Systems and methods of decoupled hydrogen generation using energy-bearing redox pairs

Abstract

Described herein are systems and methods of hydrogen generation and electrolyte regeneration as independent operations in separate redox flow cells. The operations can be decoupled by using an energy-bearing redox pair that electrochemically bears energy facilitating flexible, efficient hydrogen generation. In one example, the hydrogen generation redox flow cell can include a liquid, energy-bearing electrolyte solution in which at least one species of an energy-bearing redox pair is dissolved, to decouple the hydrogen evolution reaction from the reaction at the opposite electrode (e.g., the oxygen evolution reaction of conventional direct water electrolysis). Each species of the energy-bearing redox pair is associated with a standard electrode potential within the water electrolysis window.

Claims

1. A system of hydrogen generation comprising: A first redox flow cell generating hydrogen and having: A positive electrode side oxidizing an energy-bearing redox species dissolved in a liquid, energy-bearing, electrolyte solution to an oxidized state, wherein the liquid, energy-bearing electrolyte solution comprises an aqueous acid solution; A negative electrode side comprising a H.sup.+/H.sub.2 half-cell; and A proton permeable membrane separating the positive electrode and negative electrode sides; and A second redox flow cell regenerating the liquid, energy-bearing electrolyte solution and having: A negative electrode side reducing the energy-bearing redox species to a reduced state; A positive electrode side comprising an oxygen evolution reaction (OER) half-cell; A proton permeable membrane separating the positive electrode and negative electrode sides; A controller operably connected to the first and second redox flow cells and configured to select for operation of the first redox flow cell alone, the second redox flow cell alone, or concurrently both based on an energy-market condition; wherein the energy-bearing redox species is associated with a reversible redox reaction having a standard electrode potential within a water electrolysis voltage window for the electrolyte solution, and wherein the first and second redox flow cells are decoupled for independent operation one from another; and a circulation sub-system configured to transfer a first, liquid, energy-bearing, electrolyte solution comprising the energy-bearing redox species from the first redox flow cell to the second, and configured to transfer a second, liquid, energy-bearing, electrolyte solution comprising the energy-bearing redox species from the second redox flow cell to the first.

2. The system of claim 1, wherein the circulation sub-system further comprises a first storage container configured to store a portion of the first liquid, energy-bearing, electrolyte solution and a second storage container configured to store a portion of the second liquid, energy-bearing, electrolyte solution.

3. The system of claim 1, wherein energy-market condition comprises price of energy supply, energy demand, power grid health, H.sub.2 price, H.sub.2 demand, time of day, weather conditions, or a combination thereof.

4. The system of claim 1, wherein the energy-bearing redox species in the reduced and oxidized states comprise Fe.sup.2+ and Fe.sup.3+, respectively.

5. The system of claim 1, wherein the energy-bearing redox species comprises iodine, vanadium, bromine, chlorine, TEMPO, respectively.

6. The system of claim 1, wherein the aqueous acid solution comprises a dissolved acid having a concentration greater than or equal to 2 M, 4 M, 6 M, 8 M, or 10 M.

7. The system of claim 1, wherein the liquid, energy-bearing electrolyte solution comprises the energy-bearing redox species in an amount greater than or equal to 0.5 M, 1 M, 1.5 M, 2 M, 3M, 4 M, 5 M, or 8 M.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is an illustration of a hydrogen generation system according to embodiments described herein.

(2) FIGS. 2A and 2B include potential versus capacity graphs of a hydrogen generation redox flow cell being charged under two different conditions (100 and 300 mA/cm.sup.2, respectively).

(3) FIGS. 3A and 3B are graphs of voltage as a function of time for a hydrogen generation redox flow cell and an electrolyte regeneration redox flow cell, respectively. The total current and electrolyte flow rate of both cells are set to 0.5 A and 20 mL/min, respectively.

(4) FIGS. 4A and 4B are charts comparing levelized cost and hydrogen production cost between embodiments described herein and traditional PEM electrolysis systems.

(5) FIGS. 5A-5F are graphs of estimated levelized cost versus current density for hydrogen production in various state markets. Estimated results for the hydrogen generation redox flow cell are shown by the black horizontal line

(6) FIG. 6 is a graph comparing levelized cost versus ratios of offpeak to peak costs between embodiments described herein and traditional PEM electrolysis.

(7) FIG. 7 is a graph of percentile versus ratios of offpeak to peak costs for embodiments described herein being operated in various state energy markets

DETAILED DESCRIPTION

(8) Embodiments described herein can perform hydrogen generation and electrolyte regeneration as independent operations in separate redox flow cells. The operations can be decoupled by using an energy-bearing redox pair that electrochemically bears energy facilitating flexible, efficient hydrogen generation. The inventors have determined by Hydrogen Analysis (H2A) that in spite of the progress in recent years to reduce costs, hydrogen production via water electrolysis still faces significant challenges in meeting future production and delivery goals with regard to cost per gasoline gallon equivalent (gge). The model shows that the cost of hydrogen for both forecourt and central production will exceed four dollars per gasoline gallon equivalent even in 2025 assuming current technology development trends. The challenge is not only capital cost but also operating feedstock costs, which can limit energy storage and delivery capacity of systems based on hydrogen (i.e., systems underprovide energy relative to expectations).

(9) The problem of high-cost and delivery can be addressed by using a redox flow cell comprising a liquid, energy-bearing electrolyte solution in which at least one species of an energy-bearing redox pair is dissolved, to decouple the hydrogen evolution reaction from the reaction at the opposite electrode (e.g., the oxygen evolution reaction of conventional direct water electrolysis). Hydrogen generation, electrolyte regeneration, or both can be performed in a continuous manner, batch manner, or semi-batch manner. Each species of the energy-bearing redox pair is associated with a standard electrode potential between 0 and 1.23 V. Embodiments described herein can produce H.sub.2 at a much lower voltage and with improved efficiency than that of typical water electrolysis systems, resulting in a lower operating cost. Furthermore, since it operates under low cell voltages, it provides flexibility in using low cost materials.

(10) The redox reactions between the hydrogen generating side and the energy-bearing redox pair side of the redox flow cell allow for hydrogen production at much lower voltages and with improved efficiency compared to traditional water electrolysis systems, which often operate at 1.8 volts or higher (including an overpotential). In one example, the energy-bearing redox pair comprises Fe.sup.2+ and Fe.sup.3+. The primary cost drivers for H.sub.2 production is the feedstock fuel (65%-80%), which is mainly the electricity. The theoretical equilibrium voltage of a H.sub.2/Fe flow cell is 0.77 V, which is a 37% reduction from that of current water electrolysis (i.e., 1.23 V).

(11) During hydrogen production, the energy-bearing redox species is reduced and the spent energy-bearing electrolyte solution in which the reduced species is dissolved needs to be replaced or regenerated. Regeneration of the energy-bearing electrolyte solution can be accomplished according to several embodiments described elsewhere herein.

(12) Referring to FIG. 1, a schematic diagram illustrates one embodiment in which two independent redox flow cells utilize an energy-bearing redox species. The energy-bearing redox species bears energy for a duration in order to facilitate a decoupling of the hydrogen and oxygen evolving aspects of a conventional electrolysis system into the two independent redox flow cells. Hydrogen generation occurs in a first redox flow cell 100 having a negative electrode side 101 comprising a H.sup.+/H.sub.2 half-cell in which protons are reduced to yield hydrogen. The positive electrode side 102 comprises a liquid energy-bearing electrolyte solution comprising the energy-bearing redox species dissolved therein. The liquid electrolyte solution can comprise a solvent including, but not limited to, water, etc. The liquid electrolyte can be in acidic, neutral, or alkaline. Examples of acids, neutrals, and bases dissolved in the solution can include, but are not limited to, HCl, H.sub.2SO.sub.4, NaCl, KCl, NaOH, and KOH etc.

(13) The electrode can comprise carbonaceous materials, including but not limited to, carbon, carbon fiber, carbon felt, carbon nanotubes, and graphene materials, especially when acidic liquid electrolytes are used. When a neutral or alkaline liquid electrolyte is used, metals, including, but not limited to porous metals, metal fibers, and metal fiber felts, can also be used.

(14) A proton-permeable membrane separates the positive and negative electrode sides. Examples of membranes can include, but are not limited to, perfluorosulfonic acid membranes and other fluorinated or non-fluorinated hydrocarbon membranes. Anion exchange membranes can be used in the system, especially when an alkaline electrolyte is used. These also include fluorinated or non-fluorinated hydrocarbon membranes. A separator can also be used, such as PTFE/SiO2, PVDF/SiO2, PVC and PE/SiO2 separators.

(15) As illustrated, the redox species in the reduced and oxidized states comprise Fe.sup.2+ and Fe.sup.3+, respectively. Although the Fe.sup.2+/Fe.sup.3+ redox pair has the benefit of low-cost and fast kinetics, it is chosen as an example. Other redox species having standard electrode potentials between 0 V and 1.299 V are suitable including metal or non-metal, inorganic and organic. Examples can include, but are not limited to iodine, vanadium, Br.sub.2, Cl.sub.2, and (CH.sub.2).sub.3(CMe.sub.2).sub.2NO (i.e., TEMPO). For instance, redox pairs (i.e., redox species in reduced and oxidized states) can include, but are not limited to, Br.sub.2/Br.sup.−, I.sub.3.sup.−/I.sup.−, and V.sup.3/VO.sup.2+.

(16) During hydrogen generation, a potential is applied 104 across the two electrodes. On the positive electrode side, Fe.sup.2+ is oxidized to Fe.sup.3+. The spent liquid, energy-bearing electrolyte solution comprising energy-bearing redox species in the oxidized state is transferred from the first redox flow cell 100 to the second redox flow cell 150 for electrolyte regeneration via circulation sub-system 120. The potential applied for hydrogen generation is much lower than that required for a conventional electrolysis system. The first redox flow cell can be described by the following half reactions.
Negative electrode side: H.sup.++e.sup.−.fwdarw.½H.sub.2(g)E.sup.0=0V
Positive electrode side: Fe.sup.2+−1e.sup.−.fwdarw.Fe.sup.3+E.sup.0=0.77V

(17) The second redox flow cell 150 has a negative electrode side 151 comprising the liquid energy-bearing electrolyte solution comprising the energy-bearing redox species. The positive electrode side 152 comprises an oxygen evolution reaction (OER) half-cell. A proton permeable membrane 153 separates the positive and negative electrode sides. In some embodiments, no precious metal catalysts are utilized for oxygen reaction.

(18) The electrode can comprise carbonaceous materials, including, but are not limited to, carbon, carbon fiber, carbon felt, carbon nanotubes, and graphene materials, especially when acidic liquid electrolytes are used. When a neutral or alkaline liquid electrolyte is used, metals, including, but not limited to porous metals, metal fibers, and metal fiber felts, can also be used. Examples of membranes can include, but are not limited to, perfluorosulfonic acid membranes and other fluorinated or non-fluorinated hydrocarbon membranes. Anion exchange membranes can be used in the system, especially when an alkaline electrolyte is used. These also include fluorinated or non-fluorinated hydrocarbon membranes. A separator can also be used, such as PTFE/SiO2, PVDF/SiO2, PVC and PE/SiO2 separators.

(19) During electrolyte regeneration, potential is applied across the two electrodes. The positive electrode side 152 yields oxygen. On the negative electrode side 151 the energy-bearing redox species is reduced from the oxidized state to the reduced state. According to the illustrated embodiment, from Fe.sup.3+ to Fe.sup.2+. The regenerated liquid, energy-bearing electrolyte solution comprising energy-bearing redox species in the reduced state is transferred from the second redox flow cell 150 to the first redox flow cell 100 via circulation sub-system 121. The second redox flow cell can be described by the following half reactions:

(20) $\mathrm{Negative}\mathrm{electrode}\mathrm{side}\text{:}{\mathrm{Fe}}^{3+}+1e^{-1}.fwdarw.{\mathrm{Fe}}^{2+}{E}^0=0.77V$$\mathrm{Positive}\mathrm{electrode}\mathrm{side}\text{:}\frac{1}{2}{H}_{2}O.fwdarw.\frac{1}{4}{O}_2+H^{+}+1e^{-1}{E}^0=1.23V$

(21) Decoupling can be further facilitated by electrolyte storage tanks. A first storage tank 122 can contain a first liquid, energy-bearing electrolyte solution comprising energy-bearing redox species in the oxidized state. A second storage tank 123 can contain liquid, energy-bearing electrolyte solution comprising energy-bearing redox species in the reduced state. The volumes of the storage tanks can be scaled to meet hydrogen generation and storage needs to maximize the cost benefit.

(22) The inventors determined that decoupling the hydrogen and oxygen redox reactions from being in the same reaction cell, gives the system flexibility to overcome the sluggish high overpotential oxygen reaction and to decrease energy consumption by lowering the reaction voltage. Accordingly, while the total potential applied for hydrogen generation and electrolyte regeneration can be similar to that required for traditional electrolysis, embodiments described herein are enabled to perform the hydrogen generation during first energy-market conditions. Electrolyte regeneration can be performed at a different time when the energy-market conditions are advantageous for regeneration. For example, the electrolyte can be regenerated while hydrogen demand is low, electrical energy prices are relatively lower, and/or grid health can be improved by utilizing excess energy (for example, during wind or solar curtailment). Similarly, hydrogen generation can occur while hydrogen demand is high, electrical energy prices are low, and/or grid health can be improved by utilizing excess energy.

(23) The 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.

(24) 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.

(25) 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 approximations unless the word “about” is recited.

EXAMPLES AND COMPARISONS

(26) To further illustrate certain embodiments of the disclosed hydrogen fuel generation systems and methods, and to provide various comparative analyses and data, below are some examples with comparison test data.

(27) Traditional hydrogen generation techniques use a water electrolyzer to produce hydrogen and oxygen from water. The technique is typically slow and operates at approximately 1.8-2 A and around 2 V. The cost to operate can be a limitation and is currently approximately ˜5 USD/kg. A significant portion of the cost is electricity (i.e., feedstock) because of the high current and voltage supply requirements. Based on the highly reversible Fe.sup.3+/Fe.sup.2+ redox couple as an energy-bearing redox species, the operating voltage of a first redox flow cell generating hydrogen can be less than or equal to 1 V, which includes an overpotential allowance. In certain embodiments, a minimal operating voltage can between approximately 0.8 V and 0.9 V. Due to the direct voltage reduction, the electricity expenditure can be reduced nearly 52%. The operating voltage of a second redox flow cell regenerating the spent electrolyte solution from the first redox flow cell can be between 0.5 V and 1 V, making the total energy expenditure for both redox flow cells similar. However, the energy-bearing redox species allows for decoupling of the hydrogen generation and electrolyte regeneration so that each can be performed independently when energy-market conditions are advantageous and optimized for both. For example, hydrogen generation can be performed during the day to meet demand. The spent electrolyte solution can be stored in a container. Regeneration of the electrolyte can occur at night time, when electricity is often cheaper. In one example, windmill power is commonly more abundant at night when supply exceeds demand.

(28) Experimental data shown in FIG. 2 demonstrates hydrogen generation using a system similar to that shown in FIG. 1. The first (i.e., hydrogen-generating) redox flow cell comprised a flow cell with H.sub.2/H.sup.+ and Fe.sup.3+/Fe.sup.2+ redox pairs at the negative and positive half-cells, respectively. An interdigitated flow field was used with carbon-based CPESA electrode and Nafion 212 membranes. Specifically, the gas diffusion electrode had a 0.2 mg Pt/cm.sup.2 loading at the hydrogen electrode while pristine. The CP-ESA carbon electrode was modified with a catalyst (20 wt % of Pt/C catalyst was drop-coated onto the CP-ESA electrode (0.01 mg Pt/cm.sup.2 loading) at the iron electrode. The energy-bearing electrolyte solution comprising the Fe-based redox species had a flow rate of approximately 60 mL/min through the positive half-cell. The solution further comprised FeSO.sub.4 or FeCl.sub.2 dissolved in 2 M HCl charged at 100 (FIG. 2A) and 300 mA/cm.sup.2 (FIG. 2B), respectively. Hydrogen generation was performed at low voltage (<1.0 V). A carbon-based electrode (e.g., carbon paper—extra surface area [CPESA]) was used in the test flow cell, but other forms of carbon electrodes can be used as alternatives. Examples include, but are not limited to graphite, carbon fiber, carbon nanotube, and graphene-based electrodes. Other forms of electrodes can also be used, including metals and/or other conductive materials. Examples can include, but are not limited to, platinum and other platinum group metals (PGM). Non-PGM catalysts can be used to modify the electrode to improve the system performance. A sulfonated tetrafluoroethylene-based fluoropolymer-copolymer membrane (e.g., Nafion 212) was used in the instant example, but other polymeric, porous, microporous, nonporous, ceramic membranes can be used. The data was collected without electrolyte regeneration, which explains the voltage increase and the performance decline over time because the Fe.sup.2+ was being depleted as the redox reactions proceeded.

(29) Referring to FIG. 3A, an electrolyte-regeneration redox flow cell can be used to regenerate the spent, liquid, energy-bearing electrolyte solution from the hydrogen-production flow cell. The electrolyte-regeneration redox flow cell can be operated independently from the hydrogen generation flow cell. FIG. 3B are graphs showing the total current and electrolyte flow rate of both cells, which were set to 0.5 A and 20 mL/min, respectively.

(30) While embodiments described herein utilize more units than a traditional single unit electrolyzer, hydrogen generation costs can nevertheless be lower based on the increased flexibility allowed by the independent operation of the two flow cells. A cost model was set up using NREL's H2A model to calculate levelized cost using a standard discounted cash flow rate of return methodology. The cost model considers capital cost and feedstock cost. For all calculations we calculated the cost for a plant producing 400 kg H.sub.2/day.

(31) A very simple electrochemical model was used consistent with the system described in the instant example. The analysis compares a model for a PEM electrolyzer operating at 1.8 V (the control). The hydrogen generation redox flow cell operates at 1.0 V, and the electrolyte regeneration redox flow cell operates at 1.0 V. The electrolyzer and hydrogen generation redox flow cell were assumed to operate at 1 A/m.sup.2. The electrolyte regeneration redox flow cell was assumed to operate anywhere from 0.5 to 1 A/m.sup.2.

(32) The capital cost was calculated based on having two stacks for Iron redox, and one stack for the hydrogen PEM electrolyzer. Unit prices were found for carbon felt, the electrodes, the bipolar plates, the PVC frame, the catalyst, and the Nafion membrane. The oxygen electrode required for the electrolyte regeneration redox flow cell is significantly more expensive than the electrode in the hydrogen generation redox flow cell.

(33) Based on the target amount of hydrogen required (1000 kg H.sub.2/day), the total charge per day required is straight forward to calculate:

(34) $Q=F\frac{m_{H_2}}{M_H}$

(35) The stacks were sized by calculating the current needed to produce the desired amount of hydrogen during the peak period of time, and using that along with the maximum possible current density for each stack to obtain an area.

(36) $A_{\mathrm{HyFe}}=\frac{Q}{j_{\mathrm{HyFe}}{t}_{\mathrm{Peak}}}$$A_{\mathrm{regen}}=\frac{Q}{j_{\mathrm{regen}}{t}_{\mathrm{offPeak}}}$
The electrical feedstock required was calculated based on the voltage required for each stack.
E.sub.req=Q(V.sub.Regen+V.sub.HyFe)
After calculating the electrical feedstock required, and the area of the stack, the unit prices for the individual stack components and the electrical price data was used to calculate the capital cost and the feedstock cost.

(37) To validate the approach, the same assumptions for electricity price and capital cost were plugged into the H2A spreadsheet in order to calculate the levelized costs of a hydrogen PEM electrolyzer. The result for H2A was the same levelized cost of 4-5 $/kg (FIGS. 4A and 4B).

(38) The feedstock cost was calculated using electricity price data, which was obtained from 3 regions. Hourly data was obtained for all three regions. Pacific Northwest energy data was obtained for the Mid-Columbia Index from Powerdex, Inc. California energy market data was obtained from CAISO. New York energy market data was obtained from NYISO.

(39) From this hourly data, the peak and off-peak cost is calculated simply by averaging over peak and non-peak periods. For the first analysis, these peak and off-peak time periods were preset. In later optimization work, these were adjusted to minimize levelized cost.

(40) The cost model was run at various current densities for the hydrogen generation redox flow cell, various cost scenarios, and various electricity market regions. The corresponding model results for the hydrogen generation redox flow cell are shown by the black horizontal line in FIGS. 5A-5F.

(41) Hydrogen redox flow cell appears advantageous in cases where electricity is very expensive (e.g., in the New York and California regions). The hydrogen redox flow cell can be adapted for additional advantages in the markets in which it is operated. For example, there can be a very high variance in electricity price. If there is a large difference in price between peak and off peak, then embodiments described herein can provide significant cost advantage. The following equation is but one example of a criteria for determining cost conditions favoring embodiments described herein.

(42) ${\mathrm{Cost}}_{\mathrm{Peak}}{E}_{\mathrm{HyFe}}+{\mathrm{Cost}}_{\mathrm{OffPeak}}{E}_{\mathrm{Regen}}<{\mathrm{Cost}}_{\mathrm{Peak}}{E}_{\mathrm{PEM}}$$\frac{{\mathrm{Cost}}_{\mathrm{Offpeak}}}{{\mathrm{Cost}}_{\mathrm{Peak}}}<\frac{E_{\mathrm{PEM}}-E_{\mathrm{HyFe}}}{E_{\mathrm{Regen}}}$$\frac{{\mathrm{Cost}}_{\mathrm{Offpeak}}}{{\mathrm{Cost}}_{\mathrm{Peak}}}<0.8$
This shows that the ratio of the offpeak cost to the peak cost is a useful parameter for understanding where Fe regen cell has the advantage. If under certain operation conditions, the ratio of offpeak cost to the peak cost is lower than 0.8, it means the new system will have lower cost than the traditional PEM electrolyzer. The model was run using electricity data from various days, and the results plotted vs the offpeak to peak ratio in FIG. 6. In order to understand the distribution of the offpeak to peak ratio, it was calculated for each day, and the cumulative distribution was plotted as shown in FIG. 7.

(43) 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.