Highlights
Four main strategies for improving the hydrogen evolution reaction (HER) performance of Ru-based catalysts were summarized.
The source of HER activity of Ru-based catalysts is discussed in ...terms of catalytic mechanism.
The current states, challenges and prospects were specifically provided for Ru-based catalysts.
The investigation of highly effective, durable, and cost-effective electrocatalysts for the hydrogen evolution reaction (HER) is a prerequisite for the upcoming hydrogen energy society. To establish a new hydrogen energy system and gradually replace the traditional fossil-based energy, electrochemical water-splitting is considered the most promising, environmentally friendly, and efficient way to produce pure hydrogen. Compared with the commonly used platinum (Pt)-based catalysts, ruthenium (Ru) is expected to be a good alternative because of its similar hydrogen bonding energy, lower water decomposition barrier, and considerably lower price. Analyzing and revealing the HER mechanisms, as well as identifying a rational design of Ru-based HER catalysts with desirable activity and stability is indispensable. In this review, the research progress on HER electrocatalysts and the relevant describing parameters for HER performance are briefly introduced. Moreover, four major strategies to improve the performance of Ru-based electrocatalysts, including electronic effect modulation, support engineering, structure design, and maximum utilization (single atom) are discussed. Finally, the challenges, solutions and prospects are highlighted to prompt the practical applications of Ru-based electrocatalysts for HER.
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Proton exchange membrane water electrolyzer development requires understanding processes at the materials and interface levels to reach the required performance and lifetime targets for increasing ...market penetration. To achieve the required progress, it is critical to develop advanced in-situ diagnostics that allow observation of the changes that come with the reduction of catalyst loading combined with long-term intermittent operation. This work presents an internal voltage sensing method that enables observing internal voltage drops in an operating electrolyzer cell. It allows the total cell resistance to be separated into anode, CCM, and cathode resistance. The method is demonstrated by operating cells with different anode porous transport layers (PTLs). The changing properties of the PTLs result in significant variations of the resistances. Enhancing the PTL properties with a protective coating reduces the anode resistance significantly. In addition to these observations, the method enables a real-time monitoring of resistance related values that impact performance in water electrolyzers. Long-term experiments with the method allow us to gain insights into processes that occur during operation such as conditioning or degradation. The internal voltage sensing method presented in this study is a novel technique for diagnosing, analyzing, and optimizing water electrolyzers and other energy conversion devices.
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•Wire sensing configuration enables deconvolution of internal cell voltages•Suitable method for component resistance and interface evaluation•Anode PTL loss contributions strongly depend on material and coating configuration•Origins of performance change are observed in-situ
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
Abstract
The sluggish kinetics of oxygen evolution reaction (OER) and high iridium loading in catalyst coated membrane (CCM) are the key challenges for practical proton exchange membrane water ...electrolyzer (PEMWE). Herein, we demonstrate high-surface-area nano-metal diborides as promising supports of iridium-based OER nanocatalysts for realizing efficient, low-iridium-loading PEMWE. Nano-metal diborides are prepared by a novel disulphide-to-diboride transition route, in which the entropy contribution to the Gibbs free energy by generation of gaseous sulfur-containing products plays a crucial role. The nano-metal diborides, TaB
2
in particular, are investigated as the support of IrO
2
nanocatalysts, which finally forms a TaO
x
/IrO
2
heterojunction catalytic layer on TaB
2
surface. Multiple advantageous properties are achieved simultaneously by the resulting composite material (denoted as IrO
2
@TaB
2
), including high electrical conductivity, improved iridium mass activity and enhanced corrosion resistance. As a consequence, the IrO
2
@TaB
2
can be used to fabricate the membrane electrode with a low iridium loading of 0.15 mg cm
−2
, and to give an excellent catalytic performance (3.06 A cm
−2
@2.0 V@80
o
C) in PEMWE―the one that is usually inaccessible by unsupported Ir-based nanocatalysts and the vast majority of existing supported Ir-based catalysts at such a low iridium loading.
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•Carbon paper as anode PTLs in PEMWE cells is investigated and characterized.•Carbon FC hardware & materials can be used in initial PEMWE performance testing.•Contact between membrane ...and graphite must be avoided.
The research and development of proton exchange membrane water electrolysis (PEMWE) is an upcoming and growing area due to a rising interest in hydrogen as an energy carrier. Operating conditions are harsher than in a fuel cell system, particularly because the potentials required for the oxygen evolution reaction are significantly higher. In commercial water electrolysis systems, this is compensated by typically using titanium material sets that are often protected against oxidation through coating processes. Such material choices make small scale research hardware and porous transport layers expensive and difficult to source. In this work, we show that the stability of traditional, carbon-based fuel cell materials such as porous transport layers and graphite flow fields can be sufficient for electrolyzer initial performance characterization procedures such as cell conditioning, a limited number of polarization curve measurements, and electrochemical impedance spectroscopy. We identify and quantify the onset of carbon degradation in porous transport layers with regards to operating length and define a strategy that enables the utilization of standard fuel cell hardware for short-term PEMWE experiments. With the knowledge that existing fuel cell material sets can be applied to conduct electrolyzer research when adhering to such limitations, fuel cell research hardware and experience can be more readily transferred to the younger and rapidly growing electrolysis research field.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
Liquid/gas diffusion layers (LGDLs), which are located between the catalyst layer (CL) and bipolar plate (BP), play an important role in enhancing the performance of water splitting in proton ...exchange membrane electrolyzer cells (PEMECs). They are expected to transport electrons, heat, and reactants/products simultaneously with minimum voltage, current, thermal, interfacial, and fluidic losses. In this study, the thin titanium-based LGDLs with straight-through pores and well-defined pore morphologies are comprehensively investigated for the first time. The novel LGDL with a 400 μm pore size and 0.7 porosity achieved a best-ever performance of 1.66 V at 2 A cm −2 and 80 °C, as compared to the published literature. The thin/well-tunable titanium based LGDLs remarkably reduce ohmic and activation losses, and it was found that porosity has a more significant impact on performance than pore size. In addition, an appropriate equivalent electrical circuit model has been established to quantify the effects of pore morphologies. The rapid electrochemical reaction phenomena at the center of the PEMEC are observed by coupling with high-speed and micro-scale visualization systems. The observed reactions contribute reasonable and pioneering data that elucidate the effects of porosity and pore size on the PEMEC performance. This study can be a new guide for future research and development towards high-efficiency and low-cost hydrogen energy.
Proton exchange membrane (PEM) water electrolysis, which is one of methods of hydrogen production with the most potential, has attracted more attention due to its energy conversion and storage ...potential. In this paper, a steady state, three-dimensional mathematical model coupled with the electrochemical and mass transfer physical fields for a PEM water electrolyzer was established. The influence of the different operation parameters on the cell performance was discussed. Moreover, the different patterns of the flow field, such as parallel, serpentine, multi-serpentine, and interdigitate flow fields, were simulated to reveal their influence on the mass transfer and current distribution and how they consequently affected the cell performance. The results of the numerical modeling were in good agreement with the experimental data. The results demonstrated that a higher temperature led to a better mass transfer, current distribution, and cell performance. By comparing the polarization curve, current, velocity, and pressure distribution, the results also indicated that the PEM water electrolyzer with a parallel flow field had the best performance. The results in this study can help in optimizing the design of PEM water electrolyzers.
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Gas bubble dynamics and two-phase flow have a significant impact on the performance and efficiency of proton exchange membrane electrolyzer cells (PEMECs). It has been strongly desired to develop an ...effective experimental method for in-situ observing the high-speed/micro-scale oxygen bubble dynamics and two-phase flow in an operating PEMEC. In this study, the micro oxygen bubble dynamic behavior and two-phase flow are in-situ visualized through a high-speed camera coupled with a specific designed transparent PEMEC, which uses a novel thin liquid/gas diffusion layer (LGDL) with straight-through pores. The effects of different operating conditions on oxygen bubble dynamics, including nucleation, growth, and detachment, and two-phase flow have been comprehensively investigated. The results show that temperature and current density have great effects on bubble growth rate and reaction sites while the influence of flow rate is very limited. The number, growth rate, nucleation site, and slug flow regime of oxygen gas bubbles increase as temperature and/or current density increases, which indicates that an increase in temperature and/or current density can enhance the oxygen production efficiency. Further, a mathematical model for the bubble growth is developed to evaluate the effects of temperature and current density on the bubble dynamics. A mathematical model has been established and shows a good correlation with the experimental results. The studies on two-phase flow and high-speed micro bubble dynamics in the microchannel will help to discover the true electrochemical reaction at micro-scale in an operating PEMEC.
•Rapid micro oxygen bubble generation and growth are in-situ visualized.•Bubble growth rate and reaction sites are increased with the current density.•A model shows a good agreement with the experiment results.•Annular flow is more easily to form under high current densities.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK, ZRSKP
Better understanding of true electrochemical reaction behaviors in electrochemical energy devices has long been desired. It has been assumed so far that the reactions occur across the entire catalyst ...layer (CL), which is designed and fabricated uniformly with catalysts, conductors of protons and electrons, and pathways for reactants and products. By introducing a state-of-the-art characterization system, a thin, highly tunable liquid/gas diffusion layer (LGDL), and an innovative design of electrochemical proton exchange membrane electrolyzer cells (PEMECs), the electrochemical reactions on both microspatial and microtemporal scales are revealed for the first time. Surprisingly, reactions occur only on the CL adjacent to good electrical conductors. On the basis of these findings, new CL fabrications on the novel LGDLs exhibit more than 50 times higher mass activity than conventional catalyst-coated membranes in PEMECs. This discovery presents an opportunity to enhance the multiphase interfacial effects, maximizing the use of the catalysts and significantly reducing the cost of these devices.
•Novel TT-LGDLs with different surface treatments are investigated for the first time.•Superior PEMEC performance with a value of 1.63V at 2.0A/cm2 and 80°C is obtained.•Ohmic losses is reduced from ...0.0925Ωcm2 to 0.0700Ωcm2.•Hydrogen production rate can be greatly increased by 28.2%.•Au thin film surface treatment on titanium material shows good stability.
A proton exchange membrane electrolyzer cell (PEMEC) is one of the most promising devices for high-efficiency and low-cost energy storage and ultrahigh purity hydrogen production. As one of the critical components in PEMECs, the titanium thin/tunable LGDL (TT-LGDL) with its advantages of small thickness, planar surface, straight-through pores, and well-controlled pore morphologies, achieved superior multifunctional performance for hydrogen and oxygen production from water splitting even at low temperature. Different thin film surface treatments on the novel TT-LGDLs for enhancing the interfacial contacts and PEMEC performance were investigated both in-situ and ex-situ for the first time. Surface modified TT-LGDLs with about 180nm thick Au thin film yielded performance improvement (voltage reduction), from 1.6849V with untreated TT-LGDLs to only 1.6328V with treated TT-LGDLs at 2.0A/cm2 and 80°C. Furthermore, the hydrogen/oxygen production rate was increased by about 28.2% at 1.60V and 80°C. The durability test demonstrated that the surface treated TT-LGDL has good stability as well. The gold electroplating surface treatment is a promising method for the PEMEC performance enhancement and titanium material protection even in harsh environment.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK, ZRSKP
The electrode, as one of the most critical components in a proton exchange membrane water electrolysis (PEMWE) cell for hydrogen production, has a significant impact on cell performance. Electrodes ...that are fabricated via various techniques may exhibit different morphologies or properties, which might change the kinetics and resistances of the PEMWE. In this study, we have successfully fabricated several electrodes by different techniques, and the effects of electrode coating methods (ultrasonic spray, blade coating, and rod coating), hot press, and decal transfer processes are comprehensively investigated. The performance differences between various electrodes are due to kinetic or high frequency resistance changes, while the influences are not significant, with the biggest deviation of about 26 mV at 2.0 A cm−2. In addition, the effects of catalyst ink compositions, including ionomer to catalyst ratio (0.1 to 0.3), water to alcohol ratio (1:1 to 3:1), and catalyst weight percentage (10% to 30%), are also studied, and the electrodes’ performance variations are less than 10 mV at 2.0 A cm−2. The results show that the PEMWE electrode has superior compatibility and redundancy, which demonstrates the high flexibility of the electrode and its applicability for large-scale manufacturing.
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