This disclosure relates generally to hydrogen electrolyzers, and in particular though not exclusively, to aqueous alkaline electrolysis for the production of hydrogen gas.
The world's energy demands are projected to rise for the foreseeable future. Renewable sources of energy, such as solar and wind will contribute an increasing portion of these future energy needs. Renewable energy sources will be used to charge batteries, which will replace fossil fuels as a significant energy source for many transportation needs, such as automobile transportation. However, batteries may not provide sufficient energy/power densities to satisfy the needs of certain energy intensive transportation applications such as large craft commercial air travel and trans-oceanic trips. Hydrogen and hydrogen fuel cell technologies can provide the necessary energy density to power even these highest energy demand applications. Synthetic fuels made using hydrogen as a feedstock can also target many end use energy needs that are historically difficult to decarbonize. Examples include: high-energy-density fuels required for aviation and shipping, green fuel flexibility for gas turbine power generation, and as a feedstock for various industrial production processes. As such, hydrogen-based technologies include the promise to decarbonize what grid based or battery electrification cannot.
Green technologies (e.g., low net carbon or carbon neutral technologies) for commercial production of hydrogen gas currently require immense capital expenditures. These immense capital expenditures are significant barriers to the broad-based adoption of hydrogen fuel cell technologies and hydrogen-based synthetic fuel. Commercial scale hydrogen solutions that are capable of significantly reducing these capital expenditures, thus providing plentiful hydrogen at an economically competitive price, may hasten the deployment and adoption of green hydrogen-based technologies.
Non-limiting and non-exhaustive embodiments of the invention are described with reference to the following figures, wherein like reference numerals refer to like parts throughout the various views unless otherwise specified. Not all instances of an element are necessarily labeled so as not to clutter the drawings where appropriate. The drawings are not necessarily to scale, emphasis instead being placed upon illustrating the principles being described.
Embodiments of a system, apparatus, and method of operation for a hydrogen electrolyzer cell and cell stack-up are described herein. In the following description numerous specific details are set forth to provide a thorough understanding of the embodiments. One skilled in the relevant art will recognize, however, that the techniques described herein can be practiced without one or more of the specific details, or with other methods, components, materials, etc. In other instances, well-known structures, materials, or operations are not shown or described in detail to avoid obscuring certain aspects.
Reference throughout this specification to “one embodiment” or “an embodiment” means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the present invention. Thus, the appearances of the phrases “in one embodiment” or “in an embodiment” in various places throughout this specification are not necessarily all referring to the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
Embodiments of a hydrogen electrolyzer cell and hydrogen electrolyzer stack described herein provide a low-cost option for generation of hydrogen while only modestly trading off efficiency for substantial capital expenditure (CAPEX) savings. The CAPEX savings are derived, in significant part, from integrating a number of expensive, conventionally distinct components into an extensible structure that may be fabricated of low-cost materials, such as injection molded thermoplastic (e.g., polypropylene). CAPEX savings are also derived from the elimination of components such as gaskets, tie rods, and compression plates that are typically used in alkaline electrolyzers. For example, it is believed that a loss of approximately 10% efficiency may be traded for roughly a 10× reduction in CAPEX when compared against conventional alkaline hydrogen electrolyzers. For commercial scale megawatt electrolyzers, this CAPEX savings may mean the difference between economically viable hydrogen production options and uneconomical options that will not be deployed. The high CAPEX of conventional hydrogen electrolyzers often requires that they operate 24/7 with little down time to achieve economic viability. In these scenarios, the use of intermittent green power generation (e.g., solar or wind power) may be precluded and thus the low or zero carbon benefit of hydrogen fuel cells and hydrogen-based synthetic fuels compared to traditional fossil fuels may be reduced or even entirely lost. In contrast, the low cost, scalable nature of the embodiments described herein is expected to be more viable for use with these intermittent green power sources.
In one embodiment, the bulk of housing 170 is fabricated of an inexpensive, monolithic material. For example, housing 170 may be an injection molded thermoplastic (e.g., polypropylene). Of course other materials, compounds, or a combination of materials may be used depending upon a particular application. For example, housing 170 may be fabricated using a multilayer laminate construction combining multiple different materials having various desirable properties for heat resistance, mechanical strength, corrosion resistance, and/or thermal conductivity. Furthermore, housing 170 may be modular, meaning that it is assembled from multiple pieces, and extensible, meaning that it is formed from a repeating structure that facilities stacking multiple instances of the single cell 100 to increase hydrogen production. In one embodiment, the sidewalls and dividing wall 120 are approximately 1 mm thick polypropylene. Of course, other thickness may be used. Not only is monolithic construction from thermoplastic inexpensive, but the metal electrodes and plastic housing bodies may be reconditioned or recycled to further reduce the lifetime cost. Reconditioning may be achieved via in-situ pressurized flushing of the stack with other chemicals.
When deployed, shared reservoir 105, anode chamber 110, and cathode chamber 115 are filled with an electrolytic solution to a fill level 175 that entirely bathes (i.e., submerges) anode electrode 140 and cathode electrode 155 within the electrolytic solution. The electrolytic solution is a stagnant or static bath and need not be pumped, or actively circulated or recycled through the cell or cell stack during electrolysis, though passive convection currents may arise as a side effect of internal heat dissipation or frothing during degassing. In one embodiment, the electrolytic solution is an alkaline solution (base), such as aqueous potassium hydroxide (KOH) having 25% KOH and 75% water. Other electrolytes and/or electrolytic concentrations may be used. The electrolytic solution may include other additives such as antifouling agents or surfactants. The antifouling agents may be used to reduce biofouling, reduce chemical buildup, suppress undesirable side reactions, improve performance, or otherwise. The surfactants may be used to affect the diameter of the hydrogen/oxygen bubbles rising within cathode chamber 115 or anode chamber 110, or otherwise. As the water in the electrolytic solution is consumed during electrolysis, it may be replenished by direction injection of deionized water via DI water injection port 135.
Divider wall 120 extends up from shared reservoir 105 and separates anode chamber 110 from cathode chamber 115. In one embodiment, dividing wall 120 extends equal to or below the bottom of the electrodes 140 and 155 exposed to the electrolytic solution. Dividing wall 120 terminates at the top of shared reservoir 105 to permit transport of charged ions within the electrolytic solution under dividing wall 120 through shared reservoir 105 along conduction path 180 between anode electrode 140 and cathode electrode 155. In one embodiment, the height of shared reservoir 105 below dividing wall 120 is approximately equal to the width of each of anode chamber 110 and cathode chamber 115. Of course, other dimensions may be implemented. Dividing wall 120 is a solid non-permeable wall that blocks transport of charged ions forcing the conduction path 180 down around its distal/bottom end. Similarly, dividing wall 120 blocks mixing of the hydrogen and oxygen gases released during electrolysis. During operation, the oxygen and hydrogen gases bubble up in their respective chambers forming froths 185A and 185B (collectively referred to as froth 185) in oxygen degassing region 145 and hydrogen degassing region 160, respectively. The vertical orientation of anode chamber 110 and cathode chamber 115 facilitates this passive, buoyancy-driven separation of the oxygen and hydrogen gases during electrolysis. The integrated degassing regions significantly reduces the need for expensive external phase separators/demisters that are corrosion resistant. The height of degassing regions may be selected to ensure froth 185 does not spill over into exhaust manifolds 150 and 165 for a desired operational drive current. If froth 185 does spill over into either exhaust manifold 150 or 165, a shunting current path may be established degrading performance and may contaminate the exhaust manifolds and connecting plumbing with the caustic electrolytic solution.
Embodiments of hydrogen electrolyzer cell 100 operate without need of expensive catalysts or membranes disposed between the electrodes as used in conventional electrolyzers. In the illustrated embodiment, anode electrode 140 and cathode electrode 155 are both fabricated from metal, such as nickel. In one embodiment, anode electrode 140 and cathode electrode 155 are fabricated from a metal mesh, such as a nickel metal mesh. A woven metal mesh, an expanded metal mesh, an expanded metal foam, a metal foil, a perforated metal, an expanded metal foil, nanostructured metal features on a foil, or otherwise may also be used. Anode electrode 140 and cathode electrode 155 may assume a variety of different sizes and shapes, such as metallic foams or other 3-dimensional structures. For example, the surfaces of the electrodes may be roughened to increase overall surface area in contact with the electrolytic solution. In one embodiment, anode electrode 140 and cathode electrode 155 may each be 2 cm long, though the electrodes need not be symmetrical. In yet other embodiments, the distal tips of electrodes may be folded over to keep more surface area of the electrodes closer to the bottom tip of dividing wall 120, thereby reducing the resistance of conduction path 180. Additionally, one or both of electrodes 140 and 155 may include integrated or coated catalysts, such as palladium, iridium, etc.
As discussed in more detail below in connection with
As previously mentioned, oxygen exhaust manifold 150 is integrated into anode chamber 110 to export oxygen from cell 100, while hydrogen exhaust manifold 165 is integrated into cathode chamber 115 to export hydrogen gas from cell 100. Both oxygen exhaust manifold 150 and hydrogen exhaust manifold 165 are extensible for coupling to adjacent hydrogen electrolyzer cells in a stack. Again, by integrating the exhaust manifolds into the extensible/modular structure of housing 170 itself, costs associated with stacking large numbers of hydrogen electrolyzer cell 100 are reduced.
Similar to the other extensible components, heat exchange path 125 is also integrated into housing 170 and designed to connect with heat exchange paths 125 of adjacent cells stacked in series. In the illustrated embodiment, heat exchange path 125 is disposed adjacent to (e.g., under) shared reservoir 105 to exchange heat with the electrolytic solution. During regular operation, heat may be carried away from the electrolytic solution via circulating a heat exchange fluid (e.g., a water glycol coolant mixture, other liquid coolants, gaseous coolants, etc.) through heat exchange path 125. During a startup process, the heat exchange fluid may be preheated to a desired startup temperature to aid with startup of the electrolysis. This may be done by a heater within the coolant loop, or alternatively by running the electrolysis process in a deliberately inefficient operating regime, such as by using a higher voltage per cell than normal operation, to generate heat internally for bringing the system up to its optimal operating temperature. In an embodiment wherein housing 170 is fabricated of injection molded thermoplastic, the electrolytic solution may be cooled to maintain an operating temperature of approximately 95 degrees Celsius. This operating temperature is limited by the mechanical properties of the thermoplastic; for example, some thermoplastics that are more expensive than polypropylene can handle higher temperatures before deformation, such as polysulfone. The exhaust manifolds may be operated at atmospheric pressure, or a backpressure applied to elevate the boiling point of the electrolytic solution and operate at higher temperatures and pressures depending upon the material or materials selected to form housing 170. Operating at higher temperatures and/or pressures may increase operating efficiency though may increase the cost of the material selection for housing 170 to withstand these higher temperatures and/or pressures. Pressure regulators may be coupled to the exhaust manifolds to manage gas flows and balance back pressures between the oxygen and hydrogen exhaust manifolds.
In the illustrated embodiment, anode chamber 110 includes a gas sensor 130A and cathode chamber 115 includes a gas sensor 130B adapted to monitor for cross mixing of hydrogen and oxygen gases resulting in a combustible vapor mixture. In one embodiment, gas sensors 130A and 130B are implemented using catalytic gas detectors such as a catalytic pellistor or otherwise. Gas sensors 130A and 130B may be coupled to a controller (e.g., controller 205) configured to shut down and/or automatically purge a contaminated exhaust manifold (e.g., purge with an inert gas) in case a combustible mixture of hydrogen and oxygen is detected, due to unintentional crossover of gas bubbles below dividing wall 120. For cost efficiency reasons, these combustible gas sensors may be placed in the exhaust manifolds at the end of a stack, so that they can monitor for potentially combustible mixtures coming from multiple stacks 200 at once. While
As illustrated, cells 201 may be stacked in series to form stack 200. Although
In one embodiment, a power source 207 is a direct current (DC) to DC converter that couples to CT and AT to apply a bias voltage across the series connected cells 201. Power source 207 may further include various intermittent power sources such as solar cells or wind turbines. A controller 205 is coupled to power source 207 and stack 200. Controller 205 may include hardware and/or software logic and a microprocessor to orchestrate operation of power source 207 and stack 200. In the illustrated embodiment, controller 205 monitors various sensor signals S1, S2 . . . SN from stack 200 and uses these feedback sensor signals to control power source 207. The sensor signals may include temperature readings, gas sensor readings, voltage readings, electrolyte level readings, etc. sourced from stack 200. During regular operation, controller 205 applies a forward bias potential across CT and AT. However, in some instances, controller 205 may periodically, or on-demand, short or reverse bias CT and AT to recondition the anode and cathode electrodes. Short circuiting or reverse biasing may be particularly beneficial for anode electrode 140 due to the buildup of surface layer nickel oxides. Reverse biasing may be at a sufficiently low voltage that does not cause electrolysis and gas production, while still reconditioning the electrodes. Alternatively, the exhaust manifolds may be purged with an inert gas before and after reverse biasing if higher reverse bias potentials are desired, to prevent the buildup of potentially flammable mixtures of oxygen and hydrogen internally. In one embodiment, electromechanical (or fluid) taps may be attached to one side of each manifold port 210 and 215 for selectively injecting an inert purging gas (e.g., nitrogen) into the hydrogen and oxygen exhaust manifolds. Flow through the taps may be electronically controlled under the influence of controller 205. A periodic reconditioning schedule may leverage the diurnal rhythms of intermittent green energy. Of course, commercial scale operations having large banks of stacked cells 201 may implement a staggered reconditioning schedule that takes one or more stacks 200 offline at a time while maintaining operation of the remaining stacks 200. An effective reconditioning schedule will reverse electrode degradation while recovering and/or maintain operating efficiencies over longer durations. The above identified control strategies serve to potentially increase electrode and stack life well beyond conventional electrolyzer lifespans of approximately 7 years. For example, useful lifespans exceeding 20 years may be possible using these control strategies.
Correlating
Returning to
Electrode panels 305, 310 and divider panel 315 may be fabricated from a variety of materials; however, in one embodiment, they are fabricated from a common material, such as injection molded thermoplastic. The panels may be sealed together to form the housing structure of each cell using gaskets, hot-plate welding, adhesives, or otherwise. The extensibility comes from stacking multiple sets of panels together. In other embodiments, large stacks of cells may be fabricated using a one-step manufacturing process (rather than assembled from a set of pieces). For example, a stack of cells may be cast as a single part, 3D printed, etc.
Electrode panels 305, 310 and divider panel 315 all include oxygen exhaust manifold 340 disposed laterally (along axis 360) to hydrogen exhaust manifold 345. When the panels are sealed together into stack 200, oxygen exhaust manifold 340 and hydrogen exhaust manifold 345 both extend through the entire stack 200. Ridges 345 press against dividing panel 315 sealing oxygen exhaust manifold 340 off from cathode chambers 330 while ridges 350 press against electrode panel 305 sealing hydrogen exhaust manifold 345 off from anode chambers 325. Ridges 345 and 350 alternate from one panel to the next in the stack up to ensure oxygen and hydrogen exhaust gases do not mix between their respective exhaust manifolds.
The above description of illustrated embodiments of the invention, including what is described in the Abstract, is not intended to be exhaustive or to limit the invention to the precise forms disclosed. While specific embodiments of, and examples for, the invention are described herein for illustrative purposes, various modifications are possible within the scope of the invention, as those skilled in the relevant art will recognize.
These modifications can be made to the invention in light of the above detailed description. The terms used in the following claims should not be construed to limit the invention to the specific embodiments disclosed in the specification. Rather, the scope of the invention is to be determined entirely by the following claims, which are to be construed in accordance with established doctrines of claim interpretation.
This application claims the benefit of Provisional Application No. 63/234,519, filed Aug. 18, 2021, the contents of which are hereby incorporated by reference.
Number | Date | Country | |
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63234519 | Aug 2021 | US |