Patent Application
20220029188
The present disclosure relates to the field of redox flow battery technology. The disclosure relates more particularly, but not necessarily exclusively, to catholytes (positive electrolytes) for use in redox flow batteries.
Redox flow batteries (RFBs) are well known. They are electrochemical apparatus for power delivery and energy storage by means of a chemical redox reaction.
The chemical processes occurring in these systems can typically proceed in one direction in a power delivery mode (e.g. with a redox active species becoming reduced) and in the opposite direction during an energy storage mode (e.g. with the redox active species becoming oxidised).
In the power delivery mode, redox active species are supplied to electrodes where they react electrochemically to produce electrochemical power. RFBs can adjust their power output to meet fluctuating demand by altering the flow of electrolyte species for reaction. Because the redox active species can be stored separately from the electrode compartments and supplied when required, the generating capacity of this equipment is easily scalable.
Recent advancements in RFB systems have focussed on vanadium-type systems. Such systems can be exemplified by the following redox chemical equation:
However, there are limited worldwide reserves of vanadium and its availability can be volatile. This affects scalability and the uptake of RFB technology.
It is desirable to provide an RFB with an alternative electrolyte and/or to provide an alternative electrolyte and/or to provide an improved RFB and/or to obviate or mitigate issues with existing RFBs, whether identified herein or otherwise.
According to the present disclosure, there is provided a redox flow battery comprising a gaseous anolyte and, as a catholyte, an organic redox active species having at least one electron directing moiety, wherein the organic redox active species is not unsubstituted parabenzoquinone.
There is also provided a catholyte for use in a redox flow battery, comprising an organic redox active species having at least one electron directing moiety as defined herein.
There is also provided a use of a catholyte in a redox flow battery, wherein the catholyte is an organic redox active species having at least one electron directing moiety as defined herein.
In accordance with standard terminology in the field of redox flow batteries, the terms “anode” and “cathode” are defined by the functions of the electrodes in the power delivery mode. To avoid confusion, the same terms are maintained herein to denote the same electrodes whether in a power deliver mode of operation or an energy storage mode of operation.
The terms “anolyte” and “catholyte” are used to denote the electrolyte in contact with the “anode” and “cathode”.
A “redox flow battery” comprises an electrochemical cell for the conversion of chemical energy into electricity. A redox flow battery comprises an anode compartment comprising an anode and an anolyte fluid (i.e. a gas or liquid) and a cathode compartment comprising a cathode and a catholyte fluid (i.e. a gas or liquid). A selective membrane is provided between the two compartments and is configured to exchange ions between the two compartments. In the present disclosure, the catholyte fluid is a liquid.
The compartments of electrolyte (catholyte and anolyte) fluid may be charged separately with two different “redox active species” that are each able to undergo reversible reduction-oxidation reactions. This allows the redox active species in one compartment to undergo, for example, an oxidation reaction while the redox active species in the other compartment undergoes a reduction reaction. The redox reactions cause a net flow of electrons between the compartments, thus generating an electrical current.
The term “alkyl” refers to a straight chain or branched, substituted or unsubstituted (e.g. unsubstituted) group containing from 1 to 40 carbon atoms (optionally from 1 to 20, such as from 1 to 10, such as from 1 to 5, optionally 2 carbon atoms). An alkyl group may optionally be substituted at any position.
The term “electron directing moiety” refers to a functional moiety that either donates (“electron donating group” or “electron releasing group”) or withdraws (“electron withdrawing group”) electron density from part of a molecule, increasing or reducing electronegativity. The electron-donating or electron-withdrawing properties of several hundred of the most common substituents, reflecting all common classes of substituents have been determined, quantified, and published. The most common quantification of electron-donating and electron-withdrawing properties is in terms of Hammett a values. Hydrogen has a Hammett a value of zero, while other substituents have Hammett a values that increase positively or negatively in direct relation to their electron-withdrawing or electron-donating characteristics. Substituents with negative Hammett a values are considered electron-donating, while those with positive Hammett a values are considered electron-withdrawing. See Lange's Handbook of Chemistry, 12th ed., McGraw Hill, 1979, Table 3-12, pp. 3-134 to 3-138, which lists Hammett a values for a large number of commonly encountered substituents.
The term “polymer” or “poly” when used to qualify a molecule refers to a molecule whose structure comprises multiple repeating units. The molecule may have 5, 6, 7, 8, 9, 10, or more repeat units. The molecule may have many repeat units, such as 100, 1,000, 10,000, or more. The term “copolymer” or “co-poly” when used to qualify a molecule refers to a molecule whose structure comprises at least two types of repeating units. The molecule may have 5, 6, 7, 8, 9, 10, or more repeat units of each type. The molecule may have many repeat units of each type, such as 100, 1,000, 10,000, or more.
The term “dendrimer” refers to a branched molecule comprising a core unit and having at least three constitutional repeating units pendant from the core unit (such as 5, 6, 7, 8, 9, 10, or more constitutional repeating repeat units). A dendrimer may have many repeat units, such as 100, 1,000, 10,000, or more. The “core unit” may comprise a polymeric skeleton (e.g. a polyethylene chain) from which constitutional repeating units depend. The core unit may comprise a non-polymeric central moiety from which constitutional repeating units depend (e.g. a benzene ring comprising 6 pendant constitutional repeating units). A “constitutional repeating unit” may be any suitable moiety, such as an optionally substituted aliphatic moiety, cyclic moiety, ester moiety, amide moiety, etc.
The term “dendron” refers to a part of a molecule comprising repetitive (at least three) terminal constitutional repeating units. A dendron has one free valence and is thereby able to join to a core unit. Each path from the free valence to any end-group may comprise the same number of repeating units. A dendron may form part (e.g. be the constitutional repeat unit) of a dendrimer.
The term “halogen atom”, “halo” or “halogen”, refers to a group 7 element of the Periodic Table of the Elements, such as, fluorine, chlorine, bromine and iodine, optionally fluorine or chlorine, optionally fluorine.
The term “carbocyclic compound” as used herein refer to a saturated or unsaturated cyclic aliphatic or aromatic monocyclic or polycyclic (including fused, bridging and spiro-fused) ring system which has from 3 to 20 carbon atoms. A carbocyclic compound may have from 3 to 15, such as from 3 to 12, such as from 3 to 10, such as from 3 to 8 carbon atoms, such as from 3 to 6 carbons atoms. Carbocyclic compounds groups may be substituted or unsubstituted, branched or unbranched.
A “heterocyclic compound” is a carbocyclic compound as described above, which additionally contains one or more heteroatoms. The heterocyclic compound may contain from 1 to 5 heteroatoms, such as from 1 to 4 heteroatoms, such as from 1 to 3 heteroatoms, such as 1 or 2 heteroatoms. Heterocyclic compounds may contain from 4 to 21 atoms, such as from 4 to 16 atoms, such as from 4 to 13 atoms, such as from 4 to 11 atoms, such as from 4 to 9 atoms, such as from 4 to 7 atoms, wherein at least one atom is a carbon atom. Suitable heteroatoms are selected from O, S, N, P and Si. When heterocyclic compounds have two or more heteroatoms, the heteroatoms may be the same or different. Heterocyclic compounds groups may be substituted or unsubstituted, branched or unbranched.
As used herein, the term “optionally substituted” means that one or more of the hydrogen atoms in the optionally substituted moiety is replaced by a suitable substituent. Unless otherwise indicated, an “optionally substituted” group may have a suitable substituent at each substitutable position of the group, and when more than one position in any given structure may be substituted with more than one substituent selected from a specified group, the substituent may be either the same or different at every position. Combinations of substituents envisioned by this invention are preferably those that result in the formation of stable compounds. The term “stable”, as used herein, refers to compounds that are chemically feasible and can exist for long enough at room temperature (i.e. 16-25° C.) to allow for their detection, isolation and/or use in chemical synthesis.
Any of the above groups (for example, those referred to herein as “optionally substituted”, including alkyl, aryl and heteroaryl groups) may optionally comprise one or more substituents, preferably selected from silyl, sulfo, sulfonyl, formyl, amino, imino, nitrilo, mercapto, cyano, nitro, halogen, —NCO, —NCS, —OCN, —SCN, —C(═O)NR0R00, —C(═O)X0, —C(═O)R0, —NR0R00, C1-12alkyl, C1-12 alkenyl, C1-12 alkynyl, C6-12 aryl, C3-12cycloalkyl, heterocycloalkyl having 4 to 12 ring atoms, heteroaryl having 5 to 12 ring atoms, C1-12 alkoxy, hydroxy, C1-12 alkylcarbonyl, C1-12 alkoxy-carbonyl, C1-12 alkylcarbonyloxy or C1-12 alkoxycarbonyloxy wherein one or more H atoms are optionally replaced by F or Cl and/or combinations thereof; wherein X0 is halogen and R0 and R00 are, independently, H or optionally substituted C1-12 alkyl. The optional substituents may comprise all chemically possible combinations in the same group and/or a plurality of the aforementioned groups (for example amino and sulfonyl if directly attached to each other represent a sulfamoyl radical).
The term “alkenyl” or “vinyl” refers to an unsubstituted or substituted alkyl group [comprising from 2 to 40 carbon atoms (optionally from 2 to 20, such as from 2 to 10, such as from 1 to 5, such as from 2 to 5, optionally 2 carbon atoms)] that comprises, in the straight or branched hydrocarbon chain, one or more carbon-carbon double bonds.
The term “alkynyl” refers to an unsubstituted or substituted alkyl group [comprising from 2 to 40 carbon atoms (optionally from 2 to 20, such as from 2 to 10, such as from 2 to 5, optionally 2 carbon atoms) that comprises a straight or branched hydrocarbon chain comprising one or more carbon-carbon triple bonds.
The term “carbonyl” refers to an unsubstituted or substituted —C(O)RA group, wherein RA is hydrogen, or an alkyl, alkenyl or alkynyl group.
The term “ester” refers to an unsubstituted or substituted —C(O)ORB (C-linked ester) or —OCORB (O-linked ester) group, wherein RB is an alkyl, alkenyl or alkynyl group.
The term “amide” refers to an unsubstituted or substituted —C(O)NRC2 (C-linked amide) or —NRCCORD (N-linked amide) group, wherein each RC and/or RD are, independently, hydrogen, or an alkyl, alkenyl or alkynyl group.
The term “ether” refers to an unsubstituted or substituted —ORE group, wherein RE is or an alkyl, alkenyl or alkynyl group.
The term “amine” refers to an unsubstituted or substituted —NRF2 group, wherein RE is or an alkyl, alkenyl or alkynyl group.
The term ‘alkyl’, ‘aryl’, ‘heteroaryl’, etc. also include multivalent species, for example alkylene, arylene, ‘heteroarylene’ etc. Examples of alkylene groups include ethylene (—CH2—CH2—) and propylene (—CH2—CH2—CH2—).
When an organic redox active species is described as comprising a depicted moiety, this means that the organic redox active species may be the depicted structure, or may be part of a larger molecule. The larger molecule may be selected from a carbocyclic compound, a heterocyclic compound (such as an oxazoline compound), a polymer (such as a copolymer and/or a branched polymer, optionally a hyper-branched polymer), a dendrimer, a dendron and a metallocene. Where the organic redox active species moiety is part of a larger molecule, points of attachment to the remainder of the larger molecule may take the place of one or more hydrogen atoms of the depicted moiety. By way of example, when the organic redox active species comprises the moiety:
then a point of attachment to the remainder of the larger molecule may, for example, be as indicated at a position as indicated by the wavy bond in the structure below:
A point of attachment to the remainder of the larger molecule may, for example, be as indicated at a position as indicated by the wavy bond in a structure below:
The organic redox active species may be attached to a polymer, such as a polymer having poly(acrylic acid) units. For example, the organic redox active species-polymer may be:
The organic redox active species-polymer may be a copolymer, comprising first and second redox active moieties. The copolymer may comprise a first polymer having poly(acrylic acid) units attached to a first redox active moiety and a second polymer having poly(acrylic acid) units attached to a second redox active moiety. For example, the copolymer may be:
It will be appreciated that the moiety can be attached at multiple points, such as indicated at positions as indicated by the wavy bonds in the structure below:
The organic redox active species may, for example, form part of a bicyclic, tricyclic or other multicyclic ring, such as indicated in the structures below:
A “hyperbranched polymer” may be understood to be a three-dimensional “3D” polymeric network, where branching extends in multiple (e.g. substantially all) directions to form an interconnected network extending in multiple/all directions. A hyperbranched polymer may have a large number of branch points. A hyperbranched polymer differs from a dendrimer in that a hyperbranched polymer is not required to have constitutional repeating units. In other words, the branching in the hyperbranched polymer has a random (non-repeating) character.
According to the present disclosure, there is provided a redox flow battery comprising a gaseous anolyte and, as a catholyte, an organic redox active species having at least one electron directing moiety, wherein the organic redox active species is not unsubstituted parabenzoquinone.
The or each electron directing moiety may optionally not be oxo.
Use of a gaseous anolyte may be useful to ameliorate issues with electrolyte crossover, where anolyte and catholyte become intermixed (e.g. by permeating through a membrane between the anode and cathode compartment) and rendered inactive. Electrolyte crossover may otherwise lead to a gradual and irreversible decrease of battery performance. In the event that gaseous anolyte crosses over to the cathode compartment, it will be appreciated that separation of the gaseous anolyte from the catholyte can be achieved easily (e.g. simply by tapping off the gaseous anolyte, e.g. from an upper part of the cathode compartment). Similarly, in the event that liquid catholyte crosses over into the anode compartment, the liquid can simply be pumped out of the anode compartment (e.g. from a lower part of an anode compartment). The redox flow battery may be suitably configured to enable such tapping and/or pumping.
Furthermore, replacing liquid electrolyte storage tanks (which may be large depending on the implementation) with compressed gas storage vessels for hydrogen may reduce the amount of space taken up by the redox flow battery, further reducing costs.
The anolyte and/or catholyte may be stored externally to the anode/cathode compartments in one or more containers. The container may be a pressurised gas source vessel (e.g. for gaseous anolytes). The anolyte and/or catholyte may be supplied to the anode/cathode compartments by one or more conduits. The redox flow battery may comprise a pump configured to convey anolyte and/or catholyte (e.g. between a storage vessel and the cathode/anode compartment).
Organic redox active species are known for fast redox kinetics and scalable synthesis. In the context of energy storage at medium to large scale application, organic redox couples offer additional benefits associated with availability of raw materials (e.g. those which are not geographically restricted) and the strength of the supply chain of reagents. Thus, organic redox active species may present benefits over catholytes used in existing redox flow batteries, such as vanadium based redox systems.
Moreover, organic redox couples may represent a more environmentally-friendly alternative (e.g. having lower toxicity, lower reliance on non-renewable materials, better safety, etc.) to electrolytes for existing redox flow batteries, such as vanadium based redox systems.
The presence of at least one electron directing moiety may have a positive effect on the redox reactions taking place in the redox flow battery disclosed herein. Without wishing to be bound by theory, it is believed that the presence of at least one electron directing moiety on the organic redox active species of the present disclosure improves the ability of redox active species to undergo oxidation and/or reduction reactions by stabilising reactants, intermediates and/or products of such reactions.
By way of example, if a reaction involves a positively charged intermediate, an electron donating group may stabilise the intermediate and therefore facilitate reaction. It will be appreciated that the at least one electron directing moiety should direct electron density towards or away from regions of relatively low or high electron density (for electron donating and electron withdrawing groups respectively), to provide such a stabilising effect. By way of example, if a reaction involves a positively charged nitrogen centre, an electron donating group may direct electron density towards that positively charged nitrogen centre to provide a stabilising effect.
Thus, according to the present disclosure, the at least one electron directing moiety should provide a redox stabilising effect (i.e. stabilise the redox reaction taking place in the redox flow battery described herein).
An electron directing moiety may donate or withdraw electron density by resonance or inductive effects.
The present disclosure provides a redox flow battery that can be easily tailored to a specific implementation or application. The specific type of organic redox active species adopted, and/or its concentration in the redox flow batteries of the disclosure, can be tailored to meet desired operating parameters and/or tailored to be compatible with other components of the battery. By way of example, it may be desirable to utilise a catalyst at the anode (e.g. a platinum catalyst for batteries comprising a hydrogen half-reaction) and the present disclosure permits the selection of a specific organic redox active species which is compatible with such a catalyst. This offers flexibility with the redox flow batteries of the present disclosure.
It may also be desirable to tailor the energy densities of the batteries discussed herein and this may suitably be achieved by tailoring the concentration or nature/identity of the organic redox active species in the catholyte.
It may also be desirable to utilise an organic redox active species capable of two-electron redox reactions and organic redox active species discussed herein can be selected to this end.
The gaseous anolyte may be hydrogen. Therefore, the redox reaction which takes place at the anode may be:
The organic redox active species may comprise a plurality of electron directing moieties, such as 2, 3, 4 or more. In the event that the organic redox active species comprises more than one electron directing moiety, then the electron directing moieties may be the same as or different to one another.
The organic redox active species may be selected from a carbocyclic compound, a heterocyclic compound (such as an oxazoline compound), a polymer (optionally comprising poly(acrylic acid) units; optionally a copolymer; optionally a branched polymer; and/or optionally a hyper-branched polymer), a dendrimer, a dendron and a metallocene. The organic redox active species may be selected from a carbocyclic compound or a heterocyclic compound.
The organic redox active species may be a polymer selected from an optionally substituted polythiophene, polyaniline or polypyrrole.
The organic redox active species may comprise the optionally substituted moiety:
The organic redox active species may form part of a bicyclic, tricyclic or other multicyclic ring. The organic redox active species may comprise an optionally substituted quinone or anthraquinone moiety. The organic redox active species may comprise the optionally substituted moiety:
It will be appreciated that one or more optional substituents, if present, can take the place of a hydrogen atom on the depicted ring structure and/or on one or more of said electron directing group(s) (E).
The organic redox active species may comprise the optionally substituted moiety:
The organic redox active species may comprise the moiety:
The organic redox active species may be optionally substituted:
optionally
The organic redox active species may be:
optionally
The organic redox active species may comprise the optionally substituted moiety:
such as
It will be appreciated that one or more optional substituents, if present, can take the place of a hydrogen atom on the depicted ring structure and/or on one or more of said electron directing group(s) (E) and/or on said R group.
The organic redox active species comprise the moiety:
optionally
such as
The or each electron directing moeity may be an electron withdrawing group. An electron withdrawing group may be selected from a sulfonyl (e.g. haloalkylsulfonyl, such as trifyl, —SO2CF3), haloalkyl (such as trihalomethyl, e.g. trifluromethyl), cyano, sulfonate, sulfonic acid, nitro, ammonium, carbonyl (e.g. formyl or acetyl), carboxylic acid, acyl halide (e.g. acetyl chloride or acetyl fluoride), C-linked ester, C-linked amide or a halide group. An electron withdrawing group may be a sulfonic acid or a sulfonate group, optionally a sulfonate.
A sulfonate may be understood to comprise the functional group —SO3− and may be present together with any suitable counter ion, such as Li+, Na+, K+, Mg2+, Ca2+, etc. The counter ion may be Na+.
As indicated above, the or each electron directing moiety (e.g. the electron withdrawing group) may optionally not be oxo.
As indicated above, the or each electron withdrawing group may be optionally substituted.
The or each electron directing moeity may be an electron donating group. An electron donating group may be selected from a phenoxide, amine, ether, phenol, N-linked amide, 0-linked ester, alkyl, phenyl or a vinyl group. An electron donating group may be an optionally substituted alkyl group. An electron donating group may be an optionally substituted methyl or ethyl.
As indicated above, the or each electron donating group may be optionally substituted.
The catholyte may be aqueous.
The catholyte may have a pH between 0 and 14, depending on the nature of the organic species. The catholyte may be buffered.
The catholyte may comprise an acid, such as sulfuric acid. The catholyte may have a pH of at most about 6, optionally at most about 5, optionally at most about 4, optionally at most about 3, optionally at most about 2, optionally at most about 1, optionally at most about 0. The catholyte may have a pH of at least about 0, optionally at least about 0.5, optionally at least about 1, optionally at least about 1.5, optionally at least about 2, optionally at least about 2.5.
In the event the organic redox active species is sulfonated (e.g. if the organic redox active species is
the catholyte may be strongly acidic, having a pH of at most about 2, optionally at most about 1, optionally at most about 0.
The organic redox active species may be optionally substituted:
such as
such as
The organic redox active species may be:
such as
in which each R is independently selected from optionally substituted carboxylic acid (—COOH), —C(O)Oalkyl or hydrogen, optionally wherein each R is independently selected from carboxylic acid (—COOH), —C(O)OCH3 or hydrogen. In the event that R is not hydrogen, R may be unsubstituted.
The organic redox active species may be:
such as
The catholyte may comprise an alkali. The catholyte may have a pH of at least about 7, optionally at least about 8, optionally at least about 9, optionally at least about 10, optionally at least about 11, optionally about 11. The catholyte may have a pH of at most about 14, optionally at most about 13, optionally at most about 12, optionally at most about 11.
The concentration of the organic redox active species in the may catholyte determine the power and energy density of the redox flow battery. Therefore, the concentration of organic redox active species in the catholyte may be at least about 0.2 M, such as greater than about 0.5 M, e.g. greater than about 1 M, such as about 1.0 M. The concentration of organic redox active species in the catholyte may be at most about 3 M, such at most about 2.5 M, e.g. at most about 2 M, such as at most about 1.5 M.
The redox flow battery may comprise an ion exchange membrane. The ion exchange membrane may be an anion exchange membrane or a cation exchange membrane. The ion exchange membrane may be permeable to hydrogen ions and solvated hydrogen ions, optionally ion exchange membrane may be a proton exchange membrane. Proton exchange membranes are well known in the art, for example, the Nafion™ ion exchange membrane produced by DuPont.
The membrane may be a porous separator, such as a microporous membrane. Alternatively, the membrane may be a hybrid of both cation and anion conductors.
The redox flow battery may comprise a graphitic anode and/or cathode. The anode may be a porous electrode (such as a porous gas electrode). The cathode may be a porous or non-porous electrode (optionally a porous electrode). Examples of suitable electrodes are well known in the art.
A porous carbon electrode may be a catalysed porous carbon electrode. Examples of catalysed porous carbon electrodes include catalysed carbon paper, cloth, felt and composites. The cathode may comprise one or more catalysed carbon papers. The carbon may be graphitic, amorphous, or have a glassy structure.
Examples of other suitable electrodes include corrosion resistant metals (or metal alloys), such as titanium or alloys thereof, in form of meshes felts or foams.
The anode of the redox flow battery may comprise platinum, palladium, iridium, ruthenium, rhenium, rhodium, osmium or combinations thereof, including alloys for example a platinum/ruthenium alloy or binary catalyst such as PtCo, PtNi, PtMo etc. or ternary catalyst PtRuMo, PtRuSn, PtRuW etc. or chalcogenides/oxides as RuSe, Pt-MoOx etc. The anode may comprise platinum. The anode may be a catalysed electrode and the cathode may be a non-catalysed electrode.
The redox flow battery may be a reversible flow battery configured to operate in a power delivery mode in which it generates electrical power by the reaction of redox active species and in an energy storage mode in which it consumes electrical power to generate said redox active species.
In a power delivery mode, a redox active species is oxidised at the anode and a redox active species is reduced at the cathode to form reacted (or “spent”) redox active species. In the energy storage mode, electrochemical system is reversed and the “spent” catholyte species is electrochemically oxidised at the cathode to regenerate the corresponding redox active species.
Reversible redox flow batteries can generally be distinguished from fuel cells by their “plumbing”. A reversible redox flow battery has conduits both for supplying redox active species to the electrodes for the power delivery phase, and also for conducting the spent redox active species to a store, such as one or more storage vessels (e.g. one for spent anolyte and another for spent catholyte) so that it can be regenerated. Often the redox active species will be in the form of electrolyte that is exhausted following a power delivery phase and, in this case, conduits may be arranged to conduct exhausted (or spent) electrolyte to a store and supply it back to its half-cell during an energy storage mode, e.g. by the use of appropriate pumps.
In contrast, fuel cells are not set up to operate in energy storage mode to electrochemically replenish exhausted electrolyte. In the case of redox flow batteries having a half-cell containing a gas electrode, a compressor is generally provided to compress gas generated during the energy storage mode to enable it to be collected in a compressed gas storage tank for future power delivery phases. In contrast a fuel cell will generally not have such a compressor.
The redox flow battery may include one or more vessels configured to contain the liquid catholyte and/or anolyte containing the cathodic redox active species, which first vessel is connectable, in the power delivery mode, to the catholyte compartment for delivering liquid catholyte/anolyte containing the redox active species to the cathode and/or anode compartment. The one or more vessels may be connectable, in the energy storage mode, to the cathode and/or anode compartment for receiving catholyte containing generated redox active species from the cathode and/or anode compartment.
The redox flow battery may include one or more vessels configured to contain the liquid catholyte and/or anolyte containing spent redox active species, which one or more vessels are connectable, in the power delivery mode, to one or more conduits for receiving the catholyte containing spent redox active species from the cathode and/or anode compartment. Said one or more vessels may be connectable, in the energy storage mode, to a conduit for supplying the catholyte containing spent redox active species to the catholyte compartment.
The redox flow battery may include a pressurised gas source vessel (e.g. configured to contain hydrogen), which gas source is connectable, in the power delivery mode, to the anode. The pressurised gas source vessel may be connectable, in the energy storage mode, to the anode to receive gas (e.g. hydrogen) generated in the energy storage mode.
The redox flow battery may include at least one compressor configured to pressurise gas generated at the anode in the energy storage mode for storage in the pressurised gas source vessel, and optionally also a gas expander-generator to deliver electricity as a result of expansion of the compressed gas.
The battery can operate without a compressor, provided the gas storage tank is sufficiently large to accommodate the generated gas. The redox flow battery may comprise a means for circulating the hydrogen gas through the conduits between the storage vessel and the anode compartment, e.g. a pump or a fan. The redox flow battery may also additionally include a dryer which dries the hydrogen gas before it is stored in the source vessel. The redox flow battery may also be equipped with a hydrogen expander-generator to deliver electricity as a result of compressed gas expansion.
It will be appreciated that the redox reactions involving hydrogen will not produce any “spent” species at the gas anode in the power delivery mode as the redox active hydrogen species is transformed into protons that are dissolved in the electrolyte. Protons are selectively passed by the membrane separating the anode and cathode compartments from the anode side of the membrane to the cathode side of the membrane. The electrons produced during the oxidation of the hydrogen gas at the anode during the power delivery mode are collected by a current collector. However, any unreacted hydrogen gas may be transferred away from the anode compartment by one or more conduits and returned to a gas source vessel (which may be pressurised or unpressurised). In the energy storage mode, protons are selectively passed by the membrane separating the anode and cathode compartments from the cathode side of the membrane to the anode side of the membrane and protons are reduced at the anode to regenerate the hydrogen gas, which forms the anode redox active species.
There is also provided a catholyte for use in a redox flow battery, comprising an organic redox active species having at least one electron directing moiety as defined herein. Features of the catholyte described above in relation to the redox flow battery apply equally to the catholyte for use in a redox flow battery, mutatis mutandis.
There is also provided a use of a catholyte in a redox flow battery, wherein the catholyte is an organic redox active species having at least one electron directing moiety as defined herein. Features of the catholyte described above in relation to the redox flow battery apply equally to the use of a catholyte in a redox flow battery, mutatis mutandis.
In the power delivery mode, the liquid catholyte containing the organic redox active species (denoted herein as “Xn+2”) is pumped by a pump (11) from a compartment of fresh catholyte storage container (12A), through a conduit (12B) and into the catholyte compartment (9), where it is reduced at a cathode (2) according to the half reaction:
The catholyte containing the spent electrolyte species Xn is then carried away from the catholyte compartment through a second conduit (1) to the catholyte storage container (12A), where it is stored in a compartment separate from the fresh catholyte compartment.
The anode and at least part of the anolyte compartment (8) are formed by a porous gas flow electrode (4) and hydrogen is supplied from a pressurised gas source vessel (7) through a conduit (13), to the anode/anode compartment (8), where the hydrogen is oxidised to protons (H+) according to the half reaction:
and the current is collected by a current collector (also labelled 4). A proton exchange membrane (3) separates the anolyte and catholyte compartments (8 & 9) and selectively passes the protons from the anolyte to the catholyte side of the membrane (3) to balance the charge, thereby completing the electrical circuit. Any unreacted hydrogen is carried away from the anolyte compartment (8) by a second conduit (5) and returned to the pressurised gas source vessel (7) via compressor (6).
In the energy storage mode, the system is reversed so that the redox active species Xn is pumped from the catholyte storage container (12A), through the conduit (1) to the catholyte compartment (9), where the spent electrolyte species Xn is oxidised at the cathode (2) to form the redox active species Xn+2. The resulting regenerated electrolyte is transferred away from the catholyte container (9) by the pump (11), through the second conduit (12B) to the catholyte storage container (12A). Meanwhile, protons at the anolyte side of the proton exchange membrane (3) are catalytically reduced at the porous gas anode (4) to hydrogen gas; the hydrogen is transferred away from the porous anode (4) through the conduit (5) and compressed by the compressor (6) before being stored in the pressurised gas source vessel (7).
It will be appreciated that the above system is illustrated with an redox active species that undergoes a two-electron reduction
However, the redox active species could be one which undergoes a single-electron reduction).
The fuel cell fixture was purchased from Scribner Associates. The cell included two POCO graphite bipolar plates with a machined serpentine flow field in contact with gold-plated copper current collectors that are held together utilizing anodized aluminum end plates. Electrode dimension was 5 cm2. Commercially available 4.6 mm thick plasma activated graphite felt (SGL group, Germany, Sigracet) was used as the positive electrode. The Hydrogen negative electrode was obtained from Johnson Matthey-Alfa Aesar (0.22 mm thickness and 0.4 mg Pt cm−2 loading). The membrane was Nafion® 117 (nominal thickness 183 μm). A peristaltic pump (Masterflex easy-load, Cole-Palmer) and Masterflex platinum-cured silicone tubing (L/S 14, 25 ft) were used to pump the liquid electrolyte through the cell at flow rate of 5-120 mL min−1. Hydrogen was provided by a fuel cell test station (850e, Scribner Associates), passing through the negative side at a flow rate of 25-100 mL min−1. Galvanostatic charge and charge experiments were conducted with a Gamry potentiostat 3000.
Catholyte solutions were prepared with 0.65 M of the following organic redox active species:
(hereinafter referred to as “BO”) by dissolving corresponding amounts of BQ (Sigma-Aldrich) in 1 M concentrated sulphuric acid. A Masterflex easy-load peristaltic pump and Masterflex Chem-Durance tubing were used to pump the catholyte through the cell. This solution was used for all experiments, except where indicated otherwise.
The following procedure details the standard steps taken when performing a charge/discharge cycle. The organic redox active species and hydrogen flow rates remained constant throughout the procedure.
As can be seen, an oxidation peak occurs at 1 V vs MSE and a reduction peak occurs at 0.7 V vs MSE, and oxidation is much faster than reduction.
System parameters that affect the utilisation of redox species are current density, voltage window and electrolyte flow rate. It has been observed that as the current density increases, utilisation of electrolyte decreases. Current density also determines the operating power of the system. There is a trade-off between electrolyte utilisation and power output. The effect of BQ flow rate on capacity utilisation was studied at a current density of 60 mA/cm2 (
At a BQ flow rate of 50 mL/min, the system had a capacity utilisation of 68% (see Table 1).
Decreasing the flow rate to 30 mL/min resulted in a decrease in capacity utilisation to 58%. This shows the importance of mass transport and concentration polarisation losses to the system. Increasing the flow rate to 100 mL/min had a negative effect, resulting in a capacity utilisation to 56%.
The system was charged to a target capacity of 25 Ah, representing a 72% utilisation of the maximum theoretical capacity of 34.8 Ah. The hydrogen flowrate was maintained at 100 mL/min throughout each cycle. The effect of current density (40 mA/cm2, 60 mA/cm2, 80 mA/cm2, 100 mA/cm2) on capacity utilisation was studied at a BQ flow rate of 50 mL min−1 (
From the results it was observed that the overpotential for both charge and discharge steps increased as the current density increased. Overpotentials are due to losses associated with ohmic resistance, charge transfer and mass transport phenomena. At the start of each charge/discharge step the losses are most likely predominated by charge transfer processes while at the end it is mostly mass transport limitations that contribute to the overpotential.
The BQ concentration was 0.65 M in 1 M sulphuric acid. The liquid flow rate was 50 mL min−1 and the gas flow rate was 100 mL min−1.
Power curves were measured for the system at a BQ flow rate of 50 mL/min and at three states of charge (SOC) (
A further series of experiments were conducted. The same fuel cell fixture as described in section “1.1 General procedure” above was used, except that the Nafion membrane was activated via the following process to remove contaminants:
Catholyte solutions were prepared with 0.65 M of the following organic redox active species:
(4,5-Dihydroxy-1,3-benzenedisulfonic acid disodium salt monohydrate; hereinafter referred to as “BQDS”; available from Sigma-Aldrich; 97% assay) in 1 M sulphuric acid (utilising “Ultrapure” water from a Millipore Milli-Q water purification system <18.2 MΩ cm−1).
Rotating Disk Electrode (RDE) techniques were performed using a mirror polished glassy 5 mm diameter carbon disk electrode (Pine Instruments, AFE6R1 AU) equipped within a rotator (AFMSRCE). Electrochemical tests were performed using a potentiostat (Autolab, model PGSTAT20) and a three-compartment electrochemical glass cell which employed a Pt wire counter electrode. A saturated calomel reference electrode (SCE, E°=0.244 V vs. SHE at 25° C.) was used as the reference electrode, which was ionically connected to the main compartment of the electrochemical glass cell via a Luggin capillary.
Cyclic voltammetry (CV) and Linear-sweep voltammetry (LSV) experiments were performed with a 1 mM BQDS solution in 1 M H2SO4 electrolyte. The rotation rates were from 500 rpm to 3000 rpm. CV scan rates were from 10 mV s−1 to 200 mV s−1. LSV scan rate was 5 mV s−1.
Electrochemical Impedance Spectroscopy (EIS) measurements were conducted in the range of 300 mHz to 10 kHz by Gamry (Reference 3000, potentiostat mode). The electrolyte was flowed through the RFC 15 min before the measurement to infiltrate the graphite felt electrode and stabilize the electrolyte interface for the electrochemical reaction. The high frequency resistance at 10 kHz was also measured in the discharge polarization curves at various current densities. Open circuit potential (OCP) measurements were conducted before the charge and discharge test in potentiostatic mode.
The solubility of BQDS was determined as 0.65 M, which enables higher theoretical energy density that that of a hydroquinone system (0.5 M). Solubility of BQDS (white powder at room temperature and pressure) was determined by a gravimetric method upon dissolving a known quantity of the electrolyte in a known quantity of sulfuric acid. Once precipitation was observed, the solubility was noted.
Its standard electrochemical potential (0.86 V vs SHE) was determined from CV experiments and found to be higher than that of the (ferrocenylmethyl)trimethylammonium chloride (Fe-NCL) system (0.67 V vs SHE). Hydroquinone also had an identical potential as Fe-NCL but the solubility of the latter was very high (4 M).
The diffusion coefficients of both species (5.03×10−6 for hydroquinone and 3.74×10−6 cm2 s−1 for Fe-NCL) were also lower than that of BQDS (5.15×10−6 cm2 s−1—determined from LSV as shown in
From the Koutecký-Levich plot in
A high redox potential of the positive redox material will lead to a high cell voltage directly when coupled with the appropriate anolyte. Amongst the organic redox materials reported in the literature, the redox potential of BQDS is relatively high and this may mean that applying an electrode with a large surface area/porosity in a high concentration of electrolyte is expected to result in high current and power densities. As a consequence, this redox species was coupled with the hydrogen evolution/oxidation reaction that is being studied in the literature for RFC applications.
The hybrid RFC single cell was assembled as described in the section 2.1 above and was tested under galvanostatic conditions at deep depths of discharge (DoD) unlike other organic systems that were evaluated using a large number of shallow cycles. An advantage is the ability of the RFB to be operated reversibly at deep DoDs and its rapid response times. Shallow cycling operations do not represent an appropriate figure of merit appropriate for evaluating RFB technology suitably. It was aimed to deliver a representative performance metric for the H2/BQDS system.
The inset from
All graphs were produced using 200 ml BQDS liquid electrolyte at a constant flow rate of 50 mL min−1 and hydrogen flow rate of 100 mL min−1
During cycling experiments (
The H2/BQDS system may be comparable to anthraquinone disulfonate (AQDS)/Br2 systems in terms of cell voltage and energy density, whereas the performance of the H2/BQDS system may be reproducible over 200 cycles in comparison to only 10 for the latter. The H2/BQDS system may not face catalyst poisoning issues related to crossover of active species as for the AQDS/Br2 flow battery, thereby allowing the generation of good faradaic efficiencies over 200 cycles with minimal capacity losses. In comparison to other organic couples tested in flow systems, the H2/BQDS system may provide improved performance in terms of important figures of merit such as energy and current densities. The H2/BQDS system may show poorer cell voltage in comparison to PbSO4/BQDS and MV/4-HO-TEMPO. Hence, the H2/BQDS system may be understood to be durable and worthy of consideration for practical scaling-up opportunities despite suffering from a low practical cell voltage.
In addition, the current efficiencies under four different current densities (for single charge/discharge cycles only) may be more than 90%, which indicates the reversibility of the BQDS (
To determine the power density of the BQDS and hydrogen RFC and to find out the maximum power output condition, cell charge and discharge was conducted at different current densities (
SOC=(Discharge capacity/Maximum capacity)×100% (2)
The iR potential loss was calculated by multiplying the current (i) with the ohmic resistance value (Zreal) determined from impedance data at 10 kHz (60-110 mΩ cm2 depending on state of charge). The iR-free potential is the sum of discharge cell voltage (Ecell) and the iR potential loss (equation 3).
iR-free potential=Ecell+Zreal×I (3)
The iR-potential correction was carried out to compare the mass transport with the kinetic limitations without consideration of the ohmic loss.
As shown in
In general, the peak power density at room temperature is about 122 mW cm−2 (iR free value is almost double as shown in
| Number | Date | Country | Kind |
|---|---|---|---|
| 1819459.7 | Nov 2018 | GB | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/GB2019/053373 | 11/28/2019 | WO | 00 |
