbon than other ammonia-rich environments. Excluding oxygen is important because it used by ammonia-oxidizing microbes in a process called nitrification:

2 NH3+ + 3 O2 → 2 NO2 + 2 H+ + 2 H2O

Nitrification would have caused an electrochemical short circuit, as the electrons are transferred from the ammonia directly to the oxygen. This would have bypassed the anode (the positive electron accepting electrode) and stored the energy of the ammonia in the water − where it is useless. This is because, anodic water oxidation consumes much more energy than the oxidation of ammonia. In addition, precious metals are often necessary for water oxidation. Without producing oxygen at the anode, we were able to show that the oxidation of ammonium (the dissolved form of ammonia) is coupled to the production of hydrogen.

Oxidation of ammonium to nitrogen gas is coupled to hydrogen production in microbial electrolysis reactors. The applied potentials are +550 mV to +150 mV

It was important that the electrochemical potential at the anode was more negative than the +820 mV required for water oxidation. For this purpose, we used a potentiostat that kept the electrochemical potential constant between +550 mV and +150 mV. At all these potentials, N2 was produced at the anode and H2 at the cathode. Since the only source of electrons in the anode compartment was ammonium, the electrons for hydrogen production could come only from the ammonium oxidation. In addition, ammonium was also the only nitrogen source for the production of N2. As a result, the processes would be coupled.

In the next step, we wanted to show that this process also has a useful application. Nitrogen compounds are often found in wastewater. These compounds consist predominantly of ammonium. Among them are also drugs and their degradation products. At the same time, 1-2% of the energy produced worldwide is consumed in the Haber-Bosch process. In the Haber-Bosch process N2 is extracted from the air to produce nitrogen fertilizer. Another 3% of our energy is then used to remove the same nitrogen from our wastewater. This senseless waste of energy emits 5% of our greenhouse gases. In contrast, wastewater treatment plants could be net energy generators. In fact, a small part of the energy of wastewater has been recovered as biogas for more than a century. During biogas production, organic material from anaerobic digester sludge is decomposed by microbial communities and converted into methane:

H3C−COO + H+ + H2O → CH4 + HCO3 + H+; ∆G°’ = −31 kJ/mol (CH4)

The reaction produces CO2 and methane at a ratio of 1:1. Unfortunately, the CO2 in the biogas makes it almost worthless. As a result, biogas is often flared off, especially in places where natural gas is cheap. The removal of CO2 would greatly enhance the product and can be achieved using CO2 scrubbers. Even more reduced carbon sources can shift the ratio of CO2 to CH4. Nevertheless, CO2 would remain in biogas. Adding hydrogen to anaerobic digesters solves this problem technically. The process is called biogas upgrading. Hydrogen could be produced by electrolysis:

2 H2O → 2 H2 + O2; ∆G°’ = +237 kJ/mol (H2)

Electrolysis of water, however, is expensive and requires higher energy input. The reason is that the electrolysis of water takes place at a relatively high voltage of 1.23 V. One way to get around this is to replace the water by ammonium:

2 NH4+ → N2 + 2 H+ + 3 H2; ∆G°’ = +40 kJ/mol (H2)

With ammonium, the reaction takes place at only 136 mV, which saves the respective amount of energy. Thus, and with suitable catalysts, ammonium could serve as a reducing agent for hydrogen production. Microorganisms in the wastewater could be such catalysts. Moreover, without oxygen, methanogens become active in the wastewater and consume the produced hydrogen:

4 H2 + HCO3 + H+ → CH4 + 3 H2O; ∆G°’ = –34 kJ/mol (H2)

The methanogenic reaction keeps the hydrogen concentration so low (usually below 10 Pa) that the ammonium oxidation proceeds spontaneously, i.e. with energy gain:

8 NH4+ + 3 HCO3 → 4 N2 + 3 CH4 + 5 H+ + 9 H2O; ∆G°’ = −30 kJ/mol (CH4)

This is exactly the reaction described above. Bioelectrical methanogens grow at cathodes and belong to the genus Methanobacterium. Members of this genus thrive at low H2 concentrations.

The low energy gain is due to the small potential difference of ΔEh = +33 mV of CO2 reduction compared to the ammonium oxidation (see Pourbaix diagram above). The energy captured is barely sufficient for ADP phosphorylationG°’ = +31 kJ/mol). In addition, the nitrogen bond energy is innately high, which requires strong oxidants such as O2 (nitrification) or nitrite (anammox) to break them.

Instead of strong oxidizing agents, an anode may provide the activation energy for the ammonium oxidation, for example when poised at +500 mV. However, such positive redox potentials do not occur naturally in anaerobic environments. Therefore, we tested whether the ammonium oxidation can be coupled to the hydrogenotrophic methanogenesis by offering a positive electrode potential without O2. Indeed, we demonstrated this in our article and have filed a patent application. With our method one could, for example, profitably remove ammonia from industrial wastewater. It is also suitable for energy storage when e.g. Ammonia synthesized using excess wind energy.

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Nanomaterials in bio-electrical systems could improve performance

Since Professor Potter’s discovery of the ability of microbes to turn organic molecules into electricity using microbial fuel cells (MFC) more than a century ago (Potter MC, 1911, Proc Roy Soc Lond Ser B 84:260–276), much research was done to improve the performance. Unfortunately, this did not not produce an economically viable technology. MFCs never made it out of the professors’ class rooms. This may change now that we have advanced nanomaterials available.

The testing of nanomaterials in bio-electrical systems has experienced a Cambrian explosion. The focus usually was on electrodes, membranes, and in the electrolyte with infinite possibilities to find high performing composites. The benefits of such materials include a large surface area, cost savings, and scalability. All are required to successfully commercialize bio-electrical systems. The large-scale commercial application could be wastewater treatment. In our recently published literature survey we discovered that there is no common benchmark for performance, as it is usual in photovoltaics or for batteries. To normalize our findings, we used dollar per peak power capacity as ($/Wp) as it is standard in photovoltaics. The median cost for air cathodes of MFCs is $4,700 /Wp ($2,800 /m²). Platinum on carbon (Pt/C) and carbon nanofibers are the best performing materials with $500 /Wp (Pt/C $2,800 /m²; nanofibers $2,000 /m²).

We found that carbon-based nanomaterials often deliver performance comparable to Pt/C. While MFCs are still far away from being profitable, microbial electrolysis cells already are. With these new carbon-based nanomaterials, MFCs however, are moving closer to become an economic reality. Graphene and carbon nanotubes are promising materials when they are combined with minerals such as manganese or iron oxides. However, the price of graphene is still too expensive to let MFCs become an economic reality in wastewater treatment. The costs of microbial electrolysis, however, are already so low that it is a serious alternative to traditional wastewater treatment as we show in the featured image above. For high strength wastewater, a treatment plant can in fact turn into a power plant with excess power being offered to surrounding neighborhoods. Reducing the costs of microbial electrolysis is accomplished by using a combination of cheap steel and graphite.

Relationship between MEC reactor capacity and total electrode cost including anode and cathode. Errors are standard deviations of four different tubular reactor designs. Anodes are graphite granules and cathodes are steel pipes

 

Graphite, in turn, is the precursor of graphene, a promising material for MFC electrodes. When graphite flakes are reduced to a few graphene layers, some of the most technologically important properties of the material are greatly improved. These include the overall surface and the elasticity. Graphene is therefore a very thin graphite. Many manufacturers of graphene use this to sell a material that is really just cheap graphite. In the journal Advanced Materials Kauling and colleagues published a systematic study of graphene from sixty manufacturers and find that many high-priced graphene products consist mainly of graphite powder. The study found that less than 10% of the material in most products was graphene. None of the tested products contained more than 50% graphene. Many were heavily contaminated, most likely with chemicals used in the production process. This can often lead to a material having catalytic properties which would not have been observed without contamination, as reported by Wang and Pumera.

There are many methods of producing graphene. One of the simplest is the deposition on a metallic surface, as we describe it in our latest publication:

Single-layer graphene (SLG) and multilayer graphene (MLG) are synthesized by chemical vapor deposition (CVD) from a carbon precursor on catalytic metal surfaces. In a surface-mediated CVD process, the carbon precursor, e.g. Isopropyl alcohol (IPA) is decomposed on the metal surface, e.g. Cu or Ni. In order to control the number of graphene layers formed, the solubility of the carbon precursor on the metal catalyst surface must be taken into account. Due to the low solubility of the precursor in Cu, SLG can be formed. It is difficult to grow SLG on the surface of a metal with a high affinity for the precursor.

Protocol:
The protocol is a cheap, safe and simple method for the synthesis of MLG films by CVD in 30-45 minutes in a chemistry lab. A nickel foil is submersed in acetic acid for etching and then transferred to an airtight quartz tube. The same protects the system from ambient oxygen and water vapor. Nitrogen gas is bubbled through the IPA and the resulting IPA saturated gas is passed through the closed system. The exhaust gases are washed in a beaker with a water or a gas wash bottle. The stream is purged for 5 minutes at a rate of about 50 cc/min. As soon as the flame reaches a Meker burner 575-625 °C, it is positioned under the nickel foil, so that sufficient energy for the formation of graphene is available. The flame is extinguished after 5-10 minutes to stop the reaction and to cool the system for 5 minutes. The graphene-coated Ni foil is obtained.

But how thin must graphite flakes be to behave as graphene? A common idea supported by the International Organization for Standardization (ISO) is that flakes with more than ten graphene layers consist essentially of graphite. Thermodynamics say that each atomic layer in a flake with ten or fewer layers at room temperature behaves as a single graphene crystal. In addition, the stiffness of the graphite flakes increases with the layer thickness, which means that thin graphene flakes are orders of magnitude more elastic than thicker graphite flakes.

Unfortunately, to actually use graphene in bioelectric reactors, you still have to make it yourself. The ingredients can be found in our DIY Shop.

 
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A Durable Aluminum-Air-Battery

Non-rechargeable batteries, which depend on a reaction between aluminum and oxygen, can store significantly more energy than conventional lithium-ion batteries. The biggest limitation of such aluminum-air batteries is their short shelf life. An improved battery design could help eliminate this limitation. Aluminum and air batteries are based on the property of aluminum to corrode, which is also their weak spot:

4 Al + 3 O2 + 6H2O → 4 Al (OH)3

While an aluminum-air battery is not used, its electrodes corrode causing unwanted discharge. This self-discharge drastically shortens the shelf life of the battery. Brandon Hopkins, of the Massachusetts Institute of Technology in Cambridge, and his colleagues developed an aluminum-air battery that uses a conventional electrolyte during operation. When stored, however, the electrolyte is replaced by oil. Their article was recently published in the journal Science.

The new battery reaches a storage capacity of almost 900 Wh / kg. This makes the prototype comparable to other aluminum-air batteries. In contrast, the new corrosion protection extends the storage time 10,000-fold. The authors suggest that such a battery could be used in long-range drones and grid-independent power generation. At Frontis Energy, we believe that batteries with high storage capacity and durability can be used almost anywhere, for example for sensors and other applications.

(Photo: George Hodan)

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An inexpensive scalable multi-channel potentiostat

As our preferred reader, you know already that we work on Power-to-Gas to combat Global Warming. We think that giving CO2 a value will incentivize its recycling and recycling it into fuel turns it into a commodity that everyone needs. While the price of CO2 from air is still too high to convert it into combustion fuel, working on the other end (the CO2 conversion) will help to accommodate such high prices. We have now published an research paper that shows how how to reduce the costs of electronic equipment needed for CO2 conversion. For Power-to-Gas as well es for electrosynthesis of liquid fuels, it is necessary to poise an electrochemical potential. So far, only electronic potentiostats could do that. We have developed a software solution that can control cheap off-the-shelf hardware to accomplish the same goal. Since the software controls µA as well as MA, it is freely scalable. By stacking cheap power supplies, it can also run unlimited channels.

Frontcell© potentiostat setup with two channels. From left to right: digital multimeter (in the back), relay board (in front), two H-type electrolysis cells, power supply, control computer.

We tested the software at a typical experimental Power-to-Gas setup at −800 mV and found that the recorded potential was stable over 10 days. The small electrochemical cells could also be replaced by a larger 7 liter reactor treating real wastewater. The potential was stable as well.

The potential of −800 mV controlled by the Frontcell© potentiostat was stable for 200 ml electrolysis cells (left) as well as for a larger 7 l reactor (right).

As instrument control of mass products also makes the chemical processes involved cheap, microbial electrolysis of wastewater becomes economically feasible. Removal of wastewater organics usually occurs at positive electrochemical potentials. Indeed, the software also stabilizes such potentials at +300 mV.

The Frontcell© potentiostat stabilized a 200 ml electrolysis cells at +300 mV for ten days.

The potentiostat is currently available as command line version. We are currently accepting pre-orders at a 50% discount for the commercial version that comes with a graphical user interface and remote control using an internet browser.