IRON COMPLEXES WITH PHOSPHONATE-BASED LIGANDS AS RFB ANOLYTE MATERIALS

Abstract

An anolyte for a redox-flow battery (RFB) comprising a metal-ion complex and a phosphonate-based ligand having a phosphonic group wherein the phosphonic acid group is directly coordinated to a metal-ion.

Claims

1. An anolyte for a redox-flow battery (RFB) comprising a metal-ion complex and a phosphonate-based ligand having a phosphonic group wherein the phosphonic acid group is directly coordinated to a metal-ion.

2. The anolyte of claim 1 wherein the phosphonate groups, which are 2-charged when deprotonated.

3. The anolyte of claim 1 wherein the phosphonate-based ligand is selected from the group consisting of etidronic acid, nitrilotri(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid), iminodi(methylphosphonic acid), methylenediphosphonic acid, (aminomethyl)phosphonic acid, 2-aminoethylphosphonic acid, N,N-bis(phosphonomethyl)glycine, N-(phosphonomethyl)glycine, N-(phosphonomethyl)iminodiacetic acid, phosphonoacetic acid, pyrophosphate, and trimetaphosphate.

4. The anolyte of claim 3 wherein the ligand is etidronic acid.

5. The anolyte of claim 3 wherein the ligand is nitrilotri(methylenephosphonic acid).

6. The anolyte of claim 1, wherein the metal ion is iron.

7. The anolyte of claim 6, wherein the ligand is etidronic acid.

8. The anolyte of claim 6, wherein the ligand is nitrilotri(methylenephosphonic acid).

9. The anolyte of claim 1, wherein the metal is titanium.

10. The anolyte of claim 9, wherein the ligand is etidronic acid.

11. The anolyte of claim 10, wherein the ligand is nitrilotri(methylenephosphonic acid).

12. The anolyte of claim 1, wherein a resulting iron-complex solubility is more than 0.8M in water at a pH of 8.

13. The anolyte of claim 6, wherein ligand to metal is a ratio of 2:1.

14. The anolyte of claim 9, wherein ligand to metal is a ratio of 1:1.

15. The anolyte of claim 1, wherein ligand to metal ratio is between 1-3:1 and within pH range of 6-11.

16. The anolyte of claim 1, wherein the metal center coordination sphere of the metal ion is fully saturated by etidronic acid ligands.

17. The anolyte of claim 1, wherein the metal center coordination sphere of the metal ion are occupied by aqua, hydroxo, or oxo groups.

18. The anolyte of claim 1, wherein the ligand to metal ratio is between 1-3:1 and within pH range of 6-14.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0009] Embodiments of the invention are described below with reference to the following accompanying drawings.

[0010] FIG. 1 represents a 2:1 complex between etidronic acid and iron.

[0011] FIG. 2 represents a 3:1 complex between etidronic acid and iron.

[0012] FIGS. 3A and 3B illustrate cyclic voltammograms for mixtures of etidronic acid and nitrilotri(methylenephosphonic acid) with iron.

[0013] FIGS. 4A and 4B are graphs illustrating battery cycling data for the complexes. FIG. 4A represents capacity retention data for the solution cycled at 20 mA/cm.sup.2 long-term. FIG. 4B represents voltage profiles for varied current densities.

[0014] FIGS. 5A and 5B illustrates long-term voltage profile data obtained at 20 mA/cm.sup.2.

[0015] FIG. 6 illustrates performance of an electrolyte comprised of a 1.05:1 etidronic acid to iron ratio.

[0016] FIGS. 7A and 7B are graphical depictions of etidronic acid used to coordinate titanium ions.

[0017] FIGS. 8A and 8B are graphical depictions of example cycle flow battery data from the anolyte solution.

[0018] FIGS. 9A and 9B are graphical depictions of electrolyte solutions containing one (1) equivalent of etidronic acid per titanium provide high cell voltages.

[0019] FIGS. 10A and 10B illustrates an example of flow battery data from an anolyte solution including voltage, cycling and capacity.

[0020] FIGS. 11A and 11B illustrates an example of flow battery data from an anolyte solution including voltage, cycling and capacity.

DETAILED DESCRIPTION

[0021] The installation of grid-scale energy storage systems is increasing rapidly. These systems are being installed for a multitude of purposes by utility companies and are currently predominantly lithium-ion systems. While this technology is mature, it poses safety hazards at this this scale and still has a high cost for systems with multi-hour ratings.

[0022] The present disclosure alleviates safety concerns, since it is water-based and inherently non-flammable, uses non-toxic metals, and operates at benign pH. The use of iron and commodity-scale ligands results in low materials cost that can find application in long-duration energy storage installations where lithium-ion or VRFB would not be cost effective.

[0023] Described herein are iron complexes based on multidentate ligands with phosphonate coordination groups. These metal complexes are used as anolyte materials in aqueous redox flow batteries. Proposed all soluble iron flow batteries have a battery structure having an anolyte tank and a catholyte tank, and a flow battery stack. Compared with the vanadium redox flow battery (VRFB), the main advantage achieved by the present disclosure is the use of a cost-effective iron complex-based electrolyte to replace the high-cost vanadium electrolyte, thereby further reducing the cost of RFB technology.

[0024] The following provides a large and diverse set of chemistries that have been investigated for RFB use. While not exhaustive, the following list describes other RFB technologies and their comparison to the present disclosure.

[0025] In an example, all vanadium RFB is the most advanced RFB technology available and offers high solubility, high voltage, and long service life. However, the vanadium used by the system is currently very costly and can introduce a significant hurdle to widespread adoption of RFBs. The currently proposed iron-phosphonate complex system offers a low-cost alternative based on iron.

[0026] In another example, hybrid flow batteries, which deposit a solid metal material at the anode, have been described with all iron systems, zinc/bromine systems, and iron/zinc systems. However, the hybrid design does not allow independent tuning of energy and power, limiting the potential applications of the RFB technology to shorter duration uses. The proposed system is a true flow battery, with anolyte and catholyte materials that remain soluble throughout charging and discharging and allow true decoupling of energy and power in the system.

[0027] In another example, other iron complexes have been proposed based on EDTA, amino acids, hydroxy-acids, polypyridyl ligands, and similar ligands. As noted earlier, the use of phosphonate groups on the ligands provides additional tenability to the overall charge of the complex which can improve solubility, decrease material crossover through the ion-selective membrane, and improve cell voltage.

[0028] The embodiments described herein are directed to iron complexes with phosphonate-based ligands as RFB and anolyte materials. The application of phosphonate-based ligands as iron chelators to enable viable iron complexes that can be applied as redox-flow battery analytes. Bearing phosphonate groups, which are 2-charged when deprotonated, these complexes allow for more control over the ionic charge of the overall complex and can increase solubility, especially compared to traditional carboxylic acid-based ligands whose carboxylate group introduces a 1-charge. This is especially notable for Fe(EDTA) complexes, which are carboxylate-based and have only a net 1-charge in their Fe(III) complex and have a resultingly low solubility in water (<0.2 M).

[0029] A wide range of phosphonate-based molecules that can be used as ligands are available commercially, with a non-exclusive list which includes etidronic acid, nitrilotri(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid), iminodi(methylphosphonic acid), methylenediphosphonic acid, (aminomethyl)phosphonic acid, 2-aminoethylphosphonic acid, N,N-bis(phosphonomethyl)glycine, N-(phosphonomethyl)glycine, N-(phosphonomethyl)iminodiacetic acid, phosphonoacetic acid, pyrophosphate, trimetaphosphate.

[0030] Experimental data for two ligands, etidronic acid and nitrilotri(methylenephosphonic acid), applied to two different metal ions, iron and titanium, are described. Ligand to metal ratios ranging from 1-3:1 are described as well as pH ranges from 6-11. These ligands show rich metal binding chemistry; etidronic acid can form species with a single ligand bound to the metal center with free coordination sites occupied by aqua, hydroxo, or oxo groups that may be terminal or bridging, or bridged by another etidronic acid-metal complex to form a multirnetallic species. The ligand may also form 2:1 complexes where the metal center coordination sphere is fully saturated by the etidronic acid ligands, or where 1-2 coordination sites are occupied by aqua, hydroxo, or oxo groups. Further, the metal center may be coordinated by 3 etidronic acid ligands. Similar coordination environments where ligands can act as mono-, bi-, or tridentate can be expected for the related phosphonate ligands.

[0031] In some embodiments, the pH range can be 6-14. Complexes formed between iron and etidronic acid are also capable of electrochemical cycling at elevated pHs up to 14. For example, voltage profiles for a 20 mL solution that is 0.5M in FeCl.sub.3 with 1 equiv. of etidronic acid and was treated with 6 equivalents of KOH and additional 7 drops of 10M NaOH were cycled in elevated pH up to 14. This anolyte was cycled at 20 mA/cm.sup.2 against 20 mL of 0.5M ferrocyanide in a solution of 1.5M KCl and 0.1M KOH. Additionally, and/or alternatively, analytes comprised of a mixture of iron and titanium can also be utilized. For example, voltage profiles for a 14 mL solution that is 0.35M in FeCl.sub.3, 0.35M in TiOSO.sub.4, and 1.4 M in etidronic acid which was treated with aqueous NH.sub.3 until pH 8 and then brought to 0.1M in (NH.sub.4).sub.2HPO.sub.4. This anolyte was cycled at 20 mA/cm.sup.2 against a solution that was 0.7M ferrocyanide, 0.036M ferricyanide, 0.35M (NH.sub.4).sub.2SO.sub.4, 1.05M NH.sub.4Cl, and 0.1M in (NH.sub.4).sub.2HPO.sub.4.

[0032] Referring to the drawings, FIG. 1 and FIG. 2 illustrate the 2:1 and 3:1 complexes between etidronic acid and iron, described above. FIG. 1 is an illustration representative binding motif for an etidronic acid ligand bound as tridentate ligand to an iron metal center. FIG. 2 is an illustration representative binding motif for an etidronic acid ligand bound as bidentate ligand to an iron metal center.

[0033] FIGS. 3A and 3B represent cyclic voltammograms for mixtures of etidronic acid and nitrilotri(methylenephosphonic acid) with iron. The cyclic voltammograms of iron complexes with etidronic acid shown in FIG. 3A and nitrilotri(methylenephosphonic acid) shown FIG. 3B were obtained at pH 8 on an electrode of glassy carbon with ketjen black drop cast to the electrode, having a scan rate of 100 mV/s.

[0034] As a representative example of the phosphonate class of ligands, etidronic acid is capable of strongly binding iron ions and, in mixtures with a ligand to metal ratio of 2:1, is highly water-soluble at pH 8, in particular >0.8 M solubility. Coupled with a ferrocyanide catholyte, the iron etidronic acid complex yields an RFB with an OCV of ˜1.15 V at full charge. Representative battery cycling data for these complexes are provided in FIGS. 4A and 4B for a system that demonstrate up to 7 Wh/L.

[0035] As shown in FIGS. 4A and 4B, flow battery data from an anolyte solution of 0.9 M FeCl.sub.2 with 2 equivalents of etidronic acid, which was brought to a pH of ˜8 with 2 equivalents of NaOH per etidronic acid and then aqueous NH.sub.3, and a catholyte solution of 0.7 M Na.sub.3Fe(CN).sub.6 with a supporting electrolyte of 2 M NH.sub.4Cl and additional aqueous NH.sub.3 until pH of ˜8. FIG. 4A illustrates capacity retention data for the solution cycled at 20 mA/cm.sup.2 long-term. FIG. 4B illustrates voltage profiles for varied current densities.

[0036] Additionally, the operative pH of the system may be extended to both higher and lower pHs. Voltage profiles for flow batteries at buffered pHs between 6-7 (FIG. 5A, described further below) and also at a pH of 10-11 (FIG. 5B, described further below) are provided in FIGS. 5A and 5B.

[0037] FIGS. 5A and 5B, illustrates long-term voltage profile data obtained at 20 mA/cm.sup.2. FIG. 5A is a depiction of voltage profiles from a flow battery comprised of 11 mL of anolyte that is 0.45M in Fe.sup.3+ prepared from FeBr.sub.3 and 2.1 equivalents of etidronic acid, then treated with 4 equivalents of base per etidronic acid (equal parts NaOH and KOH) to quench all phosphonic acid protons in solution, which was then brought to 0.45M (NH.sub.4).sub.2HPO.sub.4 and 0.45M (NH.sub.4)H.sub.2PO.sub.4. The catholyte was 0.45M Fe(CN).sub.6.sup.4− from equal parts Na.sub.4Fe(CN).sub.6 and K.sub.4Fe(CN).sub.6 with the same buffer of 0.45M (NH.sub.4).sub.2HPO.sub.4 and 0.45M (NH.sub.4)H.sub.2PO.sub.4.

[0038] FIG. 5B is a depiction of voltage profiles from a flow battery comprised of 10.5 mL of anolyte that is 0.476 M in Fe.sup.2+ prepared from FeCl.sub.2 and 2.1 equivalents of etidronic acid, then treated with 4 equivalents of base per etidronic acid (equal parts NaOH and KOH) to quench all phosphoric acid protons in solution and then treated with an additional 0.4 equivalents of base per Fe.sup.2+. The catholyte was 0.5 M K.sub.3Fe(CN).sub.6 with 1 M NaCl as supporting electrolyte.

[0039] Referring to FIG. 6, in addition to mixtures containing ≥2:1 ratios of etidronic to iron, mixtures with lower ligand content are attainable and can be subjected to flow cell operation. Performance of an electrolyte comprised of a 1.05:1 etidronic acid to iron ratio is provided in FIG. 6. As shown in FIG. 6, voltage profile data obtained at 20 mA/cm.sup.2 and 5 mA/cm.sup.2 from a flow battery comprised 7.5 mL of an anolyte that is 0.67 M in Fe.sup.2+ prepared from FeCl.sub.2 and 1.05 equivalents of etidronic acid, which was then treated with 5 equivalents of base per iron (using equimolar NaOH and KOH). The catholyte was comprised of 0.7 M K.sub.3Fe(CN).sub.6with 1.4 M NaCl as supporting electrolyte.

[0040] Referring to FIGS. 7A and 7B, in addition to the iron-based electrolytes described above, etidronic acid can be used to coordinate titanium ions and produce higher voltage electrolytes. Similar to the iron electrolytes, ligand to metal ratios ranging from 1:1 to ≥2:1 can be applied in the titanium-etidronic acid system and yield total metal ion solubilities of >0.7 M.

[0041] Shown in FIGS. 7A and 7B, titanium-based electrolytes with 3.3 equivalents of etidronic acid per titanium show stable cycling and an OCV at full charge of 1.24 V. With electrolytes containing 2:1 ligand to titanium ratio, a higher voltage event appears in addition to the voltage plateaus observed in FIG. 5 along with slightly lower efficiency and capacity retention. For the flow battery test using a 2:1 ratio, the flow cell used for the 13:1 test was drained of anolyte and rinsed with water, and then the anolyte reservoir was replaced with the 2:1 electrolyte and cycling was continued. This occurred at cycle 65, as seen in FIGS. 8A and 8B (described further below), with cycles 1-64 also shown in FIG. 6, above.

[0042] Flow battery data from an anolyte solution of ˜0.45 M TiOSO.sub.4 with 3.3 equivalents of etidronic acid, which was brought to a pH of ˜8 with aqueous NH.sub.3, and a catholyte solution of 0.7 M Fe(CN).sub.6 (from equimolar Na.sub.4Fe(CN).sub.6 and K.sub.4Fe(CN).sub.6), 0.035 M K.sub.3Fe(CN).sub.6, and supporting electrolyte of 0.7M (NH.sub.4).sub.2SO.sub.4. FIG. 7A shows the capacity retention data for the solution cycled at 20 mA/cm.sup.2 long-term. FIG. 7B shows the voltage profiles from selected cycles.

[0043] Referring to FIGS. 8A and 8B, beginning at cycle 65, flow battery data from an anolyte solution of ˜0.74 M TiOSO.sub.4 with 2 equivalent of etidronic acid brought to a pH of 8-9 with ammonia and a catholyte solution of 0.7 M Fe(CN).sub.6.sup.4− (from equal parts Na.sub.4Fe(CN).sub.6 and K.sub.4Fe(CN).sub.6), 0.035 M K.sub.3Fe(CN).sub.3, and supporting electrolyte of 0.7 M (NH.sub.4).sub.2SO.sub.4. Cycled at 20 mA/cm.sup.2.

[0044] The titanium complexes may also be cycled with a lower 1:1 ratio of etidronic acid to titanium. As shown in FIGS. 9A and 9B, electrolyte solutions containing 1 equivalent of etidronic acid per titanium provide high cell voltages. The flow battery data from an anolyte solution of ˜0.74 M TiOSO.sub.4 with 1 equivalent of etidronic acid brought to a pH of 7 with ammonia and a catholyte solution of 0.7 M Fe(CN).sub.6.sup.4− (from equal parts Na.sub.4Fe(CN).sub.6 and K.sub.4Fe(CN).sub.6), 0.035 M K.sub.3Fe(CN).sub.3, and supporting electrolyte of 0.7 M (NH.sub.4).sub.2SO.sub.4. After charging at cycle 4, the FLAT electrodes at the anolyte were replaced and the catholyte was exchanged. Cycled at 20 mA/cm.sup.2.

[0045] In some embodiments, in addition to etidronic acid, other phosphonate-based ligands may be used to coordinate transition metals for application as redox flow battery electrolytes. As an additional example, nitrilotri(methylenephosphonic acid) has also been demonstrated with iron and titanium metal ions. In electrolyte mixtures with a 1:1 ligand to metal ratio, flow batteries utilizing iron or titanium produce the battery cycling performance provided in FIGS. 10A, 10B, 11A and 11B. In addition to the use of a single ligand, mixtures of different ligands may be used to yield stable-cycling electrolytes.

[0046] Referring to FIGS. 10A and 10B, the 1:1 mixture of nitrilotri(methylenephosphonic acid) and iron was treated with another equivalent of etidronic acid (pretreated with 4 equivalents of ammonia) at cycle 215, yielding improved material utilization and efficiency. FIGS. 10A and 10B show flow battery data from an anolyte solution of ˜0.71 M FeCl.sub.3 with 1 equivalent of nitrilotri(methylenephosphonic acid) brought to a pH of 8 with ammonia with an additional 0.1 M (NH.sub.4).sub.2HPO.sub.4 supporting electrolyte and a catholyte solution of 0.71 M Fe(CN).sub.6.sup.4− (from equal parts Na.sub.4Fe(CN).sub.6 and K.sub.4Fe(CN).sub.6), 0.035 M K.sub.3Fe(CN).sub.3, and supporting electrolyte of 1.4 M NH.sub.4Cl & 0.1 M (NH.sub.4).sub.2HPO.sub.4 and Cycled at 10 mA/cm.sup.2.

[0047] Referring to FIGS. 11A and 11B, flow battery data from an anolyte solution of ˜0.74 M TiOSO.sub.4 with 1 equivalent of nitrilotri(methylenephosphonic acid) brought to a pH of 7 with ammonia with an additional 0.1 M (NH.sub.4).sub.2HPO.sub.4 supporting electrolyte and a catholyte solution of 0.74 M Fe(CN).sub.6.sup.4− (from equal parts Na.sub.4Fe(CN).sub.6 and K.sub.4Fe(CN).sub.6), 0.035 M K.sub.3Fe(CN).sub.3, and supporting electrolyte of 0.25 M (NH.sub.4).sub.2SO.sub.4 & 0.1 M (NH.sub.4).sub.2HPO.sub.4, After cycle 88 the FLAT electrodes at the anolyte were replaced with a combination of carbon paper and FLAT, and the catholyte exchanged. Cycled at 20 mA/cm.sup.2 until cycle 5, then cycled at 10 mA/cm.sup.2 thereafter.

[0048] The following explanations of terms and abbreviations are provided to better describe the present disclosure and to guide those of ordinary skill in the art in the practice of the present disclosure. As used herein, “comprising” means “including” and the singular forms “a” or “an” or “the” include plural references unless the context clearly dictates otherwise. The term “or” refers to a single element of stated alternative elements or a combination of two or more elements, unless the context clearly indicates otherwise.

[0049] Unless explained otherwise, all technical and scientific terms used herein have the same meaning as commonly understood to one of ordinary skill in the art to which this disclosure belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present disclosure, suitable methods and materials are described below. The materials, methods, and examples are illustrative only and not intended to be limiting. Other features of the disclosure are apparent from the following detailed description and the claims.

[0050] Unless otherwise indicated, all numbers expressing quantities of components, molecular weights, percentages, temperatures, times, and so forth, as used in the specification or claims are to be understood as being modified by the term “about.” Accordingly, unless otherwise implicitly or explicitly indicated, or unless the context is properly understood by a person of ordinary skill in the art to have a more definitive construction, the numerical parameters set forth are approximations that may depend on the desired properties sought and/or limits of detection under standard test conditions/methods as known to those of ordinary skill in the art. When directly and explicitly distinguishing embodiments from discussed prior art, the embodiment numbers are not approximates unless the word “about” is recited.

[0051] In view of the many possible embodiments to which the principles of the disclosed invention may be applied, it should be recognized that the illustrated embodiments are only preferred examples of the invention and should not be taken as limiting the scope of the invention. Rather, the scope of the invention is defined by the following claims. We therefore claim as our invention all that comes within the scope and spirit of these claims.