EP3601300A1 - Procédés aqueux pour former des complexes de catécholate de titane et compositions associées - Google Patents

Procédés aqueux pour former des complexes de catécholate de titane et compositions associées

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Publication number
EP3601300A1
EP3601300A1 EP17887416.0A EP17887416A EP3601300A1 EP 3601300 A1 EP3601300 A1 EP 3601300A1 EP 17887416 A EP17887416 A EP 17887416A EP 3601300 A1 EP3601300 A1 EP 3601300A1
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EP
European Patent Office
Prior art keywords
titanium
catecholate
complex
salt form
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP17887416.0A
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German (de)
English (en)
Inventor
Steven Y. Reece
Emily Grace NELSON
Matthew MILLARD
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lockheed Martin Energy LLC
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Lockheed Martin Energy LLC
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Filing date
Publication date
Priority claimed from US15/473,553 external-priority patent/US10741864B2/en
Application filed by Lockheed Martin Energy LLC filed Critical Lockheed Martin Energy LLC
Publication of EP3601300A1 publication Critical patent/EP3601300A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H01M8/184—Regeneration by electrochemical means
    • H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/28—Titanium compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H01M2300/0014—Alkaline electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present disclosure generally relates to energy storage and, more specifically, to methods for synthesizing titanium catecholate complexes as active materials for use in energy storage systems.
  • Electrochemical energy storage systems such as batteries, supercapacitors and the like, have been widely proposed for large-scale energy storage applications.
  • flow batteries can be advantageous, particularly for large-scale applications, due to their ability to decouple the parameters of power density and energy density from one another.
  • Flow batteries generally include negative and positive active materials in corresponding electrolyte solutions, which are flowed separately across opposing sides of a membrane or separator in an electrochemical cell containing negative and positive electrodes.
  • the flow batter)' is charged or discharged through electrochemical reactions of the active materials that occur inside the two half-cells.
  • active material “electroactive material,” “redox-active material” or variants thereof synonymously refer to materials that undergo a change in oxidation state during operation of a flow battery or like electrochemical energy storage system (i.e., during charging or discharging).
  • Metal-based active materials can often be desirable for use in flow batteries and other electrochemical energy storage systems. Although non-ligated metal ions [e.g., dissolved salts of a redox-active metal) can be used as an active material, it can often be more desirable to utilize coordination complexes for this purpose. As used herein, the terms "coordination complex,” “coordination compound,” “metal-ligand complex,” or simply "complex”
  • the metal center can cycle between an oxidized form and a reduced form in an electrolyte solution, where the oxidized and reduced forms of the metal center represent states of full charge or full discharge depending upon the particular half-cell in which the coordination complex is present. In certain instances, additional electrons can be transferred through the oxidation or reduction of one or more of the molecules constituting the ligands.
  • Titanium complexes can be particularly desirable active materials for use in flow batteries and other electrochemical energy storage systems, since such metal complexes can provide good half-cell potentials (e.g., less than -0.3 V) and current efficiencies exceeding 85% at high current density values (e.g., greater than 100 mA/cm 2 ).
  • Various titanium catecholate complexes can be especially desirable active materials in this regard, since they are relatively stable complexes and have a significant degree of solubility in aqueous media.
  • titanium catecholate complexes also referred to herein as titanium catechol complexes, titanium catecholate coordination compounds, catechol complexes of titanium, and/or similar terms
  • residual organic solvents from currently employed syntheses of titanium catecholate complexes can become incorporated in aqueous electrolyte solutions in which the complexes are present, which can be undesirable in various instances.
  • Certain residual organic solvents for example, can cause membrane swelling in a How battery, which can compromise the flow battery's operation.
  • residual organic solvents can present environmental or safety concerns in some instances.
  • titanium catecholate complexes are usually synthesized in a salt form for incorporation in aqueous electrolyte solutions.
  • the titanium catecholate complex itself bears a formal negative charge and one or more positively charged counterions are present to maintain charge balance. If extraneous salts (i.e., salts not associated with the titanium catecholate complex) are also present in an aqueous electrolyte solution, the solubility of the complex can be undesirably lowered through a common ion effect.
  • methods for synthesizing coordination complexes containing titanium are described herein, particularly titanium catecholate complexes.
  • the methods can include: providing an aqueous solution containing a catechol compound, reacting a titanium reagent with the catechol compound in the aqueous solution to form an intermediate titanium catecholate complex, isolating the intermediate titanium catecholate complex as a solid or slurry, and reacting a ligatable compound with the intermediate titanium catecholate complex in the presence of a base to produce a salt form titanium catecholate complex further containing at least one additional ligand.
  • methods for synthesizing titanium catecholate complexes can include: providing an aqueous solution containing a catechol compound, adding a titanium reagent to the aqueous solution, and reacting the titanium reagent with the catechol compound to form an intermediate titanium catecholate complex containing a 4-coordinate titanium (IV) center and two catecholate ligands.
  • the methods can further include reacting a ligatable compound with the intermediate titanium catecholate complex in the presence of a base to produce a salt form titanium catecholate complex further containing at least one additional ligand.
  • methods of the present disclosure can include combining a catechol compound and a titanium reagent in an aqueous solution, and reacting the catechol compound with the titanium reagent in the aqueous solution to form a titanium catecholate complex containing one or more catecholate ligands.
  • the titanium reagent is titanium tetrachloride.
  • methods of the present disclosure can include providing an aqueous solution containing a hydroxybenzene compound, combining a titanium reagent with the aqueous solution to form a reaction mixture, and isolating a titanium
  • the titanium coordination complex from the reaction mixture as a solid or slurry, where the titanium coordination complex contains at least one hydroxybenzene ligand.
  • the at least one hydroxybenzene compound can include at least one catechol compound.
  • methods of the present disclosure can include providing a titanium coordination complex containing at least one hydroxybenzene ligand, and contact a slurry or melt of the titanium coordination complex with a slurry or melt of a ligatable compound to produce a titanium coordination complex containing at least one hydroxybenzene ligand and at least one additional ligand.
  • compositions of the present disclosure can include: a salt form titanium catecholate complex containing two catecholate ligands and at least one additional ligand.
  • the compositions are substantially free of organic solvents and extraneous salt not associated with the salt form titanium catecholate complex.
  • Flow batteries containing the compositions in at least one electrolyte solution are also described herein.
  • FIGURE 1 shows a schematic of an illustrative flow battery
  • FIGURES 2 and 3 show illustrative ⁇ and l 3 C NMR spectra of a titanium catecholate complex produced under aqueous conditions.
  • the present disclosure is directed, in part, to flow batteries and compositions containing salt form titanium catecholate complexes, particularly alkali metal salt forms, that are free or substantially free of extraneous salts and organic solvents.
  • the present disclosure is also directed, in part, to methods for synthesizing titanium catecholate complexes in an aqueous solution. More generally, the present disclosure is also directed to reacting a suitable titanium reagent with a hydroxybenzene compound in an aqueous solution to produce a titanium coordination complex.
  • Titanium coordination complexes particularly those containing at least one catecholate ligand, can be especially desirable due to their favorable half-cell potentials and high current efficiency values, among other factors.
  • various techniques are presently available in the art for synthesizing titanium catecholate complexes, none are believed to be suitable for producing high-purity active materials at the very large (multi-pound up to multi-ton) scales needed to support commercial energy storage applications.
  • Raw material costs, labor expenses, low yields and insufficient purity are among the factors that can be problematic at present for supplying commercially viable quantities of these types of active materials.
  • Other metal complexes containing alternative metal centers and/or ligands differing from catecholate ligands can be similarly problematic in this regard.
  • catechol refers to a compound having an aromatic ring bearing hydroxyl groups on adjacent carbon atoms (i.e., 1,2-hydroxyl groups). Optional substitution can also be present in addition to the 1,2-hydroxyl groups.
  • catecholate refers to a substituted or unsubstituted catechol compound that is bound to a metal center via a metal-ligand bond, particularly a titanium metal center.
  • unsubstituted catecholate refers to the particular case where 1 ,2-dihydroxybenzene (catechol) is bound to a metal center via a metal-ligand bond.
  • the optional substitution on catecholate ligands can serve a number of purposes such as, for example, altering the solubility
  • Monosulfonated catecholate ligands can improve the solubility of titanium coordination complexes while maintaining desirable electrochemical properties that are at least comparable to those obtained when only unsubstituted catecholate ligands are present.
  • the term "monosulfonated” refers to one sulfonic acid group or any salt thereof being present on an aromatic ring.
  • Catecholate ligands bearing an additional hydroxyl group such as pyrogallol, 1 ,2,4-trihydroxybenzene and gallic acid, for example, can be similarly advantageous in this regard.
  • Catecholates such as the foregoing can also be optionally further substituted. Other advantageous catecholate ligands bearing further substitution are discussed hereinbelow.
  • catechols and catecholates suitable for use in the present disclosure also include positional isomers that are not necessarily specifically illustrated herein.
  • monosubstituted catechols and catecholates can also be polysubstituted in some embodiments, particularly disubstituted or trisubstituted, unless otherwise indicated herein.
  • titanium coordination complexes including titanium catecholate complexes
  • an organic solvent particularly an anhydrous organic solvent
  • titanium reagents such as titanium tetrahalides and titanium oxyhalides
  • titanium dioxide is a generally intractable material and is not especially applicable toward forming titanium coordination complexes unless it undergoes further processing.
  • the production of titanium dioxide during complex formation can be exceedingly problematic, because it wastes costly titanium reagent and reduces yields of the desired titanium coordination complex.
  • the extreme insolubility of titanium dioxide can be especially problematic should this compound become incorporated in an electrolyte solution of a flow battery, where it can occlude flow pathways and damage various system components, such as a flow battery's separator.
  • organic solvents can present particular issues in some cases.
  • organic solvents When organic solvents are used during syntheses of titanium coordination complexes, residual organic solvent can be retained by the titanium coordination complexes and become incorporated in an aqueous electrolyte solution. Residual organic solvent in an aqueous electrolyte solution can contact a flow battery's membrane or separator and result in swelling, which can undesirably compromise the flow battery's operation.
  • Organic solvents also add to the material cost of fabricating a flow battery, and organic solvents can further produce undesirable environmental impacts.
  • organic solvents can retain byproduct species liberated during syntheses of the titanium coordination complexes that, if not properly managed, can lead to extraneous salt production upon generating a salt form of the titanium coordination complexes, thereby reducing purity and potentially impacting other factors such as solubility.
  • byproduct species such as hydrogen halides and other base-reactive substances, can react to form extraneous salts in addition to a desired salt form titanium coordination complex.
  • the present inventors discovered processes for synthesizing titanium catecholate complexes and other metal complexes that can proceed from readily available and relatively inexpensive starting materials and take place in an aqueous solution. These syntheses largely employ the same water-reactive titanium reagents as those used in syntheses utilizing organic solvents. The ability to utilize water-reactive titanium reagents with an aqueous solution when forming titanium catecholate complexes is extremely surprising, since one would ordinarily expect the titanium reagent to generate primarily titanium dioxide and very little of the titanium catecholate complex, if any. Use of an aqueous solution when synthesizing titanium catecholate complexes further averts many of the problematic issues accompanying syntheses taking place in organic solvents.
  • the cost, safety and environmental profile of synthesizing titanium catecholate complexes can be improved by foregoing the use of an organic solvent. Even more significantly, potential membrane swelling issues associated with incorporating residual organic solvents in an aqueous electrolyte solution can be substantially eliminated.
  • the disclosure herein can be extended to hydroxybenzene compounds, in general, for purposes of synthesizing titanium coordination complexes.
  • an aqueous solution can facilitate separation of the titanium catecholate complexes from byproduct species that can otherwise lead to extraneous salt formation.
  • hydrogen halides and similar byproduct species can become incorporated in an aqueous solution upon forming a titanium catecholate complex from a titanium reagent, the syntheses described herein allow separation of the initially formed complex to take place from the aqueous solution, thereby also removing the solubilized byproduct species from the titanium catecholate complex.
  • the inventors found that the reaction between a suitable titanium reagent and at least one catechol compound in an aqueous solution, particularly an aqueous solution with acidic pH values, leads to formation of an intermediate titanium catecholate complex that is insoluble in the reaction mixture.
  • the insolubility of the intermediate titanium catecholate complex allows the complex to be isolated by filtration, centrifugation, or decantation, for example, and separated from the byproduct species which remain solubilized in the aqueous solution. Further description of the intermediate titanium catecholate complexes is provided hereinbelow.
  • the intermediate titanium catecholate complex can be reacted with a ligatable compound, which can be a catechol compound or another ligatable substance, to form a titanium catecholate complex containing at least one additional ligand.
  • a ligatable compound which can be a catechol compound or another ligatable substance.
  • the number of additional ligands that are added to the titanium (IV) center to achieve a full coordination sphere of six metal-ligand bonds depends upon the denticity of the ligatable substance.
  • the reaction can be facilitated in the presence of a base, which can further lead to generation of a salt form titanium catecholate complex, in which two catecholate ligands and at least one additional ligand are present.
  • an especially desirable salt form for the titanium catecholate complexes can be an alkali metal salt form in some embodiments, although alternative salt forms can also be suitable, as discussed herein. Because hydrogen halide byproduct species and other base-reactive materials can be removed with the mother liquor when isolating the intermediate titanium catecholate complex, generations of the salt form titanium catecholate complexes in the presence of a base does not lead to production of substantial quantities of extraneous salt(s).
  • titanium (IV) reagents such as titanium tetrahalides and titanium oxyhalides can be used in the embodiments of the present disclosure.
  • titanium reagent refers to any chemical compound containing titanium. Titanium (IV) oxysulfate and titanium (IV) alkoxides can also be used in some alternative embodiments.
  • titanium (IV) reagents Byproduct species liberated from each of these titanium (IV) reagents upon their reaction with a catechol compound or other ligatable compound can be separated from the resulting intermediate titanium catecholate complex upon separation of the aqueous mother liquor.
  • these and similar titanium reagents can be combined with the aqueous solution more rapidly in the syntheses of the present disclosure than can be performed in corresponding syntheses employing an organic solvent.
  • the syntheses and further processing of the titanium catecholate complexes can be conducted on a wide range of scales, ranging from gram-scale laboratory processes up to multi-ton production. Because the syntheses described herein generate one or more byproduct species that can be removed with the aqueous mother liquor, salt form titanium catecholate complexes can be obtained with good purity levels in high- concentration aqueous phases that can be suitable for use in flow batteries and other
  • the syntheses described herein allow the salt form titanium catecholate complexes to be produced in an aqueous phase without forming significant amounts of extraneous salts, such as extraneous alkali metal halide salts, that are not associated with the titanium catecholate complexes in their desired salt form. That is, the syntheses described herein do not produce a substantial amount of additional salt co-product when generating the salt form titanium catecholate complexes.
  • syntheses described herein are readily amenable to scale up to a desired level. Further, the syntheses described herein can be readily extended to continuous modes of operation, rather than batchwise processes.
  • the intermediate titanium catecholate complex can be converted into an alkali metal salt form titanium catecholate complex through reaction with an alkali metal base, particularly using an alkaline aqueous solution.
  • alkali metal refers to a metal in Group I of the periodic table, such as lithium, sodium or potassium.
  • Sodium, potassium, or mixed sodium/potassium salt forms can be particularly desirable salt forms for incorporation in an electrolyte solution of a flow battery.
  • alkali metal salt form titanium catecholate complexes can be advantageous for use in conjunction with the components of flow batteries and other electrochemical systems, it is to be recognized that alternative salt forms can be synthesized using other bases.
  • alkaline earth metal salt form titanium catecholate complexes can be synthesized by using an alkaline earth metal base, such as calcium hydroxide.
  • alkaline earth metal base such as calcium hydroxide.
  • Other salt forms such as ammonium, phosphonium, sulfonium, tetraalkylammonium, tetraarylammonium, mixed alkyl and aryl tetrasubstituted ammonium, tetraarylphosphonium, iminium, and nitronium salt forms, for example, can also be prepared and used similarly.
  • Mixed salt forms which can desirably have improved aqueous phase solubility in some cases, are also possible in some embodiments of the present disclosure.
  • titanium catecholate complexes can be advantageous for use in the further applications described herein, other metal catecholate complexes can also be suitably produced via similar syntheses and incorporated in flow batteries and other electrochemical energy storage systems.
  • Metal catecholate complexes containing alternative metals such as, for example, Al, Ca, Co, Cr, Sr, Cu, Fe, Hf, Mg, Mn, Mo, Ni, Pd, Pt, Ru, Sn, Zn, Zr, V, W and U can be synthesized through similar procedures and utilized as the active material for a flow battery.
  • Lanthanide and actinide reagents that are reactive with catechol compounds can also be suitable in this regard.
  • zirconium and hafnium coordination compounds can possess highly desirable properties when utilized as an active material in a flow
  • the disclosure herein can also be extended to titanium and other metal coordination complexes that contain only catecholate ligands, combinations of one or more catecholate ligands with other non-catecholate ligands, or only non-catecholate ligands.
  • Suitable non-catecholate ligands can include any of monodentate, bidentate or tridentate ligands, some examples of which are provided hereinbelow.
  • Bidentate ligands can be especially desirable since they complex metal centers in a similar manner to catechol compounds and can serve as a direct replacement thereof.
  • the disclosure herein can be extended to other hydroxybenzene compounds, including monohydroxybenzene compunds, in some instances.
  • the present disclosure describes methods including: providing an aqueous solution containing a catechol compound, reacting a titanium reagent with the catechol compound in the aqueous solution to form an intermediate titanium catecholate complex, isolating the intermediate titanium catecholate complex as a solid or slurry, and reacting a ligatable compound with the intermediate titanium catecholate complex in the presence of a base to produce a salt form titanium catecholate complex further containing at least one additional ligand.
  • the aqueous solution can have a pH pH of about 7 or less
  • a byproduct species can be generated when forming the intermediate titanium catecholate complex.
  • the byproduct species can be soluble in the reaction mixture, whereas the intermediate titanium catecholate complex is not.
  • the byproduct species can be readily removed from the intermediate titanium catecholate complex upon isolating the intermediate titanium catecholate complex.
  • the salt form titanium catecholate complex and aqueous phases containing these complexes can be free or substantially free of extraneous salts, such as alkali metal halide salts.
  • the term "substantially free of an extraneous salt” refers to about 0.01 molar equivalents or less of the extraneous salt being present relative to the salt form titanium catecholate complex.
  • minimizing the formation of extraneous salts can be desirable for improving solubility of the salt form titanium catecholate complexes.
  • the salt form titanium catecholate complexes and aqueous phases containing these complexes can be free of organic solvents. Minimizing or eliminating the presence of residual organic solvents in aqueous phases containing salt form titanium catecholate complexes can be desirable for minimizing interactions of the organic solvent with a membrane or separator in a flow battery.
  • the methods of the present disclosure can include producing the salt form titanium catecholate complex in an aqueous phase.
  • the base used to promote production of the salt form titanium catecholate complex can be present in an alkaline aqueous solution.
  • the alkaline aqueous solution can be added to the intermediate titanium catecholate complex or vice versa, or the base can be added to a suspension of the intermediate titanium catecholate complex with water or another aqueous phase.
  • the salt form titanium catecholate complex becomes soluble in the aqueous phase.
  • the syntheses disclosed herein allow a byproduct species to be removed in an aqueous mother liquor before producing the salt form titanium catecholate complex in the aqueous phase
  • the resulting aqueous phase can be substantially free of an extraneous salt not associated with the salt form titanium catecholate complex.
  • the methods can include combining a solid base or a liquid base with the intermediate titanium catecholate complex, separately adding water or another aqueous solution, or vice versa, and reacting the ligatable compound with the intermediate titanium catecholate complex in the presence of the base to produce the desired salt form. Additional disclosure regarding suitable bases and ligatable compounds is provided hereinbelow.
  • the titanium catecholate complexes of the present disclosure contain titanium in the +4 oxidation state.
  • the most common coordination number of titanium (IV) is 6, although lower coordination numbers are known.
  • the titanium catecholate complexes of the present disclosure, particularly the salt form titanium catecholate complexes can accommodate at most five other ligands when at least one catecholate ligand is present.
  • the salt form titanium catecholate complexes can contain at most three bidentate ligands in total.
  • the intermediate titanium catecholate complexes are believed to lack a full coordination sphere and are coordinatively unsaturated complexes.
  • the ligatable compound can be an additional catechol compound.
  • the salt form titanium catecholate complex can contain only catecholate ligands.
  • the catechol compound used when forming the intermediate titanium catecholate complex can be the same as or different than the additional catechol compound.
  • the catechol compound used in conjunction with forming the intermediate titanium catecholate complex can constitute a mixture of catechol compounds, such as a first catechol compound and a second catechol compound.
  • the salt form titanium catecholate complexes can contain a titanium (IV) center and three catecholate ligands, which can all be the same, all differ, or represent a combination of two types of catecholate ligands.
  • non-catecholate ligands can be introduced when producing the salt form titanium catecholate complex from the intermediate catecholate complex, where the catecholate ligands can again be the same or differ.
  • catecholate ligands can again be the same or differ.
  • phenolate ligands and other ligatable compounds can also be suitable non- catecholate ligands in the disclosure herein.
  • Catechol compounds suitable for use in the various embodiments described herein are not considered to be particularly limited.
  • any of the catechol compounds can be o-catechol itself ⁇ i.e., unsubstituted 1 ,2-dihydroxybenzene).
  • any of the catechol compounds can include at least one substituted catechol compound, which can optionally be present in combination with an unsubstituted catechol compound.
  • the intermediate titanium catecholate complexes and salt form titanium catecholate complexes described herein can include unsubstituted catecholate ligands, substituted catecholate ligands, or any combination thereof.
  • additional ligands that are non-catecholate in nature can also be present in combination with substituted or unsubstituted catecholate ligands.
  • non-catecholate ligands and other metals can also be suitably used in alternative embodiments of the present disclosure.
  • 3,4-dihydroxybenzenesulfonic acid can be an especially desirable substituted catechol compound for promoting solubility of a titanium catecholate complex.
  • Pyrogallol, 1 ,2,4-trihydroxybenzene and gallic acid are also substituted catechol compounds that can be particularly desirable. These and other similar catechol compounds can be further substituted in some embodiments.
  • substituted catechol compounds that can be suitable for use in the embodiments described herein can include those bearing solubilizing groups to increase the aqueous solubility of the resulting complexes.
  • substituted catechol compounds that can be suitable for use in the embodiments described herein can include those having a structure of
  • Z is a heteroatom functional group selected from the group consisting of A'R A I , A 2 R A2 , A 3 R a3 , CHO, and sulfonic acid.
  • Variable n is an integer ranging between 1 and 4, such that one or more Z are bound to the substituted catechol compound at an open aromatic ring position.
  • Each Z is the same or different when more than one Z is present.
  • a 1 is -(CH 2 ) a - or -(CHOR)(CH 2 ) a -
  • R AI is -OR 1 or a is an integer ranging between 0 and about 6
  • b is an integer ranging between 1 and about 10.
  • a 2 is -(CH 2 ) C - or -CH(OR 2 )(CH 2 )d-
  • X is -O- or -NR 6 -
  • c is an integer ranging between 0 and about 6
  • d is an integer ranging between 0 and about 4.
  • a 3 is -O- or -NR 2 -
  • R is H, C1 -C6 alkyl, heteroatom-substituted Ci-C 6 alkyl, or C] -C6 carboxyalkyl.
  • R 1 is H, methyl, ethyl, a C 2 -C 6 polyol bound through an ether linkage or an ester linkage, or C]-C 6 carboxyalkyl.
  • R 2 , R 3 , R 4 and R 6 are independently selected from the group consisting of H, C 1 -C6 alkyl, or heteroatom-substituted Ci-C 6 alkyl.
  • R 5 is H, Ci-C 6 alkyl, heteroatom-substituted Ci-C 6 alkyl, a C 2 -C 6 polyol bound through an ester linkage, a
  • R is H or OH.
  • R is H, Ci-C 6 alkyl, heteroatom-substituted C
  • substituted catechol compounds of the structure shown above can be covalently bonded to another such structure, each of which can be independently substituted with (Z) n as set forth above.
  • Such structures can be joined to one another a single bridging group or a double bridging group.
  • the ligatable compound can be a compound that is non- catecholate in nature.
  • the salt form titanium catecholate complex can contain a mixture of catecholate ligands and at least one additional non-catecholate ligand.
  • the salt form titanium catecholate complex can contain one additional ligand further to the catecholate ligands, thereby achieving a full coordination sphere.
  • the salt form titanium catecholate complex can contain two additional ligands further to the catecholate ligands to achieve a full coordination sphere.
  • the salt form titanium catecholate complexes can contain a titanium (IV) center and two catecholate ligands in further combination with one or two non- catecholate ligands.
  • ligands in addition to substituted or unsubstituted catecholate ligands can be present in the complexes described herein.
  • Other ligands that can be present alternatively and/or in combination with catecholate ligands include, for example, amines, diamines, amino alcohols, amino acids, ascorbate, citrate, glycolate, a polyol, gluconate, hydroxyalkanoate, acetate, formate, benzoate, malate, maleate, phthalate, sarcosinate, salicylate, oxalate, urea, polyamine, aminophenolate, acetylacetonate, and lactate.
  • such ligands can be optionally substituted with at least one group selected from among Ci -6 alkoxy, Ci -6 alkyl, Ci -6 alkenyl, C] _6 alkynyl, 5- or 6- membered aryl or heteroaryl groups, a boronic acid or a derivative thereof, a carboxylic acid or a derivative thereof, cyano, halide, hydroxyl, nitro, sulfonate, a sulfonic acid or a derivative thereof, a phosphonate, a phosphonic acid or a derivative thereof, or a glycol, such as polyethylene glycol.
  • compositions such as glycols having a hydrocarbon backbone can optionally contain one or more double or triple carbon-carbon bonds.
  • Alkanoate includes any of the alpha, beta, and gamma forms of these ligands.
  • Polyamines include, but are not limited to, ethylenediamine, ethylenediamine tetraacetic acid (EDTA), and diethylenetriamine pentaacetic acid (DTPA).
  • ligands that can be present in the complexes of the present disclosure can include monodentate, bidentate, and/or tridentate ligands.
  • monodentate ligands that can be present in the complexes of the present disclosure include, for example, carbonyl or carbon monoxide, nitride, oxo, hydroxo, water, sulfide, thiols, pyridine, pyrazine, and the like.
  • bidentate ligands that can be present in the complexes of the present disclosure include, for example, bipyridine, bipyrazine, ethylenediamine, diols (including ethylene glycol), and the like, any of which can contain optional carbon-carbon double or triple bonds.
  • tridentate ligands that can be present in the complexes of the present disclosure include, for example, terpyridine, diethylenetriamine, triazacyclononane.
  • Li and L 2 are catecholate ligands and each catecholate ligand is complexed to the titanium (IV) center in a bidentate manner.
  • the titanium (IV) center has a coordination number of 4, thereby rendering it coordinatively unsaturated.
  • Li and L 2 are the same catecholate ligands.
  • L] and L 2 are different catecholate ligands.
  • the intermediate titanium catecholate complex is electrically neutral and bears no counterions.
  • This feature advantageously allows the counterion form to be set definitively upon producing the salt form titanium catecholate complex upon reacting the intermediate titanium catecholate complex with a ligatable compound in the presence of a base.
  • At least one counterion can be associated with the intermediate titanium catecholate complex.
  • a negatively ionized functional group e.g., a sulfonic acid or carboxylic acid group
  • one or more cations can be present to maintain charge balance.
  • L ⁇ and/or L 2 bears a positively ionized functional group (e.g., an ammonium, quaternary ammonium or phosphonium group)
  • one or more anions can be present to maintain charge balance.
  • L] and L 2 represent two ionized catecholate ligands that bear the same charge (+1 or -1), for example, two counterions (either two cations or two anions) can be associated with the intermediate titanium catecholate complex to maintain charge balance.
  • the intermediate titanium catecholate complex can again lack a counterion.
  • the intermediate titanium catecholate complex can be converted into a salt form titanium catecholate complex through reaction with a ligatable compound in the presence of a base.
  • the base promotes the bonding of an additional ligand to the coordination sphere of the titanium (IV) center and additionally results in generation of a salt form of the titanium (IV) catecholate complex, which is now coordinatively saturated.
  • the salt form titanium catecholate complexes of the present disclosure are believed to be defined by Formula 2
  • L 3 can also be a catecholate ligand, in which case the salt form titanium catecholate complexes bear only catecholate ligands.
  • L3 is a non- catecholate ligand.
  • L 3 is a bidentate ligand and bonds with the titanium (IV) center to fill the coordination sphere with six metal-ligand bonds.
  • L3 can represent a monodentate ligand, in which case two molar equivalents of L3 are present to fill the coordination sphere.
  • the molar equivalents of D can range between 1 and 6 depending on whether D is a monovalent or divalent cation, and whether L1 -L3 contain any ionizable functional groups.
  • D is a monovalent cation, such as an alkali metal ion
  • L1 -L3 are uncharged catecholate ligands
  • 2 molar equivalents of the monovalent cation are present to maintain charge balance (i.e., the salt form titanium catecholate complexes have a formula of D 2 Ti(Li)(L 2 )(L3)).
  • D can also include any alternative cations (e.g, a single alkaline earth metal ion, a mixture of alkaline earth metal ions, phosphonium ions, ammonium ions, tetralkylammonium ions, and the like), optionally in combination with one or more alkali metal ions, in which case the molar equivalents of D that are present reflect the amount needed to maintain charge balance.
  • any alternative cations e.g, a single alkaline earth metal ion, a mixture of alkaline earth metal ions, phosphonium ions, ammonium ions, tetralkylammonium ions, and the like
  • salt form titanium catecholate complexes of the present disclosure can have a structure defined by Formula 3
  • both m and n are non-zero numbers, and they can be equal or non-equal to one another.
  • a ratio of m to n can range between about 1 : 10 to about 10: 1 , or between about 1 :5 or about 5: 1.
  • substantially equal molar quantities of sodium and potassium can be present in the salt form titanium catecholate complexes. Complexes having mixtures of sodium and potassium counterions can be desirable in terms of their potentially increased solubility in aqueous phases. As indicated above, non- catecholate ligands can also be present in such complexes.
  • the salt form of the titanium catecholate complexes described herein can depend upon the cation associated with the base used to promote formation of the salt form. Suitable bases are not considered to be particularly limited, provided that they have sufficient basicity to produce the salt form titanium catecholate complex.
  • Suitable bases can include, for example, a metal hydroxide, a metal oxide, a metal bicarbonate, a metal carbonate, an ammonium base, a tetraalkylammonium base, a deprotonated ligand base, an amine, a borate, a metal borohydride, a metal hydride, a metal phosphate, a sulfonium base, a phosphazenium base, a guanidinium base, a metal azide, a cyanate base, a thiocyanate base, a metal carboxylate, a phenolate base, a carbamate base, an imide base, a deprotonated sulfonamide base, a nitroxyl base, a basic anion- exchange resin, a metal chalcogenide, a phosphonium base, a tetraalkylphosphonium base, a tetraarylphosphonium base, or any combination
  • the base can be an alkali metal base or combination of alkali metal bases.
  • the alkali metal base can include an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, or any combination thereof.
  • the alkali metal base can be a mixture of sodium hydroxide and potassium hydroxide. The molar ratios of the sodium hydroxide and potassium hydroxide can lie within the counterion ranges disclosed above.
  • Complexes having mixed sodium and potassium counterions can be especially desirable due to their potentially increased solubility values compared to those obtained when only a single alkali metal counterion is present.
  • alkali metal bases such as alkali metal oxides, alkali metal carbonates, and alkali metal bicarbonates can be used to promote a reaction with the ligatable compound and convert the intermediate titanium catecholate complex into the corresponding salt form titanium catecholate complex.
  • these alkali metal bases can be used in combination with the alkali metal hydroxide bases discussed above.
  • a mixture of sodium and potassium counterions can be introduced through the choice of the alkali metal bases used to produce the salt form titanium catecholate complex.
  • an alkali metal hydroxide having a first alkali metal counterion can be combined with an alkali metal carbonate or bicarbonate having a second alkali metal counterion to accomplish the foregoing.
  • ammonium bases such as ammonium hydroxide
  • an alkaline aqueous solution can contain a mixture of ammonium hydroxide and an alkali metal base, in which case the resulting salt form titanium catecholate complex can contain a mixture of ammonium and alkali metal counterions.
  • Some ammonium cations can be alkyl substituted, such as tetraalkylammonium cations, and can be suitably incorporated in the salt form titanium catecholate complexes.
  • suitable titanium reagents for use in the syntheses disclosed herein can include titanium tetrahalides and titanium oxyhalides.
  • Suitable titanium tetrahalides can include titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, and titanium mixed tetrahalides.
  • titanium mixed tetrahalide refers to a titanium tetrahalide containing two or more different halides, such as TiC Br, TiCl 2 Br 2 and TiClBr 3 .
  • Titanium tetrafluoride and the related TiF 6 2" complex anion are extended polymeric solids and can react with catechol compounds and other ligatable compounds less readily.
  • titanium tetrafluoride and TiF 2' generate hydrogen fluoride upon reacting with ligatable compounds, which can be especially problematic to address from a manufacturing standpoint due to the high reactivity and toxicity of this hydrogen halide gas.
  • Titanium tetrachloride can be a particularly desirable titanium reagent for use in the embodiments of the present disclosure, since it can be added as a liquid to the aqueous solution containing the catechol compound.
  • Suitable titanium oxyhalide reagents can include titanium oxychloride (TiOC ), titanium oxybromide (TiOBr 2 ) and titanium oxyiodide (TiOI 2 ).
  • TiOC titanium oxychloride
  • TiOBr 2 titanium oxybromide
  • TiOI 2 titanium oxyiodide
  • the related titanium oxyfluoride compound (TiOF 2 ) can present similar handing and toxicity issues as titanium tetrafluoride.
  • the titanium oxyhalide can be generated in situ by combining a titanium tetrahalide with water or ice below about 0°C, which can then be combined with the aqueous solution containing the catechol compound.
  • titanium oxysulfate can be a suitable titanium reagent.
  • the byproduct species generated with this titanium reagent is sulfuric acid, which can similarly be retained in the reaction mixture upon formation and isolation of the intermediate titanium catecholate complex.
  • this titanium reagent can be used similarly to titanium tetrahalides and titanium oxyhalides.
  • titanium (IV) alkoxides can include titanium (IV) alkoxides. Instead of forming a hydrogen halide or sulfuric acid byproduct species, these titanium reagents produce an alcohol as a byproduct species. Although alcohol byproduct species do not present an issue with respect to salt formation, they still can be separated from the intermediate titanium catecholate complexes according to the methods described herein. Specifically, the alcohol byproduct species is also soluble in the reaction mixture and undergoes separation in a like manner to the other byproduct species described above. [0063] In some embodiments, combining the titanium reagent with the aqueous solution can include adding the titanium reagent to the aqueous solution.
  • the aqueous solution can help dissipate the heat produced upon introduction of the titanium reagent thereto.
  • the titanium reagent can be added at a rate such that the temperature in the reaction mixture rises between about 10°C to about 20°C.
  • the use of an aqueous solution in the embodiments of the present disclosure can allow the titanium reagent to be added at a faster rate than in analogous processes employing organic solvents, in which a much larger exotherm occurs even with slow addition of the titanium reagent due to its extreme reactivity.
  • the titanium reagent can be added portionwise, continuously, or substantially all at once.
  • combining the catechol compound and the titanium reagent can include adding the catechol compound to the titanium reagent.
  • the titanium reagent can be combined with the aqueous solution at about room temperature (i.e., 25°C). In some or other embodiments, the titanium reagent can be combined with the aqueous solution at a temperature ranging between about 20°C and about 100°C, or between about 30°C and about 80°C. In still other embodiments, the titanium reagent can be combined with the aqueous solution at a temperature of about 5°C or above, or about 10°C or above, or about 15°C or above, or about 20°C or above. In some embodiments, the titanium reagent can be added under conditions wherein titanium oxychloride or other titanium oxyhalides are not generated in the aqueous solution upon addition of the titanium reagent.
  • the reaction between the intermediate titanium catecholate complex and the ligatable compound can similarly be heated, if necessary. Heating to produce the salt form titanium catecholate complex can take place at a temperature of above 25°C and less than about 50°C, or less than about 75°C, or less than about 100°C, according to some embodiments.
  • some embodiments of the present disclosure can include isolating the intermediate titanium catecholate complex from the reaction mixture before generating the salt form titanium catecholate complex.
  • Isolation can involve optionally contacting the intermediate titanium catecholate complex with a washing solvent, followed by filtration, centrifugation, decantation, and the like. Isolation of the intermediate titanium catecholate complex can help avert the formation of extraneous salts upon generating the salt form titanium catecholate complex.
  • the intermediate titanium catecholate complex is not isolated from the reaction mixture.
  • Non-isolation of the intermediate titanium catecholate complex from the reaction mixture can be desirable, for example, when the production of extraneous salts is acceptable upon generating the salt form titanium catecholate complex.
  • methods of the present disclosure can include: providing an aqueous solution containing a catechol compound, adding a titanium reagent to the aqueous solution, and reacting the titanium reagent with the catechol compound in the reaction mixture to form an intermediate titanium catecholate complex containing a 4- coordinate titanium (IV) center and two catecholate ligands.
  • the methods can include reacting a ligatable compound with the intermediate titanium catehcolate complex in the presence of a base to produce a salt form titanium catecholate complex further containing at least one additional ligand.
  • Suitable catechol compounds, titanium reagents, ligatable compounds, bases and salt forms are set forth in more detail above.
  • the methods can include isolating the intermediate titanium catecholate complex as a solid or slurry before reacting the ligatable compound with the intermediate titanium catecholate complex.
  • methods of the present disclosure can include combining a catechol compound and a titanium reagent in an aqueous solution, in which the titanium reagent is titanium tetrachloride, and reacting the catechol compound with the titanium reagent in the aqueous solution to form a titanium catecholate complex containing one or more catecholate ligands.
  • the titanium tetrachloride can be added under conditions at which titanium oxychloride is not formed in the aqueous solution.
  • the titanium catecholate complex can be further reacted with one or more additional ligatable compounds, such as under alkaline conditions.
  • methods of the present disclosure can include providing an aqueous solution containing a hydroxybenzene compound, combining a titanium reagent with the aqueous solution to form a reaction mixture, and isolating a titanium coordination complex from the reaction mixture as a solid or slurry, in which the titanium coordination complex contains at least one hydroxybenzene compound. Any combination of additional ligatable compounds can be further reacted with the initially produced titanium coordination complex to form a titanium coordination complex containing at least one addition ligand.
  • methods of the present disclosure can include providing a titanium coordination complex containing at least one hydroxybenzene ligand, and contacting a slurry or melt of the titanium coordination complex with a slurry or melt of a ligatable compound to produce a titanium coordination complex containing at least one hydroxybenzene ligand and at least one additional ligand.
  • compositions containing salt form titanium catecholate complexes.
  • the compositions described herein include a salt form titanium catecholate complex containing two catecholate ligands and at least one additional ligand, such as an alkali metal salt form.
  • the compositions can be free or substantially free of organic solvents and also free or substantially free of extraneous salt not associated with the salt form titanium catecholate complex.
  • the compositions are free of organic solvents and contain about 0.01 molar equivalents or less of extraneous salts relative to the salt form titanium catecholate complex.
  • the compositions can contain an aqueous phase, in which the salt form titanium catecholate complex is present.
  • the aqueous phase can be substantially free of alkali metal halide salts when the salt form titanium catecholate complex is an alkali metal salt form.
  • aqueous phases containing the salt form titanium catecholate complexes of the present disclosure can have a concentration of the complex of aboui 0.5 M or above.
  • the concentration of the salt form titanium catecholate complex can range between about 0.5 M and about 2 M, or between about 0.75 M and about 1.5 M or between about 1 M and about 2 M.
  • the aqueous phase can be free of organic solvents and consist of water alone as a solvent for the salt form titanium catecholate complex. In other embodiments of the present disclosure, the aqueous phase can contain at least about 98% water by weight.
  • the aqueous phase can contain at least about 55% water by weight, or at least about 60% water by weight, or at least about 65% water by weight, or at least about 70% water by weight, or at least about 75% water by weight, or at least about 80%) water by weight, or at least about 85% water by weight, or at least about 90% water by weight, or at least about 95% water by weight.
  • the aqueous phase can include a viscosity modifier, a wetting agent, a buffer, or any combination thereof.
  • Suitable viscosity modifiers can include, for example, corn starch, corn syrup, gelatin, glycerol, guar gum, pectin, and the like. Other suitable examples will be familiar to one having ordinary skill in the art.
  • Suitable wetting agents can include, for example, various non-ionic surfactants and/or detergents.
  • the aqueous phase can further include a glycol or a polyol.
  • Suitable glycols can include, for example, ethylene glycol, diethylene glycol, and polyethylene glycol.
  • Suitable polyols can include, for example, glycerol, mannitol, sorbitol, pentaerythritol, and
  • Illustrative buffers that can be present include, but are not limited to, salts of phosphates, borates, carbonates, silicates, tris(hydroxymethyl)aminomethane (TRIS), 4-(2-hydroxyethyl)-l-piperazineethanesulfonic acid (HEPES), piperazine-N,N'- bis(ethanesulfonic acid) (PIPES), or any combination thereof.
  • TIS tris(hydroxymethyl)aminomethane
  • HEPES 4-(2-hydroxyethyl)-l-piperazineethanesulfonic acid
  • PPES piperazine-N,N'- bis(ethanesulfonic acid)
  • Inclusion of any of these components in the aqueous phase can help maintain the salt form titanium catecholate complex in a dissolved form and/or facilitate the incorporation of the aqueous phase in a flow battery, for example.
  • the aqueous phases described herein can further include one or more mobile ions (i.e., an extraneous electrolyte) for use as an electrolyte solution in a flow battery or similar electrochemical system.
  • suitable mobile ions can include proton, hydronium, or hydroxide.
  • mobile ions other than proton, hydronium, or hydroxide can be present, either alone or in combination with proton, hydronium or hydroxide.
  • Such alternative mobile ions can include, for example, alkali metal or alkaline earth metal cations (e.g., Li + , Na + , K + , Mg 2+ , Ca 2+ and Sr + ) and halides (e.g., F ⁇ , Cf, or Br " ).
  • Other suitable mobile ions can include, for example, ammonium and tetraalkylammonium ions, chaicogenides, phosphate, hydrogen phosphate, phosphonate, nitrate, sulfate, nitrite, sulfite, perchlorate, tetrafluoroborate, hexatluorophosphate, and any combination thereof.
  • less than about 50% of the mobile ions can constitute protons, hydronium, or hydroxide. In other various embodiments, less than about 40%, less than about 30%, less than about 20%, less than about 10%, less than about 5%, or less than about 2% of the mobile ions can constitute protons, hydronium, or hydroxide. In other various embodiments, aqueous phases containing the salt form titanium catecholate complexes of the present disclosure can lack an extraneous electrolyte altogether.
  • the salt form titanium catecholate complexes of the present disclosure particularly alkali metal salt form titanium catecholate complexes, and related aqueous phases containing these complexes can be incorporated in flow batteries and other electrochemical systems. Further disclosure on suitable flow batteries and their operating parameters follows hereinafter.
  • flow batteries of the present disclosure can include a first half-cell containing a first electrolyte solution therein, in which the first electrolyte solution constitutes a salt form titanium catecholate complex of the present disclosure in an aqueous phase. More specific discussion regarding the salt form titanium catecholate complexes and their associated compositions is provided above.
  • flow batteries of the present disclosure can also include a second half-cell having a second electrolyte solution therein, where the second electrolyte solution contains an active material differing from that in the first electrolyte solution.
  • the second electrolyte solution can be an aqueous solution containing an iron hexacyanide complex. Iron hexacyanide complexes can be particularly desirable active materials due to their facile electrode kinetics and substantially reversible electrochemical behavior within the working electrochemical window of aqueous solutions.
  • Nitroxide compounds can be similarly advantageous active materials for the second electrolyte solution in some embodiments.
  • these substances can allow high open circuit potentials and cell efficiencies to be realized, particularly in combination with a salt form titanium catecholate complex as the active material in the first electrolyte solution.
  • flow batteries of the present disclosure can include the first electrolyte solution in contact with a negative electrode of the flow battery and the second electrolyte solution in contact with the positive electrode of the flow battery.
  • the flow batteries of the present disclosure are, in some embodiments, suited to sustained charge or discharge cycles of several hour durations. As such, they can be used to smooth energy supply/demand profiles and provide a mechanism for stabilizing intermittent power generation assets (e.g., from renewable energy sources such as solar and wind energy). It should be appreciated, then, that various embodiments of the present disclosure include energy storage applications where such long charge or discharge durations are desirable.
  • the flow batteries of the present disclosure can be connected to an electrical grid to allow renewables integration, peak load shifting, grid firming, baseload power generation and consumption, energy arbitrage, transmission and distribution asset deferral, weak grid support, frequency regulation, or any combination thereof.
  • the flow batteries of the present disclosure can be used as power sources for remote camps, forward operating bases, off-grid telecommunications, remote sensors, the like, and any combination thereof.
  • the disclosure herein is generally directed to flow batteries, it is to be appreciated that other electrochemical energy storage media can incorporate the aqueous phases described herein, specifically those utilizing stationary electrolyte solutions.
  • flow batteries of the present disclosure can include: a first chamber containing a negative electrode contacting a first aqueous electrolyte solution; a second chamber containing a positive electrode contacting a second aqueous electrolyte solution, and a separator disposed between the first and second electrolyte solutions.
  • the first aqueous electrolyte solution can be an aqueous phase containing a salt form titanium catecholate complex defining a composition of the present disclosure, as described above.
  • the chambers provide separate reservoirs within the cell, through which the first and/or second electrolyte solutions circulate so as to contact the respective electrodes and the separator. Each chamber and its associated electrode and electrolyte solution define a corresponding half-cell.
  • the separator provides several functions which include, for example, (1) serving as a barrier to mixing of the first and second electrolyte solutions, (2) electrically insulating to reduce or prevent short circuits between the positive and negative electrodes, and (3) to facilitate ion transport between the positive and necative electrol v te chambers.
  • the negative and positive electrodes provide a surface where
  • electrochemical reactions can take place during charge and discharge cycles.
  • electrolyte solutions can be transported from separate storage tanks through the corresponding chambers.
  • electrical power can be applied to the cell such that the active material contained in the second electrolyte solution undergoes a one or more electron oxidation and the active material in the first electrolyte solution undergoes a one or more electron reduction.
  • the second active material is reduced and the first active material is oxidized to generate electrical power.
  • illustrative flow batteries of the present disclosure can include: (a) a first aqueous electrolyte solution containing a first coordination complex; (b) a second aqueous electrolyte solution containing a second coordination complex or nitroxide compound; (c) a separator positioned between said first and second aqueous electrolyte solutions; and (d) an optional mobile ion in the first and second aqueous electrolyte solutions.
  • the separator can be an ionomer membrane, and it can have a thickness of less than 100 microns and have an associated net charge that is the same sign as that of the first and second coordination complexes.
  • FIGURE 1 depicts a schematic of an illustrative flow battery containing a single electrochemical cell. Although FIGURE 1 shows a flow battery containing a single
  • electrochemical cell approaches for combining multiple electrochemical cells together are known and are discussed in brief hereinbelow.
  • flow batteries transport (e.g., via pumping) redox-active energy storage materials from storage tanks through an electrochemical stack.
  • This design feature decouples the electrical energy storage system power from the energy storage capacity, thereby allowing for considerable design flexibility and cost optimization.
  • flow battery 1 includes an electrochemical cell that features separator 20 (e.g., a membrane) that separates the two electrodes 10 and 10' of the electrochemical cell.
  • separator 20 e.g., a membrane
  • the terms “separator” and “membrane” synonymously refer to an ionically conductive and electrically insulating material disposed between the positive and negative electrodes of an electrochemical cell.
  • Electrodes 10 and 10' are formed from a suitably conductive material, such as a metal, carbon, graphite, and the like.
  • FIGURE 1 has shown electrodes 10 and 10' as being spaced apart from separator 20, electrodes 10 and 10' can also be abutted with separator 20 in more particular embodiments.
  • the material(s) forming electrodes 10 and 10' can be porous, such that they have a high surface area for contacting first electrolyte solution 30 and second electrolyte solution 40, the active materials of which are capable of cycling between an oxidized state and a reduced state during operation of flow battery 1 .
  • electrodes 10 and 10' can be formed from a porous carbon cloth or a carbon foam in particular embodiments.
  • Pump 60 affects transport of first electrolyte solution 30 containing a first active material from tank 50 to the electrochemical cell.
  • the flow battery also suitably includes second tank 50' that holds second electrolyte solution 40 containing a second active material.
  • the second active material in second electrolyte solution 40 can be the same material as the first active material in first electrolyte solution 30, or it can be different.
  • Second pump 60' can affect transport of second electrolyte solution 40 to the electrochemical cell. Pumps (not shown in FIGURE 1 ) can also be used to affect transport of the first and second electrolyte solutions 30 and 40 from the electrochemical cell back to tanks 50 and 50'.
  • FIGURE 1 Also shown in FIGURE 1 is power source or load 70, which completes the circuit of the electrochemical cell and allows a user to collect or store electricity during its operation. Connection to the electrical grid for charging or discharging purposes can also occur at this location.
  • FIGURE 1 depicts a specific, non-limiting embodiment of a flow battery. Accordingly, flow batteries consistent with the spirit of the present disclosure can differ in various aspects relative to the configuration of FIGURE 1.
  • a flow battery system can include one or more active materials that are solids, gases, and/or gases dissolved in liquids. Active materials can be stored in a tank, in a vessel open to the atmosphere, or simply vented to the atmosphere.
  • the flow batteries are configured such that the mobile ions and the active materials remain continuously dissolved in the electrolyte solutions.
  • potential issues associated with circulating solids can be averted.
  • multiple electrochemical cells can also be combined with one another in an electrochemical stack in order to increase the rate that energy can be stored and released during operation. The amount of energy released is determined by the overall amount of active materials that are present.
  • An electrochemical stack utilizes bipolar plates between adjacent electrochemical cells to establish electrical communication but not fluid communication between the two cells across the bipolar plate. Thus, bipolar plates contain the electrolyte solutions in an appropriate half-cell within the individual electrochemical cells.
  • Bipolar plates are generally fabricated from electrically conductive materials that are fluidically non-conductive on the whole. Suitable materials can include carbon, graphite, metal, or a combination thereof. Bipolar plates can also be fabricated from non-conducting polymers having a conductive material dispersed therein, such as carbon particles or fibers, metal particles or fibers, graphene, and/or carbon nanotubes. Although bipolar plates can be fabricated from the same types of conductive materials as can the electrodes of an electrochemical cell, they can lack the continuous porosity permitting an electrolyte solution to flow completely through the latter. It should be recognized that bipolar plates are not necessarily entirely non-porous entities, however.
  • Bipolar plates can have innate or designed flow channels that provide a greater surface area for allowing an electrolyte solution to contact the bipolar plate.
  • Suitable flow channel configurations can include, for example, interdigitated flow channels.
  • the flow channels can be used to promote delivery of an electrolyte solution to an electrode within the electrochemical cell.
  • an electrolyte solution can be delivered to and withdrawn from each electrochemical cell via a fluid inlet manifold and a fluid outlet manifold (not shown in FIGURE 1).
  • the fluid inlet manifold and the fluid outlet manifold can provide and withdraw an electrolyte solution via the bipolar plates separating adjacent electrochemical cells. Separate manifolds can provide each electrolyte solution individually to the two half-cells of each electrochemical cell.
  • the fluid inlet manifold and the fluid outlet manifold can be configured to supply and withdraw the electrolyte solutions via opposing lateral faces of the bipolar plates (e.g. by supplying and withdrawing the electrolyte solution from opposing ends of the flow channels of the bipolar plate).
  • the terms “separator” and “membrane” refer to an ionically conductive and electrically insulating material disposed between the positive and negative electrodes of an electrochemical cell.
  • the separator can be a porous membrane in some embodiments and/or an ionomer membrane in other various embodiments. In some
  • the separator can be formed from an ionically conductive polymer.
  • Polymer membranes can be anion- or cation-conducting electrolytes. Where described as an "ionomer,” the term refers to polymer membrane containing both electrically neutral repeating units and ionized repeating units, where the ionized repeating units are pendant and covalently bonded to the polymer backbone.
  • the fraction of ionized units can range from about 1 mole percent to about 90 mole percent. For example, in some embodiments, the content of ionized units is less than about 15 mole percent; and in other embodiments, the ionic content is higher, such as greater than about 80 mole percent.
  • the ionic content is defined by an intermediate range, for example, in a range of about 15 to about 80 mole percent.
  • Ionized repeating units in an ionomer can include anionic functional groups such as sulfonate, carboxylate, and the like. These functional groups can be charge balanced by, mono-, di-, or higher-valent cations, such as alkali or alkaline earth metals.
  • Ionomers can also include polymer compositions containing attached or embedded quaternary ammonium, sulfonium, phosphazenium, and guanidinium residues or salts. Suitable examples will be familiar to one having ordinary skill in the art.
  • polymers useful as a separator can include highly fluorinated or perfluorinated polymer backbones.
  • Certain polymers useful in the present disclosure can include copolymers of tetrafluoroethylene and one or more fluorinated, acid- functional co-monomers, which are commercially available as NAFIONTM perfluorinated polymer electrolytes from DuPont.
  • substantially non-fluorinated membranes that are modified with sulfonic acid groups (or cation exchanged sulfonate groups) can also be used.
  • Such membranes can include those with substantially aromatic backbones such as, for example, polystyrene, polyphenylene, biphenyl sulfone (BPSH), or thermoplastics such as polyetherketones and polyethersulfones.
  • Battery-separator style porous membranes can also be used as the separator.
  • membranes are typically impregnated with additives in order to function.
  • These membranes typically contain a mixture of a polymer and inorganic filler, and open porosity.
  • Suitable polymers can include, for example, high density polyethylene, polypropylene, polyvinylidene difluoride (PVDF), or polytetrafluoroethylene (PTFE).
  • Suitable inorganic fillers can include silicon carbide matrix material, titanium dioxide, silicon dioxide, zinc phosphide, and ceria.
  • Separators can also be formed from polyesters, polyetherketones, polyvinyl chloride), vinyl polymers, and substituted vinyl polymers. These can be used alone or in combination with any previously described polymer.
  • Porous separators are non-conductive membranes which allow charge transfer between two electrodes via open channels filled with electrolyte.
  • the permeability increases the probability of chemicals (e.g., active materials) passing through the separator from one electrode to another and causing cross-contamination and/or reduction in cell energy efficiency.
  • the degree of this cross-contamination can depend on, among other features, the size (the effective diameter and channel length), and character (hydrophobicity hydrophilicity) of the pores, the nature of the electrolyte, and the degree of wetting between the pores and the electrolyte.
  • the pore size distribution of a porous separator is generally sufficient to substantially prevent the crossover of active materials between the two electrolyte solutions.
  • Suitable porous membranes can have an average pore size distribution of between about 0.001 nm and 20 micrometers, more typically between about 0.001 nm and 100 nm.
  • the size distribution of the pores in the porous membrane can be substantial.
  • a porous membrane can contain a first plurality of pores with a very small diameter (approximately less than 1 nm) and a second plurality of pores with a very large diameter (approximately greater than 10 micrometers). The larger pore sizes can lead to a higher amount of active material crossover.
  • the ability for a porous membrane to substantially prevent the crossover of active materials can depend on the relative difference in size between the average pore size and the active material.
  • the average diameter of the coordination complex can be about 50% greater than the average pore size of the porous membrane.
  • the average diameter of the coordination complex can be about 20% larger than the average pore size of the porous membrane.
  • the average diameter of a coordination complex is increased when it is further coordinated with at least one water molecule.
  • the diameter of a coordination complex of at least one water molecule is generally considered to be the hydrodynamic diameter.
  • the hydrodynamic diameter is generally at least about 35% greater than the average pore size.
  • the hydrodynamic radius can be about 10% greater than the average pore size.
  • the separator can also include reinforcement materials for greater stability. Suitable reinforcement materials can include nylon, cotton, polyesters, crystalline silica, crystalline titania, amorphous silica, amorphous titania, rubber, asbestos, wood or any combination thereof.
  • Separators within the flow batteries of the present disclosure can have a membrane thickness of less than about 500 micrometers, or less than about 300 micrometers, or less than about 250 micrometers, or less than about 200 micrometers, or less than about 100 micrometers, or less than about 75 micrometers, or less than about 50 micrometers, or less than about 30 micrometers, or less than about 25 micrometers, or less than about 20 micrometers, or less than about 15 micrometers, or less than about 10 micrometers.
  • Suitable separators can include those in which the flow battery is capable of operating with a current efficiency of greater than about 85% with a current density of 100 m A/cm 2 when the separator has a thickness of 100 micrometers.
  • the flow battery is capable of operating at a current efficiency of greater than 99.5% when the separator has a thickness of less than about 50 micrometers, a current efficiency of greater than 99% when the separator has a thickness of less than about 25 micrometers, and a current efficiency of greater than 98% when the separator has a thickness of less than about 1 0 micrometers.
  • suitable separators include those in which the flow battery is capable of operating at a voltage efficiency of greater than 60% with a current density of 100 mA/cm 2 .
  • suitable separators can include those in which the flow battery is capable of operating at a voltage efficiency of greater than 70%, greater than 80% or even greater than 90%.
  • the diffusion rate of the first and second active materials through the separator can be less than about 1 ⁇ 10 "5 mol cm “2 day “1 , or less than about 1 ⁇ 10 "6 mol cm “2 day “1 , or less than about l x l 0 "7 mol cm “2 day “ 1 , or less than about l x l 0 “9 mol cm “2 day “1 , or less than about l x l O "1 1 mol cm “2 day “1 , or less than about 1 10 "l j mol cm “2 day “1 , or less than about
  • the flow batteries can also include an external electrical circuit in electrical communication with the first and second electrodes.
  • the circuit can charge and discharge the flow battery during operation.
  • Reference to the sign of the net ionic charge of the first, second, or both active materials relates to the sign of the net ionic charge in both oxidized and reduced forms of the redox active materials under the conditions of the operating flow battery.
  • a flow battery provides that (a) the first active material has an associated net positive or negative charge and is capable of providing an oxidized or reduced form over an electric potential in a range of the negative operating potential of the system, such that the resulting oxidized or reduced form of the first active material has the same charge sign (positive or negative) as the first active material and the ionomer membrane also has a net ionic charge of the same sign; and (b) the second active material has an associated net positive or negative charge and is capable of providing an oxidized or reduced form over an electric potential in a range of the positive operating potential of the system, such that the resulting oxidized or reduced form of the second active material has the same charge sign (positive or negative sign) as the second active material and the ionomer membrane also has a net ionic charge of the same sign; or both (a) and (b).
  • the net ionic charge in both the oxidized and reduced forms can be negative.
  • the matching charges of the first and/or second active materials and the ionomer membrane can provide a high selectivity. More specifically, charge matching can provide less than about 3%, less than about 2%, less than about 1 %, less than about 0.5%, less than about 0.2%, or less than about 0.1 % of the molar flux of ions passing through the ionomer membrane as being attributable to the first or second active material.
  • the term "molar flux of ions” refers to the amount of ions passing through the ionomer membrane, balancing the charge associated with the flow of external electricity/electrons. That is, the flow battery is capable of operating or operates with the substantial exclusion of the active materials by the ionomer membrane, and such exclusion can be promoted through charge matching.
  • Flow batteries incorporating the electrolyte solutions of the present disclosure can have one or more of the following operating characteristics: (a) where, during the operation of the flow battery, the first or second active materials comprise less than about 3% of the molar flux of ions passing through the ionomer membrane; (b) where the round trip current efficiency is greater than about 70%, greater than about 80%, or greater than about 90%; (c) where the round trip current efficiency is greater than about 90%; (d) where the sign of the net ionic charge of the first, second, or both active materials is the same in both oxidized and reduced forms of the active materials and matches that of the ionomer membrane; (e) where the ionomer membrane has a thickness of less than about 100 ⁇ , less than about 75 ⁇ , less than about 50 u,m, or less than about 250 urn; (f) where the flow battery is capable of operating at a current density of greater than about 100 mA/cm 2 with a round trip voltage efficiency of greater than about 60%;
  • a user may desire to provide higher charge or discharge voltages than available from a single battery cell.
  • several battery cells can be connected in series such that the voltage of each cell is additive.
  • An electrically conductive, but non-porous material e.g., a bipolar plate
  • the positive electrode compartments and negative electrode compartments of individual cells can be fluidically connected via common positive and negative fluid manifolds in the stack. In this way, individual cells can be stacked in series to yield a voltage appropriate for DC applications or conversion to AC applications.
  • the cells, cell stacks, or batteries can be incorporated into larger energy storage systems, suitably including piping and controls useful for operation of these large units.
  • Piping, control, and other equipment suitable for such systems are known in the art, and can include, for example, piping and pumps in fluid communication with the respective chambers for moving electrolyte solutions into and out of the respective chambers and storage tanks for holding charged and discharged electrolytes.
  • the cells, cell stacks, and batteries of this disclosure can also include an operation management system.
  • the operation management system can be any suitable controller device, such as a computer or microprocessor, and can contain logic circuitry that sets operation of any of the various valves, pumps, circulation loops, and the like.
  • a flow battery system can include a flow battery
  • the flow battery cell stack accomplishes the conversion of charging and discharging cycles and determines the peak power.
  • the storage tanks contain the positive and negative active materials, such as the coordination complexes disclosed herein, and the tank volume determines the quantity of energy stored in the system.
  • the control software, hardware, and optional safety systems suitably include sensors, mitigation equipment and other
  • a power conditioning unit can be used at the front end of the energy storage system to convert incoming and outgoing power to a voltage and current that is optimal for the energy storage system or the application.
  • the power conditioning unit in a charging cycle can convert incoming AC electricity into DC electricity at an appropriate voltage and current for the cell stack. In a discharging cycle, the stack produces DC electrical power and the power
  • conditioning unit converts it to AC electrical power at the appropriate voltage and frequency for grid applications.
  • energy density refers to the amount of energy that can be stored, per unit volume, in the active materials. Energy density refers to the theoretical energy density of energy storage and can be calculated by Equation 1 :
  • Equation 2 Equation 2
  • [e ⁇ ] [active materials] x N/ 2 (Equation 2) where [active materials] is the molar concentration of the active material in either the negative or positive electrolyte, whichever is lower, and N is the number of electrons transferred per molecule of active material.
  • charge density refers to the total amount of charge that each electrolyte contains. For a given electrolyte, the charge density can be calculated by Equation 3
  • current density refers to the total current passed in an electrochemical cell divided by the geometric area of the electrodes of the cell and is commonly reported in units of mA/cm 2 .
  • the term "current efficiency” can be described as the ratio of the total charge produced upon discharge of a cell to the total charge passed during charging.
  • the current efficiency can be a function of the state of charge of the flow battery. In some non- limiting embodiments, the current efficiency can be evaluated over a state of charge range of about 35% to about 60%.
  • the term “voltage efficiency” can be described as the ratio of the observed electrode potential, at a given current density, to the half-cell potential for that electrode (x 100%).
  • Voltage efficiencies can be described for a battery charging step, a discharging step, or a "round trip voltage efficiency.”
  • the round trip voltage efficiency (V e ff,rt) at a given current density can be calculated from the cell voltage at discharge (V d j SC
  • the terms “negative electrode” and “positive electrode” are electrodes defined with respect to one another, such that the negative electrode operates or is designed or intended to operate at a potential more negative than the positive electrode (and vice versa), independent of the actual potentials at which they operate, in both charging and discharging cycles.
  • the negative electrode may or may not actually operate or be designed or intended to operate at a negative potential relative to a reversible hydrogen electrode.
  • the negative electrode is associated with a first electrolyte solution and the positive electrode is associated with a second electrolyte solution, as described herein.
  • the electrolyte solutions associated with the negative and positive electrodes may be described as negolytes and posolytes, respectively.
  • a titanium catecholate complex was prepared by adding titanium tetrachloride to an aqueous catechol solution. Gallol was combined thereafter in the presence of an aqueous base.
  • the ⁇ and 13 C NMR spectra were consistent with complex formation.
  • FIGURES 2 and 3 show illustrative ⁇ and 13 C NMR spectra in acetone-d 6 of a titanium catecholate complex formed under aqueous conditions. Tetraethylammonium chloride (TEAC1) was included as an internal standard.
  • TEAC1 Tetraethylammonium chloride

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Abstract

La présente invention concerne des complexes de catécholate de titane qui peuvent être des matériaux actifs souhaitables pour des batteries à circulation et d'autres systèmes de stockage d'énergie électrochimique, en particulier lorsqu'ils sont incorporés dans des solutions électrolytiques aqueuses. Selon l'invention, il peut être souhaitable d'éviter l'introduction de certains solvants organiques et/ou de sels étrangers dans des solutions électrolytiques aqueuses. Des procédés de synthèse de complexes de catécholate de titane qui peuvent aider à éviter l'introduction indésirable de solvants organiques et/ou de sels étrangers dans des solutions électrolytiques aqueuses peuvent consister à : fournir une solution aqueuse contenant un composé catéchol, faire réagir un réactif de titane avec le composé catéchol dans la solution aqueuse pour former un complexe de catécholate de titane intermédiaire, isoler le complexe de catécholate de titane intermédiaire en tant que solide ou boue, et faire réagir un composé pouvant être ligaturé avec le complexe de catécholate de titane intermédiaire en présence d'une base pour produire un complexe de catécholate de titane sous forme de sel contenant au moins un ligand supplémentaire.
EP17887416.0A 2017-03-29 2017-05-01 Procédés aqueux pour former des complexes de catécholate de titane et compositions associées Withdrawn EP3601300A1 (fr)

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US15/473,553 US10741864B2 (en) 2016-12-30 2017-03-29 Aqueous methods for forming titanium catecholate complexes and associated compositions
PCT/US2017/030449 WO2018125273A1 (fr) 2016-12-30 2017-05-01 Procédés aqueux pour former des complexes de catécholate de titane et compositions associées

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