Zinc-air batteries are a promising alternative to expensive lithium-ion batteries. Compared with lithium-ion technology, zinc-air batteries have a greater energy density, very low production cost, and superior safety. However, their fundamental inability to recharge has lowered their wide-scale adoption.
Zinc-air batteries use charged zinc particles to store large amounts of electricity at a time. When electricity is required, the charged zinc is combined with oxygen from the air (and water), releasing the stored electricity and producing zincate. This process is known as oxygen reduction reaction (ORR).
Theoretically, this zincate can again be broken down into oxygen and zinc ions by passing electricity through it. This process, in turn, is called oxygen evolution reaction (OER). Using these reactions, zinc-air batteries can be made rechargeable, competing with lithium-ion batteries.
The major challenge of the recharging process is the sluggish kinetics of the reactions which lead to poor cycle life. These batteries require a catalyst that could potentially enhance the ORR and the OER reactions, making their kinetics fast. Hence, the development of highly efficient catalysts is of paramount importance for rechargeable zinc-air batteries.
Previous studies have suggested transition-metal oxides as great bifunctional ORR / OER catalysts because of their ability to provide sites for the reversible adsorption of oxygen. But the methods involved in creating well-defined defects for reversible adsorption of oxygen in such oxides are challenging.
To investigate the use of cobalt(II) oxide nanosheets deposited on stainless steel or carbon cloth as a bifunctional catalyst, a group of researchers from different universities of China and Canada collaborated and conducted several experiments. Their research findings were published in the journal Nano Energy .
Preparation of catalyst
Different nano-structures were prepared using simple heat treatment and electrodeposition to test them as bifunctional electrocatalysts. The type of nano-structures prepared were:
Cobalt hydroxide nanosheets on steel and carbon cloth
Layered cobalt (II) oxide nanosheet on steel and carbon cloth
Cobalt (II) oxide on steel
Layered cobalt tetroxide nanosheet on steel
To understand the characteristics of the prepared samples, various analyticaland tests were carried out:
Study of surface chemistry using atomic force microscopy and other equipment. To draw correlations between the oxygen vacancy defects and intrinsic ORR / OER activity linear sweep voltammogram of the samples were investigated in a three-electrode electrochemical cell.
Charging and discharging tests
Later discharge and charge cycling tests of single cells were operated by the battery testing system.
The simple heat treatment strategy created oxygen vacancy sites. According to the authors, layered cobalt-oxide nano-sheets exhibited excellent bifunctional ORR / OER performance. Investigations suggested abundant oxygen vacancies and cobalt sites be the reason for enhanced ORR / OER performance. Later, the developed layered cobalt-oxide nanosheets on steel were used as an electrode in a rechargeable zinc-air flow battery and a record-breaking cycle life of over 1,000 hours with nearly unchanged voltage was observed. Galvanostatic discharging-charging cycles also demonstrated long life and high energy efficiency.
This research carried out provides a new method to design highly efficient bifunctional ORR / OER catalysts that could be used to enhance the cycle life of rechargeable zinc-air flow batteries. At Frontis Energy we are looking forward to industrial applications.
Reference: https://doi.org/10.1016/j.nanoen.2020.105409 Wu et al., Cobalt (II) oxide nanosheets with rich oxygen vacancies as highly efficient bifunctional catalysts for ultra-stable rechargeable Zn-air flow battery, 2021
An abandoned or unproductive oilfield can be reused for methane production from CO2 using renewable electrical power. Exhausted oilfields can be reactors for the conversion of renewable energy to natural gas using microbes. To achieve this, an oilfield can be made electrically conductive and catalytically active to produce natural gas from renewable power sources. The use of natural gas is superior to any battery because of the existing infrastructure, the use in combustion engines, the high energy density and because it can be recycled from CO2. Oilfields are superior to any on-ground production because of the enormous storage capacities. They are already well explored and these geological formations underwent environmental risk assessments. Lastly, the microbial power-to-gas technology is already available.
Whole process (end-to-end via methane)
50% electrical efficiency
Energy density of methane
180 kWh kg−1
Storage capacity per oilfield
3 GWh day−1
Investment (electrodes, for high densities)
Cost per kWh (>5,000 hours anode lifetime)
To address the problem of storing renewable energy, batteries have been proposed as a possible solution. Lithium ion batteries have a maximum energy storage capacity of 0.3 kWh kg−1. To date, this is considered the best trade-off between cost and efficiency but these batteries are still too inefficient to replace gasoline, which has a capacity of about 13 kWh kg−1. This makes battery driven cars heavier than conventional cars. Lithium air batteries are considered a possible alternative because they can reach theoretical capacities of 12 kWh kg−1 but technical difficulties have prevented them from being used for transportation.
In contrast, methane has an energy density of 52 MJ kg−1 corresponding to 180 kWh kg−1 which is second only to hydrogen with 500 kWh kg−1, not counting in nuclear energy. This high energy density of methane and other hydrocarbons along with their facile usage, is the reason why they are used in combustion and jet engines that drive nearly all transportation to date. While electrical cars seem to be a tempting green alternative, the fact that combustion engines and the fueling infrastructure are so wide-spread makes it difficult to switch.
In addition to the difficulty of changing habits, battery-driven electrical cars need other limited natural resources such as lithium. To equip all 94 million automobiles produced worldwide in 2017, 3 mega tons lithium carbonate would need to be mined annually. This is nearly 10% of the entire recoverable lithium resources of 35 mega tons worldwide. Although lithium and other metals can be recycled, it is clear that metal based batteries alone will not build the bridge between green energy and traditional ways of transportation due to the low energy densities of metals. And this does not even take into account other energy demands such as industrial nitrogen fixation, aviation or heating.
For Germany, with its high proportion of renewable energy, fuel for cars is not the only problem. As renewable energy is generated in the north, but many energy consumers are in the south, the grid capacity is frequently reached during peak production hours. A steadier energy output can only be accomplished by decentralizing the production or by energy storage. To decentralize production, homeowners were encouraged to equip their property with solar panels or windmills. As tax incentives phase out, homeowners face the problem of energy storage. The best product for this group of customers so far are again lithium ion batteries but investment costs of $0.10 kWh−1 are still unattractive especially because these products store the energy as electricity which can only be used for a short time and is less efficient than natural gas when used for heating.
Natural gas is widely used as energy source today and the global energy infrastructure is designed for natural gas and other fossil fuels. Increasing demand and limited resources for these fossil fuels were the main drivers of oil and gas prices during the last years, slowed by the recent economic crises and hydraulic fracturing (fracking). The high oil price attracted investors to recover oil using techniques that become increasingly expensive and are environmental risks such as deep-sea drilling or tar sand extraction. Ironically, the high oil price made costly renewable energies an economically feasible alternative and helped driving down their cost. Since habits are difficult to change and building an entirely new infrastructure only for renewable energies does not seem economically feasible today while CO2 drives global warming, a more realistic solution needs to be found.
Microbial Power-to-Gas could be a bridging technology that integrates renewable energy into the existing fossil fuel infrastructure. It reaches break even in less than 2 years if certain preconditions are met. This is accomplished by integrating methane produced from renewable energy into the current oil and gas producing infrastructure. The principal idea is to use carbon instead of metals as energy carrier because of its high energy density when bound to hydrogen. The benefits are:
High energy density of 180 kWh kg−1 methane
Low investments due to existing infrastructure (natural gas, oilfield equipment)
Carbon is not a limited resource
Low CO2 footprint due to CO2 recycling
Methane is a transportation fuel
Methane is the energy carrier for the Haber-Bosch process
Inexpensive catalysts further reduce initial investments
Low temperatures due to bio-catalysis
No toxic compounds used
No additional environmental burden because existing oilfields are reused
Methane can be synthesized by microbes or chemically. Naturally, methane is produced by anaerobic (oxygen-free) microbial biomass decomposition. The energy for biomass synthesis is provided by sunlight or chemical energy like hydrogen. In the case of methanogens (methane producing microbes), energy is harvested after CO2 and hydrogen were released from biomass decomposition following a 1-to-4 stoichiometry:
CO2 + 4 H2 → CH4 + 2 H2O
Without microbes, methane is produced by the Nobel-prize winning Sabatier reaction and several attempts are currently underway to use it on industrial scale. It is necessary to split water into hydrogen and use this to reduce CO2 in the gas phase. A major drawback of the Sabatier reaction is the need for high temperatures around 385ºC, and a nickel catalyst that becomes quickly spent. Methanogens use iron-nickel enzymes called hydrogenases to harvest energy from hydrogen, but do so at ambient temperatures.
The future challenge will be to accelerate methane production rates as has been reported for a high temperature oilfield cultures. Besides increasing the temperature, the most obvious solution is to use a higher reactive surface and bringing both electrodes closer together. Using carbon brushes that are poor hydrogen catalysts but provide a higher surface for microbial attachment is one possibility. Methane production correlates with microbial cell numbers in the reactors.
To overcome the problem of expensive carbon (and also steel) brushes for large scale applications,exhausted gas and oilfields could be used. They provide a high surface area and are usually economic liabilities and not assets. Methanogens inhabit oilfields where they carry out the final step in anaerobic petroleum degradation. Hence, oilfields can be seen as bioreactors at geological scale. Geological formations provide ideal conditions for producing, storing and extracting methane.
But how fast can microbes produce methane in an hypothetical oilfield? Under optimal conditions, methanogens that grow on electrodes (typically the genus Methanobacterium or Methanobrevibacter) can produce methane at a rate of 100-200 nmol ml−1 day−1 (equals 2.24-4.48 ml l−1 day−1) depending on catalyst and potential. Using a production rate of 15 J ml−1 day−1 of methane (190 nmol ml−1 day−1), the entire microbially accessible oilfield (2%) has a capacity of 3.6 million MBtu per year. Microbes would theoretically consume 1 TWh per year for 3.6 million MBtu methane production if there were no losses and electrical power is translated into methane 1-to-1. A power generator of 121 MW would be sufficient to supply the entire oilfield at these rates. However, all German off-shore windfarms produce 7,000 MW meaning that only 3% off-peak power can be captured by our example oilfield. Therefore, the catalytic surface and activity must be increased to accelerate methane conversion rates.
Since methanogens produce methane from hydrogen, not only the 2% porespace big enough for cells can be used resulting in an increased catalytic surface to nearly 60%. A hydrogen catalyst needs to be found that does not out-pace methanogen growth to keep the reservoir pH within the limits of 6-8 required for methanogen growth. This hydrogen catalyst must be cheap and render an oilfield electrically conductive. A chemical formulation that mimics microbial hydrogen catalysis could be used. It has the potential to turn a non-conductive and non-catalytic oilfield into a conductive hydrogen catalyst sufficient to sustain methane production needed to store all of Germany’s electricity produced by off-shore windfarms. This catalyst is soluble in water when inactive. To become active, it coats mineral surfaces by precipitation that can be triggered by indigenous microbes or by electrical polarization. The investment would be $2.3 million per MW storage capacity ($16 billion for the entire 7,000 MW). Due to microbial growth, the catalytic activity of the system improves during operation and there is no need for the second component if an immediate production is not crucial. The investments made on the cathode side would then be as low as $600 per MW ($4.2 million for 7,000 MW).
As the cathodic side of the reaction can be excluded as limiting factor, the anode needs to be designed. Several commercially available anodes such as mixed metal oxides (up to 750 A m−2) with platinum on carbon black or niobium anodes (Pt/C, 5-10 kA m−2) could be used. Anodes based on platinum are the most cost-efficient material available on the market. Investments made for Pt/C (10%, 6 mg cm−2) anodes will amount to $50,000 per MW ($350 million for 7,000 MW). However, the exact amount of Pt needed for the reaction still needs to be evaluated in an experiment because the corrosion rate at 2 V cell voltage is unknown. An often cited value for the lifetime of fuel cells is 5,000 hours and is used here to determine the costs per kWh. For 5,000 hours lifetime, the costs per kWh will be at the targeted limit of $0.01 but may be well below that because Pt/C anodes can be recycled and the Pt load may be reduced to 3 mg cm−2 (5%). Alternatively, steel anodes (SS316, 2.5 kA m−2, $54,000 per MW) can be used but it is unclear when steel anodes fail to electrolyze. In conclusion, the anodic side is the cost-driving factor. Hopefully, better water splitting anodes will lower these costs in future.
Cost estimation summary
Already in place
Natural gas capturing equipment
Already in place
Wastewater from oil rig
Total (>5,000 hours anode lifespan)
Energy and conversion efficiencies
The whole cell voltage for microbial power-to-gas reactions varies from 0.6 to 2.0 V, depending on cathodic rates, anodic corrosion and the presence of a membrane. Higher voltages will accelerate anode corrosion, again, making anodes the limiting factor. As the voltage decreases, methane production rates become slower but also more efficient. The voltage also depends on the pH of the oilfield. An oilfield that underwent CO2 injection as enhanced recovery method will have a low pH, providing better conditions for hydrogen production but not for microbial growth and must be neutralized using seawater. As stated above, the oilfield, being the cathode, is not limiting the the system. The use of Pt/C anodes eliminates the overpotential problem on the anode side. Hence, we can assume an ideal system that splits water at 1.23 V. However, the voltage is often 2 V due to anode and cathode overpotentials. Optimized cultures and cathodes produce about 190 nmol ml−1 day−1 methane which equals 0.15 J ml−1 day−1 using the energy of combustion of 0.8 MJ mol−1. The same electrolysis cell consumes 0.2 mW at a cell voltage of 2 V which equals 0.17 J ml−1 day−1 and the resulting energy efficiency is 91%. The anodes can be simple carbon brushes and the two chambers of the cell are separated by a Nafion™ membrane. The system can still be optimized by using Pt/C anodes and by avoiding membranes.
The overall electricity-methane-electricity efficiency also depends on the consumption side efficiency where methane is used in combustion engines and gas fired power plants. Such power plants frequently operate at efficiencies of 40- 60%. Assuming a reasonable power efficiency of 80% (see above), the overall electrical power recovery using gas fired power plants will be up to 50%. Besides the high efficiency of gas fired power plants, they are also easy to build and therefore contribute the a better power grid efficiency. Coal fired power plants can be upgraded to gas fired power plants.
The conversion efficiencies of charge (Coulombs) transported across the circuit are usually between 70-100% in these systems depending on the electrode material. Another efficiency limitation could arise from mass transport inhibition. Mass transport can be improved by pumping electrolyte adding more costs for pumping which still have to be determined. However, since most oilfields undergo seawater injection for enhanced oil recovery the additional cost may be negligible. The total efficiency has yet to be determined in scale-up experiments and will depend on the factors mentioned above.
Controlling the pH is crucial. Alkaline pHs significantly impede hydrogen production and therefore methanogenesis. This can be addressed by a software that monitors the pH and adjusts the potential accordingly. Addition of acids is not desired as this drives the costs. The software can also act as potentiostat that then fully controls the methane production process. To test the process under more realistic conditions, a drill core from an oilfield must be obtained.
Return of investment of the microbial power-to-gas process
The the microbial power-to-gas process in unproductive oilfields is economically superior to all other storage strategies because of the low start-up and operating costs. This is achieved because the major investments are the installation of oil- and gas production equipment and renewable power plants which are already in place as a precondition. These investments break even in a short amount of time.
But how can the microbial Power-to-Gas process accelerate the return of investment in renewable energy? Only 8 out of 28 active off-shore windfarms reported their investment costs. These 8 produce roughly half the overall power of 1,600 MW corresponding to $7 billion. While the maximum production of an oilfield with unlimited supply of electricity would yield hypothetical 3.6 million MBtu natural gas per year resulting a return of $13 million per year the real production is limited by off-peak power generated by renewable energy production. Assuming that the maximum annual methane production corresponds to 10% excess electrical power, $15 million per year can by generated by selling 4.3 million MBtu methane per year on the market. These are $15 million that are not lost during off-peak shutdowns. Clearly, this conservative estimate can help to compensate the investment in renewable energy earlier. It also decreases the investment risk because the investment calculations for new wind farms can be made on a more reliable basis.
In the example using all German windfarms (7,000 MW) this compensation roughly doubles. Using the $60 million generated by methane sales per year, the investment of $4 million for the cathodic catalyst and the $36 million for the Pt/C anodes are compensated for within less than a year. No other investments are required because the target oilfield already produced oil and gas and all necessary installation are in working condition. The target oilfield is swept using seawater as secondary extraction method. Electrical installations are in place for cathodic protection of production equipment in order to prevent microbial corrosion, which, however, may need to be upgraded to pass the now higher power densities. Moreover, CO2 is used from CO2 injection as tertiary enhanced oil recovery method. Only the pH may then need to be adjusted to sustain life by sweeping with seawater.
And this is not the end of oilfield storage capacity. In theory, an oilfield can store the entire amount of renewable energy produced in one year globally, allowing more than enough head room for future development and CO2 sequestration.
Proximity to both Scandinavia and mainland Europe makes exporting and importing power rather easy for the Danish system operator, Energinet.dk. This provides Denmark with the flexibility needed to achieve significant penetration of intermittent energy sources like wind while maintaining grid stability.
While the results to-date have been promising, getting to 100 percent renewable energy will still require a significant leap and the official policies that Denmark will use to guide this transition have yet to be delivered. However, there has been some indication at what the ultimate policies may look like. In their report Energy Scenarios for 2020, 2035 and 2050, the Danish Energy Agency outlined four different scenarios for becoming fossil-free by 2050 while meeting the 100 percent renewable electricity target of 2035. The scenarios, which are primarily built around deployment of wind energy or biomass, are:
Wind Scenario – wind as the primary energy source, along with solar PV, and combined heat and power. Massive electrification of the heat and transportation sectors.
Biomass Scenario – less wind deployment that in the wind scenario, with combined heat and power providing electricity and district heating. Transportation based on biofuels.
Bio+ Scenario – existing coal and gas generation replaced with bioenergy, 50% of electricity from wind. Heat from biomass and electricity (heat pumps).
Hydrogen Scenario – electricity from wind used to produce hydrogen through electrolysis. Hydrogen used as renewable energy storage medium, as well as transportation fuel. Hydrogen scenario would require massive electrification of heat and transport sectors, while requiring wind deployment at faster rate than the wind scenario.
Agora Energiewende and DTU Management Engineering, have postulated that this scenario report does in fact show that transitioning the Danish energy sector to 100 percent renewables by 2050 is technically feasible under multiple pathways. However, Danish policy makers must decide before 2020 whether the energy system will evolve into a fuel-based biomass system, or electricity-based wind energy system (they must decided which of the four scenarios to pursue).
Energy Storage Facilities – Denmark
Regardless of which energy policy scenario Denmark decides to pursue, energy storage will be a central aspect of a successful energy transition. There are currently three EES facilities operating in Denmark, all of which are electro-chemical (batteries). A fourth EES facility – the HyBalance project – is currently under construction and will convert electricity produced by wind turbines to hydrogen through PEM electrolysis (proton exchange membrane).
The HyBalance project is the pilot plant undertaking of Power2Hydrogen, a working group comprised of major industry players and academic research institutions aimed at demonstrating the large-scale potential for hydrogen from wind energy. The plant will produce up to 500 kg/day of hydrogen, used for transportation and grid balancing.
Worth noting is the decommissioned BioCat Power-to-Gas project, a pilot plant project which operated from 2014 to 2016 in Hvidovre, Denmark. The project, a joint collaboration between Electrochaea and several industry partners (funded by Energienet.dk), was a 1 MWe Power-to-Gas (methane) facility built to demonstrate the commercial capabilities of methane power-to-gas. The BioCat project was part of Electrochaea’s goal of reaching commercialization in late 2016, however, as of early 2017 no further updates have been given.
Energy Storage Market Outlook − Denmark
The energy storage market in Denmark will be most primed for growth should policy follow the Hydrogen Scenario, where massive amounts of hydrogen production will be needed to eliminate the use of fossil fuels across all sectors.
Renewable energy produced gases (hydrogen, methane) have the potential to balance the electricity grid in two primary ways: balancing supply and demand (“smart grid”), and balancing through physical storage. The smart grid, an intelligent electricity grid where production and consumption are administered centrally, presents significant opportunity for electrolysis technologies as short-term “buffer” storage (seconds to minutes). Bulk physical storage of renewable energy produced gases can act as a longer-term storage solution (hours, days, weeks, months) to help maintain flexibility in a fossil-free energy grid (The Danish Partnership for Hydrogen and Fuel Cells).
Without the hydrogen scenario, the potential for hydrogen-based energy storage in Denmark will be limited. In their 2016 report “potential of hydrogen in energy systems”, the Power2Hydrogen working group concluded that:
hydrogen electrolysers would not provide any significant upgrade on flexibility for renewables integration over today’s sufficiently flexible system, and;
by 2035, with the increased wind production, it was concluded that hydrogen electrolysers would in fact improve system flexibility, allowing for even more extensive penetration of wind energy in the system.
The potential for renewable energy produced gases in Demark is extremely high. There is a very distinct possibility that power-to-gas type of systems will be the linchpin of Denmark’s energy transition. While there appears to be little opportunity in the short-term, there will be extensive opportunity in the medium-to-long-term should the official energy transition policy focus on the hydrogen scenario, or a similar renewable gas based policy.
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.