Patent Application
20240363881
Accumulating CO2 emissions from the burning of fossil fuels are resulting in an alarming rate of climate change. Consequently, there are increasing efforts worldwide to reduce societal reliance on fossil fuel-based energy and to switch to carbon-free sources such as solar and wind. However, due to the intermittent nature of solar and wind power, integrating them into the grid requires grid-scale energy storage. So far, most of the energy storage is achieved by pumped-hydroelectric and lithium-ion batteries. The former is limited by its geographical requirement while the latter is unsuitable for long-duration discharge due to its coupled energy and power, not to mention its flammable nature and difficulty in recyclability.
Aqueous organic redox flow batteries (AORFB) provide a much better solution to energy storage. They have decoupled energy and power, so that one can increase the power just by increasing the stack size while independently controlling the capacity/energy by controlling the size of the electrolyte reservoirs. This allows AORFBs to discharge for an arbitrary amount of time, which is ideal for grid-scale energy storage. Since the solvent of electrolytes is just water, it is nonflammable. The redox active organic materials are simple organics that are potentially inexpensive, scalable through facile synthesis and easily recyclable, making them strong competitors to existing technologies. While the energy storage methods promise to reduce carbon emission in the future, carbon capture, e.g., carbon capture and sequestration (CCS) (e.g., capture from flue gas) or direct air capture (DAC), is required to avoid severe consequences of global warming (greater than 2° C. above pre-industrial era levels) and irreversibly deleterious changes to natural habitats and ecosystems that would threaten the viability of human civilization.
In addition to power storage, the organic molecules used in AORFB can be used for carbon capture. Molecules that undergo proton-coupled electron transfers (PCET), change the solution pH from near neutral to highly basic during charging, and from highly basic to near neutral during discharging. In other words, hydroxide is reversibly generated during charging and consumed during discharging. Since hydroxide binds with CO2 to form carbonate and then bicarbonate, the electrolyte captures CO2 upon charging and releases CO2 upon discharging. The energy cost for capturing from a 0.1 bar CO2 stream and releasing into a 1 bar stream at 40 mA/cm2 costs 86 KJ/molCO2, which is highly competitive compared to traditional amine scrubbing processes that typically cost more than 100 KJ/molCO2. In addition, electrochemical flow cell capture systems such as those described herein rely solely on electrical work, while amine scrubbing requires high thermal input, and the amines and related decomposition products are volatile and environmental hazards. For air capture, redox flow methods such as described herein are projected to cost 110 KJ/molCO2 at 40 mA/cm2, which is again very competitive compared with existing technologies costing more than 150 KJ/molCO2.
The above systems require an oxygen-free environment. This is because when the redox active organic molecules are reduced (e.g., when the systems are charged), they may be susceptible to oxidation by molecular oxygen, thereby stopping the discharge process from happening, causing an incomplete cycle and, e.g., resulting an accumulation of hydroxide and dissolved carbon species in the electrolyte. Eventually the device, whether a battery or carbon capture device, will be fully oxidized in both sides and no longer functional. In real life application, a perfectly sealed flow battery is difficult to achieve. Even if initially perfectly sealed, external factors such as aging of cell components or the sealing material, extreme weather, geological changes or even vandalism may cause molecular oxygen to come into contact with the electrolyte. For carbon capture, molecular oxygen is almost always unavoidable, as there is 1 to 3% of oxygen in factory flue gas and ˜20% oxygen in air. Therefore, mitigating the adverse effect of oxygen is essential to the operation of an AORFB and electrochemical carbon capture flow cell.
The invention features methods to extend the life of electrochemical systems by electrochemically rebalancing electrolytes unbalanced by reaction of redox active species with molecular oxygen.
An aspect of the invention provides a method of rebalancing an electrochemical device including providing an electrochemical device including a negolyte including a first redox active species having an oxidized form and a reduced form in contact with a first electrode, a posolyte including a second redox active species having an oxidized form and a reduced form in contact with a second electrode, and a barrier separating the negolyte and posolyte. When the electrochemical device is charged, the reduced form of the first redox active species reacts with molecular oxygen to form the oxidized form of the first redox active species while the second redox active species remains in the oxidized form, thereby electrochemically unbalancing the electrochemical device. A discharge reaction or reaction with molecular oxygen produces an OH− ion. The method includes applying an electrical pulse across the electrochemical device sufficient to produce a gaseous oxidation product (e.g., molecular oxygen) in the negolyte. The electrical pulse may also revert the oxidized form of the second redox active species to the reduced form of the second redox active species. The device may be operated symmetrically, i.e., where the first and second redox active species cycle between oxidized and reduced forms of the same redox active species. Alternatively, the first and second redox active species may cycle between different oxidized and reduced forms.
In some embodiments, the method further includes removing the gaseous oxidation product from the negolyte. In some embodiments, the electrical pulse is applied every 100 cycles. In some embodiments, the gaseous oxidation product is removed by flowing a carrier gas through the electrochemical device or by applying negative pressure to the negolyte. In some embodiments, the electrical pulse lowers the pH of the negolyte.
In some embodiments, the method further includes monitoring a capacity of the electrochemical device or a pH of the negolyte to determine when to apply the pulse. In some embodiments, the pulse is applied when the pH is greater than 9, e.g., is about 14. In some embodiments, the pulse is applied when the capacity is below 90% of an initial capacity.
In some embodiments, the electrochemical device provided is a battery (e.g., a flow battery), and the method further includes applying a voltage across the first and second electrodes charging the battery and connecting a load to the first and second electrodes allowing the battery to discharge. In some embodiments, the method further includes biasing the battery at a voltage more negative than a discharging voltage of the battery. In some embodiments, the gaseous oxidation product is molecular oxygen, and the method incudes oxidizing OH− or H2O in the negolyte to molecular oxygen.
In some embodiments, the electrochemical device is a carbon capture cell (e.g., a carbon capture flow cell), and the method further includes applying a voltage across the first and second electrodes to charge the electrochemical device and produce OH− ions, providing a source of CO2 to the negolyte to capture the CO2 therein, e.g., by dissolution or reaction with the OH− ions, and connecting a load to the first and second electrodes and allowing the electrochemical device to discharge and release CO2.
By “about” is meant ±10% of a recited value.
By “alkoxy” is meant a group of formula —OR, where R is an alkyl group, as defined herein.
By “alkyl” is meant straight chain or branched saturated groups from 1 to 6 carbons. Alkyl groups are exemplified by methyl, ethyl, n- and iso-propyl, n-, sec-, iso- and tert-butyl, neopentyl, and the like, and may be optionally substituted with one or more, substituents.
By “alkylene” is meant a divalent alkyl group.
By “alkyl thio” is meant —SR, where R is an alkyl group, as defined herein.
By “alkyl ester” is meant —COOR, where R is an alkyl group, as defined herein.
By “aryl” is meant an aromatic cyclic group in which the ring atoms are all carbon. Exemplary aryl groups include phenyl, naphthyl, and anthracenyl. Aryl groups may be optionally substituted with one or more substituents.
By “carbocyclyl” is meant a non-aromatic cyclic group in which the ring atoms are all carbon. Exemplary carbocyclyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Carbocyclyl groups may be optionally substituted with one or more substituents.
By “halo” is meant, fluoro, chloro, bromo, or iodo.
By “hydroxyl” is meant-OH. An exemplary ion of hydroxyl is —O−.
By “amino” is meant —NH2. An exemplary ion of amino is —NH3+.
By “nitro” is meant —NO2.
By “carboxyl” is meant —COOH. An exemplary ion of carboxyl is —COO.
By “phosphoryl” is meant —PO3H2. Exemplary ions of phosphoryl are —PO3H− and —PO32−.
By “phosphonyl” is meant —PO3R2, where each R is H or alkyl, provided at least one R is alkyl, as defined herein. An exemplary ion of phosphoryl is —PO3R−.
By “oxo” is meant ═O.
By “sulfonyl” is meant —SO3H. An exemplary ion of sulfonyl is —SO3−.
By “thiol” is meant —SH.
By “heteroaryl” is meant an aromatic cyclic group in which the ring atoms include at least one carbon and at least one O, N, or S atom, provided that at least three ring atoms are present. Exemplary heteroaryl groups include oxazolyl, isoxazolyl, tetrazolyl, pyridyl, thienyl, furyl, pyrrolyl, imidazolyl, pyrimidinyl, thiazolyl, indolyl, quinolinyl, isoquinolinyl, benzofuryl, benzothienyl, pyrazolyl, pyrazinyl, pyridazinyl, isothiazolyl, benzimidazolyl, benzothiazolyl, benzoxazolyl, oxadiazolyl, thiadiazolyl, and triazolyl. Heteroaryl groups may be optionally substituted with one or more substituents.
By “heteroalkylene” is meant an alkylene group in which one or more CH2 units are replaced with one or more heteroatoms selected from O, N, and S. Heteroalkylene groups can be substituted by oxo (═O). An exemplary heteroalkylene includes an amido group, e.g., —(CH2)nC(O)NH(CH2)m—, wherein n and m are independently 1-6.
By “heterocyclyl” is meant a non-aromatic cyclic group in which the ring atoms include at least one carbon and at least one O, N, or S atom, provided that at least three ring atoms are present. Exemplary heterocyclyl groups include epoxide, thiiranyl, aziridinyl, azetidinyl, thietanyl, dioxetanyl, morpholinyl, thiomorpholinyl, piperazinyl, piperidinyl, pyrrolidinyl, tetrahydropyranyl, tetrahydrofuranyl, dihydrofuranyl, tetrahydrothienyl, dihydrothienyl, dihydroindolyl, tetrahydroquinolyl, tetrahydroisoquinolyl, pyranyl, pyrazolinyl, pyrazolidinyl, dihydropyranyl, tetrahydroquinolyl, imidazolinyl, imidazolidinyl, pyrrolinyl, oxazolidinyl, isoxazolidinyl, thiazolidinyl, isothiazolidinyl, dithiazolyl, and 1,3-dioxanyl. Heterocyclyl groups may be optionally substituted with one or more substituents.
By “hydrocarbyl” is meant a branched, unbranched, cyclic, or acyclic group including the elements C and H. Hydrocarbyl groups may be monovalent, e.g., alkyl, or divalent, e.g., alkylene. Hydrocarbyl groups may be substituted with groups including oxo (═O).
By an “oxygen protecting group” is meant those groups intended to protect an oxygen containing (e.g., phenol, hydroxyl, or carbonyl) group against undesirable reactions during synthetic procedures. Commonly used oxygen protecting groups are disclosed in Greene, “Protective Groups in Organic Synthesis,” 3rd Edition (John Wiley & Sons, New York, 1999), which is incorporated herein by reference. Exemplary oxygen protecting groups include acyl, aryloyl, or carbamyl groups, such as formyl, acetyl, propionyl, pivaloyl, t-butylacetyl, 2-chloroacetyl, 2-bromoacetyl, trifluoroacetyl, trichloroacetyl, phthalyl, o-nitrophenoxyacetyl, α-chlorobutyryl, benzoyl, 4-chlorobenzoyl, 4-bromobenzoyl, t-butyldimethylsilyl, tri-iso-propylsilyloxymethyl, 4,4′-dimethoxytrityl, isobutyryl, phenoxyacetyl, 4-isopropylpehenoxyacetyl, dimethylformamidino, and 4-nitrobenzoyl; alkylcarbonyl groups, such as acyl, acetyl, propionyl, and pivaloyl; optionally substituted arylcarbonyl groups, such as benzoyl; silyl groups, such as trimethylsilyl (TMS), tert-butyldimethylsilyl (TBDMS), tri-iso-propylsilyloxymethyl (TOM), and triisopropylsilyl (TIPS); ether-forming groups with the hydroxyl, such methyl, methoxymethyl, tetrahydropyranyl, benzyl, p-methoxybenzyl, and trityl; alkoxycarbonyls, such as methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, n-isopropoxycarbonyl, n-butyloxycarbonyl, isobutyloxycarbonyl, sec-butyloxycarbonyl, t-butyloxycarbonyl, 2-ethylhexyloxycarbonyl, cyclohexyloxycarbonyl, and methyloxycarbonyl; alkoxyalkoxycarbonyl groups, such as methoxymethoxycarbonyl, ethoxymethoxycarbonyl, 2-methoxyethoxycarbonyl, 2-ethoxyethoxycarbonyl, 2-butoxyethoxycarbonyl, 2-methoxyethoxymethoxycarbonyl, allyloxycarbonyl, propargyloxycarbonyl, 2-butenoxycarbonyl, and 3-methyl-2-butenoxycarbonyl; haloalkoxycarbonyls, such as 2-chloroethoxycarbonyl, 2-chloroethoxycarbonyl, and 2,2,2-trichloroethoxycarbonyl; optionally substituted arylalkoxycarbonyl groups, such as benzyloxycarbonyl, p-methylbenzyloxycarbonyl, p-methoxybenzyloxycarbonyl, p-nitrobenzyloxycarbonyl, 2,4-dinitrobenzyloxycarbonyl, 3,5-dimethylbenzyloxycarbonyl, p-chlorobenzyloxycarbonyl, p-bromobenzyloxy-carbonyl, and fluorenylmethyloxycarbonyl; and optionally substituted aryloxycarbonyl groups, such as phenoxycarbonyl, p-nitrophenoxycarbonyl, o-nitrophenoxycarbonyl, 2,4-dinitrophenoxycarbonyl, p-methyl-phenoxycarbonyl, m-methylphenoxycarbonyl, o-bromophenoxycarbonyl, 3,5-dimethylphenoxycarbonyl, p-chlorophenoxycarbonyl, and 2-chloro-4-nitrophenoxy-carbonyl); substituted alkyl, aryl, and alkaryl ethers (e.g., trityl; methylthiomethyl; methoxymethyl; benzyloxymethyl; siloxymethyl; 2,2,2,-trichloroethoxymethyl; tetrahydropyranyl; tetrahydrofuranyl; ethoxyethyl; 1-[2-(trimethylsilyl) ethoxy]ethyl; 2-trimethylsilylethyl; t-butyl ether; p-chlorophenyl, p-methoxyphenyl, p-nitrophenyl, benzyl, p-methoxybenzyl, and nitrobenzyl); silyl ethers (e.g., trimethylsilyl; triethylsilyl; triisopropylsilyl; dimethylisopropylsilyl; t-butyldimethylsilyl; t-butyldiphenylsilyl; tribenzylsilyl; triphenylsilyl; and diphenymethylsilyl); carbonates (e.g., methyl, methoxymethyl, 9-fluorenylmethyl; ethyl; 2,2,2-trichloroethyl; 2-(trimethylsilyl)ethyl; vinyl, allyl, nitrophenyl; benzyl; methoxybenzyl; 3,4-dimethoxybenzyl;
and nitrobenzyl); carbonyl-protecting groups (e.g., acetal and ketal groups, such as dimethyl acetal, and 1,3-dioxolane; acylal groups; and dithiane groups, such as 1,3-dithianes, and 1,3-dithiolane); carboxylic acid-protecting groups (e.g., ester groups, such as methyl ester, benzyl ester, t-butyl ester, and orthoesters; and oxazoline groups.
By a “nitrogen protecting group” is meant those groups intended to protect an amino group against undesirable reactions during synthetic procedures. Commonly used nitrogen protecting groups are disclosed in Greene, “Protective Groups in Organic Synthesis,” 3rd Edition (John Wiley & Sons, New York, 1999), which is incorporated herein by reference. Nitrogen protecting groups include acyl, aryloyl, or carbamyl groups such as formyl, acetyl, propionyl, pivaloyl, t-butylacetyl, 2-chloroacetyl, 2-bromoacetyl, trifluoroacetyl, trichloroacetyl, phthalyl, o-nitrophenoxyacetyl, α-chlorobutyryl, benzoyl, 4-chlorobenzoyl, 4-bromobenzoyl, 4-nitrobenzoyl, and amino acids such as alanine, leucine, and phenylalanine; sulfonyl-containing groups such as benzenesulfonyl, and p-toluenesulfonyl; carbamate forming groups such as benzyloxycarbonyl, p-chlorobenzyloxycarbonyl, p-methoxybenzyloxycarbonyl, p-nitrobenzyloxycarbonyl, 2-nitrobenzyloxycarbonyl, p-bromobenzyloxycarbonyl, 3,4-dimethoxybenzyloxycarbonyl, 3,5-dimethoxybenzyloxycarbonyl, 2,4-dimethoxybenzyloxycarbonyl, 4-methoxybenzyloxycarbonyl, 2-nitro-4,5-dimethoxybenzyloxycarbonyl, 3,4,5-trimethoxybenzyloxycarbonyl, 1-(p-biphenylyl)-1-methylethoxycarbonyl, α,α-dimethyl-3,5-dimethoxybenzyloxycarbonyl, benzhydryloxy carbonyl, t-butyloxycarbonyl, diisopropylmethoxycarbonyl, isopropyloxycarbonyl, ethoxycarbonyl, methoxycarbonyl, allyloxycarbonyl, 2,2,2,-trichloroethoxycarbonyl, phenoxycarbonyl, 4-nitrophenoxy carbonyl, fluorenyl-9-methoxycarbonyl, cyclopentyloxycarbonyl, adamantyloxycarbonyl, cyclohexyloxycarbonyl, and phenylthiocarbonyl, alkaryl groups such as benzyl, triphenylmethyl, and benzyloxymethyl, and silyl groups, such as trimethylsilyl. Preferred nitrogen protecting groups are alloc, formyl, acetyl, benzoyl, pivaloyl, t-butylacetyl, alanyl, phenylsulfonyl, benzyl, t-butyloxycarbonyl (Boc), and benzyloxycarbonyl (Cbz).
For the purposes of this invention, the term “quinone” includes a compound having one or more conjugated, C3-10 carbocyclic, fused rings, substituted, in oxidized form, with two or more oxo groups, which are in conjugation with the one or more conjugated rings. Preferably, the number of rings is from one to ten, e.g., one, two, or three, and each ring has 6 members.
As noted, substituents may be optionally substituted with halo, optionally substituted C3-10 carbocyclyl; optionally substituted C1-9 heterocyclyl having one to four heteroatoms independently selected from O, N, and S; optionally substituted C6-20 aryl; optionally substituted C1-9 heteroaryl having one to four heteroatoms independently selected from O, N, and S; —CN; —NO2; —ORa; —N(Ra)2; —C(═O)Ra; —C(═O)ORa; —S(═O)2Ra; —S(═O)2ORa; —P(═O)Ra2; —O—P(═O)(ORa)2, or —P(═O)(ORa)2, or an ion thereof; where each Ra is independently H, C1-6 alkyl; optionally substituted C3-10 carbocyclyl; optionally substituted C1-9 heterocyclyl having one to four heteroatoms independently selected from O, N, and S; optionally substituted C6-20 aryl; optionally substituted C1-9 heteroaryl having one to four heteroatoms independently selected from O, N, and S; an oxygen protecting group; or a nitrogen protecting group. Cyclic substituents may also be substituted with optionally substituted C1-6 alkyl. In specific embodiments, substituents may include optionally substituted with halo, optionally substituted C3-10 carbocyclyl; optionally substituted C1-9 heterocyclyl having one to four heteroatoms independently selected from O, N, and S; optionally substituted C6-20 aryl; optionally substituted C1-9 heteroaryl having one to four heteroatoms independently selected from O, N, and S; —NO2; —ORa; —N(Ra)2; —C(═O)Ra; —C(═O)ORa; —S(═O)2Ra; —S(═O)2ORa; —P(═O)Ra2; —O—P(═O)(ORa)2, or —P(═O)(ORa)2, or an ion thereof; where each Ra is independently H, C1-6 alkyl; optionally substituted C3-10 carbocyclyl; optionally substituted C1-9 heterocyclyl having one to four heteroatoms independently selected from O, N, and S; optionally substituted C6-20 aryl; optionally substituted C1-9 heteroaryl having one to four heteroatoms independently selected from O, N, and S; an oxygen protecting group; or a nitrogen protecting group, and cyclic substituents may also be substituted with C1-6 alkyl. In specific embodiments, alkyl groups may be optionally substituted with one, two, three, or, in the case of alkyl groups of two carbons or more, four substituents independently selected from the group consisting of halo, hydroxyl, C1-6 alkoxy, SO3H, amino, nitro, carboxyl, phosphoryl, phosphonyl, thiol, C1-6 alkyl ester, optionally substituted C1-6 alkyl thio, and oxo, or an ion thereof.
Exemplary ions of substituent groups are as follows: an exemplary ion of hydroxyl is —O−; an exemplary ion of —COOH is —COO−; exemplary ions of —PO3H2 are —PO3H− and —PO32−; an exemplary ion of —PO3HRa is —PO3Ra−, where Ra is not H; exemplary ions of —PO4H2 are —PO4H− and —PO42−; and an exemplary ion of —SO3H is —SO3−.
Here we demonstrate a simple yet effective method, called electrochemical rebalancing, that can remove the adverse effect of molecular oxygen on electrochemical systems. The methods ameliorate the deleterious impacts of reaction with molecular oxygen with only a small energy cost.
This method involves coupling an anodic gaseous oxidation product (e.g., molecular oxygen or CO2) evolution reaction in the negolyte reservoir, with the cathodic reduction reaction in the posolyte reservoir through the application of an electrical pulse to the imbalanced electrochemical system. The system may be symmetrical or asymmetrical, i.e., the posolyte and negolyte may include redox active species that can cycle between the same redox states or between different redox states. When the system is completely out-of-balance, both sides are oxidized, e.g., electrochemically or by reaction with molecular oxygen, and reduction may occur on either side. When the system is partially out-of-balance, e.g., one side is 100% oxidized while the other sized is partially oxidized, reduction may also occur on either side, with accompanying oxygen evolution on the other side. The side on which reduction occurs during discharge is referred to as the posolyte herein.
In an embodiment, the method involves coupling an anodic oxygen evolution reaction in the negolyte reservoir with cathodic Fe(CN)63− reduction reaction in the posolyte reservoir (see, e.g., Table 1). After the electrochemical rebalancing step, the posolyte side will once again be in reduced form (Fe(CN)64−) and the accumulated hydroxide in the negolyte side all converts to oxygen (and water), which is carried away by a carrier gas such as nitrogen. In other words, the initial healthy state of the electrochemical system (e.g., battery or carbon capture cell) is restored by this method.
The scheme of a typical setup is shown in
In Table 1, processes #1 (charge) and #6 (discharge) denote the normal reactions in an AORFB. Process #3 denotes the oxygen oxidation of reduced Q, i.e., QH2. Note that after process #3, since oxygen has oxidized QH2 to Q, process #6, can no longer proceed, as the negolyte now lacks QH2. A consequence of not going through process #6 is the accumulation of hydroxide, which is produced in process #1, in the negolyte side, and the accumulation of Fe(CN)63− in the posolyte side. In other words, process #3 not only causes the battery to discharge without generating electrical power, but also induces an imbalance of electrochemical species, which makes the battery un-rechargeable (cannot undergo process #1). One way to recover the initial condition of the battery is to replace the posolyte with fresh Fe(CN)64− solution; as for the negolyte, the Q molecules need to be extracted from the out-of-balance solution and re-dissolved into a solution with the correct pH and supporting salt concentration. These additional remediations take enormous resources, including material, labor, and time and make the maintenance of such flow batteries impractically expensive.
Processes #2, #5, and #7 are processes related to PCET-mediated carbon capture. Process #2 denotes reaction of CO2 with OH− produced by process #1 to make HCO3− and/or CO32− ions. Processes #7 denotes the reverse reaction of process #2, e.g., to release the captured CO2, e.g., for storage. Process #5 denotes the CO2 evolution reaction induced by the electrical pulse.
Here we introduce the electrochemical rebalancing method, an embodiment of which is shown as process #4. By applying a potential (e.g., via an electrical pulse) that causes process #4, the cell imbalance problem is solved. In embodiments such as shown in Table 1, the accumulated hydroxide in the negolyte is repelled from the solution in the form of oxygen, and the accumulated Fe(CN)63− in the posolyte side is reduced to Fe(CN)64−. As a result, the initial, healthy battery composition is restored, and it can proceed with process #1 again. Other embodiments, using other posolytes and negolytes, e.g., negolytes that do not include proton-coupled changes in oxidation state, are amenable to the methods of the invention.
Devices, e.g., batteries or carbon capture devices, such as those having flow cells, that may be rebalanced according to methods of the invention may include a negolyte that includes, e.g., an organic species, e.g., an anthrahydroquinone dissolved or suspended in aqueous solution; a posolyte that includes, e.g., a redox active species; and a barrier separating the two. The device, e.g., flow device, further includes at least two electrodes, one in contract with the negolyte and one in contact with the posolyte.
In some embodiments, the negolyte includes an organic species that is a hydroquinone. The hydroquinone may be a reduced form of an anthraquinone (e.g., as QH2 in Table 1), e.g., of formula (I):
where each of R1, R2, R3, R4, R5, R6, R7 and R8 is independently selected from H; halo; optionally substituted C1-6 alkyl; oxo; optionally substituted C3-10 carbocyclyl; optionally substituted C1-9 heterocyclyl having one to four heteroatoms independently selected from O, N, and S; optionally substituted C6-20 aryl; optionally substituted C1-9 heteroaryl having one to four heteroatoms independently selected from O, N, and S; —CN; —NO2; —ORa (e.g., hydroxyl or C1-6 alkoxy); —SRa (e.g., thiol or C1-6 alkyl thio); —N(Ra)2 (e.g., amino); —C(═O)Ra; —C(═O)ORa (e.g., carboxyl); —S(═O)2Ra; —S(═O)2ORa (e.g., SO3H); —P(═O)Ra2; and —P(═O)(ORa)2 (e.g., phosphonyl or phosphoryl); or any two adjacent groups selected from R1, R2, R3, and R4 are joined to form an optionally substituted 3-6 membered ring, or an ion thereof, where each Ra is independently H; C1-6 alkyl; optionally substituted C3-10 carbocyclyl; optionally substituted C1-9 heterocyclyl having one to four heteroatoms independently selected from O, N, and S; optionally substituted C6-20 aryl; optionally substituted C1-9 heteroaryl having one to four heteroatoms independently selected from O, N, and S; an oxygen protecting group; or a nitrogen protecting group. An anthraquinone of the invention may be a source of electrons during discharge and not merely a charge transfer agent. In embodiments, the anthraquinone is water soluble.
In certain embodiments, each of R1, R2, R3, R4, R5, R6, R7 and R8 is independently selected from H, optionally substituted C1-6 alkyl, halo, hydroxyl, optionally substituted C1-6 alkoxy, SO3H, amino, nitro, carboxyl, phosphoryl, phosphonyl, and oxo, or an ion thereof. In particular embodiments, each of R1, R2, carboxyl, and SO3H, such as each of R1, R2, R3, R4, R5, R6, R7 and R8 being independently selected from H, hydroxyl, optionally substituted C1-4 alkyl (e.g., methyl), and oxo. In embodiments, at least one, e.g., at least two, of R1, R2, R3, R4, R5, R6, R7, and R8 is not H.
In other embodiments, the anthraquinone, such as a 9,10-anthraquinone, is substituted with at least one hydroxyl group and optionally further substituted with an optionally substituted C1-4 alkyl, such as methyl. Exemplary quinones include 2,6-dihydroxy-9,10-anthraquinone (2,6-DHAQ), 1,5-dimethyl-2,6-dihydroxy-9,10-anthraquinone, 2,3,6,7-tetrahydroxy-9,10-anthraquinone, 1,3,5,7-tetrahydroxy-2,4,6,8-tetramethyl-9,10-anthraquinone, and 2,7-dihydroxy-1,8-dimethyl-9,10-anthraquinone. Ions and reduced species thereof are also contemplated. Quinones having one or more hydroxyl groups may include at least one carboxy C1-4 alkyl (e.g., carboxymethyl) group. An exemplary quinone for use in the device and methods of the invention is 1,8-dihydroxy-2,7-dicarboxymethyl-9,10-anthraquinone:
(DCDHAQ) or a salt thereof.
Other organic species amenable to rebalancing according to methods of the invention include, but are not limited to, naphthoquinones (e.g., hydronaphthoquinones), reduced forms of phenazines (e.g., the reduced form of 7,8-dihydroxyphenazine-2-sulfonic acid), reduced monoquaternized or N,N′-diquaternized phenazines, reduced phenoxazines, reduced phenothiazine, or reduced forms of diquaternized bipyridines (e.g., alkyl viologen radical monocations).
Exemplary reduced phenazines, a N,N′-disubstituted phenazines, monoquaternized phenazines, or N,N′-diquaternized phenazines are, e.g., reduced forms (e.g., 5,10-dihydrophenazines) of formula (II):
or a salt thereof,
In certain embodiments, each of R1, R2, R3, R4, R5, R6, R7 and R8 is independently selected from H, optionally substituted C1-6 alkyl, halo, hydroxyl, optionally substituted C1-6 alkoxy, SO3H, amino, nitro, carboxyl, phosphoryl, phosphonyl, and oxo, or an ion thereof. In particular embodiments, each of R1, R2, R3, R4, R5, R6, R7, and R8 is independently selected from H, hydroxyl, optionally substituted C1-4 alkyl, carboxyl, and SO3H, such as each of R1, R2, R3, R4, R5, R6, R7 and R8 being independently selected from H, hydroxyl, optionally substituted C1-4 alkyl (e.g., methyl), and oxo. In embodiments, at least one, e.g., at least two, of R1, R2, R3, R4, R5, R6, R7, and R8 is not H. In some embodiments, at least one of R1-R8 is a substituted alky or substituted alkoxy.
Exemplary phenazines include, e.g., 7,8-dihydroxyphenazine-2-sulfonic acid. Ions and reduced species thereof are also contemplated.
Exemplary reduced phenoxazines and phenothiazines are reduced forms of, e.g., formula (III):
or a salt thereof,
In certain embodiments, each of R1, R2, R3, R4, R5, R6, R7 and R8 is independently selected from H, optionally substituted C1-6 alkyl, halo, hydroxyl, optionally substituted C1-6 alkoxy, SO3H, amino, nitro, carboxyl, phosphoryl, phosphonyl, and oxo, or an ion thereof. In particular embodiments, each of R1, R2, carboxyl, and SO3H, such as each of R1, R2, R3, R4, R5, R6, R7 and R8 being independently selected from H, hydroxyl, optionally substituted C1-4 alkyl (e.g., methyl), and oxo. In embodiments, at least one, e.g., at least two, of R1, R2, R3, R4, R5, R8, R7, and R8 is not H. In some embodiments, at least one of R1-R8 is a substituted alky or substituted alkoxy.
Exemplary reduced diquaternized bipyridines are reduced forms (e.g., singly reduced radical monocations or doubly reduced 4,4′-bipyridinylidenes) of, e.g., formula (IV):
or a salt thereof,
or a salt thereof.
In particular embodiments, the water-solubilizing group is charged at a pH between 6-8. Further embodiments of diquaternized bipyridines may have the above formula, except that the two pyridines are linked 2-2′ instead of 4-4′. Ions and reduced species thereof are also contemplated.
In some embodiments, the negolyte includes an organic species that is a naphthohydroquinone. The naphthohydroquinone may be a reduced for of a naphthoquinone, e.g., of formula (V):
or a salt thereof,
wherein the dashed bonds are single or double bonds; where either W and X, Wand Z, or Z and Y are C═O, and where the two of W, X, Y, or Z that are not C═O are independently selected from C—R, where R is H; halo; optionally substituted C1-6 alkyl; optionally substituted C3-10 carbocyclyl; optionally substituted C1-9 heterocyclyl having one to four heteroatoms independently selected from O, N, and S; optionally substituted C6-20 aryl; optionally substituted C1-9 heteroaryl having one to four heteroatoms independently selected from O, N, and S; —CN; —NO2; —ORa (e.g., hydroxyl or C1-6 alkoxy); —SRa (e.g., thiol or C1-6 alkyl thio); —N(Ra)2 (e.g., amino); —C(═O)Ra; —C(═O)ORa (e.g., carboxyl); —S(═O)2Ra; —S(═O)2ORa (e.g., SO3H); —P(═O)Ra2; and —P(═O)(ORa)2 (e.g., phosphonyl or phosphoryl); or any two adjacent R groups are joined to form an optionally substituted non-aromatic 3-6 membered ring, or an ion thereof, where each Ra is independently H; C1-6 alkyl; optionally substituted C3-10 carbocyclyl; optionally substituted C1-9 heterocyclyl having one to four heteroatoms independently selected from O, N, and S; optionally substituted C6-20 aryl; optionally substituted C1-9 heteroaryl having one to four heteroatoms independently selected from O, N, and S; an oxygen protecting group; or a nitrogen protecting group; where each of R1, R2, R3, and R4 is independently selected from H; halo; optionally substituted C1-6 alkyl; oxo; optionally substituted C3-10 carbocyclyl; optionally substituted C1-9 heterocyclyl having one to four heteroatoms independently selected from O, N, and S; optionally substituted C6-20 aryl; optionally substituted C1-9 heteroaryl having one to four heteroatoms independently selected from O, N, and S; —CN; —NO2; —ORa (e.g., hydroxyl or C1-6 alkoxy); —SRa (e.g., thiol or C1-6 alkyl thio); —N(Ra)2 (e.g., amino); —C(═O)Ra; —C(═O)ORa (e.g., carboxyl); —S(═O)2Ra; —S(═O)2ORa (e.g., SO3H); —P(═O)Ra2; and —P(═O)(ORa)2 (e.g., phosphonyl or phosphoryl); or any two adjacent groups selected from R1, R2, R3, and R4 are joined to form an optionally substituted 3-6 membered ring, where each Ra is independently H; C1-6 alkyl; optionally substituted C3-10 carbocyclyl; optionally substituted C1-9 heterocyclyl having one to four heteroatoms independently selected from O, N, and S; optionally substituted C6-20 aryl; optionally substituted C1-9 heteroaryl having one to four heteroatoms independently selected from O, N, and S; an oxygen protecting group; or a nitrogen protecting group.
In certain embodiments, each of R1, R2, R3, and R4 is independently selected from H, optionally substituted C1-6 alkyl, halo, hydroxyl, optionally substituted C1-6 alkoxy, SO3H, amino, nitro, carboxyl, phosphoryl, phosphonyl, and oxo, or an ion thereof. In particular embodiments, each of R1, R2, R3, and R4 is independently selected from H, hydroxyl, optionally substituted C1-4 alkyl, carboxyl, and SO3H, such as each of R1, R2, R3, and R4 being independently selected from H, hydroxyl, optionally substituted C1-4 alkyl (e.g., methyl), and oxo. In embodiments, at least one, e.g., at least two, of R1, R2, R3, and R4 is not H. In some embodiments, at least one of R1-R4 is a substituted alkyl or substituted alkoxy. Ions and reduced species thereof are also contemplated.
Organic species, e.g., hydroquinones, may be present in a mixture. An organic species of the invention is a source of electrons during discharge and not merely a charge transfer agent. In embodiments, the organic species is water soluble. In some embodiments, the negolyte is a polymer, e.g., a polymer including a redox active species described herein, e.g., a polyquinone.
Organic species may be, e.g., those described in WO 2019/157437, WO 2018/032003, WO 2019/136374, WO2014/052682, and WO 2015/048550, which are hereby incorporated by reference.
In some embodiments, the negolyte includes an inorganic redox active species, e.g., vanadium (e.g., V3+/V2+) and a polysulfide (e.g., S42−/S44−).
The devices may also employ 2,2,6,6-tetramethylpiperidine N-oxyl (TEMPO) or a substituted version thereof (e.g., substituted like a heterocycle as described herein). Such species may be employed to capture CO2 on the positive side of the device.
Examples of redox active species for the posolyte include bromine, chlorine, iodine, vanadium, chromium, cobalt, iron (e.g., ferricyanide/ferrocyanide or a ferrocene derivative, e.g., as described in WO 2018/032003), aluminum, e.g., aluminum (III) biscitrate monocatecholate, manganese, cobalt, nickel, copper, or lead, e.g., a manganese oxide, a cobalt oxide, or a lead oxide. A benzoquinone may also be used as the second redox active species. Other redox active species suitable for use in batteries of the invention are described in WO 2014/052682, WO 2015/048550, WO 2016/144909, and WO 2020/072406, the redox active species of which are incorporated by reference. The redox active species may be dissolved or suspended in solution (such as aqueous solution) or be in the solid state.
In some embodiments, the electrolytes are both aqueous, where the negolyte and posolyte, e.g., an anthraquinone and redox active species, are in aqueous solution or aqueous suspension. In addition, the electrolyte may include other solutes, e.g., acids (e.g., HCl) or bases (e.g., LiOH, NH4OH, NaOH, or KOH) or alcohols (e.g., methyl, ethyl, or propyl) and other co-solvents to increase the solubility of a particular species, e.g., quinone/hydroquinone. Counter ions, such as cations, e.g., NH4+, Li+, Na+, K+, or a mixture thereof, may also be present. In certain embodiments, the pH of one or both of the electrolytes may be >7, e.g., at least 8, 9, 10, 11, 12, 13, or 14, 8-14, 9-14, 10-14, 11-14, 12-14, 13-14, or about 14. In certain embodiments, the pH of one or both of the electrolytes may be <7, e.g., at less than 7, 6, 5, 4, 3, 2, or 1, e.g., 7-1, 7-5, 6-4, 5-2, 3-1, 2-1, or about 1. The pH may be less than 1. The pH may be a negative pH. The electrolyte may or may not be buffered to maintain a specified pH. The negolyte and posolyte will be present in amounts suitable to operate the device, e.g., battery or carbon capture device, for example, from 0.1-15 M, or from 0.1-10 M. In some embodiments, the solution is at least 10%, 20%, 30%, 40%, 50%, 60%, 70%, or 80% water, by mass. Negolytes, e.g., organic species, e.g., quinones, hydroquinones, salts, and/or ions thereof, or inorganic species, e.g., polysulfides, may be present in a mixture.
The concentration of the organic species and redox active species may be any suitable amount. Ranges include, for example, from 0.1 M to liquid species, e.g., 0.1-15 M. In addition to water, solutions or suspensions may include alcohols (e.g., methyl, ethyl, or propyl) and other co-solvents to increase the solubility of a particular species. In some embodiments, the solution or suspension is at least 10%, 20%, 30%, 40%, 50%, 60%, 70%, or 80% water, by mass. Alcohol or other co-solvents may be present in an amount required to result in a particular concentration of species. The pH of the aqueous solution or suspension may also be adjusted by addition of acid or base, e.g., to aid in solubilizing a species.
Electrodes are disposed to provide an electrical pulse to the posolyte and negolyte. The voltage requirements for the electrical pulse may depend upon the electrochemical properties of the posolyte and negolyte. In certain embodiments the electrodes are disposed to provide the electrical pulse at a potential sufficient to reduce the redox active species in the posolyte and oxidize a component of the negolyte (e.g., an oxidation reaction product of the first redox active species with molecular oxygen, e.g., H2O or OH−) to a gaseous oxidation product (e.g., molecular oxygen or water), e.g., at a potential that is more negative than the discharge cycle voltage of the electrochemical system, e.g., about 50-100 mV, 100-300 mV, 200-600 mV, 100-700 mV, 500-1000 mV, 400-800 mV, 300-900 mV, 1000-1500 mV, 800-1200 mV, 400-1400 mV, or 1200-1500 mV, e.g., about 50 mV, 100 mV, 200 mV, 300 mV, 400 mV, 500 mV, 600 mV, 700 mV, 800 mV, 900 mV, 1000 mV, 1100 mV, 1200 mV, 1300 mV, 1400 mV, or 1500 mV, e.g., at least 100 mV, 200 mV, 300 mV, 400 mV, 500 mV, 600 mV, 700 mV, 800 mV, 900 mV, 1000 mV, 1100 mV, 1200 mV, 1300 mV, 1400 mV, or 1500 mV more negative than the reduction potential of a redox active species in the posolyte.
The barrier allows the passage of ions, such as sodium or potassium, but not a significant amount of the negolyte or other redox active species. Examples of ion conducting barriers are NAFION®, i.e., sulfonated tetrafluoroethylene based fluoropolymer-copolymer, FUMASEP®, i.e., non-fluorinated, sulfonated polyaryletherketone-copolymer, e.g., FUMASEP® E-620(K), hydrocarbons, e.g., polyethylene, and size exclusion barriers, e.g., ultrafiltration or dialysis membranes with a molecular weight cut off of 100, 250, 500, or 1,000 Da. For size exclusion membranes, the required molecular weight cut off is determined based on the molecular weight of the negolytes and posolytes employed. Porous physical barriers may also be included, e.g., when the passage of redox active species is tolerable. A redox cell may have two barriers and a central compartment disposed therebetween.
A device, e.g., battery or carbon capture device, amenable to rebalancing according to methods of the invention may include additional components as is known in the art. Negolytes and posolytes may be housed in a suitable reservoir. A device, e.g., battery or carbon capture device, may include one or more flow cells and further include one or more pumps to pump the posolyte and/or negolyte past one or both electrodes. Alternatively, the electrodes may be placed in a reservoir that is stirred or in which the solution or suspension is recirculated by any other method, e.g., convection, sonication, etc. A device, e.g., battery or carbon capture device, may also include graphite flow plates and corrosion-resistant metal current collectors.
The device may further include fluid handling and storage elements, and voltage and round-trip energy efficiency measurements can be made. Systems configured for measurement of negolyte and posolyte flows and pH, pressure, temperature, current density and cell voltage may be included and used to evaluate cells, e.g., to determine when to apply the electrical pulse. Fluid sample ports can be provided to permit sampling of both electrolytes, which will allow for the evaluation of parasitic losses due to reactant crossover or side reactions. Electrolytes can be sampled and analyzed with standard techniques.
Suitable cells, electrodes, membranes, and pumps for redox flow batteries are known in the art, e.g., WO 2014/052682, WO 2015/048550, WO 2016/144909, and WO 2020/072406, the battery components of which are hereby incorporated by reference.
Carbon Capture with Proton-Coupled Redox Active Species
The invention can be used for an electrochemical CO2 capture system, e.g., employing proton-coupled redox active species whose protonation and deprotonation can be controlled electrochemically to modify the pH of an aqueous solution or aqueous suspension. This change in pH can be used to sequester and release CO2. The CO2 capture device can be used to sequester gaseous CO2 from a point source, such as flue gas, or from ambient air. The total possible amount of sequestered carbon, the Dissolved Inorganic Carbon (DIC), depends on the partial pressure of CO2 above the aqueous solution or aqueous suspension, and the pH determines the form of the carbon, e.g., dissolved CO2, HCO3−; or CO32−. CO2 can be captured from a gaseous source, e.g., point sources or ambient air, by dissolving into an aqueous solution. More CO2 can be dissolved as the pH of the aqueous solution or aqueous suspension increases, resulting in the conversion of CO2 into HCO3− or CO32− ions. More CO2 can be dissolved in an aqueous solution or aqueous suspension as HCO3− or CO32− than CO2, resulting in supersaturation of CO2 in the aqueous solution or aqueous suspension. Once captured, the CO2 can be released by acidifying the aqueous solution or aqueous suspension. In principle, the pure CO2 obtained after separation can be converted back into useful chemical fuels and feedstocks with carbon-free energy, thus providing fuels and feedstocks without added CO2 emissions.
The use of redox-active species and cell architectures that impose minimal kinetic losses while preserving the pH gradient would be advantageous to realizing electrochemical CCS at low energetic cost. In some embodiments, the electrochemical carbon capture cycle described herein may operate with an ion-selective membrane and be able to make use of any redox-active species within a wide array of reactants capable of PCET. In the AORFB literature, several organic molecules have been shown to have kinetic rate constants on the order of 10−3 cm/s or above on inexpensive carbon electrodes, demonstrating the wide availability of reactants for CO2 separation that will impose minimal energetic losses in an electrochemical cell.
In addition to minimal energetic losses, another important criterion for wide scale adoption of CO2 separation technology is the use of low-cost cell components and working fluids. The process described here can, in principle, use water-soluble molecules and aqueous electrolytes. This is in contrast to most of the electrochemical CO2 separation methods that do not feature the use of a pH swing which have been described in the literature, involving direct binding of CO2 to reduced quinones and oxygen-assisted conversion of CO2 to oxalate species-all of which require more expensive organic solvents to operate.
Electrochemically mediated amine regeneration (EMAR) has been experimentally demonstrated to require an exceptionally low electrical energy input of 100 KJ/molCO2, which is comparable to what may be expected of our process assuming similar second-law efficiencies.
When a voltage is applied to an aqueous solution or aqueous suspension containing a proton-coupled redox active species, e.g., a hydroquinone, a hydrophenazine, or others, the proton-coupled redox active species is reversibly oxidized, releasing one or more protons or electrons. The protons released reduce the pH of the aqueous solution or aqueous suspension, resulting in the release of CO2 from the aqueous solution. Reducing the proton-coupled redox active species after releasing CO2 then increases the pH of the aqueous solution or aqueous suspension by removing protons, thereby allowing absorption of more CO2 at higher pH.
An advantage of this invention is the reduced energy input required to capture CO2. In general, all methods of capturing CO2 require some level of energy input, e.g., thermal, electrical, or both. Most currently available methods require anywhere from ˜100 to 600 KJ/molCO2 to capture CO2 because of losses from metal catalyst interactions (e.g., binding), water splitting reactions, and/or other endothermic processes, such as material regeneration. In contrast, CO2 capture devices used with the present invention eliminate the need for thermal energy input and reduce the electrical energy input required to potentially between 15-70 KJ/molCO2 (e.g., 30-70 KJ/molCO2), about 30% less energy intensive than competing technologies. The present invention also does not require water splitting or metal catalysts for operation.
CO2 capture devices to which methods of the invention may be applied can be based on the use of a proton-coupled redox active species, e.g., those disclosed herein, e.g., a hydrophenazine/phenazine couple, hydroquinone/quinone couple, or other redox-active couple.
Nitrogen or other inert gas may be used to purge the negolyte of dissolved gases, e.g., oxygen or CO2. The outlet may be connected to a storage container for CO2.
In some cases, the CO2 capture device includes two or more electrochemical cells, with each cell having its electrodes separated by both a cation-exchange membrane (CEM) and an anion exchange membrane (AEM). In this configuration, the use of both a CEM and an AEM in each electrochemical cell blocks the crossover of anionic proton acceptors and H+, respectively. This device configuration allows the electrochemical cell to be integrated within an aqueous flow battery architecture for simultaneous CCS and energy storage/conversion. Each electrochemical cell is configured to include additional redox processes occurring counter to the redox processes of the redox-active couple that drives the capture and release of CO2 in the device. The counter redox processes may be symmetric with respect to the redox-active couple that drives the capture and release of CO2 in the device, e.g., if the redox process driving CO2 capture and release is Q/QH2, then the counter process is QH2/Q. Alternatively, the counter redox processes may be asymmetric with respect to the redox-active couple that drives the capture and release of CO2 in the device. The counter redox active species may be any suitable species, such as bromine, chlorine, iodine, oxygen, vanadium, chromium, cobalt, iron, e.g., ferricyanide/ferrocyanide, aluminum, e.g., aluminum (III) biscitrate monocatecholate, manganese, cobalt, nickel, copper, or lead, e.g., a manganese oxide, a cobalt oxide, or a lead oxide.
During invasion, the high-pH liquid may be sprayed down through a solid lattice, providing a liquid/gas interface for CO2 in the gas to enter the liquid. A similar lattice may be employed when CO2 gas is released from the liquid.
The ion conducting barrier allows the passage of ions from an aqueous solution, but preferably not a significant amount of the proton-coupled redox active species. In particular, an anionic exchange membrane can be used, e.g., to allow chloride ions to pass. Anion specific conducting barriers are typically ionomers, e.g., ion-conducting polymers, including, but not limited to aromatics, e.g., xylylenes, polysulfones, e.g., polyethersulfone, and amine functionalized fluoropolymers, e.g., FUMASEP®. Examples of membranes include Selemion DSV and Selemion AMV. Other anion-specific ion conducting barriers are known in the art.
Exemplary proton-coupled redox active species for use in carbon capture redox flow cells include organic species such as described herein, e.g., quinones, phenazines (e.g., phenazine dihydroxysulfonic acid), alloxazines, isoalloxazines, polyoxometalates (e.g., tungsten-based polyoxoanion), and their reduced counterparts. The ability of phenazines and quinones to both accept and release a proton at modest electrical potentials makes them ideal candidates for creating pH “swings” in an aqueous solution.
Electrodes for use with batteries and CO2 capture devices may include any carbon electrode, e.g., glassy carbon electrodes, carbon paper electrodes, carbon felt electrodes, or carbon nanotube electrodes. Titanium electrodes may also be employed. Electrodes can also be made of a high specific surface area conducting material, such as a nanoporous metal sponge (T. Wada, A. D. Setyawan, K. Yubuta, and H. Kato, Scripta Materialia 65, 532 (2011)), which has been synthesized previously by electrochemical dealloying (J. D. Erlebacher, M. J. Aziz, A. Karma, N. Dmitrov, and K. Sieradzki, Nature 410, 450 (2001)), or a conducting metal oxide, which has been synthesized by wet chemical methods (B. T. Huskinson, J. S. Rugolo, S. K. Mondal, and M. J. Aziz, arXiv: 1206.2883 [cond-mat.mtrl-sci]; Energy & Environmental Science 5, 8690 (2012); S. K. Mondal, J. S. Rugolo, and M. J. Aziz, Mater. Res. Soc. Symp. Proc. 1311, GG10.9 (2010)). Chemical vapor deposition can be used for conformal coatings of complex 3D electrode geometries by ultra-thin electrocatalyst or protective films. Other electrodes are known in the art.
As described, the invention provides methods for reducing the loss of capacity due to reactions with molecular oxygen in electrochemical systems, e.g., AORFB or PCET carbon capture systems. In the methods, an electrical pulse sufficient to generate a gaseous oxidation product (e.g., molecular oxygen) on the negolyte side rebalances the electrochemical system unbalanced by reaction of the negolyte with molecular oxygen (e.g., to produce oxidized redox active species and OH−). The electrical pulse may also reduce the redox active species in the posolyte.
In addition to carbon capture cells (e.g., flow cells), which employ organic PCET systems that have pH swing ranging from neutral to basic, the electrochemical rebalancing method can be applied to other aqueous based electrochemical systems, including organic and inorganic, PCET or non-PCET, acidic or basic, dissolved or solid redox active materials. The following are examples of electrochemical systems to which the methods of the invention may be applied.
Organic Non-PCET System in Neutral Aqueous Solution: Fe(CN)6 (posolyte)|Viologen (negolyte) Flow Battery
When the viologen-based redox flow battery is charged: oxygen can chemically oxidize the reduced viologen to the oxidized state, accumulating hydroxide in the negolyte, leading to the negolyte to discharged state and the posolyte active species maintaining the oxidized state. Since the redox active core of viologens have two positive charges, their oxidized is Vi2+ and the single-electron reduced form is Vi+. The battery gets “self-discharged.”
½O2+2Vi++H2O→Vi2++2OH−
The electrochemical rebalancing method can remove the accumulated hydroxide, repelling O2:
2OH−→1OH2+H2O+2e−
During the electrochemical rebalancing process, the electrons are transferred to the posolyte side, which has accumulated Fe(CN)63−, and eventually both negolyte and posolyte sides are recover the their initial composition, i.e., Fe(CN)64− in posolyte and Vi2+ in negolyte, rebalancing the system.
Inorganic Non-PCET system in strongly acidic aqueous solution: VO2+/VO+ (posolyte)|V3+/V2+ (negolyte) Flow Battery
When a vanadium redox flow battery negolyte contains the charged form, i.e., V2+: if oxygen diffuses into the negolyte, it can chemically oxidize V2+ to V3+, and hydroxide is accumulated in the negolyte,
½O2+2V2++H2O→V3++2OH−
The electrochemical rebalancing method can remove the accumulated hydroxide, repelling O2:
2OH−→½O2+H2O+2e−
Since the electrolyte of a vanadium redox flow battery is strongly acidic, the hydroxide is readily neutralized to water. Hence the oxidation reaction is:
½O2+2V2++2H+→V3++H2O
Thus, instead of generating two hydroxides in the negolyte, the oxidation by oxygen reaction causes the loss of two protons. And the electrochemical rebalancing method in such scenario is as follows:
H2O→½O2+2H++2e−
During the electrochemical rebalancing process, the electrons are transferred to the posolyte side, which has accumulated the oxidized form VO2+, through
(2VO2++2e−→2VO2+)
and eventually both negolyte and posolyte sides are restored to the initial state (VO2+ for posolyte and V3+ for negolyte), thus rebalancing the system.
Inorganic Non-PCET System in Basic Aqueous Solution: Air (Posolyte)|S42−/S44− (Negolyte) Battery
When a sulfur-air flow battery is charged: if oxygen diffuses into the polysulfide negolyte, oxygen can chemically oxidize polysulfide, and hydroxide is accumulated in the negolyte:
½O2+2S44−+H2O→2S42−+2OH−
The electrochemical rebalancing method can remove the accumulated hydroxide, repelling O2:
2OH−→½O2+H2O+2e−
During the electrochemical rebalancing process, the electrons are transferred to the posolyte side externally, eventually both negolyte and posolyte sides are discharged, thus rebalancing the system.
Liu et al. (Nature Communications 2020, 11, 2278) demonstrated a solid quinone aqueous carbon capture system, where the cathode is LiFePO4 and the anode is a polyquinone (PAQ) tethered to a carbon electrode. The authors utilized a 20 molal LiTFSI aqueous solution to ensure that the reduced PAQ are deprotonated, i.e., PAQ2−, which then binds with CO2 to form PAQ-CO2 adduct. Oxygen in this system can cause long term imbalance (accumulation of oxidized cathode material and accumulated LiOH in the anode side).
When the anode is charged: oxygen can chemically oxidize the air-sensitive anode, and hydroxide is accumulated in the negolyte:
½O2+H2O+PAQ2−→PAQ+2OH−
The electrochemical rebalancing method can remove the accumulated hydroxide, repelling O2:
2OH−→½O2+H2O+2e−
During the electrochemical rebalancing process, the electrons are transferred to the cathode side externally, eventually both anode and cathode are discharged, rebalancing the system.
Methods of the invention include rebalancing the electrochemical device by, e.g., application of an electrical pulse. For example, providing an electrical pulse of appropriate potential to the negolyte and posolyte for a time sufficient to revert at least half of the redox active species in the posolyte to its reduced form and produce an amount of gaseous oxidation product equimolar to at least half the amount of negolyte redox active species to have been oxidized by molecular oxygen. The electrical pulse may be sufficient to revert, for example, at least 1% of the redox active species in the posolyte to its reduced form, e.g., from about 1% to 100% (e.g., about 1-10%, about 10-20%, about 20-30%, about 30-40%, about 40-50%, about 50-60%, about 60-70%, about 70-80%, about 80-90%, or about 90-100% or at least about 10%, at least about 25%, at least about 50%, at least about 75%, or at least about 95%).
The duration of the electrical pulse may depend on, e.g., the volume of negolyte. The electrical pulse may be applied for at least 1 min (e.g., about 1 to 2 min, 2 to 3 min, 3 to 4 min, 4 to 5 min, 5 min to 6 min, 6 min to 7 min, 7 min to 8 min, 8 min to 9 min, or 9 min to 10 min), or, e.g., at least 10 min (e.g., about 10 to 20 min, 20 to 30 min, 30 to 40 min, 40 to 50 min, or 50 min to 60 min, or longer). The electrical pulse may be applied for between about 0.1 to about 48 hours (e.g., about 0.1 to 1 hours, 1 to 2 hours, 2 to 3 hours, 3 to 5 hours, 5 to 10 hours, 10 to 20 hours, 20 to 30 hours, 30 to 40 hours, or about 40 to 50 hours). The duration of the electrical pulse may be several days, e.g., between about 1 to 14 days (e.g., about 1 to 2 days, 2 to 5 days, 5 to 10 days, or 10 to 14 days.
The pulse can either be ‘potentiostatic’ (e.g., at constant potential), or ‘galvanostatic’ (e.g., at constant current), or mixture of both. The potential during the pulse may be variable. Where the potential during the pulse is variable, it may range between 50 mV to 1500 mV, e.g., about 50-100 mV, 100-300 mV, 200-600 mV, 100-700 mV, 500-1000 mV, 400-800 mV, 300-900 mV, 1000-1500 mV, 800-1200 mV, 400-1400 mV, or 1200-1500 mV, e.g., about 50 mV, 100 mV, 200 mV, 300 mV, 400 mV, 500 mV, 600 mV, 700 mV, 800 mV, 900 mV, 1000 mV, 1100 mV, 1200 mV, 1300 mV, 1400 mV, or 1500 mV, e.g., at least 100 mV, 200 mV, 300 mV, 400 mV, 500 mV, 600 mV, 700 mV, 800 mV, 900 mV, 1000 mV, 1100 mV, 1200 mV, 1300 mV, 1400 mV, or 1500 mV more negative than the open circuit voltage in fully discharged state, e.g., for at least about 1% of the pulse time, e.g., about 1% to 99% of the pulse time, (e.g., about 1-10%, 10-20%, 20-30%, 30-40%, 40-50%, 50-60%, 60-70%, 70-80%, 80-90%, or 10-100% of the pulse time).
In embodiments of the methods described herein, the device is cycled for a given number of cycles, e.g., 100 times, 1000 time, 10,000 times, etc., before the pulse is applied. In some embodiments, the pulse is applied once the device is measured to have a certain condition, e.g., having the capacity fully or partially (e.g., 1-10% 100-20%, 20-30%, 30-40%, 40-50%, 50-60%, 60-70%, 70-80%, 80-90%, or 90-99%) depleted, or, e.g., having a certain pH (e.g., between 9 and 14, or about 14, or greater than 14). The method may be automated. A neutral carrier gas may be used to purge the gaseous oxidation product generated by the electrical pulse. Alternatively, a negative pressure may be applied to remove the gaseous oxidation product. In a carbon capture system, components for collecting captured carbon may be applied to remove CO2 produced (see Table 1) by the electrical pulse.
The methods of the invention may be employed to reduce loss of capacity as a function of time (independent of the number of cycles). In embodiments, the methods reduce the loss of capacity to a rate of less than 5% per day, e.g., less than 4, 3, 2, 1, 0.5, 0.1, 0.05, or 0.001. For example, the loss of capacity may be between 0.0001-5% per day, e.g., 0.0001-1%, 0.0001-0.1%, 0.0001-0.05%, 0.001-1%, 0.001-0.1%, 0.001-0.05%, 0.01-1%, 0.01-0.5%, or 0.01-0.1%. The methods may be practiced for a period of at least one week, one month, six months, or one year. The method may be applied to any organic or organometallic redox active species, such as an anthraquinone as described herein.
The invention will be further described by the following non-limiting examples.
Electrochemical rebalancing according to methods of the invention was demonstrated with a flow battery composed of 35 mL 0.1 M Fe(CN)64− plus 0.04 M Fe(CN)63− in 1 M KCl solution as posolyte and 11 mL 0.1 M sodium 3,3′-(phenazine-2,3-diyl)bis(propane-1-sulfonate) (DSPZ) in 1 M KCl as negolyte. Note that the theoretical capacity of the posolyte side and negolyte side is 472 Coulombs and 212 (capacity-limiting) Coulombs, respectively and both sides have an initial pH of ˜9. The membrane used is Fumasep E-620 (K) cation exchange membrane, and the electrodes are 4 pieces Sigracet SGL39AA.
The battery was first cycled (repeatedly going through processes #1 and #6) under inert (N2) atmosphere. The cycling protocol was at a constant current of ±40 mA/cm2 with potential cutoffs of 1.65 V for charging and 0.2 V for discharging. When the potential cutoff is reached, the cell keeps going through potentiostatic cycling until the current reaches ±10 mA/cm2 cutoff. As shown in
As shown in
After the electrochemical rebalancing step, the electrolytes were once again purged continuously with nitrogen.
The electrochemical reactions that take place in an electrochemical carbon capture flow cell are essentially the same as in a flow battery. The additional reactions, however, are the chemical reactions between hydroxide and CO2. Process #2 and #4 in Table 1 denote the CO2 capture and evolution steps, respectively. Note that only the bicarbonate reaction is included here for convenience. When it comes to the adverse effect of oxygen, process #3 once again shifts the balance of the posolyte side toward complete Fe(CN)63−, but now HCO3−, instead of OH−, accumulates in the negolyte side. Again, without rebalancing, the cell is not capable of performing further carbon capture duties. As the electrochemical rebalancing process proceeds, there will be simultaneous decomposition of HCO3− and evolution of CO2, i.e., process #5, the cell balance will be restored eventually.
Other embodiments are in the claims.
This invention was made with government support under DE-AC05-76RLD1830, awarded by the Department of Energy. The government has certain rights in the invention.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/US2022/041188 | 8/23/2022 | WO |
| Number | Date | Country | |
|---|---|---|---|
| 63236169 | Aug 2021 | US |
