Fabrication of NiCu interconnected porous nanostructures for highly selective methanol oxidation coupled with hydrogen evolution reaction

Electrocatalytic water electrolysis is the most promising clean and efficient process for pure and clean generation of hydrogen. However, water oxidation reaction requires a large overpotential owing to its slow kinetics, causing a lower efficiency of hydrogen production and high energy consumption. Herein, we report the bimetallic NiCu interconnected porous nanostructures on copper foil (NiCu@Cu) prepared by hydrogen bubbles templating electrodeposition technique for methanol oxidation reaction (MOR), which replaces the kinetically sluggish water oxidation reaction and enhances the hydrogen production with lower energy input. With their high macroporosity, interconnected growth on copper foil with excellent conductivity and easy flow of electrolyte on electrode interface, and stabilization of active sites due to bimetallic synergistic effects, the NiCu@Cu electrocatalysts exhibit outstanding activities for HER and MOR. The NiCu@Cu requiring just 1.32 V anodic potential vs RHE at 10 mA cm^?2 for MOR which is significantly lower than that for water oxidation reaction. Moreover, the electrolyzer using NiCu@Cu/NiCu@Cu for anodic MOR and cathodic H₂ production only needs a low input voltage of 1.45 V to deliver a current density of 10 mA cm^?2 with impressive durability.     

Nickel doped MoS2 nanoparticles as precious-metal free bifunctional electrocatalysts for glucose assisted electrolytic H2 generation

Hydrogen, as the one of clean energy source, has the advantages of high energy density and carbon-free emission. Water electrolysis is one of the most promising ways to generate hydrogen, but the rather high energy required seriously hinders its widespread applications yet. In this study, we report an alkaline electrolyzer to implement energy-saving H₂ generation by coupling cathodic hydrogen evolution reaction (HER) with anodic glucose oxidation reaction (GOR) other than oxygen evolution reaction, in which nickel-doped MoS₂ nanoparticles (Ni–MoS₂ NPs) has been developed as bifunctional electrocatalyst for HER and GOR. The electrolyzer only requires a cell voltage of 1.67 V to reach an electrolysis current density of 10 mA cm⁻², about 270 mV lower than the corresponding value in the traditional electrolyzer. Electrolytic H₂ generation with the assistance of biomass derived materials may open a new way for the future sustainable development.     

In-situ growth of Fe–Co Prussian-blue-analog nanocages on Ni(OH)2/NF and the derivative electrocatalysts with hierarchical cage-on-sheet architectures for efficient water splitting

To design an efficient and cost-effective electrocatalyst based on Prussian blue and its analogs are a promising choice to realize energy transformation and storage via water-splitting. Herein, a facile and practical method is developed to in-situ grow Fe–Co Prussian-blue-analog (PBA) nanocages with an open hole in each face center on Ni(OH)₂/NF substrate to form the hierarchical cage-on-plate structure. Furthermore, the Fe–Co PBA nanocages attached to Ni(OH)₂/NF plates are hydrogenated and nitrogenized into FeCoNi/NF and FeCoNiN/NF electrodes, respectively. As-prepared electrodes successfully retain the 3D hierarchical micro-nano structures of Fe–Co PBA@Ni(OH)₂/NF precursor and can be used as a bifunctional water-splitting catalyst for overall water splitting. Compared to FeCoNi/NF, FeCoNiN/NF shows more efficiency and durability in the electrolytic water splitting tests in alkaline media. For the FeCoNiN/NF electrocatalyst, ultralow overpotentials for hydrogen evolution reaction (HER) are only 56 and 290 mV at current densities of 10 and 500 mA cm^?2. Meanwhile, overpotentials for oxygen evolution reaction (OER) are 267 and 374 mV at current densities of 50 and 500 mA cm^?2. The FeCoNiN/NF electrode can act both the cathode and the anode for overall water splitting, this electrolyzer only requires a cell voltage of 1.492 V to afford a current density of 10 mA cm^?2. This electrolyzer can stably deliver a viable high current density of 625 mA cm^?2 for 40 h to meet the condition of industrial application.     

Petal-like NiCoP sheets on 3D nitrogen-doped carbon nanofiber network as a robust bifunctional electrocatalyst for water splitting

Searching high-active, stable and abundant bifunctional catalysts to replace noble metals for hydrogen and oxygen evolution reactions (HER and OER) is desired. Herein, petal-like NiCoP sheets were synthesized on carbon paper covered with a 3D nitrogen-doped carbon nanofiber network (NiCoP/CNNCP) by a simple hydrothermal process followed by phosphorization. The HER overpotential in 0.5 M H₂SO₄ and OER overpotential in 1 M KOH of the NiCoP/CNNCP electrode only required 55 mV and 260 mV to drive a current density of 10 mA cm^?2, respectively, which was comparable or even better than most nickel-and cobalt-based phosphide catalysts. The overall water-splitting electrolyzer with an asymmetric electrolyte system assembled using NiCoP/CNNCP as bifunctional electrodes required an extremely low cell voltage of 1.04 V to achieve a current density of 10 mA cm^?2, which was much lower than almost all alkaline electrolysis systems.     

Facile hydrothermal synthesis of rare earth phosphate for boosting hydrogen evolution reaction

The water electrolysis process has attracted great attention due to the production of high energy density pure hydrogen. However, the involved cell reactions in this process such as hydrogen and oxygen evolution reactions are kinetically sluggish and demands high input energy to accelerate the rate of these reactions. Therefore, the development and application of efficient electrocatalyst is essential for hydrogen evolution reaction (HER) as well as oxygen evolution reaction (OER). In the present work, we have successfully synthesized two rare earth phosphates through the hydrothermal route and used as a catalysts towards HER in an acidic medium. The rare earth phosphate PrPO₄ exhibits better catalytic activity than YPO₄ catalyst. The overpotential of PrPO₄, YPO₄ and standard Pt/C were found as 147, 484.3 and 58 mV vs. reversible hydrogen electrode, respectively, to reach current density 10 mA·cm^?2 and corresponding Tafel slopes were found as 107.58, 118.73 and 80.89 mV decade^?1, respectively in 0.5 M H₂SO₄. The catalytic activity of PrPO₄ (472.83 mA·cm^?2) overcome standard Pt/C (179.60 mA·cm^?2) at high overpotential 450 mV vs. reversible hydrogen electrode. The prepared PrPO₄ shows efficient electrocatalytic activity towards HER in acidic medium because it possess high BET surface area, large ECSA value and small charge transfer resistance than YPO₄.     

Assessment of hydrogen production from waste heat using hybrid systems of Rankine cycle with proton exchange membrane/solid oxide electrolyzer

A techno-economic assessment of hydrogen production from waste heat using a proton exchange membrane (PEM) electrolyzer and solid oxide electrolyzer cell (SOEC) integrated separately with the Rankine cycle via two different hybrid systems is investigated. The two systems run via three available cement waste heats of temperatures 360 °C, 432 °C, and 780 °C with the same energy input. The waste heat is used to run the Rankine cycle for the power production required for the PEM electrolyzer system, while in the case of SOEC, a portion of waste heat energy is used to supply the electrolyzer with the necessary steam. Firstly, the best parameters; Rankine working fluid for the two systems and inlet water flow rate and bleeding ratio for the SOEC system are selected. Then, the performance of the two systems (Rankine efficiency, total system efficiency, hydrogen production rate, and economic and CO₂ reduction) is investigated and compared. The results reveal that the two systems' performance is higher in the case of steam Rankine than organic, while a bleeding ratio of 1% is the best condition for the SOEC system. Rankine output power, total system efficiency, and hydrogen production rate rose with increasing waste heat temperature having the same energy. SOEC system produces higher hydrogen production and efficiency than the PEM system for all input waste heat conditions. SOEC can produce 36.9 kg/h of hydrogen with a total system efficiency of 23.8% at 780 °C compared with 27.4 kg/h and 14.45%, respectively, for the PEM system. The minimum hydrogen production cost of SOEC and PEM systems is 0.88 $/kg and 1.55 $/kg, respectively. The introduced systems reduce CO₂ emissions annually by about 3077 tons.     

Porous Co2P film coated on carbon fiber as highly performance electrocatalyst toward overall water splitting

Designing porous active materials and enhancing their contact with conductive substrates is an effective strategy to improve electrolytic water splitting performance of noble metal-free catalysts. Herein, a facile nanostructured electrode, composed of porous Co₂P films coated on carbon fiber (CF@P–Co₂P), is designed and prepared. The unique three-dimensional interconnected pore structure of Co₂P and the close contact between porous Co₂P and CF not only increase specific surface areas to expose abundant catalytic sites but also stimulate the transport of electron, mass and gaseous products in catalytic process. Benefit from the reasonable electrode structure, the self-supported CF@P–Co₂P electrodes present perfect performance with only needing overpotentials of 107.7/175.5/141.8 mV for hydrogen evolution reaction (HER) in acidic/neutral/alkaline solution and 269.4 mV for oxygen evolution reaction (OER) in alkaline solution to get current density of 20 mA cm^?2. In addition, alkaline electrolyzer equipped with CF@P–Co₂P bifunctional electrodes only needs a cell voltage of 1.657 V to get water-splitting current density of 20 mA cm^?2. Even better, the electrolyzer can continuously electrolyze over 50 h with negligibly decreasing current density and the Faraday efficiency is close to 100% toward both HER and OER.     

Pulse-activation engineering induced lattice transformation of layered double hydroxides for efficient alkaline hydrogen evolution

In order to accelerate water dissociation kinetics and improve hydrogen evolution reaction (HER) in alkaline electrolyzer, pulse-activation engineering was proposed to induce lattice transformation of layered double hydroxides (LDHs) electrocatalysts. Physicochemical characterizations and density functional theory (DFT) calculations confirmed that FeOOH crystals diminished with a pulse potential of 1000 cycles (cls) in non-Faradaic region (?0.8～0 V) and transformed into more stable CoFeLDH nanosheet arrays in Fe-rich system. The above transformation effectively reduced H¹ adsorption energy to accelerate water decomposition for efficient hydrogen evolution reaction. This was because pulse-activation accelerated electron transfer from Co²⁺ to Fe^(3+δ)+ through intermittent input negative potential, reducing the high oxidation state of Fe^(3+δ)+ in FeOOH to generate more stable CoFeLDH. The optimized pulse-activation with CoFeLDH electrocatalyst after 1000 cls decreased the overpotential of alkaline hydrogen evolution by 36%, from 225 mV to 144 mV at ?10 mA cm^?2.     

A novel in-situ strategy develops for Mo2C nanoparticles incorporated on N,P co-doped stereotaxically carbon as efficient electrocatalyst for overall water splitting

Developing cost-effective and remarkable electrocatalysts toward oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) performs excelling role in boosting the hydrogen energy application. Herein, a novel in-situ one-pot strategy is developed for the first time to synthesize molybdenum carbide nanoparticles (Mo₂C NPs) incorporated on nitrogen (N) and phosphorous (P) co-doped stereotaxically carbon (SC). The optimized Mo₂C NPs/N, P–SC–800 electrocatalyst exhibits lower overpotentials of 131 and 287 mV for HER and OER to deliver a current density of 10 mA cm^?2 in 1.0 M KOH medium with smaller Tafel slopes of 58.9 and 74.4 mV/dec, respectively. In addition, an electrolyzer using Mo₂C NPs/N, P–SC–800 electrode as cathode and anode delivers a current density of 10 mA cm^?2 at a small voltage of 1.64 V for overall water splitting. The excellent water splitting performance could be ascribed to optimum Mo₂C NPs for more accessible active sites, highly active N, P-SC networks for accelerated electron transfers, and synergetic effect between Mo₂C NPs and N, P-SC networks. The N, P-SC network not only enhances the overall dispersion of Mo₂C NPs but also contributes numerous electroactive edges to enhance the performance of HER, OER, and overall water splitting activity. This research work explores the in-situ one-step strategies of advanced, cost-effective, and non-precious metal electrocatalysts for efficient water splitting and motivates the consideration of a novel class of heteroatom doped stereotaxically carbon nanocomposites for sustainable energy production.     

Efficient MOF- derived V–Ni3S2 nanosheet arrays for electrocatalytic overall water splitting in alkali

The synergistic achievement of low-cost earth-abundant electrocatalysts and high efficiency to meet renewable energy need is highly desirable yet challenging. Here, we developed a simple Ni foam self -templating route for V-doped Ni₃S₂ nanosheet arrays through in situ formation of metal-organic frameworks (MOFs) combined with subsequent conversion. The as-prepared MOF-V-Ni₃S₂/NF catalyst delivers outstanding electrocatalytic performance in the alkaline solution, which requires low overpotentials of 118.1 mV @10 mA cm^?2 and 268 mV @10 mA cm^?2 for hydrogen evolution reaction and oxygen evolution reaction, respectively. The V-doping and MOF-derived 3D hieratical nanostructure play a vital role in the catalytic process, which provides efficient active sites and large surface areas. Furthermore, an alkaline electrolyzer was assembled with two pieces of MOF-V-Ni₃S₂/NF, which achieves efficient water splitting at 1.58 V @10 mA cm^?2. This strategy opens up new channels to synthesize MOF-based bifunctional electrocatalysts toward overall water spitting.     

Synthesis of nest-like porous MnCo–P electrocatalyst by electrodeposition on nickel foam for hydrogen evolution reaction

It is very important to develop hydrogen evolution catalyst with high activity and low cost to solve energy crisis. The abundant non-precious metals and phosphides have attracted much attention and are expected to replace platinum catalysts. Herein, we report an approach to prepare nest-like porous MnCo–P electrocatalyst on the nickel foam by two-step electrodeposition. The prepared bimetallic phosphide MnCo–P₃/NF has excellent hydrogen catalytic activity. In the 1 M NaOH solution, the current density of 10 mA cm^?2 required overpotential is only 47 mV, its Tafel slope is 56.4 mV dec^?1, and the higher current density 100 mA cm^?2 required overpotential is only 112 mV. More importantly, the MnCo–P₃/NF catalyst has a long-term stability of electrocatalytic hydrogen evolution. After 24 h catalytic hydrogen evolution test at a constant current density of 20 mA cm^?2, its potential basically does not change. Furthermore, the current density only changes slightly after 1500 cycles of CV test. All these well prove that the prepared MnCo–P₃/NF catalyst has a long-term hydrogen evolution stability. According to performance testing and morphological characterization, the MnCo–P₃/NF has a high hydrogen catalytic activity and stability are due to its larger active area, lower interface charge transfer resistance and stronger mechanical stability. In summary, the study explores a method of preparing bimetallic phosphides as an efficient and stable hydrogen evolution catalyst.     

Fe7Se8@Fe2O3 heterostructure nanosheets as bifunctional electrocatalyst for urea electrolysis

Water electrolysis for producing hydrogen is considered to be the most feasible means to develop new green energy. Compared with above, urea electrolysis can improve energy conversion efficiency by introducing urea, and can also be used for purification of wastewater rich in urea. In this paper, a bifunctional electrocatalyst with heterostructure, namely Fe₇Se₈@Fe₂O₃ nanosheets supported on nickel foam, were synthesized for the first time through typical hydrothermal and partial oxidation processes. Iron cation promotes electron transfer and adjusts electron structure under the synergistic action of selenium and oxygen anion, thus achieving excellent catalytic activity of urea electrolysis. In an alkaline solution of 1 M KOH with 0.5 M urea, the Fe₇Se₈@Fe₂O₃/NF catalyst can drive the current density of 10 mA cm^?2 with requiring only potential of 1.313 V and overpotential of 141 mV for urea oxidation reaction (UOR) and hydrogen evolution reaction (HER), respectively. What is noteworthy is that Fe₇Se₈@Fe₂O₃/NF heterostructure is used as bifunctional electrocatalyst to form urea electrolyzer device, which only needs potential of 1.55 V to drive current density of 10 mA cm^?2, which is one of the best catalytic activities reported so far, and the electrode couple showed remarkable stability for 15 h. Density functional theory shows that the Fe₇Se₈@Fe₂O₃/NF material exhibits the minimum Gibbs free energy for the adsorption of hydrogen. This work provides a new method for exploring novel and environmentally friendly bifunctional electrocatalysts for urea electrolysis.     

Bimetallic-metal organic framework-derived Ni3S2/MoS2 hollow spheres as bifunctional electrocatalyst for highly efficient and stable overall water splitting

Herein, strongly coupled Ni₃S₂/MoS₂ hollow spheres derived from NiMo-based bimetal-organic frameworks are successfully synthesized for overall water splitting via a one-pot solvothermal method followed by sulfurization. A well-defined hollow spherical structure with a heterointerface between Ni₃S₂ and MoS₂ is constructed using solvothermal and sulfurization processes. Owing to their bimetallic heterostructure, porous hollow carbon structure with large surface area, and numerous exposed active sites, the Ni₃S₂/MoS₂ hollow spheres are found to be efficient electrocatalysts for both the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). The heterostructured Ni₃S₂/MoS₂ hollow spheres show small overpotentials of 303 and 166 mV to reach a current density of 10 mA cm^?2 for the OER and HER in 1.0 M KOH, respectively. Furthermore, an overall water-splitting electrolyzer consisting of the Ni₃S₂/MoS₂ hollow spheres as both the anode and cathode requires a very low cell voltage of 1.62 V to drive a current density of 10 mA cm^?2 with outstanding long-term stability for 100 h. Our findings offer a new pathway for the design and synthesis of electrochemically advanced bifunctional catalysts for various energy storage and conversion applications.     

Flower-shaped and sea urchin-shaped structures coexisting in cobalt-based phosphate and oxides achieve efficient electrochemical overall water electrolysis

Active site engineering for electrocatalysts is an essential strategy to improve their intrinsic electrocatalytic capability for practical applications and it is of great significance to develop a new excellent electrocatalyst for overall water splitting. Here, Co₃O₄/nickel foam (NF) and Co₂(P₄O₁₂)/NF electrocatalysts with flower-shaped and sea urchin-shaped structures are synthesized by a simple hydrothermal process and followed by a post-treatment method. Among them, Co₂(P₄O₁₂)/NF shows good catalytic activity for hydrogen evolution reaction (HER), and at the current density of 10 mA cm^?2, the overpotential is only 113 mV Co₃O₄/NF exhibits good catalytic activity for oxygen evolution reaction (OER), and the overpotential is 327 mV at 20 mA cm^?2. An alkaline electrolyzer with Co₃O₄/NF and Co₂(P₄O₁₂)/NF catalysts respectively as anode and cathode displays a current density of 10 mA cm^?2 at a cell voltage of 1.59 V. This work provides a simple way to prepare high efficient, low cost and rich in content promising electrocatalysts for overall water splitting.     

High throughput preparation of Ni–Mo alloy thin films as efficient bifunctional electrocatalysts for water splitting

The synthesis of cost-effective and high-performance electrocatalysts for water splitting is the main challenge in electrochemical hydrogen production. In this study, we adopted a high throughput method to prepare bi-metallic catalysts for oxygen/hydrogen evolution reactions (OER/HER). A series of Ni–Mo alloy electrocatalysts with tunable compositions were prepared by a simple co-sputtering method. Due to the synergistic effect between Ni and Mo, the intrinsic electrocatalytic activity of the Ni–Mo alloy electrocatalysts is improved, resulting in excellent HER and OER performances. The Ni₉₀Mo₁₀ electrocatalyst shows the best HER performance, with an extremely low overpotential of 58 mV at 10 mA cm^?2, while the Ni₄₀Mo₆₀ electrocatalyst shows an overpotential of 258 mV at 10 mA cm^?2 in OER. More significantly, the assembled Ni₄₀Mo₆₀//Ni₉₀Mo₁₀ electrolyzer only needs a cell voltage of 1.57 V to reach 10 mA cm^?2 for overall water splitting.     

Integrating Co3O4 nanoparticles with MnO2 nanosheets as bifunctional electrocatalysts for water splitting

Developing high-efficiency and low-cost electrocatalyst is significant for the application of water splitting technology. Herein, Co₃O₄ nanoparticles and MnO₂ nanosheets are separately synthesized and subsequently assembled into a unique 0/2-dimensional heterostructure via van der Waals interactions. The consequent composites expose abundant accessible active sites and expedite the reaction kinetics, which can be testified by the superiorities in Tafel slope, exchange current density and double-layer capacitance, only requiring overpotentials of 355 and 129 mV for oxygen and hydrogen evolution reactions in 1.0 M KOH at 10 mA cm^?2, respectively. Moreover, a cell voltage of 1.660 V can drive the electrolyzer at 10 mA cm^?2. Benefitted from robust integration, the original aggregation and restacking of individual materials have been overcome, thereby leading to superior elelctrocatalysis durability. This facile and universal strategy may inspire the researchers on the design and construction of advanced functional composites.     

Solid oxide cells with cermet of silver and gadolinium-doped-ceria symmetrical electrodes for high-performance power generation and water electrolysis

A cermet of silver and gadolinium-doped-ceria (Ag-GDC) is investigated as novel symmetrical electrode material for (ZrO₂)_0.92(Y₂O₃)_0.08 (YSZ) electrolyte-supported solid oxide cells (SOCs) operated in fuel cell (SOFC) and electrolysis (SOEC) modes. The electrochemical performances are evaluated by measuring the current density-voltage characteristics and impedance spectra of the SOCs. The activity of hydrogen and air electrodes is investigated by recording overpotential versus current density in symmetrical electrode cells, respectively in hydrogen and air, using a three-electrode method. Conventional hydrogen electrode, Ni-YSZ, and oxygen electrode, LSCF (La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ)-GDC, are tested as comparison. The results show that, as an oxygen electrode, Ag-GDC is more active than LSCF-GDC in catalyzing both oxygen reduction reaction (ORR) in an SOFC and oxygen evolution reaction (OER) in an SOEC. As a hydrogen electrode, Ag-GDC is more active than Ni-YSZ in catalyzing hydrogen oxidation reaction (HOR) in an SOFC and hydrogen evolution reaction (HER) in an SOEC, especially in high steam concentration. An SOC with symmetrical Ag-GDC electrodes operated in a fuel cell mode, with 3% H₂O humidified H₂ as the fuel, displays a peak power density of 395 mWcm^?2 at 800 °C. Its polarization resistance at open circuit voltage is 0.21 Ω cm². Ag-GDC electrode can be operated even at pure steam. An SOEC operated for electrolyzing 100% H₂O, the current density reaches 720 mA cm^?2 under 1.3 V at 800 °C.     

Okra-like hollow Cu0.15-CoP/Co3O4@CC nanotube arrays catalyst for overall water splitting

The manufacture of hydrogen energy by overall water splitting (OWS) has been broadly considered as a promising candidate for constant energy systems. Herein, we report an okra-like hollow Cu_0.15-CoP/Co₃O₄@CC nanotube arrays catalyst through a simple hydrothermal-phosphating method. As a noble-metal-free catalyst, it exhibits outstanding HER (hydrogen evolution reaction) catalytic activity with an overpotential of 13 mV to achieve 10 mA cm^?2 in 1 M KOH electrolyte. For OER (oxygen evolution reaction), it demands 225 mV to achieve 10 mA cm^?2. When okra-like hollow Cu_0.15-CoP/Co₃O₄@CC is used as both cathode and anode electrode materials, 1.487 V is required to reach 10 mA cm^?2 for OWS, better than numerous electrocatalysts that have been reported. Moreover, it displays excellent stability in a continuously 60 h i-t test, proving an enormous potential for large-scale applications. The theoretical calculation of density functional theory (DFT) further reveals that Cu doping can bring localized structure polarization and reduce the hydrogen adsorption free energy (ΔG_H1) on the interstitial sites, thus leading to a significant increase in catalytic activity.     

High temperature electrolysis of hydrogen bromide gas for hydrogen production using solid oxide membrane electrolyzer

Using solid oxide membrane, this paper presents the theoretical modeling of the high temperature electrolysis of hydrogen bromide gas for hydrogen production. The electrolysis of hydrogen halides such as hydrogen bromide is an attractive process, which can be coupled to hybrid thermochemical cycles. The high temperature electrolyzer model developed in the present study includes concentration, ohmic, and activation losses. Exergy efficiency, as well as energy efficiency parameters, are used to express the thermodynamic performance of the electrolyzer. Moreover, a detailed parametric study is performed to observe the effects of various parameters such as current density and operating temperature on the overall system behavior. The results show that in order to produce 1 mol of hydrogen, 1.1 V of the applied potential is required, which is approximately 0.8 V less compared to high temperature steam electrolysis under same conditions (current density of 1000 A/m² and temperature of 1073 K). Furthermore, it is found that with the use of the presented electrolyzer, one can achieve energy and exergy efficiencies of about 56.7% and 53.8%, respectively. The results presented in this study suggest that, by employing the proposed electrolyzer, two-step thermochemical cycle for hydrogen production may become more attractive especially for nuclear- and concentrated solar-to-hydrogen conversion applications.     

The effect of sintering aids on BaCe0·7Zr0·1Y0.1Yb0.1O3-δ as the electrolyte of proton-conducting solid oxide electrolysis cells

Proton-conducting solid oxide electrolysis cells (H-SOECs) are attracting attentions of researchers due to their unique advantages. The proton-conducting material BaCe_0·7Zr_0·1Y_0.1Yb_0.1O_3-δ (BZCYYb) has both the advantages of barium ceria-based and barium zirconate-based materials. BZCYYb material usually is synthesized by solid-state reaction (SSR) method, hence the densification of this electrolyte material is the key to restrict the application of H-SOECs. In this paper, effects of adding 1 wt% of different sintering aids (NiO, CuO, ZnO) to BZCYYb on the grain size and the conductivity are investigated. After adding 1 wt% of NiO and CuO sintering aids, BZCYYb electrolyte achieves ideal density. The electrical conductivity of four samples (BZCYYb without adding sintering aid, BZCYYb with 1 wt% NiO, CuO, ZnO, respectively) is tested under different steam concentrations of air, nitrogen, hydrogen, and nitrogen-hydrogen mixture. The conductivity increased after the sintering aid is added. With the increase of steam concentration, the conductivity decreased slightly and then increased due to electron holes under oxygen atmosphere with steam at high temperature. In other atmospheres, the conductivity increases with the steam concentration. In the atmosphere of 20 vol% H₂O-Air and H₂, the conductivity of the BZCYYb samples with 1 wt% CuO is about 1.087 × 10^?2 S cm^?1 and 9.02 × 10^?3 S cm^?1 at 650 °C, and the conductivity of the BZCYYb samples with 1 wt% NiO is 1.277 × 10^?2 S cm^?1 and 8.24 × 10^?3 S cm^?1, respectively. However, compared with NiO, CuO has advantages in promoting hydration reaction and proton conduction of BZCYYb electrolyte.