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The Impact of Ink and Spray Variables on Catalyst Layer Properties, Electrolyzer Performance, and Electrolyzer Durability
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Operating Strategies for Dispatchable PEM Electrolyzers that Enable Low-Cost Hydrogen Production
Hydrogen is a pathway to enabling decarbonization across multiple economic sectors that cannot be directly decarbonized with electricity including heat for industrial operations, medium- and heavy-duty transportation applications, long-duration energy storage, and as a feedstock for chemical synthesis. Producing hydrogen at low costs and carbon footprint is likely essential to economically decarbonize these otherwise "hard to decarbonize" sectors. Low-temperature polymer electrolyte membrane (PEM) electrolysis produces hydrogen from water and electricity and is a rapidly developing pathway towards making hydrogen at the scales required for decarbonization applications. The levelized cost of electrolytic hydrogen is dependent on the capital cost, efficiency, and durability of the electrolyzer system as well as the price of electricity supplied to the electrolyzer and the annual utilization of the electrolyzer (capacity factor). Electricity price and capacity factor depend on the source of energy that the system uses and impact other economic factors. Electricity price and capacity factor and the connections between other aspects of hydrogen production via PEM electrolyzers are the focus of this work. PEM electrolyzers have conventionally been operated at high capacity factors using electricity purchased from utilities with a constant price throughout the year. To achieve lower effective electricity prices, recent work has investigated opportunities for electrolyzers to purchase electricity in wholesale markets, where the cost of electricity varies hourly. This option can lead to lower electricity costs when the electrolyzer is a controllable load that ramps up and down rapidly and turns on and off frequently. This configuration and operating strategy capitalizes on times of low wholesale electricity prices and results in lower hydrogen levelized costs than constant operation due to reduced electricity costs even though the reduced capacity factor increases the cost of recovering the capital investment. Cycling on and off frequently also has implications for electrolyzer durability. An electrolyzer configuration where it is directly connected to renewable generation such as wind or solar, only running when the generator is producing energy, has similar implications on operating strategy, hydrogen levelized cost, capacity factor, and durability. This work provides insight into the relationships between dispatchable electrolyzer operating strategies and the cost of producing hydrogen from these systems, outlining strategies and opportunities to minimize production costs while minimizing operations that are likely to negatively impact system durability and efficiency. We find strategies that minimize electrolyzer cycling and the resulting durability impacts while increasing the hydrogen levelized cost only slightly above the minimum. We also find opportunities for batteries to minimize the number of cycles in systems directly connected to renewable generation. These findings outline key opportunities for future electrolyzer deployments and the synergistic benefits between electrolyzers and increased deployment of renewable energy generation like wind and solar. They also inform research and development that is reducing electrolyzer capital cost while managing durability impacts.
SPE (tm) water electrolyzers in support of mission from planet Earth
During the 1970's, the Solid Polymer Electrolyte (SPE) water electrolyzer, which uses ion exchange membranes as its sole electrolyte, was developed for nuclear submarine metabolic oxygen production. SPE water electrolyzer developments included operation at up to 3,000 psia and at current densities in excess of 1,000 amps per square foot. The SPE water electrolyzer system has accumulated tens of thousands of system hours with the Navies of both the United States and the United Kingdom. During the 1980's, the basic SPE water electrolyzer cell structure developed for the Navies was incorporated into several demonstrators for NASA's Space Station Program. Among these were: (1) the SPE regenerative fuel cell for electrical energy storage; (2) the SPE water electrolyzer for metabolic oxygen production; and (3) the high pressure SPE water electrolyzer for reboost propellant production. In the 1990's, emphasis will be the development of SPE water electrolyzers for Mission from Planet Earth. Currently defined potential applications for the SPE water electrolyzer include: (1) SPE water electrolyzers operating at high pressure as part of a regenerative fuel cell extraterrestrial surface energy storage system; (2) SPE water electrolyzers for propellant production from extraterrestrial indigenous materials; and (3) SPE water electrolyzers for metabolic oxygen and potable water production from reclaimed water.
SPE water electrolyzers in support of the lunar outpost
During the 1970s, the SPE water electrolyzer, which uses ion exchange membranes as its sole electrolyte, was developed for nuclear submarine metabolic oxygen production. These developments included SPE water electrolyzer operation at up to 3,000 psia and at current densities in excess of 1,000 amps per square foot. The SPE water electrolyzer system is now fully qualified for both the U.S. and U.K. Navies with tens of thousands of system hours accumulated at sea. During the 1980s, the basic SPE water electrolyzer cell structure developed for the Navies was incorporated into several demonstrations for NASA's Space Station Program. Among these were: the SPE regenerative fuel cell for electrical energy storage; the SPE water electrolyzer for metabolic oxygen production; and the high pressure SPE water electrolyzer for reboost propulsion reactant production. In the 1990s, one emphasis will be the development of SPE water electrolyzers for the Lunar Outposts Currently defined potential Lunar Outpost applications for the SPE water electrolyzer include: SPE water electrolyzers for metabolic oxygen and potable water production from reclaimed water; and SPE water electrolyzers operating at high pressure as part of stationary and mobile surface energy storage systems.
Pressure Dome for High-Pressure Electrolyzer
A high-strength, low-weight pressure vessel dome was designed specifically to house a high-pressure [2,000 psi (approx. = 13.8 MPa)] electrolyzer. In operation, the dome is filled with an inert gas pressurized to roughly 100 psi (approx. = 690 kPa) above the high, balanced pressure product oxygen and hydrogen gas streams. The inert gas acts to reduce the clamping load on electrolyzer stack tie bolts since the dome pressure acting axially inward helps offset the outward axial forces from the stack gas pressure. Likewise, radial and circumferential stresses on electrolyzer frames are minimized. Because the dome is operated at a higher pressure than the electrolyzer product gas, any external electrolyzer leak prevents oxygen or hydrogen from leaking into the dome. Instead the affected stack gas stream pressure rises detectably, thereby enabling a system shutdown. All electrical and fluid connections to the stack are made inside the pressure dome and require special plumbing and electrical dome interfaces for this to be accomplished. Further benefits of the dome are that it can act as a containment shield in the unlikely event of a catastrophic failure. Studies indicate that, for a given active area (and hence, cell ID), frame outside diameter must become ever larger to support stresses at higher operating pressures. This can lead to a large footprint and increased costs associated with thicker and/or larger diameter end-plates, tie-rods, and the frames themselves. One solution is to employ rings that fit snugly around the frame. This complicates stack assembly and is sometimes difficult to achieve in practice, as its success is strongly dependent on frame and ring tolerances, gas pressure, and operating temperature. A pressure dome permits an otherwise low-pressure stack to operate at higher pressures without growing the electrolyzer hardware. The pressure dome consists of two machined segments. An O-ring is placed in an O-ring groove in the flange of the bottom segment and is trapped by the flange on the top dome segment when these components are bolted together with high-strength bolts. The pressure dome has several unique features. It is made (to ASME Pressure Vessel guidelines) in a high-strength aluminum alloy with the strength of stainless steel and the weight benefits of aluminum. The flange of the upper dome portion contains specially machined flats for mounting the dome, and other flats dedicated to the special feedthroughs for electrical connections. A pressure dome can be increased in length to house larger stacks (more cells) of the same diameter with the simple addition of a cylindrical segment. To aid in dome assembly, two stainless steel rings are employed. One is used beneath the heads of the high-strength bolts in lieu of individual hardened washers, and another is used instead of individual nuts. Like electrolyzers could be operated at low or high pressures simply by operating the electrolyzer outside or inside a pressurized dome.
Manufacturing Cost Analysis for PEM Electrolyzers and Perspectives for Future Cost Reduction
Electrolyzer capital costs strongly influence the total levelized cost of hydrogen production and have implications for hydrogen deployment. Current electrolyzer costs are high, and large cost reductions may be needed to achieve competitive hydrogen costs and targets. Understanding pathways for cost reduction via R&D and deployment is a critical research area for informed energy planning and enabling hydrogen use. This work presents bottom-up cost estimates of polymer electrolyte membrane (PEM) electrolyzer systems tied to design specifications and discusses perspectives for cost reduction opportunities based on ongoing research. We use a detailed manufacturing and process model for a 1 MW PEM electrolyzer stack and balance of plant (BOP) for rigorous cost estimation. This allows for robust estimates of component and manufacturing costs and examination of key cost contributors. Stack costs are dominated by material costs such as iridium and platinum catalysts, especially at high manufacturing rates; power electronics and hydrogen purification equipment are the largest contributors to BOP cost. At higher manufacturing rates, better equipment utilization could reduce stack costs significantly, and we estimate that experience and bulk purchasing will allow for cost reductions to some BOP components. Still, many well-established BOP technologies and stack material costs are less likely to see significant cost reductions at high manufacturing rates. As such, manufacturing scale is limited in how much it can reduce electrolyzer costs, and additional advances for cost reduction may be needed to achieve cost targets. It will likely take many combined strategies to achieve significant cost reductions for electrolyzers and enable low-cost hydrogen production. We can use our manufacturing cost model to quantify potential cost reductions from the considerations described above and demonstrate pathways to lower cost electrolyzers. This allows for better understanding of cost reduction strategies and enables more informed research, development, and deployment for electrolyzers.
Performance and long-term stability of CO 2 conversion to formic acid using a three-compartment electrolyzer design
The electrochemical reduction of CO 2 to formate and formic acid has attracted a great amount of academic and commercial interest over the past five years. A number of experimental studies have generated data on the Faradaic performance and stability of various candidate catalyst materials in producing formate or formic acid. However, most of the data has been conducted at low current densities and over short time periods, typically hours to days. There is a critical need in providing long-term catalyst stability as well as electrolyzer-based operating data, which are needed for the commercial scale-up and operation of this technology, especially at high current densities. In this paper, the electrochemical CO 2 conversion to pure formic acid was conducted using a three-compartment design electrolyzer, demonstrating electrolyzer catalyst and performance stability for over 1000 h at current densities up to 200 mA cm -2 . Depending on the operation conditions, the electrolyzer directly produced a 6.03 to 12.92 wt% (1.3 to 2.8 M) formic acid product at Faradaic efficiencies ranging between 73.0 to 91.3%. Data on electrolyzer performance, including formic acid product generation rate, energy efficiency, and energy consumption are reported at three different current densities, 100, 200, and 250 mA cm -2 . Finally, a long term 1000 h electrolyzer stability run at 200 mA cm -2 is presented, providing information on the operating conditions required in obtaining stable electrolyzer performance. All the data will be extremely useful in the commercial scale-up of this technology.
A simple convertible electrolyzer in membraneless and membrane-based modes for understanding water splitting mechanism
State-of-the-art membrane-based electrolyzers such as proton exchange membrane electrolyzer cells, are costly, susceptible to degradation, and time-consuming for electrode evaluation and triple-phase boundary electrochemical reaction studies. Here, a simple convertible electrolyzer in membraneless and membrane-based modes is proposed. For the first time, this enables comprehensive investigations of water splitting with pure water, acidic and alkaline electrolytes in one cell. With the simple electrolyzer and high-speed visualization system, the influences of flow rate, electrolytes, concentration, and Nafion membrane on the oxygen evolution reactions (OERs), hydrogen evolution reactions (HERs) and electrolyzer performance are comprehensively investigated. Visualization results reveal that water splitting only occurred at the edge between the electrode and the Nafion membrane in pure water. However, they occurred on the whole electrode surface in alkaline and acidic electrolytes, indicating easily tunable reaction sites with the convertible electrolyzer. This demonstrates the feasibility of using the simple convertible electrolyzer for understanding the water splitting mechanism. The relation between electrolyte thickness and resistances with different electrolytes is also quantified. This research provides an insight for optimizing electrochemical devices while delivering an inexpensive and fast way for electrode evaluations and electrochemical reaction studies.
Hydrogen-oxygen proton-exchange membrane fuel cells and electrolyzers
Hydrogen-oxygen SPE fuel cells and SPE electrolyzers (products of Hamilton Standard) both use a Proton-Exchange Membrane (PEM) as the sole electrolyte. The SPE cells have demonstrated a ten year life capability under load conditions. Ultimate life of PEM fuel cells and electrolyzers is primarily related to the chemical stability of the membrane. For perfluorocarbon proton-exchange membranes an accurate measure of the membrane stability is the fluoride loss rate. Millions of cell hours have contributed to establishing a relationship between fluroride loss rates and average expected ultimate cell life. Several features were introduced into SPE fuel cells and SPE electrolyzers such that applications requiring greater than or equal to 100,000 hours of life can be considered. Equally important as the ultimate life is the voltage stability of hydrogen-oxygen fuel cells and electrolyzers. Here again the features of SPE fuel cells and SPE electrolyzers have shown a cell voltage stability in the order of 1 microvolt per hour. That level of stability were demonstrated for tens of thousands of hours in SPE fuel cells at up to 500 amps per square foot (ASF) current density. The SPE electrolyzers have demonstrated the same at 1000 ASF. Many future extraterrestrial applications for fuel cells require that they be self recharged. To translate the proven SPE cell life and stability into a highly reliable extraterrestrial electrical energy storage system, a simplification of supporting equipment is required. Static phase separation, static fluid transport and static thermal control will be most useful in producting required system reliability. Although some 200,000 SPE fuel cell hours were recorded in earth orbit with static fluid phase separation, no SPE electrolyzer has, as yet, operated in space.
Reformer-electrolyzer-purifier (REP) assembly for hydrogen production, systems incorporating same and method of producing hydrogen
A high temperature electrolyzer assembly comprising at least one electrolyzer fuel cell including an anode and a cathode separated by an electrolyte matrix, and a power supply for applying a reverse voltage to the at least one electrolyzer fuel cell, wherein a gas feed comprising steam and one or more of CO2 and hydrocarbon fuel is fed to the anode of the at least one electrolyzer fuel cell, and wherein, when the power supply applies the reverse voltage to the at least one electrolyzer fuel cell, hydrogen-containing gas is generated by an electrolysis reaction in the anode of the at least one electrolyzer fuel cell and carbon dioxide is separated from the hydrogen-containing gas so that the at least one electrolyzer fuel cell outputs the hydrogen-containing gas and separately outputs an oxidant gas comprising carbon dioxide and oxygen.
Bulk Grid Frequency Support Using Electrolyzers
Increasing renewable penetration in the bulk power systems has resulted in declining inertial response of the generation during system disturbances. This results in larger frequency deviations and oscillations during such events. This paper proposes a strategy for controlled dispatch of electrolyzers as loads to improve the system’s frequency response. A droop based controller with constraints based on electrolyzer operating limits has been developed to regulate its load. Consecutively, a localized frequency based control strategy has been developed to support the bulk system during disturbances. The impact of the electrolyzer support has been demonstrated using the 23-bus SAVNW system, and the 240-bus WECC system for baseline, 25% and 50% renewable penetration. The impact of changing droop settings and the available controllable electrolyzer capacities on the system’s frequency response has also been presented. Overall, the dispatchable electrolyzers helps improve (reduce) both the maximum frequency deviation and the settling times during common disturbances like loss of load/generation, and line faults. Systems with lower inertia were seen to benefit more from the controlled electrolyzer dispatch.
Power Converter Topologies for Electrolyzer Applications to Enable Electric Grid Services
Hydrogen electrolyzers, with their operational flexibility, can be configured as smart dynamic loads which can provide grid services and facilitate the integration of more renewable energy sources into the electrical grid. However, to enable this ability, the electrolyzer system should be able to control both active and reactive power in coordination with the low-level controller of the electrolyzer via the power electronics system interface between the utility grid and electrolyzer. This paper discusses power converter topologies and the control scheme of this power electronics interface for electrolyzer applications to enable electricity grid services. For the sake of unity, in this paper, we consider the power converter system interfacing the utility grid at the line-to-line root mean square (RMS) value of 480 VAC-60 Hz and supplying to the 3500 A-750 kW PEM electrolyzer stack.
Controlling Mass Transport in Direct Carbon Dioxide Zero-Gap Electrolyzers via Cell Compression
The development of high-performance CO 2 electrolyzers is crucial for accelerating the sustainable production of fuels and chemicals integrated with renewable energy sources. Here, we introduce a methodology to actively control mass transport inside a realistic zero-gap membrane electrode assembly of a CO 2 electrolyzer by varying the gasket thickness, which consequently changes the cell compression. This allows control over the thickness and porosity of the gas diffusion electrodes, influencing the overall electrolyzer performance, as demonstrated using Ag-deposited electrodes. At low operating voltages (<2.9 V), both high- and low-compression electrolyzers exhibit similar faradaic efficiencies and partial current densities for CO formation. However, at high voltages, the low-compression electrolyzer with high electrode porosity demonstrates superior CO selectivity and activity with suppressed H 2 formation. These experimental results are validated by the computational membrane electrode assembly (MEA) model developed by using the measured in situ electrode thicknesses and electrode porosities. Additionally, liquid electrolyte saturation at the catalyst layer is found to play a dominant role in determining the mass transport, resulting in a decreased electrolyzer performance with low electrode porosity. Finally, the systematic investigation in this study improves the understanding of the transport dynamics in MEA-based devices and provides insights into optimizing device design parameters for industry-relevant CO 2 electrolysis.
Findings from Large Bench-Scale Testing of Denitration Electrolyzers for the EDCGe Project
This report highlights the key findings and outcomes relevant to the processability of waste supernatant at Hanford using a denitration electrolyzer. The Electrosynthesis Company issued a Phase 1 report to the Savannah River National Laboratory (SRNL), summarizing the evaluation of large bench-scale denitration electrolyzers to support the electrochemical denitration and caustic generation (EDCGe) project. The Electrosynthesis Company’s report (attached as Appendix A) provides insights into the initial steps required to implement an electrolyzer system at Hanford. Phase 1 experiments focused on validating the denitration electrolyzer’s performance, operating parameters, and reaction products. The robustness of the electrochemical denitration process was demonstrated by two electrolyzer flow cell systems (a 100 cm 2 ElectroCell MP and a 150 cm 2 NESI NS01 cell), both of which achieved significant nitrate and nitrite removal (>50%) with a current efficiency of ~95% for both systems. Higher current densities (500 mA cm –2 ) improved nitrate and nitrite removal rates compared to lower current densities (333 mA cm –2 ), while maintaining a current efficiency of ~94%. The NS01 cell achieved a nitrate species removal rate of ~0.41 mol h –1 at 5 kA m –2 (equiv. to 500 mA cm –2 ). The primary reaction product was ammonia (NH 3 ), constituting 78.3–91.6% of the products (excluding OH – formation). NH 3 was predominantly retained in the catholyte liquid phase rather than being off-gassed. Additionally, the NS01 cell reported an NH 3 generation rate of ~0.36 mol h –1 at 5 kA m –2 . Other gas formation included ~7% N 2 , ~7% H 2 , and trace amounts of N 2 O. The estimated power requirement (extrapolated from the 0.015 m 2 cell data) for a full-scale denitration electrolyzer is approximated to be ~1.6 MW (DC-only) to treat 50% of nitrate and nitrite in a waste stream and generates ~2.1 kmol h –1 of NH 3 with an initial concentration of 4 M NO 3 – /NO 2 – at 300 gal h –1 . Simulated waste containing aluminate, carbonate, oxalate, and halogens exhibited no adverse effects on denitration performance. A preliminary experiment comparing alkaline anolyte (5 M NaOH) with a nickel based anode to acidic media (2 M H 2 SO 4 ) with a DSA-O 2 anode showed a lower operating voltage and generated less H 2 than the acid media. Maintaining a stable 5 M OH – concentration in the anolyte through periodic additions of caustic did not significantly impact denitration performance. This operational mode will be required for long-term experiments. All the experiments demonstrated that electrochemical denitration is a promising approach for treating nitrate and nitrite in simulated waste streams, achieving significant conversion and robustness across varying experimental conditions and electrochemical cell configurations. Lastly, the ability to generate a nearly pure NH 3 stream may prove advantageous for processing at other locations within the Hanford site.
Electrolyzers Enhancing Flexibility in Electric Grids
This paper presents a real-time simulation with hardware-in-the-loop (HIL) based approach for verifying the performance of electrolyzer systems in providing grid support. Hydrogen refueling stations premdominantly use electrolyzer systems to generate hydrogen, and are proposed to have the potential of becoming smarter loads which can pro-actively provide grid services. Based on experimental findings electrolyzer systems are observed to have a high level of controllability and hence can add flexibility to the grid from demand side. Greater awareness and controllability is proposed, developed, implemented, and tested by a 'frond end controller' in real-time environment. It can optimize the operation of electrolyzer systems based on the information collected by a communication module. Real-time tests are performed to verify the performance of front end controller driven electrolyzers to provide grid support that enables greater economic revenue and grid support for hydrogen producers under dynamic conditions. The front end controller proposed in this paper is tested with electrolyzers, however it is proposed as a generic control topology that is applicable to any load.
Alkaline static feed electrolyzer based oxygen generation system
In preparation for the future deployment of the Space Station, an R and D program was established to demonstrate integrated operation of an alkaline Water Electrolysis System and a fuel cell as an energy storage device. The program's scope was revised when the Space Station Control Board changed the energy storage baseline for the Space Station. The new scope was aimed at the development of an alkaline Static Feed Electrolyzer for use in an Environmental Control/Life Support System as an oxygen generation system. As a result, the program was divided into two phases. The phase 1 effort was directed at the development of the Static Feed Electrolyzer for application in a Regenerative Fuel Cell System. During this phase, the program emphasized incorporation of the Regenerative Fuel Cell System design requirements into the Static Feed Electrolyzer electrochemical module design and the mechanical components design. The mechanical components included a Pressure Control Assembly, a Water Supply Assembly and a Thermal Control Assembly. These designs were completed through manufacturing drawing during Phase 1. The Phase 2 effort was directed at advancing the Alkaline Static Feed Electrolyzer database for an oxygen generation system. This development was aimed at extending the Static Feed Electrolyzer database in areas which may be encountered from initial fabrication through transportation, storage, launch and eventual Space Station startup. During this Phase, the Program emphasized three major areas: materials evaluation, electrochemical module scaling and performance repeatability and Static Feed Electrolyzer operational definition and characterization.
High Pressure Electrolyzer System Evaluation
This report documents the continuing efforts to evaluate the operational state of a high pressure PEM based electrolyzer located at the NASA Glenn Research Center. This electrolyzer is a prototype system built by General Electric and refurbished by Hamilton Standard (now named Hamilton Sunstrand). It is capable of producing hydrogen and oxygen at an output pressure of 3000 psi. The electrolyzer has been in storage for a number of years. Evaluation and testing was performed to determine the state of the electrolyzer and provide an estimate of the cost for refurbishment. Pressure testing was performed using nitrogen gas through the oxygen ports to ascertain the status of the internal membranes and seals. It was determined that the integrity of the electrolyzer stack was good as there were no appreciable leaks in the membranes or seals within the stack. In addition to the integrity testing, an itemized list and part cost estimate was produced for the components of the electrolyzer system. An evaluation of the system s present state and an estimate of the cost to bring it back to operational status was also produced.