Patent Application
20250027211
The present invention relates to anion-conducting polymer membrane electrochemical devices including electrolyzers. The invention also relates to the composition of the anolyte used in the electrolyzer. The electrochemical devices made in accordance with this invention include electrolyzers where the electro-inactive salts in the anolyte improve the electrolyzer performance by improving the hydrogen generating cathode performance.
The production of renewable electricity can replace hydrocarbon-based electrical energy sources and provide global energy independence. Renewable energy is intermittent by nature and benefits from converting the electrical energy to a chemical form. The electrolysis of water provides a cost-effective way to produce and store chemical energy for use in chemical synthesis or transportation. Hydrogen can be produced on-site in a distributed manner by electrolysis of water from renewable energy including wind, solar and hydro sources, or from non-renewable electricity.
The electrolysis of water can be performed using a high pH, alkaline liquid electrolyte (ALE), proton exchange membrane (PEMEL), or anion exchange membrane (AEMEL) electrolysis device. The AEMEL offers advantages over both ALE and PEMEL. AEMEL devices can use low-platinum or no-platinum catalysts, as compared to PEMEL which use iridium and platinum catalysts. The solid polymer electrolyte can be operated at higher current density than an ALE liquid electrolyte and the membrane can support a pressure difference between the two electrodes allowing high-pressure hydrogen to be produced.
Compact AEMEL devices can be constructed by attaching the high surface area anode and cathode electrodes to the solid polymer membrane, sometimes called a zero-gap electrode. The high surface area electrodes allow (i) chemical reactants/products, (ii) ions, and (iii) electrons from the external circuit to reach the catalytic electrode sites where the electrochemical reactions occur. Three-dimensional electrodes are necessary because they enable a high surface area within a small, compact volume situated on the membrane.
The AEMEL combines the advantages ALE and PEMEL electrolyzers. The oxygen evolution reaction (OER) is more facile in AEMEL at high pH compared to low pH PEMEL electrolyzers. Also, AEMEL enables the use of non-platinum group metal (PGM) catalysts because it operates at high pH.
In alkaline electrolysis, hydroxide is oxidized at the positive electrode (i.e., anode) producing oxygen and water. Water is reduced at the negative electrode (i.e., cathode) producing hydrogen and hydroxide ions. Liquid water can be fed to the anode. The cathode can be operated without a liquid feed, sometimes called a “dry-cathode”, so that the hydrogen does not have to be separated from the liquid at the cathode. In the case of the dry-cathode, water is transported to the cathode from the anolyte by diffusion through the AEM. It is important to control the water uptake and ion exchange capacity (IEC) of the ion conducting polymers, sometimes called ionomers, used in the ink to make the cathode so that dry-out does not occur at the cathode because water is the cathode reactant. AEMEL performance improves when a hydrophilic ionomer is used in the cathode to retain water.
A high pH supporting electrolyte can be used in the water fed to the anode (i.e., anolyte) to improve electrolyte performance, as measured by lowering the required electrolysis voltage at a specific current density. The high pH anolyte improves cell performance because hydroxide is the reactant at the anode and a high concentration in the anolyte increases the anode reactant concentration. The hydroxide also improves the ion conductivity within the 3-D anode so that the anode catalyst particles deep within the anode are more effectively used without suffering a voltage drop from low ion conductivity anolyte.
However, the high pH of the anolyte is a durability concern because the ion conducting polymer used in the anode and the anion exchange membrane (AEM) can undergo nucleophilic attack by the hydroxide at high pH. In addition, operating the AEMEL without a liquid feed to the cathode can cause dry-out at the cathode because water delivery to the cathode is by diffusion from the anolyte through the AEM. The cathode current density cannot exceed the rate of water diffusion through the AEM. Thus, operating the cathode without a liquid feed can result in lower current density electrolysis due to inadequate water delivery from the anode to the cathode.
Therefore, there is a need for a system which can more effectively deliver water from the anolyte to the cathode through the AEM when the cell is operated in the absence of direct water feed to the cathode without increasing the pH of the anolyte. Excessively high anolyte pH can lead to long-term durability problems including polymer degradation and metal corrosion.
The disadvantages of the prior art are overcome by the present invention which, in one aspect, is an electrochemical electrolyzer device that includes a cathode including a hydrogen evolution reaction (HER) catalyst and an anode spaced apart from the cathode, the anode including an oxygen evolution reaction (OER) catalyst. An anion exchange membrane (AEM) is disposed between the cathode and the anode. An anolyte having a hydroxide ion concentration is disposed against the anode and has a cation concentration that exceeds the hydroxide ion concentration in the anolyte.
In another aspect, the invention is an electrochemical electrolyzer that includes an anolyte having a cation concentration that exceeds a hydroxide ion concentration.
In yet another aspect, the invention is a method of operating an electrochemical electrolyzer device that employs a cathode for producing hydrogen, an anode for producing oxygen and being spaced apart from the cathode, an anion exchange membrane (AEM) disposed between the cathode and the anode, in which an anolyte having a cation concentration that exceeds hydroxide ion concentration in the anolyte is placed against the anode.
These and other aspects of the invention will become apparent from the following description of the preferred embodiments taken in conjunction with the following drawings. As would be obvious to one skilled in the art, many variations and modifications of the invention may be effected without departing from the spirit and scope of the novel concepts of the disclosure.
A preferred embodiment of the invention is now described in detail. Referring to the drawings, like numbers indicate like parts throughout the views. Unless otherwise specifically indicated in the disclosure that follows, the drawings are not necessarily drawn to scale. The present disclosure should in no way be limited to the exemplary implementations and techniques illustrated in the drawings and described below. As used in the description herein and throughout the claims, the following terms take the meanings explicitly associated herein, unless the context clearly dictates otherwise: the meaning of “a,” “an,” and “the” includes plural reference, the meaning of “in” includes “in” and “on.” Since all numbers, values and/or expressions referring to quantities of ingredients, reaction conditions, etc., used herein and in the claims appended hereto, are subject to the various uncertainties of measurement encountered in obtaining such values, unless otherwise indicated, all are to be understood as modified in all instances by the term “about.” Where a numerical range is disclosed herein such range is continuous, inclusive of both the minimum and maximum values of the range as well as every value between such minimum and maximum values.
As used herein, the expression “dry-cathode” means a cathode operated with little or no direct liquid water feed. It is understood that the gaseous environment in the cathode chamber may be humid because water is transported through the AEM and water is the reactant at the dry-cathode.
The term “ion-conducting polymer” and “ion conductive ionomer” means a molecule with at least one monomer in the form R—XY. R is an organic moiety and —XY is an ionizable moiety. For example, in the case of an anion-conducting polymer, the ionizable moiety yields R—X+ and Y—. The cation X+ is immobile because it is chemically bonded to the polymer, R, and the anion Y— is a mobile anion because it is liberated or ionized from its counter ion. It is also understood that an ion-conducting ionomer or polymer may also be synthesized in the form R—Z, where the moiety —Z is converted into —XY in a post synthesis treatment. When the ion conductive polymer is used to form the electrode, the term ion conductive ionomer is often used.
Surprisingly, it has been found that the addition of pH-neutral, electro-inactive alkali salts to the anolyte significantly improves the cathode performance even though the anolyte solution is fed only to the anode and not the cathode. The present invention uses electro-inactive, Group 1 alkali salts in the anolyte to improve the cathode performance. The Group 1 alkali cations can be added to the anolyte without increasing the anolyte pH. The electrolyzer performance is improved due to the enhanced water delivery from the anode to the cathode via the AEM and durability is improved because the operating voltage with the pH neutral alkali salt is lower and the high pH induced degradation of the electrodes and AEM is lessened.
The poly(norbornene) AEMs used in one experimental embodiment of the present invention were composed of butyl norbornene (BuNB) and bromobutyl norbornene (BBNB) at a molar ration of 25:75. It is understood that other AEMs can be used in place of membranes used in the examples described here.
Poly(norbornene) terpolymer anion-conductive ionomers used to make the anode and cathode were composed of butyl norbornene (BuNB), bromobutyl norbornene (BBNB), and norbornene propionic acid ethyl ester (NBPEE). The NBPEE was used to form a pendant carboxylic acid by reaction with concentrated HCl. Bis-phenyl-A-diglycidyl ether (BPADGE) adhesive was added to the electrode ink to react with the carboxylic acid via an esterification reaction. The ratio of the three monomers in the ionomers (X:Y:Z) reflect their mole ratio (BuNB:BBNB:NBPEE). 50:30:20 ionomer was used in oxygen evolution reaction (OER) anode, and 4:90:6 ionomer was used in the hydrogen evolution reaction (HER) cathode. The IEC of 50:30:20 ionomer was 1.64 meq/g, and the IEC of 4:90:6 ionomer was 4.0 meq/g.
The OER and HER electrodes were fabricated using the solvent cast method with an airbrush (Eclipse HP-CS, Iwata) to spray-coat the catalyst ink onto each porous transport layer (PTL) as reported previously. The OER ink formulation used 11 mg of 50:30:20 ion conductive ionomer, dissolved in 5 ml of tetrahydrofuran (THF, Sigma Aldrich). 56 mg of BPADGE adhesive was dissolved in the solution. 46 mg of NiFe2O4 catalyst (Pajarito Powder) was added to the solution and sonicated in an ice bath for 1 hr. The slurry was sprayed onto 25 cm2 of 680 μm thick Ni felt PTL (Technetics group), resulting in 0.5 mg/cm2, 0.12 mg/cm2, and 0.6 mg/cm2 of catalyst, ionomer, and adhesive. The HER electrode was prepared with the same fabrication method, except using 4:90:6 ionomer and Pt3Ni HER catalyst (ECS-3701, Pajarito Powder). 1.2 mg/cm2, 0.6 mg/cm2, and 0.1 mg/cm2 of catalyst, ionomer, and adhesive were spray-coated onto 14.63 cm2 of 250 μm thick non-wet proofed carbon paper PTL. The anodes and cathodes were cured at 160° C. under vacuum for 1 hr to complete the esterification reaction between BPADGE and NBPEE carboxylic acid. The electrodes were aminated by soaking in aqueous trimethyl amine (TMA) solution for 24 hr at room temperature.
The membrane electrode assembly (MEA) used 4 cm2 anode and cathode. The anion exchange membrane (AEM) was 40 μm thick GT75-5 (Xergy Inc.). GT75-5 was made with 25:75:0 polynorbornene ion conductive polymer (described above) with 5 mol % N,N,N,N-tetramethyl hexadiamine crosslinker. The mole percent crosslinker was with respect to the available bromobutyl sites. The anode, cathode, and AEM were ion-exchanged in 0.1 M NaOH under N2 atmosphere for 1 hr prior to use. The AEM was placed between the anode and cathode. A 250 am thick Pt wire (Alfa Aesar) in contact with the cathode side of the AEM was used as a pseudo reference electrode (pRE). The wire was placed on top of the AEM next to the cathode, maintaining 2 mm distance from the cathode electrode. The pRE was exposed to the hydrogen gas during electrolysis, however, the exact partial pressure of hydrogen gas and pH of the AEM varied slightly from run-to-run making it only a pseudo-reference electrode. Tefzel gaskets were used for the integration of pRE into the MEA. The MEAs were pressed between a pair of serpentine flow-patterned stainless-steel blocks with 25 in-lb of torque in the cell hardware.
The electrolysis cells were tested using a custom test station, operated at 60° C. The aqueous electrolyte was recirculated through the anode flow-field with a dry cathode at 17.9 mL/min flow rate using a peristaltic pump (YT25, Golander). The cell was conditioned at 0.1 A/cm2 for 40 min using a DC power supply (N5742A, Keysight). The applied current was then gradually increased to 1 A/cm2. The beginning-of-life (BOL) impedance spectra were recorded galvanostatically at 1 A/cm2 using SP-300 (BioLogic) after 1 A/cm2 operation for 5 min to develop steady-state mass transport of reactants and products within the cell. The end-of-life (EOL) impedance spectra were recorded at 1 A/cm2. The data points for the polarization curves were recorded by stepping the current from zero to 1 A/cm2 in 0.0125 A/cm2 steps and holding for 3 min before recording the voltage.
The sodium ion concentration in the AEM was determined by inductively coupled plasma mass spectroscopy (ICP-MS) analysis. Three AEM samples were dried in an oven at 80° C. under vacuum overnight to determine the dry weight (wAEM, dried). The AEM samples were soaked in (i) DI water, (ii) 0.01 M NaOH, and (iii) 0.01 M+1.0 M NaNO3. The samples were removed from the solutions and the excess liquid was wiped from the surface and the AEM mass was obtained (wAEM,soaked). The AEMs were immersed in a known mass of DI water (wDIW,added) and soaked overnight to extract the sodium salt from the membranes. The sodium ion concentration in these three liquid samples (Table 1: Samples #1, #2, and #3) was obtained by ICP-MS. A portion of an AEM used for 40 hr electrolysis at 1 A/cm2 using 0.01 M NaOH anolyte was immersed in a known amount of DI water and its concentration was obtained (Table 1: Sample #4) by ICP-MS. The mass of sodium ions in the analyzed water was converted to equivalents/gAEM, Table 1.
The electrolysis voltage vs current density for three anolyte concentrations, 0.01 M, 0.1 M, and 1.0 M NaOH is shown in
A pRE was integrated into the electrolysis cell to investigate the current-voltage behavior at each electrode independently. The reference electrode consisted of a platinum wire in contact with the AEM on the hydrogen side of the membrane in a region where it was exposed to hydrogen gas being produced by the cathode, but not in electrical contact with the cathode itself. Also, the relative humidity of the hydrogen gas (hydrogen gas partial pressure) was not controlled. Thus, the potential of the pseudo-reference may be slightly different from cell-to-cell. The potential of the anode and cathode (vs. pRE) in
There are several striking features in
The second notable feature of
Third, it is surprising that the anolyte concentration affected the conductivity and mass transport of both electrodes (especially the cathode), not just the anode. The anolyte concentration has a more dramatic effect on the cathode overpotential and mass transport than the anode, as shown by the dramatic change in cathode slope when going from 0.01 M NaOH to 0.1 M NaOH anolyte. Clearly, the intra-cathode ionic conductivity and mass transport, which come only from its thin ionomer layer, improved with anolyte NaOH concentration. It is not clear from
To further investigate the change in overpotential, the electrochemical impedance spectra (EIS) for the three cells in
The cause of the cathode overpotential change in
To differentiate between the effect of hydroxide and sodium ion concentration in the anolyte on the cell performance, seven anolyte feeds were used.
Inclusion of the pRE allows examination of the overpotential at each electrode as a function of current density.
It is noted that there was a slight increase in anode activation overpotential (i.e., low current density (<0.1 A/cm2) region of
The Nyquist plots in
It is known that AEMs do not have perfect salt rejection and a small amount of salt from the electrolyte can be taken up in the membrane. Sodium ions present in the membrane migrate to the hydrogen cathode during electrolysis, while carrying multiple waters of hydration (
It is also known that the addition of salts to the poly(norbornene) AEM plasticizes the membrane and increases ion diffusivity. This water delivery mechanism swells and hydrates the AEM and cathode. Water is the reactant at the cathode. Thus, in the case where the sodium ion concentration was increased by adding NaOH (
The concentration of sodium ions in the membrane was measured by ICP-MS to show that sodium ions are available for diffusion and migration through the membrane. Table 1 shows the concentration of sodium ions in AEM under different conditions. An AEM soaked in 0.01 M NaOH did not show a detectable sodium content. The AEM has high salt rejection when the salt concentration in the liquid phase is low (i.e., 0.01 M NaOH). When the NaNO3 concentration approached that in the AEM (third row of Table 1: 0.01 M NaOH+1.0 M NaNO3), sodium ions were found in the membrane. The DI water used to soak the membrane contained 26 ppm sodium which corresponds to 0.147 meq/g of sodium ions in the AEM, assuming all the sodium ions were extracted during the DI water soak. The IEC of the AEM was 3.58 meq/g. Thus, for every 100 quaternary ammonium cations tethered to the polymer backbone in the AEM, there are about 4 sodium ions when the AEM was soaked in 1.0 M NaNO3. This shows that the membrane does take-up a small amount of sodium ions. The AEM after electrolysis with 0.1 M NaOH anolyte for 40 hr had 0.08 meq/g of sodium ions. It is noted that during electrolysis, the sodium ions migrate to the cathode which would increase their concentration in the AEM. These findings provide clear evidence that the sodium ions are in the AEM during electrolysis and can travel through the AEM by diffusion and migration. Although sodium ions are electro-inactive at the cathode, they can drag water in their hydration shell toward the cathode, and the sodium ions plasticize the AEM increasing the diffusivity and mobility of all ions. These factors serve to lower the cathode overpotential (
The effect of higher concentrations of NaNO3 in the anolyte was investigated by increasing the NaNO3 molarity in 0.01 M NaOH to 0.25 M, 0.5 M, and 1.0 M,
A steady-state voltage-time profile with 0.01 M NaOH+0.15 M NaNO3 anolyte at 1 A/cm2 is shown in
The beneficial effect of different alkali cations in the anolyte was demonstrated.
The anode potential (top four curves) and cathode potential (bottom four curves) vs. pRE as a function of current density is shown in
The Nyquist plots for the different anolytes is shown in
The interfacial resistance (Rint) decreased (i.e., smaller is better) in a slightly different sequence than the HFR: K+<Li+<Cs+<Na+<none. Rint consists of the charge transfer and mass transfer resistances. The interfacial capacitance (Cint) is related to the total effective catalyst surface area (i.e., bigger is usually better): none<Cs+<Na+<Li+<K+. A greater water flux delivered by the cation in the AEM via migration increases the effective electroactive surface area of the catalyst. This leads to a decrease in the charge and mass transfer resistance at the 3-D cathode because the catalyst is more effectively used. The trend of Rint and Cint shows that the cation and water mass transfer improvement and HER electroactive surface area are improved with addition of a more mobile anolyte cation.
The presence of the alkali cation in the AEM, and relative importance of the different alkali cations was further demonstrated by measuring the transference number for each alkali cation in the anolyte at 0.01 M. The transference number for a particular ion is the fraction of the total ionic charge which is carried by that ion in the absence of a concentration gradient. The sum of all the transference numbers is equal to one. The poly(norbornene) AEMs have a tethered quaternary ammonium cation which makes the quaternary ammonium cation immobile in the AEM. The polymer chains in the AEM are bulky with a molecular weight of about 60,000 g/mole and the polymer chains are also 5% crosslinked making the whole membrane a thermoset polymer.
Table 3 shows the transference number for the hydroxide anion and alkali cation in 0.01 M and 0.1 M hydroxide electrolytes. When the anolyte concentration was 0.01 M, the cation transference number was 0.13 to 0.16. When the anolyte concentration was increased to 0.1 M, the cation transference number increased to 0.20 to 0.23. The higher concentration of alkali ion in the anolyte increased the alkali cation concentration in the AEM leading to a higher cation transference number because the ratio of mobile alkali cations to immobilized quaternary ammonium cations tethered to the polymer increased as the anolyte concentration increased. Cs+ shows the highest cation transference number, however, the electrolysis voltage (i.e., cathode overpotential) of the cell with Cs+ was not the lowest. This result shows that water transport is not only related to the cation mobility, but is also affected by the cation hydration number. Cations with a higher hydration number, such as potassium, can deliver more water per ion which improves the cathode performance because water is the reactant at the cathode.
The benefits to the AEMEL device by the addition of pH-neutral anolyte salts, rather than hydroxide containing alkali salts, have been described. It has been discovered that the addition of hydroxide or pH-neutral alkali salt has a dramatic effect on the cathode performance, even though the ion-containing electrolyte is only in contact with the anode. The benefits of using a pH-neutral salt are not limited by the particular examples described here.
Although specific advantages have been enumerated above, various embodiments may include some, none, or all of the enumerated advantages. Other technical advantages may become readily apparent to one of ordinary skill in the art after review of the figures and description. It is understood that, although exemplary embodiments are illustrated in the figures and described herein, the principles of the present disclosure may be implemented using any number of techniques, whether currently known or not. Modifications, additions, or omissions may be made to the systems, apparatuses, and methods described herein without departing from the scope of the invention. The components of the systems and apparatuses may be integrated or separated. The operations of the systems and apparatuses disclosed herein may be performed by more, fewer, or other components and the methods described may include more, fewer, or other steps. Additionally, steps may be performed in any suitable order. As used in this document, “each” refers to each member of a set or each member of a subset of a set. It is intended that the claims and claim elements recited below do not invoke 35 U.S.C. § 112(f) unless the words “means for” or “step for” are explicitly used in the particular claim. The above-described embodiments, while including the preferred embodiment and the best mode of the invention known to the inventor at the time of filing, are given as illustrative examples only. It will be readily appreciated that many deviations may be made from the specific embodiments disclosed in this specification without departing from the spirit and scope of the invention. Accordingly, the scope of the invention is to be determined by the claims below rather than being limited to the specifically described embodiments above.
This application claims the benefit of U.S. Provisional Patent Application Ser. No. 63/514,615, filed Jul. 20, 2023, the entirety of which is hereby incorporated herein by reference.
This invention was made with government support under grant number DE-EE0008833, awarded by the Department of Energy. The government has certain rights in the invention.
| Number | Date | Country | |
|---|---|---|---|
| 63514615 | Jul 2023 | US |
