Patent Application
20230051932
A redox flow battery (RFB) stores elertriral energy in reduced and oxidized species dissolved in two separate electrolyte solutions. The negative electrolyte and the positive electrolyte circulate through cell electrodes separated by an ion exchange membrane or a separator. Redox flow batteries are advantageous for energy storage because they are capable of tolerating fluctuating power supplies, repetitive charge/discharge cycles at maximum rates, overcharging, over-discharging, and because cycling can be initiated at any state of charge.
With a growing push for decarbonization of the electric grid and the need to balance intermittent power generation from renewable resources, the need for scalable energy storage technologies has gained significant attention. While traditional lithium-ion battery technologies excel at high power/low energy applications, long-duration energy storage capable of supplying multi-hour to multi-day power is not viable with existing battery technologies. Redox flow batteries are well suited to long duration storage since their modular design allows for simple upscaling of the energy content of a system by increasing the size of the external storage tanks. However, most of the current redox flow battery chemistries do not meet the cost or scale requirements for long duration systems. For instance, vanadium redox flow batteries are hindered by the high cost of the vanadium, all-iron systems utilizing Fe0 plating at the anode cannot independently scale their energy content since the size of the power generating stack determines the system energy (which also occurs with Zn0-based systems), and new technologies based on aqueous soluble organics still require significant development to allow for scalable synthesis and improvements to long-term stability.
The concept of using iron coordination complexes has recently received attention, and some iron complexes based on EDTA, amino acids, hydroxy-acids, polypyridyl ligands, and similar ligands have been reported. However, demonstration of iron complexes that meet all the solubility, voltage, and stability requirements for a viable flow battery has not yet occurred. Therefore, iron complexes that can meet all these criteria and remain low-cost are of significant interest.
The following provides a description of the application of phosphonate-based ligands as iron chelators to enable viable iron complexes that can be applied as redox-flow battery anolytes. 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).
Disclosed herein are iron complexes with phosphonate-based ligands as RFB and analyte materials. As a representative example of the phosphonate class of ligands, etidronic acid is capable of strongly binding Fe(III) ions in a 2:1 ratio and is highly soluble at pH 8. At this mild pH the complex bears a 5-charge, yielding a water-soluble species, specifically >0.8 M solubility. This highly negative charge of the complex further contributes to high RFB performance by negatively shifting the reduction potential of the iron center. Coupled with a ferrocyanide catholyte, the iron etidronic acid complex yields an RFB with a cell voltage of ˜1.15 V at full charge.
The purpose of the foregoing summary and the latter abstract is to enable the United States Patent and Trademark Office and the public generally, especially the scientists, engineers, and practitioners in the art who are not familiar with patent or legal terms or phraseology, to determine quickly from a cursory inspection the nature and essence of the technical disclosure of the application. Neither the summary nor the abstract is intended to define the invention of the application, which is measured by the claims, nor is it intended to be limiting as to the scope of the claims in any way.
Embodiments of the invention are described below with reference to the following accompanying drawings.
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.
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.
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.
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.
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.
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.
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.
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).
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.
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.
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 FeCl3 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/cm2 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 FeCl3, 0.35M in TiOSO4, and 1.4 M in etidronic acid which was treated with aqueous NH3 until pH 8 and then brought to 0.1M in (NH4)2HPO4. This anolyte was cycled at 20 mA/cm2 against a solution that was 0.7M ferrocyanide, 0.036M ferricyanide, 0.35M (NH4)2SO4, 1.05M NH4Cl, and 0.1M in (NH4)2HPO4.
Referring to the drawings,
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
As shown in
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 (
Referring to
Referring to
Shown in
Flow battery data from an anolyte solution of ˜0.45 M TiOSO4 with 3.3 equivalents of etidronic acid, which was brought to a pH of ˜8 with aqueous NH3, and a catholyte solution of 0.7 M Fe(CN)6 (from equimolar Na4Fe(CN)6 and K4Fe(CN)6), 0.035 M K3Fe(CN)6, and supporting electrolyte of 0.7M (NH4)2SO4.
Referring to
The titanium complexes may also be cycled with a lower 1:1 ratio of etidronic acid to titanium. As shown in
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
Referring to
Referring to
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.
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.
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.
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.
This invention claims priority from provisional patent application No. 63/233,595, filed Aug. 16, 2021, and entitled Iron Complexes with Phosphonate-Based Ligands as RFB Anolyte Materials.
This invention was made with Government support under Contract DE-AC0576RL01830 awarded by the U.S. Department of Energy. The Government has certain rights in the invention.
| Number | Date | Country | |
|---|---|---|---|
| 63233595 | Aug 2021 | US |
