Patent Application
20240150918
The present invention relates to a method for electrochemical ammonia synthesis, and an apparatus for said electrochemical ammonia synthesis.
Ammonia is one of the most important necessities for modern society, and is currently the second most produced industrial chemical. It is primarily used as a fertilizer, enabling the explosive growth of the global population during the past century, as well as a reactant in the chemical industry. Recently, ammonia is also being considered as an energy carrier for renewable energy sources. The main advantage as an energy carrier lies in its ease of transportation, as ammonia can be liquefied and stored at comparatively milder conditions than hydrogen.
The production of ammonia currently relies on the Haber-Bosch process, which requires high temperatures of 400-500° C., high pressures above 100-150 bar, and a hydrogen source. Consequently, the Haber-Bosch process is highly energy demanding, resulting in ca. 1% of the global energy consumption, and since the hydrogen is typically supplied from steam-reformed natural gas, the process gives rise to significant CO2 emissions. Additionally, the high-pressure reaction conditions require large centralized facilities, with a high cost of installation and cost for transportation to the point of use of the produced ammonia.
Alternatively, ammonia may be produced electrochemically by reduction of nitrogen (N2) to ammonia (NH3), as shown by equation 1, where the energy can be provided from renewable sources like wind or solar power:
N2+6 H++6 e−→2 NH3 (Eq. 1)
The electrochemical ammonia synthesis may be carried out under mild conditions, i.e. below 100° C. and at near atmospheric pressure. However, the process selectivity towards ammonia, and hence the faradaic efficiency of the process, will depend on the process parameters, including temperature, pressure, current supply and potential, and the types of reactants.
The electrochemical ammonia synthesis may be lithium mediated, as observed experimentally and illustrated in
The reaction line for converting Li ions (Li+) to metallic lithium (Li0), further to lithium nitride Li3N as intermediate compound, and further into ammonia (NH3) is also illustrated in the middle part of
Simultaneously with the ammonia synthesis at the cathode, hydrogen evolution occurs at the cathode by reaction of metallic lithium (Li0) and the proton source (HA), as illustrated by equation 2 below.
Li0+2 HA→Li++2 A−+H2 (Eq. 2)
The hydrogen reaction competes with the ammonia synthesis, and thus affects the ammonia selectivity and faradaic efficiency. Initial faradaic efficiencies of 18.5% (at ambient pressure, and a current density of 8 mA/cm2) and 30% (at 10 bar, and a current density of 2 mA/cm2) may be obtained via the lithium mediated nitrogen reduction to ammonia.
However, the energy efficiencies are known to decrease rapidly within a few hours, due to degradation mechanisms at the cathode. The main degradation mechanism is speculated to be related to the intermediate lithium compounds, such as lithium nitride, which remains deposited, and decreases the efficiency. WO 2012/129472 [1] discloses that the cathode may be cleaned by washing with steam/water and subsequent drying, whereby the deposited lithium nitride may be removed and the cathode reused.
The process may be simplify by using air instead of pure nitrogen as the source of nitrogen. However, the efficiency of the ammonia synthesis is known to decrease in the presence of oxygen, because the oxygen reduction reaction competes with the ammonia synthesis, as described by Tsuneto et al. [5]. US 2006/0049063 [6] discloses electrochemical ammonia synthesis based on purified hydrogen and nitrogen.
The present disclosure provides an electrochemical ammonia synthesis method with improved efficiency and stability. This is surprisingly obtained when the electrochemical ammonia synthesis is carried out in the presence of oxygen, meaning that oxygen must be present in a defined amount. Specifically this is obtained when the oxygen is present in a predefined or specified concentration supplied by a source of oxygen, thereby providing a predefined oxygen concentration. For example, particularly high efficiencies may be obtained with a source of oxygen providing a predefined oxygen concentration below 20 mol %, such as between 0.1-10 mol %, more preferably between 0.2-2 mol %, corresponding to an oxygen partial pressure of between 0.02-2.5 bar. Additionally, this is surprisingly obtained when the electrochemical ammonia synthesis is carried out in the presence of oxygen, and particular in the presence of an oxygen concentration below 2 vol % corresponding to 2 mol %, in addition to the reactants nitrogen and protons, and any mediating cations. The method is seen to provide a peak in the faradaic efficiency, with efficiencies above 30%, such as up to 40%, 60%, and 80%.
An aspect of the disclosure relates to a method for electrochemical ammonia synthesis, comprising the steps of:
Particularly improved efficiency and stability may be obtained when the cathode is contacted with a source of mediating cations, in addition to oxygen and the reactants nitrogen and protons. For example, the electrolysis cells may comprise the source of cations, e.g. as part of the electrolyte, which may be a solvent electrolyte into which the cations are dissolved. Particularly high efficiencies have been seen for ammonia synthesis mediated by lithium cations, and electrolysis cells including lithium cations. The sources of protons may also be comprised within the electrolysis cell, e.g. the electrolyte, or be supplied externally to the electrolysis cells, The sources of nitrogen and/or oxygen are preferably supplied to the electrolysis cells, and more preferably the source is a combined nitrogen and oxygen source.
A further aspect of the disclosure relates to an apparatus for electrochemical ammonia synthesis configured for the method according to the first aspect. This may be obtained by an apparatus comprising the one or more electrolysis cells, and means to regulate the power source input and the nitrogen and/or oxygen input to the electrolysis cells.
Another aspect of the disclosure relates to an apparatus for electrochemical ammonia synthesis, comprising:
It follows that the apparatus may be adapted for different types of electrolysis cells, and preferably the apparatus is adapted for electrolysis cells, which comprise a source of cations. Preferably, the cations are one or more metal cations, where the metal is selected from groups 1-13 of the periodic table and combinations thereof, more preferably the metal is selected from the group consisting of: alkali metals, alkaline earth metals, and/or transition metals, more preferably the metal is selected from groups 1, 2, 3 of the periodic table and combinations thereof, and most preferably the metal is selected from the group consisting of: lithium (Li), sodium (Na), potassium (K), magnesium (Mg), calcium (Ca), barium (Ba), yttrium (Y), and combinations thereof.
The presently disclosed electrochemical ammonia synthesis method and apparatus may provide further improved efficiency and stability, by use of a pulsed cathode potential, including a pulsed cathodic current load. The pulsed cathode potential may be obtained by cycling the potential of the cathode between a cation reduction potential, such as the lithium reduction potential, and a less negative potential, e.g. the potential corresponding to the cell open circuit voltage.
The pulsed cathode potential, and the associated pulsed cathodic current load, implies that at periods of high negative cathode potential, e.g. at the lithium reduction potential, and periods of high cathodic current load, the cations/Li ions are reduced and reoxidised at the cathode, simultaneously with conversion of nitrogen and protons into ammonia. The pulsed operation further implies that at periods of lower negative cathode potential, e.g. where the cell voltage is OCP, and periods of no/low cathodic current load, the cathode is regenerated, and/or the cathode potential is regenerated.
The invention will in the following be described in greater detail with reference to the accompanying drawings.
The invention is described below with the help of the accompanying figures. It would be appreciated by the people skilled in the art that the same feature or component of the device are referred with the same reference numeral in different figures. A list of the reference numbers can be found at the end of the detailed description section.
Ammonia may be produced electrochemically by reduction of nitrogen (N2) to ammonia (NH3). In addition to nitrogen as reactant, protons and electrons are required as indicated by equation (1). The electrochemical reaction may further be mediated by the presence of additional substances. For example, the selectivity of the electrochemical production of ammonia may be promoted by the presence of cations, e.g. lithium cations, as well as specific solvents and solvent additives, into which the cations may be dissolved.
The reactants and substances taking part in the electrochemical ammonia synthesis are either continuously supplied from externally to the reaction site in the cell, or present and stored within the cell. For example, an ammonia electrolysis cell may be operated by external sources supplying power, nitrogen, oxygen, cations, and protons, e.g. supplied as hydrogen. The substances which are not directly consumed reactants, e.g. the cations, may be supplied or stored within the cell, e.g. in the form of an electrolyte comprising a solvent with dissolved cations and additives.
In an embodiment of the disclosure, the electrolysis cell is connectable to at least one power source, at least one nitrogen source, and at least one oxygen source.
Preferably, the cell is further fluidly connectable to at least one proton source, and/or cation source. For example, the electrolysis cell have an electrolyte comprising a proton source and/or cation source.
Hence, electrochemical ammonia synthesis is carried out in an electrolysis cell, i.e. a device where an external voltage and/or current load, may be applied to drive the synthesis reaction. For example, when Li ions in a solution are subjected to a potential of −3 V vs. reversible hydrogen electrode (RHE), the so-called lithium reduction potential, including a current supply at the cathode, the Li ions are reduced to Li metal on the surface of the cathode by electrolysis.
The electrical potential is applied across the electrodes of the electrolysis cell, i.e. the anode and cathode, where the electrodes are separated by the electrolyte comprising the solution of Li ions. However, to precisely control the potential of the cathode, the cathode potential is measured by use of a reference electrode (RE). Hence, the reference electrode only controls, or more specifically only measures, the cathode potential and passes no current.
At the cathode, reduction can take place, and electrons are consumed to e.g. reduce Li ions to Li metal. Thus, the cathode is also referred to as the working electrode (WE), and the consumed electrons referred to as the cathodic current load. At the anode, oxidation takes place, and the corresponding amount of electrons are released e.g. by oxidation of hydrogen. Thus, the anode is also referred to as the counter electrode (CE), and the produced electrons or current may be referred to as an anode current load.
According to the present disclosure, the cathode potential is advantageously varied. For example, it may be changed between the lithium reduction potential, i.e. −3 V, and a less negative cathode potential, such as the cell voltage corresponding to the open circuit voltage. The open circuit voltage (OCV), also referred to as the open circuit potential (OCP), is the potential when no external load is connected to the cell, corresponding to the cathode potential, where the cathode current load is zero. Hence, at the lithium reduction potential the cathode potential is negative, and includes a cathodic current load, and at the less negative cathode potential, e.g. cell OCP, no cathodic current load is present.
A change in the cathode potential from e.g. the lithium reduction potential and to cell OCP may be referred to as one cycle. Advantageously, the cathode potential, and the associated cathodic current load, is operated cyclic, i.e. the cycle is repeated multiple times, and preferably repeated in a periodic manner without interruption of the operation cell. This operation may also be referred to as a continuously pulsed operation, comprising pulses of a first cathode potential, including a first cathodic current load, and pulses of a second cathode potential, including a second cathodic current load.
The electrolysis selectivity towards ammonia, and hence the faradaic efficiency of the process, will depend on the process parameters, including the voltage/current supply pattern, as well as the operational temperature, pressure, and the types of reactants. The energy efficiency will further depend on the electrolysis configuration and cell type, e.g. whether it is a single compartment cell or a flow cell.
In the present disclosure, the electrochemical ammonia synthesis is exemplified as being mediated by lithium ions. However, the skilled person will know that the synthesis may be similarly mediated by other cations, and/or additional cations, and their corresponding metal, having similar properties to lithium. Metals in the vicinity of lithium in the periodic table of elements may have similar solubility, reactivity, and/or reduction potentials as lithium. Thus, advantageously, the synthesis may be mediated by one or more metal cations selected from the groups 1-13 of the periodic table of elements. This means that the synthesis is mediated by one or more metals and their corresponding cations. Advantageously, the synthesis is mediated by one or more metal cations selected from the groups consisting of: alkali metals, alkaline earth metals, and/or transition metals. Advantageously, the synthesis is mediated by cations which are reduced to metal at a similar cation reduction potential as lithium, and/or which have similar reactivity towards nitridation and protonation, such as sodium (Na), potassium (K), magnesium (Mg), calcium (Ca), barium (Ba), yttrium (Y), and combinations thereof.
It also follows that the associated apparatus for the electrochemical ammonia synthesis may be adapted for different types of electrolysis cells, and preferably the apparatus is adapted for electrolysis cells, which comprise a source of cations. Preferably, the apparatus comprises electrolysis cells comprising a source of cations, e.g. an electrolyte comprising dissolved cations, which preferably are lithium cations.
In an embodiment of the disclosure, the cations are one or more metal cations, where the metal is selected from groups 1-13 of the periodic table and combinations thereof, more preferably the metal is selected from the group consisting of: alkali metals, alkaline earth metals, and/or transition metals, more preferably the metal is selected from groups 1, 2, 3 of the periodic table and combinations thereof, and most preferably the metal is selected from the group consisting of: lithium (Li), sodium (Na), potassium (K), magnesium (Mg), calcium (Ca), barium (Ba), yttrium (Y), and combinations thereof.
The Faradaic efficiency (FE) of an electrochemical ammonia synthesis is calculated based on the concentration, CNH3, of synthesized ammonia in the electrolyte, which is measured via either a colorimetric or isotope sensitive method, along with the total electrolyte volume, V, after each measurement. This is compared with the total charged passed, Q, as shown in Equation 3, where F is Faraday's constant, and 3 is the number of electrons transferred during the reaction for each mole of NH3.
The energy efficiency, η, of an electrochemical ammonia synthesis is based on the total amount of energy put into the system via the potentiostat, Ein, and compared that to the energy contained in the total amount of ammonia produced during the experiment, Eout, as shown in Equation 4.
Eout is defined by the free energy of reaction of ammonia oxidation to N2 and water times the amount of ammonia produced, while Ein is given by the total cell voltage between the counter electrode (CE) and working electrode (WE), multiplied by the current to get the instantaneous power, and integrated over time, as shown in Equations 5 and 6.
E
out
=ΔG
R
·n
NH3 (Eq. 5)
E
in=∫(VCE(t)−VWE(t))·I(t)dt (Eq. 6)
In an embodiment of the disclosure, electrochemical ammonia synthesis experiments were carried out as described in Examples 1-2. Using the method described in Example 1, a comparative experiment was performed where a steady cathodic current load of −2 mA/cm2 was applied, as described in Example 3. The steady cathodic current load implies continuous Li ion reduction and continuous Li metal deposition at the cathode, and the operation condition of the cell is therefore also denoted as the deposition potential.
The resulting electrode potentials as a function of time for lithium mediated ammonia synthesis under the constant cathodic current load of −2 mA/cm2 are shown in
The cathode degradation mechanism is speculated to be related to the lithium salt reduction, where not all of the metallic lithium undergoes further reactions, e.g. nitridation, as illustrated by the possible reaction mechanism (not balanced) in
The deposits therefore decrease the overall efficiency of the system, as well as decrease the ionic conductivity of the solution as the lithium ions are depleted from solution, thereby increasing the overall resistance in the cell. The continuous deposition of lithium limits the up-scalability of the process, as a continued supply of lithium salt would be required to sustain synthesizing ammonia. This also leads to an accumulation of lithium species on the electrode surface, which slowly increases the needed potential to run the reaction.
The degradation mechanism is further supported by visual inspection of the cathodes. The electrode surface of the constant deposition experiment of Example 3 had big deposits of lithium species on the surface, as shown in
In an embodiment of the disclosure, electrochemical ammonia synthesis experiments were carried out as described in Examples 1-2, using cyclic or pulsed cathode potential and current load. Using the method described in Example 1, the cathode current load was pulsed between −2 mA/cm2 and 0 A, corresponding to cathode potential pulses between the lithium reduction potential and OCV. The experiments are further described in Example 4. The pulsed operation implies alternating periods of Li deposition and no deposition.
The resulting electrode potentials as a function of time for lithium mediated ammonia synthesis under the pulsed cathodic current load are shown in
The regeneration of the degraded cathode during the periods of cell OCV, is speculated to be due removal of the build-up lithium species on the surface of the electrode. The resting time between the deposition pulses may allow the lithium to react fully with nitrogen in solution significantly prevented the WE potential from drifting cathodic over time. Hence, the cycling procedure stabilizes the WE potential because it “resets” the surface by removing the deposited material, and replenishes the lithium in the solution, and produces ammonia. This is further supported by visual inspection of the cathodes. The electrode surface of the pulsed experiment of Example 4 shown in
The Faradaic efficiency also increases with the continuous cycling method, as charge is not wasted on forming unreactive lithium deposits. Furthermore, the overall energy efficiency is improved, due to the decrease in needed potential to sustain the same current, i.e. the average WE potential is lower. Moreover, by cycling the potential from a very negative lithium reducing potential, to a less negative potential at which lithium is not reduced, while potentially still synthesizing ammonia, the Faradaic and energy efficiency is further increased, since ammonia may be formed at potentials less negative than −3 V vs RHE.
The improvement in Faradaic efficiency and energy efficiency, as well as the efficiency of the cathode regeneration, will depend on the cyclic or pulsed operation patterns. Further, for operational simplicity, the pulsed operation is regular and periodical, i.e. similar pulse sizes and durations are applied. Advantageously, the cathode potential, including the cathodic current load, is changed between two configurations, such that the cathode potential is pulsed between a first cathode potential, including a first cathodic current load, and a second cathode potential, including a second cathodic current load. Further advantageously, the cathode potential may be pulsed between the lithium reduction potential, and a less negative cathode potential, such as the potential corresponding to the cell OCV.
In an embodiment of the disclosure, the cathode potential is pulsed between a first cathode potential, including a first cathodic current load, and a second cathode potential, including a second cathodic current load. In a further embodiment, the cathode potential is pulsed between the cation reduction potential and a less negative cathode potential. In a further embodiment, the cathode potential is pulsed between the lithium reduction potential and a less negative cathode potential. In a further embodiment, the cathode potential is pulsed between the lithium reduction potential and the cell OCP.
It was surprisingly found that by increasing/decreasing the current load of the pulses and the duration of the pulses, the Faradaic efficiency, energy efficiency, and cathode regeneration, may be further improved. For example, advantageously, the duration of the pulses at the second cathode current load may be longer than the duration of the pulses at the first cathode current load. However, for electrochemical ammonia synthesis including oxygen as described below, the duration of the pulses at the second cathode current load may advantageous be the same or shorter than the duration of the pulses at the first current load. For example, the duration of both the first and second pulses may be 1 min.
In an embodiment of the disclosure, the duration of the pulses at the first cathode potential is between 0.5-60 min, more preferably between 0.7-30 min, and most preferably between 0.8-10 min, such as 1 or 2 min. In a further embodiment, the duration of the pulses at the second cathode potential is between 1-120 min, such as 1 or 2 min, more preferably between 2-60 min, and most preferably between 3-30 min, such as 3-5 or 10 min.
In an embodiment of the disclosure, the pulses of at the first cathodic current load has a duration of between 0.5-60 min, more preferably between 0.7-30 min, and most preferably between 0.8-10 min, such as 1 or 2 min. In a further embodiment, the pulses at the second cathodic current load has a duration of between 1-120 min or 5-120 min, such as 1 or 2 min, more preferably between 2-60 min or 6-60 min, and most preferably between 3-30 min or 7-30 min, such as 8 or 10 min.
It was further found that by increasing/decreasing the current load of the pulses, as well as the relative current load between the pulses, the Faradaic efficiency, energy efficiency, and cathode regeneration, may be further improved. For example, advantageously, the first cathodic current load is below −1 mA/cm2, preferably around −100 mA/cm2, and the second cathodic current load is −0.5 mA/cm2, preferably 0 mA/cm2 or even positive, where the current load is based on the geometrical area of the electrode, referred to in the units by cmgeo2. When the second cathodic current is negative or zero, the pulsed operation may be referred to as pulsating DC. When the second cathodic current is positive, the pulsed operation may be referred to as pulsating AC. Advantageously, high current load pulses are obtainable for cathodes comprising high surface area electrodes, as described in Example 11.
In an embodiment of the disclosure, the pulsed cathodic current load is pulsating DC and/or pulsating AC. In a further embodiment, the pulses at the first cathodic current load has a current density below −1 mA/cm9geo2, such as −2, 5, or −10 mA/cmgeo2, more preferably above −50 mA/cmgeo2, such as −60, −70, −80, −90, −100, −200, −400, −600, −800, or −1000 mA/cmgeo2. In a further embodiment, the pulses at the second cathodic current load has a current density above −0.5 mA/cmgeo2, such as 0 mA/cmgeo2 or 0.1 MA/CMgeo2.
The faradaic efficiency of the process and the energy efficiency, will depend on other process parameters than the voltage/current pattern. For example, it was found that surprisingly high efficiencies may be obtained at mild temperature and pressure conditions, such as temperatures between 10-150° C., and/or a pressure equal to or below 20 bar.
In an embodiment of the disclosure, the temperature is between 10-150° C., more preferably between 20-130° C., and most preferably between 25-120° C., such as 50 or 100° C. In a further embodiment, the pressure is equal to or below 20 bar, such as 15, 10, 5, 1 bar or ambient pressure.
The faradaic efficiency of the process and the energy efficiency, will also depend on the reactant type and concentrations, as well as their accessibility and costs. For example, certain reactants were found advantageous as sources of Li ions, nitrogen, and protons. Furthermore, to ensure sufficient concentration of the reactants, the reactants may be supplied via a filter, e.g. protons may be supplied to the cathode via a proton exchange membrane.
Since the cations are not consumed and regenerated during the ammonia synthesis, the source of cations is advantageously comprised within the electrolysis cell, e.g. as part of a liquid electrolyte. Hence, the cation source is stored within the cell from which it may be supplied to the reaction sites. The liquid may be a molten salt or a solution comprising the cations, such as lithium cations. To improve the mediation and reaction kinetics and selectivity for the ammonia synthesis, a cation concentration which is sufficient for facilitating the mediation, and which at the same time do not impede the availability of other reactants at the reaction sites, is further advantageous. For example, for a solvent electrolyte, the lithium concentration is preferably between 0.1-3 M.
In an embodiment of the disclosure, the source of Li ions is selected from the group consisting of: molten Li salt, Li solutions, and combinations thereof, such as LiCIO4, LiPF6, LiBF4, LiAsF6, Lithium tri(pentaflouroethyl)trifluorophosphate, lithium trifluoromethanesulfonate, lithium bis(fluorosulfonyl)imide, lithium cyclo-difluoromethane-1,1-bis(sulfonyl)imide, lithium cyclo-hexafluoropropane-1,1-bis(sulfonyl)imide, lithium bis(trifluoromethanesulfonyl)imide), lithium bis(perfluoroethanesulfonyl)imide, lithium bis(oxalate)borate, lithium difluoro(oxalate)borate, lithium bis(fluoromalnato)borate solutions. In a further embodiment, the solutions has a Li concentration below 3 M or 1 M, such as 0.1, 0.2, 0.5, or 2 M.
The source of nitrogen is advantageously continuously supplied from externally to the cell, such that the consumed nitrogen is continuously replaced and the synthesis may be carried out continuously. Nitrogen is easily accessible as air, which comprises ca. 78 vol % N2, or correspondingly a mole fraction of 78%. However, the Faradaic efficiency will depend on the nitrogen concentration, as illustrated in
In an embodiment of the disclosure, the source of nitrogen is selected from the group consisting of: gaseous N2, liquidly dissolved N2, and combinations thereof.
The source of protons may also be continuously supplied from externally to the cell, such that the consumed protons are continuously replaced and the synthesis may be carried out continuously. For example, gaseous hydrogen may be supplied to an anode of the electrolysis cell, where the hydrogen is oxidized to protons that are dissolved in the liquid electrolyte. Alternatively, the source of protons may be supplied or stored within the cell, e.g. as part of an electrolyte which acts as a proton source or comprises dissolved protons. To further improve the reaction kinetics and selectivity for the ammonia synthesis, a sufficient proton concentration is desired. This may for example be obtained by the dissolved protons being transferred to the reaction sites at the cathode via a proton exchange membrane.
In an embodiment of the disclosure, the source of protons is selected from the group consisting of: gaseous H2, liquidly dissolved H2, ethanol (EtOH), water (H2O), alkyl alcohols, especially tent-butanol, perfluorinated alcohols, polyethyleneglycols, ethanethiol, alkyl thiols, alkyl ketones, alkyl esters, and combinations thereof. In a further embodiment, the concentration of the protons within the proton source is between 0.01-100 vol %, more preferably between 0.01-5 vol %, and most preferably between 0.05-3 or 0.1-2 vol %. In a further embodiment, the source of protons is combined with a proton exchange membrane.
The reaction kinetics and the selectivity of the ammonia synthesis at the cathode, also depends on the simultaneous electrochemical reactions occurring, e.g. the competing hydrogen evolution which may occur at the cathode, as described in equation (2). To improve the ammonia selectivity, the method or the electrolysis cell advantageously comprises a liquid electrolyte comprising an essentially aprotic solvent, such as tetrahydrofuran (THF) or propylene carbonate or any organic carbonates, which can be diethyl carbonate, ethyl methyl carbonate, ethylene carbonate and variations of these.
In an embodiment of the disclosure, the method or electrolysis cell comprises an essentially aprotic solvent, selected from the group of: tetrahydrofuran (THF), oxane, diethyl ether, dipropyl ether, diglyme, dimethoxyethane, triglyme, tetraglyme, polyethyleneglycol alkyl ethers, dioxane, organic carbonates, e.g. dimethyl carbonate, ethylene carbonate, diethyl carbonate, ethyl methyl carbonate, propylene carbonate, dialkyl carbonates, butyrolactone, cyclopentanone, cyclohexanone, sulfolane, ethylene sulfate (DTD), trimethylglycerol, and mixtures thereof, and preferably is selected from the group of: tetrahydrofuran, organic carbonates, propylene carbonate, and mixtures thereof.
By the term essentially aprotic is meant that the electrolyte may comprise a mixture of the aprotic solvent and the proton source, whereby the electrolyte solvent is essentially or near aprotic. For example, the electrolyte may comprise a mixture of THF with 1 vol % ethanol as proton source.
In an embodiment of the disclosure, the aprotic solvent is selected from the group consisting of: tetrahydrofuran (THF), ethanol (EtOH), and combinations thereof, such as THF-1 vol % EtOH or THF with 1 vol % EtOH.
In addition to specific solvents, the selectivity and stability of the electrochemical production of ammonia may be further promoted by the presence of solvent additives. For example, additives which may prevent solvent degradation under the operational potential and current loads, are preferably included. Such additives are preferably included in a suitable concentration, which is typically below 5 vol % of the solvent.
In an embodiment of the disclosure, the essentially aprotic solvent comprises one or more additives selected from the group of: perfluorinated hydrocarbons, perfluorinated ethers, highly fluorinated organic tetrkisalkyl phosphonium perfluorinated phosphates, tetrakisalkyl phosphonium perfluoroalkyl sulfonates, tetrakisalkyl phosphonium perfluoroalkyl carboxylates, crown ethers, and mixtures thereof, wherein preferably the concentration of the additives is between 0-100 vol %, more preferably between 0.01-5 vol %, and most preferably is between 0.05-3 or 0.1-2 vol %.
As described above, the selectivity and stability of the electrochemical ammonia synthesis may be mediated and/or promoted by the presence of specific cations, solvents, and solvent additives. It was further surprisingly seen that the selectivity and stability of the electrochemical ammonia synthesis may be mediated by the presence of low concentrations of oxygen at the cathode. Hence, the electrochemical ammonia synthesis is advantageously carried out in the presence of oxygen, meaning that oxygen must be present in a defined amount. Specifically this is obtained when the oxygen is present in a predefined or specified concentration supplied by a source of oxygen, thereby providing a predefined oxygen concentration. Particularly high efficiencies, selectivity, and/or stability may be obtained with a source of oxygen providing a predefined oxygen concentration below 20 vol % or correspondingly a mole fraction below 20%. For example, the oxygen concentration is advantageously below 20 mol %, such as between 0.1-10 mol %, more preferably between 0.2-5 mol%. The partial pressure of a gas, e.g. oxygen (pO2), is generally directly proportional to the gas mole fraction, e.g. the oxygen mole fraction, and the temperature. Hence, a specific oxygen mole fraction range of ca. 1.4% may correspond to an oxygen partial pressure of ca. 0.14 bar at 10 bar, as illustrated in
Thus, the preferred partial pressure of oxygen is directly related to the amount of oxygen present irrespective of the pressure. Specifically it was seen that oxygen concentrations below 2 vol %, more preferably oxygen concentrations below 1 vol %, such as between 0.2-0.8 vol %, resulted in surprisingly high Faradaic efficiencies for the ammonia synthesis. It follows from the above that though oxygen may be present as an impurity or trace component in various systems and gasses, then such impurity or trace amounts cannot be present in a defined amount which is sufficient to obtain the improved performance and efficiency. For example, oxygen impurities may be highly variable during the operation of a system, and e.g. be absent at some points, and typically amount to very small amounts such as less than 10 ppm.
The surprising effect of small amount of oxygen particularly improves the cost-efficiency of the method and related apparatus and systems. Since highly pure nitrogen gas (>99.999%), where the O2 is removed from air down to ppm levels via cryogenic separation in large facilities, is not needed. Thus, the method is particularly suitable for decentralized systems. The positive effect of the O2 content on the Faradaic efficiency is surprising, because previously established experiments using synthetic air was shown to be detrimental to the system, and significantly reducing the FE to <4% [5], In an embodiment of the disclosure, the cathode is contacted with a source of oxygen, wherein the oxygen concentration is below 2%, while subjecting the cell to a potential and current load, whereby ammonia is synthesized.
In an embodiment of the disclosure, the cathode is contacted with a source of oxygen providing a predefined oxygen concentration. In a further embodiment of the disclosure, the oxygen concentration is below 20%, such as between 0.1 -10%, such as 0.2-5%, 0.2-2% or 0.2-1.5%, more preferably between 0.3-1%, and most preferably between 0.4-0.8%. In an alternative or further embodiment, the source of oxygen comprises an oxygen partial pressure of between 0.02-2.5 bar, such as 0.01-0.5 bar or 0.02-0.4 bar, more preferably between 0.02-0.3 bar or between 0.05-0.4 bar, and most preferably between 0.05-0.2 bar or between 0.06-0.3 bar, such as 0.07, 0.1, 0.15, or 0.2 bar.
Air is a convenient and accessible source of both nitrogen and oxygen. Hence, advantageously the air is continuously supplied from externally to the cell in combination with the nitrogen. For example the nitrogen and oxygen source may be oxygen separated or purified nitrogen, which is supplied as gas to the electrolysis cell, e.g. to the liquid electrolyte, where it liquidly dissolved. Other sources of oxygen which may be utilized and may show an equally beneficial behaviour include, but is not limited to, gasses such as CO2, CO, NOx, or H2O, and alcohols, aldehydes, peroxides, superoxides, and organic acids which contain oxygen, and oxygen from transition metal electrodes in the form of oxides and carbonates. The sources of oxygen may be continuously supplied from externally to the cell, e.g. as gas to the cell, and/or be supplied or stored within the cell, e.g. as part of an electrolyte.
In an embodiment of the disclosure, the sources of nitrogen and/or oxygen are supplied to the electrolysis cells, and more preferably the source is a combined nitrogen and oxygen source.
Oxygen mediation of the electrochemical ammonia synthesis is particularly surprising because the presence of oxygen conventionally is expected to decrease the Faradaic efficiency, because oxygen reduction together with hydrogen evolution as mentioned in Equation (2), will be competing reactions to the ammonia synthesis.
However, despite this prejudice, a surprising peak in Faradaic efficiency may be observed for oxygen concentrations below 2 vol %, and particularly 1 vol %.
The influence of the oxygen concentration is further illustrated in
The presence of oxygen may further improve the stability of the system, and particularly the stability of the working electrode.
The steady cathodic current load may imply continuous cation reduction and deposition, e.g. continuous Li metal deposition, at the cathode. Alternatively, or additionally, to a steady cathodic current, the ammonia synthesis may advantageously be operated by using cyclic or pulsed cathode potential and current load, where the pulsed operation implies alternating periods of cation/Li deposition and no deposition. For example, the method described in Examples 1 and 4 may be used, where the cathode current load is pulsed between −2 mA/cm2 and 0 A, corresponding to cathode potential pulses between the lithium reduction potential and OCV.
The surprising effect of oxygen has further been verified experimentally as well as by mathematical models. Example 7 describes a model of oxygen's effect on lithium diffusivity and the lithium mediated electrochemical nitrogen reduction. Example 8 describes an embodiment of oxygen mediated electrochemical nitrogen reduction, and Example 9 describes an embodiment of the stability of oxygen mediated electrochemical nitrogen reduction.
The electrochemical ammonia synthesis may be carried out in any type of electrolysis cell. Advantageously, the synthesis is done in a single compartment cell, as further described in Examples 1-5, or a flow cell, as described in Example 6.
In an embodiment of the disclosure, the electrolysis cell is selected from the group consisting of: single compartment cells, and flow cells.
The need for voluminous tanks or containers to store reactants and/or products, and the need for flow controlling means ensuring the essential flow of fluid and/or gaseous reactants and products to and from the cell, influences the energy density and energy efficiency of the system. The flow controlling means, also known as balance-of-system components, may include a number of compressors, expanders, condensers, and pumps.
The electrolysis cells may be assembled into an apparatus connectable to one or more independent or decentralized power sources, which advantageously are renewable power sources such as wind power, hydropower, solar energy, geothermal energy, bioenergy, and mixtures thereof. Thus, the apparatus may be operated as an on-site ammonia production unit at a decentralised location, and the apparatus may further be adapted to be mobile, and to synthesize ammonia in amounts of 0.01-10 kg/day, more preferably 0.1-10 kg/day, and most preferably 0.1-5 kg/day, such as up to 1, 2, 3, or 4 kg/day, with a Faradaic efficiency above 50%, and operated at current loads equal to or above 100 mA/cm2.
An on-site, decentralised ammonia production unit, further has the advantage that voluminous tanks or containers for storing the produced ammonia product may be avoided or reduced. Due to the controllable and restricted amount of power, and thus corresponding restricted amounts of synthesized ammonia per day, the ammonia may be extracted from the electrolysis cell and directly distributed to a site of demand and further matched to the demand. For example, the ammonia may be extracted from the electrolyte of the cell, and continuously supplied to an irrigation system of a greenhouse or farm, thereby providing fertilizer for the plants after demand. This way a more simple apparatus and system may be obtained without, or with a reduced, need for product storage.
The operational conditions of the electrolysis cells, including the potential and current load, may be controlled by a controller, such as a potentiostat. Further advantageously the controller is configured for both regulating the power source input to the cells, as well as the supply of reactants and additives into the cells, and particularly the supply of nitrogen and/or oxygen.
In an embodiment of the disclosure, the apparatus comprises at least one electrolysis cell and a potentiostat configured for carrying out the method according to the present disclosure.
In another embodiment of the disclosure, the apparatus comprises one or more electrolysis cells connectable to one or more power sources and one or more nitrogen and/or oxygen sources, and at least one controller configured for regulating the power source input and the oxygen input to the electrolysis cells, such that the cells are operated according to the method according to the present disclosure.
In a further embodiment, the apparatus comprises one or more power sources, preferably renewable power sources, optionally selected from the group of: wind power, hydropower, solar energy, geothermal energy, bioenergy, and mixtures thereof. In a further embodiment, the apparatus is configured as a decentralized and/or mobile unit, adapted to synthesize ammonia in amounts of 0.01-10 kg/day, more preferably 0.1-10 kg/day, and most preferably 0.1-5 kg/day, such as up to 1, 2, 3, or 4 kg/day, preferably with a Faradaic efficiency above 50%, and operated at current loads equal to or above 100 mA/cm2.
The nitrogen and oxygen source are advantageously a combined nitrogen and oxygen source, such as air. To ensure sufficient nitrogen and oxygen supply, the apparatus preferably further comprises an oxygen separator fluidly connectable to the oxygen and/or nitrogen source. For flexible and cost-efficient operation, the oxygen separator is preferably configured to provide separated air with an oxygen concentration above 0% and below 20%, preferably below 2, 5, or 10%, and most preferably between 0.8 — 1.5%, such as 0.3, 0.4, 0.5, 0.8, or 1%.
In an embodiment of the disclosure, the apparatus comprises an oxygen separator fluidly connectable to the oxygen source and/or nitrogen source.
To further improve the performance and FE, as well as the electrochemical and mechanical stability of the cathode, the cathode advantageously comprises a high surface area (HAS) electrode or substrate, By the term “high surface electrode” is meant an electrode with high porosity and fine pore sizes, such that the specific surface area or the electrochemical active surface area (ECSA) is high, compared to the geometrical surface area as measurable on the bulk electrode.
For example, a high surface cathode may have a geometrical surface area of 1 cmgeo2, corresponding to the electrode having a length and width of 1 cm, whereas the specific surface area or the ECSA including the surface roughness and tortuosity due to the porosity, is much higher.
A minor degree of surface roughness, e.g. a roughness factor due to scratches, may result in an ECSA of ca. 1.5-2.0 cm2ECSA/cmgeo2, as measured via capacitive cycling as described in Examples 11-12. In contrast, high surface electrodes may have a roughness factor above 5, more preferably above 10. Particularly for the present disclosure, surprisingly improved performance and FE may be obtained for a cathode configured to have a surface roughness factor between 10-100 or 30-80 such as 50, 60, or 70, as measured via capacitive cycling as described in Examples 11-12.
High surface area electrodes may be obtained by any suitable synthesis routes, which may provide porosity between 25-55%, such as 30-50%, and/or average pore diameters of between 100 nm -50 μm, such as 500 nm-1 μm, and/or specific surface areas or ECSA of between 1-100 cm2/g. For example, a high surface electrode may be synthesized by hydrogen bubbling templating (HBT) on a substrate, which results in an alveolate, highly and finely porous dendritic structure. The electrode porosity and surface area characteristics are typically measured by gas adsorption techniques, such as the BET method.
Example 11 describes an embodiment of a high surface area electrode, exemplified as a high surface area Cu electrodes synthesized through hydrogen bubbling templating (HBT) on a transition metal substrate, preferably a porous transition metal substrate, such as Ni foam or stainless steel mesh substrates. The porous transition metal substrate is advantageously a highly porous substrate, having macropores and a porosity between 50-95%, more preferably 75-90%, and pore, such as a metal foam or mesh.
A resulting Cu electrode may be referred to as HBTCu. A HBTCu was characterized as described in Example 11 and
In an embodiment of the disclosure, the cathode comprises a high surface area metal electrode, preferably a high surface area electrode comprising a metal selected from the group of: Cr, Fe, Ni, Cu, Zn, and combinations thereof. In a further embodiment, the cathode comprises a Cu electrode made by hydrogen bubbling templating on a transition metal substrate, preferably a porous transition metal substrate, such as Ni foam or stainless steel mesh substrate.
In an embodiment of the disclosure, the cathode comprises a porosity of between 25-55%, such as 30-50%. In a further embodiment, the cathode comprises pores having an average pore diameter of between 100 nm-50 μm, such as 500 nm-1 μm, In a further embodiment, the cathode is configured to have a specific surface area between 1-100 cm2/g, such as 2-50 cm2/g, 3-25 cm2/g, or 2-10 cm2/g, as measured by BET. In a further embodiment, the cathode is configured to have a surface roughness factor of above 5, more preferably above 10, and most preferably between 10-100 or 30-80 such as 50, 60, or 70, as measured by capacitive cycling.
The invention is further described by the examples provided below.
The measurements were done in a 3-electrode single compartment glass cell enclosed in an electrochemical autoclave. 30 mL electrolyte of 0.3 M LiClO4 (Battery grade, dry, 99.99%, Sigma Aldrich) in 99 vol. % tetrahydrofuran (THF, anhydrous, >99.9%, inhibitor-free, Sigma Aldrich) and 1 vol. % ethanol (EtOH, anhydrous, Honeywell) was prepared in an Ar glovebox. The electrolyte was pre-saturated with purified (SAES Pure Gas, MicroTorr MC1-902F) N2 (5.0, Air Liquide) gas for 1-2 hours at approximately 5 mL/min, in a sealed glass cell in the glovebox. This gas cleaning was done to avoid any ammonia or labile nitrogen containing contaminants in the gas itself.
The working electrode (WE) was a Mo foil (+99.9%, Goodfellow) spot-welded with Mo wire (99.85%, Goodfellow) for electrical connection. Prior to electrochemical tests, the WE was dipped in 2% HCl (VWR Chemicals) to dissolve any surface species of Li, and rinsed in ultrapure water (18.2 MΩ resistivity, Millipore, Synergy UV system), then EtOH. The WE was polished using Si-C paper (Buehler, CarbiMet P1200), and rinsed thoroughly in EtOH. The counter electrode (CE) consisted of a Pt mesh (99.9%, Goodfellow), and the reference electrode (RE) was a Pt wire (99.99%, Goodfellow). The CE and RE were both boiled in ultrapure water, and dried overnight at 100° C., then flame-annealed.
The single compartment glass cell and a magnetic stirring bar (VWR, glass covered) was cleaned in ultra pure water, and dried overnight at 100° C. The WE and CE were ˜0.5 cm apart, and the surface area of the WE facing the CE was 1.8 cm2. Prior to an electrochemical experiment, we introduced Ar gas (5.0, Air Liquide) into the empty assembled cell placed in the autoclave for 1 hour. The denser Ar gas substantially displaced the atmospheric N2 and O2 in the system. Next, we injected electrolyte into the cell in Ar atmosphere, checked that the stirring bar in the cell was rotating despite the thickness of the autoclave bottom, and the autoclave was closed. Finally, the pressure was increased to 10 bar with either N2 or Ar depending on the intended experiment, and de-pressurized to 3 bar a total of 9 times, then filled to 10 bar, and the electrochemical experiments were started.
The electrochemical experimental procedure included potential controlled impedance spectroscopy to determine the resistance in our cell, with 85% manual iR-drop correction, a linear sweep voltammetry (LSV) from open circuit voltage (OCV) until lithium reduction was clearly seen, then chronopotentiometry (CP), followed by another impedance measurement to ensure that the resistance has not changed. We determined the lithium reduction potential scale based on the LSV. The onset for lithium reduction was quite clear, and we thereby denoted the potential vs Li+/Li. During CP, either a steady current density of −2 mA/cm2 was used (hereafter denoted deposition potential), or a cyclic method with −2 mA/cm2 for 1 min, followed by 0 mA/cm2 (hereafter denoted resting potential) for 3-8 min, depending on whether the WE potential needed to be increased, decreased or stabilized.
Synthesized ammonia was quantified by a modified colorimetric indophenol method, previously described [2]. The sample absorbance was analysed by UV/Vis spectroscopy (UV-2600, Shimadzu) in the range from 400 nm to 1000 nm. The blank solution was subtracted from each spectrum, and the difference between the peak around 630 nm and the trough at 850 nm was used. A fitted curve of the difference between the peak and trough of each concentration showed a linear regression with an R2 value of 0.998. We utilized this method, as opposed to the more common peak based method, because long experiments might have solvent breakdown, which can give a falsely high peak at the ammonia wavelength, due to interference from the evolved solvent background. The amount of ammonia in the headspace was quantified by de-gassing the system through an ultrapure water trap. For each measurement, a 0.5 mL sample of the water trap was taken, and four 0.5 mL samples were taken from the electrolyte. One sample from the electrolyte was used as a background, and the mean and standard deviation of the remaining 3 samples was reported. The uncertainty reported therefore stems from the indophenol procedure. The remaining samples were treated as described previously [2], to determine the ammonia concentration. If the expected concentration of ammonia exceeded the concentration limits of the indophenol method, the sample was accordingly diluted with ultrapure water after drying.
Although the method described in Example 1 has been proven to synthesize ammonia, we performed a simplified version of the protocol to further validate our results.
To perform an Ar blank experiment, the electrolyte was pre-saturated with Ar instead of N2, and after injection into the autoclave cell, the pumping and purging procedure was carried out with Ar instead of N2. An electrochemical cycling experiment with −2 mA/cm2 for 1 min followed by 0 mA/cm2 for 3-4 minutes was carried out, with a 3 hour rest at 0 mA/cm2 after around 15 hours, to allow full diffusion of any potential ammonia in solution. Additionally, ammonia contamination in blank measurements at OCV for 24 hours at 10 bar N2, were also measured.
For Ar blank experiments, with 100.7 C passed, a background of 15±2 μg of ammonia was measured, corresponding to 0.5±0.1 p.p.m. using indophenol. NMR on a single sample gave a concentration of 0.4 p.p.m of 14NH3 for comparison, as seen in
For 24-hour N2 experiments at OCP, with pre-purging of the electrolyte with cleaned N2 gas, 11±1 μg of ammonia was measured, corresponding to 0.4±0.1 p.p.m. We believe more ammonia was measured in the Ar blank, as there is some nitrogen in the system due to the autoclave assembly procedure. This trapped N2 will be reduced to NH3, leading to more in the Ar blank wherein we reduce a significant amount of lithium, as opposed to N2 at OCP. We also inherently have a high level of contamination in our system due to the amounts of ammonia produced in regular experiments (sometimes above 100 p.p.m.), which will stick to the autoclave walls and pipes, and is unfortunately hard to get rid of. However, as we are making 1-2 orders of magnitude more ammonia in each measurement, this contamination is insignificant in comparison.
We also carried out a single isotope labelled experiment. For the isotopically labelled nitrogen measurement, a mass spectrometer (Pfeiffer, OmniStar GSD 320) was connected to the autoclave, to determine the supplied ratio of 15N2 to 14N2 gas. The total internal autoclave volume was approximately 380 mL at STP, and around 320 mL of gas volume at STP with the electrochemical cell inside. To carry out the isotope experiment, we aimed for a 1:3 gas ratio of 15N2 (98%, Sigma Aldrich) to 14N2 at 10 bar. The pressure in the autoclave was raised to 10 bar and purged to 3 bar a total of 9 times with 14N2, then the 15N2 gas was added up to 5.5 bar, and lastly the 14N2 gas up to bar. The relative ratio measured via mass spectrometry was 78% 14N2 and 22% 15N2 supplied to the system. Two 0.5 mL samples from the electrolyte were taken after electrolysis, and one of them was diluted 5:1 to fall in the appropriate range of the calibration curve previously made. The samples were then treated according to the previously published protocols to quantitatively determine the isotope concentration of the produced ammonia via NMR, where the undiluted sample was used to ensure the desired ratio of 5 from the dilution step.
The autoclave volume was 380 cm3, and experiments were all at 10 bar, meaning we could not fill up the entire autoclave with 15N2, as those bottles are 416 mL, and contain a total of 5 L of gas. For this reason, we aimed at utilizing a mixed composition gas of 14N2 and 15N2, and confirmed via mass-spectroscopy that approx. 78 vol. % 14N2 and 22 vol. % 15N2 was achieved. From the single NMR sample seen in
The method described in Example 1 was used, where during CP, a steady current density of −2 mA/cm2 was used (also denoted deposition potential). The resulting electrode potentials as a function of time for lithium mediated ammonia synthesis under the constant cathodic current load of −2 mA/cm2 are shown in
The 3 separate experiments of
As is seen from
In conclusion, it has proved difficult to achieve a stable WE potential while applying a constant current, which continuously reduces lithium. Due to high sensitivity of the system to small amounts of O2 and H2O, which reacts with the deposited lithium layer forming passivated compounds, the potential needed to maintain a given current increases. Furthermore, if the lithium deposition occurs at a very high rate, metallic lithium is deposited on top of metallic lithium that has not yet reacted to form lithium nitride. This leads to an inefficiency in the system, as charge is wasted depositing excess lithium, which will react and not generate ammonia, and there will be a slow build-up of lithium on the electrode. Over long experiments, this decreases the salt concentration, while increasing the resistance of the cell due to lowering the conductivity and increasing the electrode resistance.
The method described in Example 1 was used, where the method consisted of short deposition pulses of 1 min at -2 mA/cm2 followed by 3-8 min at 0 mA/cm2, as seen in
It was seen that the instability issue described in Example 3 due to build-up of lithium species on the surface of the electrode, was avoided when using the cyclic method. Applying short current pulses for lithium deposition, with a resting time between each pulse to allow the lithium to react fully with nitrogen in solution significantly prevented the WE potential from drifting cathodic over time.
It is speculated that this is due to the absence of significant unreactive lithium species build-up on the electrode in the cyclic method, since it provides time for the deposit to chemically react with our electrolyte, and dissolve from the surface, as seen by the change of the WE potential during the resting time,
The measurement shown in
The cyclic method further has the advantage that the potential is cycled from a very negative lithium reducing potential, to a less negative potential at which lithium is not reduced, while potentially still synthesizing ammonia. This leads to both a vast improvement of stability of the system, and a significant increase in energy efficiency. The cycling enables the reduced metallic lithium to react with nitrogen at a lower potential without depositing more lithium, thereby fully forming the nitride and producing ammonia. The lithium in solution will also not deplete over time, as all the plated lithium has time to dissolve from the surface of the cathode, thereby stabilizing the working electrode potential. Furthermore, the overall energy efficiency of the cycling will be higher compared to the continuous deposition process, as ammonia could be formed at potentials less negative than −3 V vs RHE.
In conclusion, the electrochemical lithium mediated nitrogen reduction process with a constant applied potential or current described in Example 3, resulted in constant deposition of lithium onto the WE invariably leading to a build up of unreactive species on the surface, increasing the needed potential to continue running the experiment over time. The issue was circumvented by the cycling method, wherein lithium was reduced for 1 min at −2 mA/cm2, and then allowed to rest at 0 mA/cm2 for a variable time of 3-8 min, until the surface species of lithium was chemically dissolved. This assured a high lithium concentration near the surface of the electrode, and allowed for fine control of the WE potential throughout the experiment.
Furthermore, due to the increase in FE during the cycling compared to constant deposition, it is suspected that ammonia is formed during the resting time, wherein no current is passed. This significantly increases the energy efficiency of the system, beyond anything previously reported.
Based on Example 4, a long-term experiment spanning 125 hours and passing 180 C was carried out. By varying the resting potential time, the WE potential was controlled to be in the desired low potential region across the entire experiment, with the CE potential reaching a maximum of 5 V vs Li+/Li. This experiment used 2 vol. % EtOH instead of 1 vol. %, as passing such large amounts of charge would significantly impact the total EtOH concentration throughout the experiment. The proton source must eventually be replenished in this system, as the current source is EtOH oxidation on the CE.
This experiment made 3470±104 μg (110.9±3.5 p.p.m.), equaling a FE of 33.1±0.1%, and an energy efficiency of 5.3±0.2%. We speculate the slightly lower yield is due to the increase in EtOH concentration, as that has previously been shown to impact the faradaic efficiency, however this experiment still had a higher FE and energy efficiency compared to the constant deposition.
A continuous deposition experiment with lithium, wherein there is a perfect balance between the amount deposited, and the amount of Li dissolving when synthesizing ammonia, may be carried out.
Even if not all the deposited lithium forms a nitride, but some other non-reactive or passive deposits are also formed, which builds up on—and eventually passivates—the electrode, during the resting cycle, the lithium species have enough time to chemically dissolve, mitigating a build-up on the electrode.
Visually, the electrode surface of the constant deposition experiment of Example 3 had big deposits of lithium species on the surface, shown in
Furthermore, the increase in FE and energy efficiency during the cycling compared to constant deposition implied that ammonia was formed even during the resting periods, wherein the WE potential was lower than the lithium reduction potential and no net current flows.
The measurements of Examples 4-5 may be repeated using a flow cell instead of the 3-electrode single compartment glass cell. For example, the measurements may be carried out in a flow cell as shown in
The 30 mL electrolyte of 0.3 M LiClO4 of Examples 1, 4 and 5 may be substituted with an electrolyte comprising one or more metal cations, where the metal is lithium (Li), sodium (Na), potassium (K), magnesium (Mg), calcium (Ca), barium (Ba), and/or yttrium (Y).
Examples 4 and 5 are repeated, and similar ammonia synthesis with improved efficiency and stability, by use of the pulsed cathode potential, including a pulsed cathodic current load, can be obtained.
The competition of Li+, H+, and N2 to the surface governs the FE of the lithium-mediated nitrogen reduction (LiNR). Specifically, reducing the diffusion rate of Li+and
H+ and increasing the diffusion rate of N2 may result in an increased FE, as illustrated in the heatmap of the predicted FE in
A critical component in limiting diffusion rates of Li+ and H+ is believed to be the SEI (solid electrolyte interphase), which is an electrically isolating, but ionically conducting solid electrolyte interphase layer. The SEI is an organic layer may created through various parasitic side reactions between reduced lithium and solvent species.
The SEI layer may increase the stability of lithium-ions by restricting the access to the reduced lithium at the cathode. It is further speculated that oxygen can have a significant impact on the SEI layer's composition resulting in increased homogeneity as well as reduced lithium diffusivity. This effect on lithium diffusivity could have a significant impact on the FE.
If rLi is lowered selectively relative to rH and rN
While this effect is hard to quantitatively predict due to the complexity of modelling the SEI layer, we have estimated the effect by modelling a reduction rLi relative to rH and rN
This effect to far larger than either reducing proton activity or increasing nitrogen pressure, as shown visually by
If oxygen's presence changes the SEI composition and reduces the lithium diffusivity, an optimal oxygen concentration would be expected. This follows from the trade-off between oxygen improving the FE at low concentrations due to restricted lithium diffusivity, and significantly reducing it at high concentrations due to ORR's (oxygen reduction reaction) domination over NRR (nitrogen reduction reaction).
The expected behavior of this oxygen peak is that the location and height should directly correlate with nitrogen pressure until NRR is pushed into the H-limited regime. This follows graphically from
Taken together this model shows that small amounts of oxygen could potentially act as an SEI additive greatly improving the overall FE in the system. It is further indicated that at higher pressures, a higher amount of oxygen will provide maximum FE.
To verify the predictions made by the theoretic model, a set of experiments with different amounts of O2 added at two pressures (10 and 20 bar) were conducted. All experiments were performed in a home-built autoclave at a constant current of -2 or 4 mA/cm2 until the system either overloaded or reached 50 C.
From
The optimum at higher O2 contents for higher pressures, as also predicted by the model in Example 8, is also seen in
Similar experimental conditions as for Example 9 were used, and the stability of the systems were investigated. Specifically, stability experiments were carried out using chronopotentiometry with −4 mA/cm2 at 20 bar N2 with variable O2 content.
Hence, the addition of oxygen may improve the stability and durability of the system. The stability may be further improved by operating the system cyclic as described in Examples 4-5.
Cycling experiments are also conducted for systems including oxygen concentrations below 1 vol %. The cycling is as described in Examples 4-5, and shows the beneficial coupling of the stability achieved from cycling with the increased FE and stability from the addition of O2.
A substrate such as Ni foam (99.5%, porosity: 95%, pores/cm: 20, Goodfellow), stainless steel mesh, or other transition metal substrates was cut into 0.5 cm2 pieces, cleaned in H3PO4 (85%, Supelco) and sonicated three times in ethanol (EtOH). Representative SEM (scanning electron microscope) images of the pristine Ni foam is seen in
Afterwards, the substrate was attached to a Cu wire (99.98+%, Goodfellow) and used as the working electrode. Two Pt meshes (Ageo=˜2 cm2, 99.9%, Goodfellow), were electrically connected and used as a split counter electrode, where the Ni foam working electrode was positioned in the middle during deposition. As electrolyte copper salt containing acidic solution such as a 0.4 M CuSO4 (Merck) in 1.5 M H2SO4 (99.999%, Sigma Aldrich) solution was used. In this two-electrode setup, a constant current was applied for a certain time such that the porous Cu deposited on the Ni foam. For example-5A may be applied for 15 seconds. After the deposition process, the electrodes were cleaned in EtOH and dried in vacuum before being stored in an Ar glovebox to prevent oxidation of Cu.
Representative SEM images of Cu electrodeposited on Ni foam (HBTCu) with the hydrogen bubble template (HBT) method is seen in
For example, the synthesized HBTCu electrode may comprise a porosity of between 25-55%, such as 30-50%, and pores having an average pore diameter of between 100 nm -50 μm, such as 500 nm -1 μm, Advantageously, the pore size and porosity of the dendritic structure is templated such that the specific surface area is between 1-100 cm2 /g, such as 2-50 cm2/g, 3-25 cm2/g, or 2-10 cm2/g, as measured by gas adsorption techniques, such as the BET method.
The HBTCu electrode structure was further characterized by SEM-EDX and XPS.
The HBTCu electrode is tested for lithium mediated ammonia synthesis under constant and cyclic cathodic current load, as described in Examples 3 and 4. After the electrochemical tests, the HBTCu structure is characterized by SEM.
It follows that improved faradaic efficiency, and stability may be obtained for the electrochemical ammonia synthesis including HBTCu electrodes, as indicated in the Table below. Further, it follows that increased current density is obtained by synthesizing high surface area Cu electrodes through hydrogen bubbling templating (HBT) on Ni foam substrates. It is believed, that further optimization of the templating method and ammonia synthesis conditions will improve the faradaic efficiency and rate even further.
The electrochemical active surface area (ECSA) and corresponding roughness factor of the HBTCu electrode of Example 11 may be determined with capacitive cycling.
For this, a potential window was chosen where no faradaic reactions take place (−0.2 to 0V vs OCV) and several cyclic voltameteries (CV) were taken at different scan speeds. Since in this region the current is only depended on the electrolyte, electrode material and scan speed, the ECSA can be determined.
First, the specific capacitance of the investigated material (Cu) has to be determined. Therefore, a polycrystalline Cu stub with known surface area (0.2 cm2) was polished and CVs were taken at scan rates ranging from 10 to 60 mV/s in an electrolyte similar to the one used for the Li mediated ammonia synthesis (2M LiClO4 in THF), as illustrated in
The change in current is determined at the middle of the potential window (−0.1 V vs OCV) and plotted against the scan rate, as illustrated in
For the determination of the ECSA of the high surface area electrodes the procedure was repeated and the slope of the graph was divided by the previously determined specific capacitance.
Based on the determined ECSA of the high surface area electrode, the corresponding roughness factor may be calculated by conversion as known to the skilled person within the field. In this context, the roughness factor is the ratio of the ECSA divided by the geometric surface area. For example, the average ECSA of 66.5 cm2 of Example 11 may be converted to a corresponding roughness factor of about 66.5 (0.5 cm2 geometric surface area, 2 sided electrode), when measured via the capacitive cycling.
The presently disclosed may be described in further detail with reference to the following items.
40. The apparatus according to any of items 34-39, wherein the apparatus is configured as a decentralized unit and/or a mobile unit, and adapted to synthesize ammonia in amounts of between 0.01-10 kg/day, more preferably 0.1-10 kg/day, and most preferably 0.1-5 kg/day, such as up to 1, 2, 3 or 4 kg/day.
[1] WO 2012/129472.
[2] P. L. Searle, “The berthelot or indophenol reaction and its use in the analytical chemistry of nitrogen. A review,” Analyst, vol. 109, no. 5, p. 549, 1984.
[3] S. Z. Andersen et al., “A rigorous electrochemical ammonia synthesis protocol with quantitative isotope measurements,” Nature, vol. 570, no. 7762, pp. 504-508, 2019.
[4] A. C. Nielander et al., “A Versatile Method for Ammonia Detection in a Range of Relevant Electrolytes via Direct Nuclear Magnetic Resonance Techniques,” ACS Catal., vol. 9, no. 7, pp. 5797-5802, July 2019.
[5] A. Tsuneto et al., “Lithium-mediated electrochemical reduction of high pressure N2 to NH3”, Journal of Electroanalytical Chemistry, vol. 367, issues 1-2, pp. 183-188, 1994.
[6] US 2006/0049063.
| Number | Date | Country | Kind |
|---|---|---|---|
| PA 2021 70128 | Mar 2021 | DK | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2022/054365 | 2/22/2022 | WO |
| Number | Date | Country | |
|---|---|---|---|
| 63151890 | Feb 2021 | US |
