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Wind Energy

Wind energy is short for the conversion of energy captured from wind to electrical or mechanical energy. Wind power turbines produce electrical energy and windmills produce mechanical energy. Other forms for wind energy conversion are wind pumps which use wind energy to pump water or sails which drive sail boats.

The cheapest US energy prices by source and county, Source: Energy Institute, University of Texas Austin

Since its first use on sail boats, wind energy is wide spread. Windmills have been used for more than 2,000 years as source of mechanical energy. The Scotsman James Blythe was the first who demonstrated the transformation of wind energy into electrical energy. As wind energy is a renewable source of energy, electrical energy generated by wind turbines is a clean and sustainable form of energy. Wind energy is often also cheaper than natural gas, for example throughout the entire American Midwest, as shown by the Energy Institute of University of Texas, Austin. It is therefore not surprising that wind energy is one of the fastest growing markets in the renewable energy sector worldwide. In 2015, 38% of all renewable energy in the United States and the European Union was generated by wind turbines.

Wind and solar energy production in the US and Canada in 2015. Sources: EIA, Statistics Canada

More efficient than single wind turbines is the use of wind parks where clusters of large turbines constantly generate electrical power. There are two kinds of wind parks, on-shore and off-shore wind parks. Off-shore wind parks are often more expensive but do not use valuable farmland as it is often the case for on-shore wind parks. However, wind parks on farmland can be a valuable addition for farmers seeking an extra income.

Wind and solar energy production in the European Union and the Euro-zone in 2015. WSH is the fraction of renewable energy of the European energy market. “Hydro” is the fraction of hydro power an Wasserkraft. Source, Eurostat
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Fuel Cells

Fuel cells are a special type of galvanic cells. They can be fueled by solid, liquid, or gaseous fuel. The electrochemical oxidation of the fuel is coupled to energy gain, which is captured in form of electricity – as opposed to heat during chemical oxidation. Hence, fuel cells are direct energy converters with high efficiency. Most fuel cells achieve an energy conversion efficiency of 70-90%. If the conversion is 100%, no waste heat is produced. This ideal case of energy conversion is called ‘cold combustion’ which has been demonstrated for the first time in 1955 by Justi & Winsel. The fuel for this process is hydrogen gas, H2. It enters a porous nickel tube (gas diffusion electrode) where it is dissociated into protons and electrons according to:

H2 → 2 H+ + 2 e

Hydrogen fuel (H2) and oxygen (O2) are pumped into a fuel cell where two electrodes and the electrolyte fuse them to water.

During desorption, each H atom releases a proton (H+) and an electron (e). The electron is discharged onto the electrode, called anode, and the proton into the electrolyte. As a result of the dissociation process, the anode becomes negatively charged. On the second electrode, called cathode, oxygen gas, O2, is then charged with the electron and converted into O2− ions. The cathode becomes positively charged. Both electrodes are submerged in electrolytes which is in most cases a potassium hydroxide, KOH, solution of water. In the electrolyte, cations (H+) and anions (O2−) form water by chemical fusion. Theoretically, the efficiency is 92% accompanied by little waste heat – as opposed to normal combustion where heat of ~3,000ºC is produced.

2 H2 + O2 → H2O

Unlike heat power generators, fuel cells achieve high direct energy conversion efficiency because they avoid the additional step of heat generation. Besides shortcutting heat generation, fuel cells operate without mechanical parts and emit no noise, flue gas, or radioactivity, which puts them in focus of future developments. Due to their high energy efficiency and the high energy density of hydrogen, fuel cells are ideal for electric vehicles. In space flight, fuel cells were first used during Apollo Program between 1968 and 1972, in the Skylab Project 1973, the Apollo-Soyus Program, the Space Shuttle Program, and on board the International Space Station. There, they provide the electrical power for tools and water treatment. One benefit is that the final product of cold combustion in fuel cells is that water is the final product which is used by astronauts on their missions.

There are various types of fuel cells but all have in common that they consist of electrodes for fuel and O2 activation, and electrolytic conductors between these electrodes. Recent variations of fuel cells include methane fuel cells and microbial fuel cells. Due to the high activation energy of methane, methane fuel cells usually operate at high temperature using solid electrolytes. Microbial fuel cells, use microbes as anodic catalyst and organic matter in water as fuel. This makes them ideal for wastewater treatment.

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Corrosion

Corrosion is the chemical attack on a material leading eventually to its destruction if not stopped. It is caused by electrolytes, gases, solutions, or smelt. Corrosion occurs in different forms depending on the material under corrosive attack and the attacking agent. On metals, iron, for instance, its most visible manifestation is aerial or localized rust, such as needle holes in the surface. Crystalline corrosion of metals follows grain boundaries on surfaces. Corrosion is highly accelerated if the corroding material is in electrolytical contact with a more noble material. If this electrolytical contact is a liquid or humid substance, then corrosion is further accelerated. The reason is that the corroding material acts as anode (local cell) of a galvanic cell. Mechanical strain can accelerate corrosion as well.

A simple galvanic cell. The metal on the left side acts as anode and is dissolved into metal ions (M+). On the cathode water is transformed to hydrogen gas.

Corrosion protection is accomplished by coating the vulnerable material with corrosion resistant dense films. Such coating can be other metals such as zinc or chrome, as well as glazing, for example enamel. Protective paint is a wide-spread measure and is accomplished by adding pigments such as red (minium) or white lead, or organic substances. Tight plastic wrap is used as well. Iron is protected through transformation into stainless steel by adding chrome, nickel, etc.

The sacrificial anode is not a dissolving metal but soil or sewer organics. Microbes destroy these organics and produce CO2

If the material is exposed to water permanently, cathodic protection is frequently employed. To accomplish cathodic protection, the vulnerable material is connected to sacrificial anodes such as rods or plates that dissolve over time. Alternatively, directed current is used in many applications. Our patent pending solution provides a microbial anode that uses organic matter in soil or sewer as sacrificial anode. Instead of dissolving the metal, organic matter is degraded by microbes.

If a potentiostat is added to the galvanic cell, cathodic protection can be tailored to the protected material or the organics.

Besides metals, natural (wood, silk) and artificial polymers (plastics, rubber) can corrode as well. Softwood is generally more resistant than hardwood. Weak acids usually do no harm to wood. However, corrosion protection of wood is accomplished by painting or soaking it using protective agents. Artificial polymers rarely corrode as quickly as metals and if they do, a protective agent is mixed into the polymer formula at the time of its synthesis.

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Bioenergy

Bioenergy is renewable energy derived from biomass. Biomass is organic material that was produced by living organisms. Each type of biomass was once converted into chemical energy using sunlight and then stored.

Since biomass is stored chemical energy, it can be burned directly. Biofuels can be produced from biomass in solid, liquid or gaseous form. Bio-electricity is both the direct use of biomass and the conversion of biomass into oils, biogas or other fuels for power generation.

Wood that is burned to make fire is another example of biomass. Wood is the world’s most widely used biofuel. Ethanol is also a popular biofuel. It is produced by fermentation of sugars. The process is the same as in alcoholic fermentation for the production of beer or wine. Usually, yeasts carry out fermentation, but other microorganisms, such as clostridia are capable of producing alcohols and other volatile organics as well.

While combustion of biomass produces about the same amount of CO2 as fossil fuels, biofuels are produced in the present day and their combustion does not release additional CO2 into the atmosphere. Biofuels can also be used as fuel additives to reduce carbon emissions from gasoline prices. But there are also vehicles that are powered mainly by biofuels. Bioethanol is widespread in the United States and Brazil, while more biodiesel is produced in the European Union.

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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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Better heat exchangers for concentrated solar power

Solar thermal systems are a good example of the particle-wave dualism expressed in Planck’s constant h: E = hf. Where h is the Planck constant, f is the frequency of the light and E is the resulting energy. Thus, the higher the frequency of the light, the higher the amount of energy. Solar thermal metal collectors transform the energy of high-frequency light by generating them to an abundance of low-frequencies through Compton shifts. Glass or ceramic coatings with high visible and UV transmittance absorb the low frequency light generated by the metal because they effectively absorb infrared light (so-called heat blockers). The efficiency of the solar thermal system improves significantly with increasing size, which is also the biggest advantage of such systems compared to photovoltaic generators. One disadvantage, however, is the downstream transformation of heat into electricity with the help of heat exchangers and turbines − a problem not only in solar thermal systems.

To provide the hot gas (supercritical CO2) to the turbines, heat exchangers are necessary. These heat exchangers transfer the heat energy generated by a power plant to the working fluid in a heat engine (usually a steam turbine) that converts the heat into mechanical energy. Then, the mechanical energy is used to generate electricity. These heat exchangers are operated at ~800 Kelvin and could be more efficient if the temperature were at >1,000 Kelvin. The entire process of converting heat into electricity is called a power cycle and is a critical process in power generation by solar thermal plants. Obviously, heat exchangers are pivotal elements in this process.

Ceramics are a great material material for heat exchanger because they can withstand extreme temperature fluctuations. However, unlike metals, ceramics are not easy to shape. Relatively coarse shapes, in turn, are made quickly and easily. In contrast, metals can be easily formed and have a high mechanical strength. Metals and ceramics have been valued for centuries for their distinctive properties. For example, bronze and iron have good impact resistance and are so malleable that they have been made into complex shapes such as weapons and locks. Ceramics, like those used to make pottery, have been formed into simpler shapes. Their resistance to heat and corrosion made ceramics a valued material. A new composite of metal and ceramic (a so-called cermet) combines these properties in amazing ways. A research group led by Mario Caccia reported now in the prestigious journal Nature about a cermet with properties that makes it usable for heat exchangers in solar thermal systems.

The history of such composites goes back to the middle of the 20th century. The advent of jet engines has created a need for materials with high resistance to heat and oxidation. On top of that, they had to deal with rapid temperature changes. Their excellent mechanical strength, which often surpassed that of existing metals, was highly appreciated by the newly created aerospace industry. Not surprisingly, the US Air Force funded more research into the production of cermets. Cermets have since been developed for multiple applications, but in most cases have been used for small parts or surfaces. The newly released composite withstands extreme temperatures, high pressures and rapid temperature changes. It could increase the efficiency of heat exchangers in solar thermal systems by 20%.

To produce the composite, the authors first produced a precursor, which was subject to further processing, comparable to potting the unfired version of a clay pot. The authors compacted tungsten carbide powder into the approximate shape of the desired article (the heat exchanger) and heated it at 1,400 °C for 2 minutes to bond the parts together. They then further processed this porous preform to produce the desired final shape.

Next, the authors heated the preform in a chemically reducing atmosphere (a mixture of 4% hydrogen in argon) at 1,100 °C. At the same temperature, they immersed the preform in a tank of liquid zirconium and copper (Zr2Cu). Finally, the preform was removed by heating to 1,350 °C. In this process, the zirconium displaces the tungsten from the tungsten carbide, producing zirconium carbide (ZrC) as well as tungsten and copper. The liquid copper is displaced from the ZrC matrix as the material solidifies. The final object consists of ~58% ZrC ceramic and ~36% tungsten metal with small amounts of tungsten carbide and copper. The beauty of the method is that the porous preform is converted into a non-porous ZrC / tungsten composite of the same dimensions. The total volume change is about 1-2%.

The elegant manufacturing process is complemented by the robustness of the final product. At 800 °C, the ZrC / tungsten cermet conducts heat 2 to 3 times better than nickel based iron alloys. Such alloys are currently used in high-temperature heat exchangers. In addition to the improved thermal conductivity, the mechanical strength of the ZrC / tungsten composite is also higher than that of nickel alloys. The mechanical properties are not affected by temperatures of up to 800 ° C, even if the material has previously been subjected to heating, e.g. for cooling cycles between room temperature and 800 °C. In contrast, iron alloys, e.g. stainless steels, and nickel alloys loose at least 80% of their strength.

(Photo: Wikipedia)

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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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White Christmas, going … gone

In Germany, we seem to remember White Christmas from fairy tales only. Now there is also scientific evidence that winter snow cover in Europe is thinning. Thanks to global warming, the snow cover decrease accelerated

The research group behind Dr. Fontrodona Bach of the Royal Netherlands Meteorological Institute in De Bilt analyzed snow cover and climate data from six decades from thousands of weather stations across Europe. The researchers found that the mean snow depth, with the exception of some local extremely cold spots, has been decreasing since 1951 at 12% per decade. The researchers recently published their research results in the journal Geophysical Research Letters. The amount of “extreme” snow cover affecting local infrastructure has declined more slowly.

The observed decline, which accelerated after the 80s, is the result of a combination of rising temperatures and the impact of climate change on precipitation. The decreasing snow cover can reduce the availability of fresh water during the spring melt, the authors noted.

(Photo: Doris Wulf)

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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.

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Ammonia energy storage #1

The ancient, arid landscapes of Australia are not only fertile soil for huge forests and arable land. The sun shines more than in any other country. Strong winds hit the south and west coast. All in all, Australia has a renewable energy capacity of 25 terawatts, one of the highest in the world and about four times higher than the world’s installed power generation capacity. The low population density allows only little energy storage and electricity export is difficult due to the isolated location.

So far, we thought the cheapest way to store large amounts of energy was power-to-gas. But there is another way to produce carbon-free fuel: ammonia. Nitrogen gas and water are enough to make the gas. The conversion of renewable electricity into the high-energy gas, which can also be easily cooled and converted into a liquid fuel, produces a formidable carrier for hydrogen. Either ammonia or hydrogen can be used in fuel cells.

The volumetric energy density of ammonia is almost twice as high than that of liquid hydrogen. At the same time ammonia can be transported and stored easier and faster. Researchers around the world are pursuing the same vision of an “ammonia economy.” In Australia, which has long been exporting coal and natural gas, this is particularly important. This year, Australia’s Renewable Energy Agency is providing 20 million Australian dollars in funding.

Last year, an international consortium announced plans to build a $10 billion combined wind and solar plant. Although most of the 9 terawatts in the project would go through a submarine cable, part of this energy could be used to produce ammonia for long-haul transport. The process could replace the Haber-Bosch process.

Such an ammonia factories are cities of pipes and tanks and are usually situated where natural gas is available. In the Western Australian Pilbara Desert, where ferruginous rocks and the ocean meet, there is such an ammonia city. It is one of the largest and most modern ammonia plants in the world. But at the core, it’s still the same steel reactors that work after the 100 years-old ammonia recipe.

By 1909, nitrogen-fixing bacteria produced most of the ammonia on Earth. In the same year, the German scientist Fritz Haber discovered a reaction that could split the strong chemical bond of the nitrogen, (N2) with the aid of iron catalysts (magnetite) and subsequently bond the atoms with hydrogen to form ammonia. In the large, narrow steel reactors, the reaction produces 250 times the atmospheric pressure. The process was first industrialized by the German chemist Carl Bosch at BASF. It has become more efficient over time. About 60% of the introduced energy is stored in the ammonia bonds. Today, a single plant produces and delivers up to 1 million tons of ammonia per year.

Most of it is used as fertilizer. Plants use nitrogen, which is used to build up proteins and DNA, and ammonia delivers it in a bioavailable form. It is estimated that at least half of the nitrogen in the human body is synthetic ammonia.

Haber-Bosch led to a green revolution, but the process is anything but green. It requires hydrogen gas (H2), which is obtained from pressurized, heated steam from natural gas or coal. Carbon dioxide (CO2) remains behind and accounts for about half of the emissions. The second source material, N2, is recovered from the air. But the pressure needed to fuse hydrogen and nitrogen in the reactors is energy intensive, which in turn means more CO2. The emissions add up: global ammonia production consumes about 2% of energy and produces 1% of our CO2 emissions.

Our microbial electrolysis reactors convert the ammonia directly into methane gas − without the detour via hydrogen. The patent pending process is particularly suitable for removing ammonia from wastewater. Microbes living in wastewater directly oxidize the ammonia dissolved in ammonia and feed the released electrons into an electric circuit. The electricity can be collected directly, but it is more economical to produce methane gas from CO2. Using our technology, part of the CO2 is returned to the carbon cycle and contaminated wastewater is purified:

NH3 + CO2 → N2 + CH4