Electrochemical Energy Conversion Research Articles

Enhancing the oxygen evolution reaction activity and stability of high-valent CoOOH by switching the catalytic pathway through doping low-valent Cu

The oxygen evolution reaction (OER) is a critical process in electrochemical energy storage and conversion systems. The adsorbate evolution mechanism (AEM) pathway possesses the characteristics of high stability but slow catalytic kinetics. We propose that combining AEM with the lattice oxidation mechanism (LOM) pathway can potentially enhance the OER catalytic activity and stability. However, the triggering of LOM is an important challenge due to the high thermodynamic activation barrier of lattice oxygen. To solve this problem, we performed theoretical calculations and experiments which suggest that the introduction of low-valent Cu in CoOOH (CuxCo1−xOOH) could directionally modulate the local coordination environment of CoO bonds. This approach can activate lattice oxygen and generate oxygen vacancies to enhance the nucleophilic attack of *OH and directly establish OO coupling, thereby facilitating the smoothly switching from AEM to LOM pathway by increasing voltage and thus activating lattice oxygen in CuxCo1−xOOH. The switching of AEM and LOM enables CuxCo1−xOOH showing an outstanding overpotential of only 252 mV (10 mA cm−2) and durability of only 2.80 % degradation after 280h. This work provides a new way for designing efficient and stable electrocatalysts with AEM and LOM pathway switching.

Design and regulation of defective electrocatalysts.

Electrocatalysts are the key components of electrochemical energy storage and conversion devices. High performance electrocatalysts can effectively reduce the energy barrier of the chemical reactions, thereby improving the conversion efficiency of energy devices. The electrocatalytic reaction mainly experiences adsorption and desorption of molecules (reactants, intermediates and products) on a catalyst surface, accompanied by charge transfer processes. Therefore, surface control of electrocatalysts plays a pivotal role in catalyst design and optimization. In recent years, many studies have revealed that the rational design and regulation of a defect structure can result in rearrangement of the atomic structure on the catalyst surface, thereby efficaciously promoting the electrocatalytic performance. However, the relationship between defects and catalytic properties still remains to be understood. In this review, the types of defects, synthesis methods and characterization techniques are comprehensively summarized, and then the intrinsic relationship between defects and electrocatalytic performance is discussed. Moreover, the application and development of defects are reviewed in detail. Finally, the challenges existing in defective electrocatalysts are summarized and prospected, and the future research direction is also suggested. We hope that this review will provide some principal guidance and reference for researchers engaged in defect and catalysis research, better help researchers understand the research status and development trends in the field of defects and catalysis, and expand the application of high-performance defective electrocatalysts to the field of electrocatalytic engineering.

Analysing the thermal and electrical properties of Cocos nucifera shell-based nanofluids as coolant feasibility proton exchange membrane fuel cell

For an enhancement of the thermal and electrical conductivity of the proton exchange membrane fuel cell (PEMFC), extensive research is actively conducted on various waste bio sources. PEMFC offers the cleanest form of energy, an electrochemical energy conversion device that possesses zero emissions with by-products such as heat and water. In PEMFC, conventional coolants such as water and water:ethylene glycol mixture does not attain the substantial results in terms of heat dissipation, which impacts performance gradually reduces the operating life of the cell. Usually, bio-sources are environmentally friendly and have merits over chemically prepared methods. Bio-based nanofluids have remarkable performance in terms of heat transfer, lower electrical conductivity, and low corrosiveness in the system compared to other metal-based fluids and base fluids, which have also gained a great deal of scrutiny over the past few decades. In this research, bio-sourced Cocos nucifera shell (CNS) is utilised at various concentrations, such as 0.1 vol.-%, 0.3 vol.-% and 0.5 vol.-%, dispersed with a base fluid such as water (W), and ethylene glycol (EG) (80:20) is analysed prior to actual full stack PEMFC. Consequently, heat transfer has been improved by 13% for CNS in 80:20 (W:EG) at 0.5% volume concentration compared with W:EG (80:20). On the basis of findings on thermal, hydraulic and electrical conductivity, various properties have also been determined. Despite the drawbacks of the experimental design, it was concluded that up to 0.5 vol.-% CNS in an 80:20 (W:EG) nanofluid could be used as a cooling medium for PEMFCs with no adverse effects on the electrical performance. It was also observed that the nanofluid improved the efficiency of the fuel cells by reducing the ohmic losses.

Recent advantages on mass transfer structure construction in transition metal‐based cost‐effective catalyst toward alkaline oxygen evolution

The electrochemical oxygen evolution reaction (OER) can be combined with various reactions to fabricate electrochemical energy conversion and storage devices while the slow kinetics and poor mass transfer capability at high current densities were the key constraints to its large‐scale application. Therefore, this review primarily focuses on design and optimization of mass transfer structures of TM‐metal‐based OER catalysts. Nanostructuring, porous design, and the creation of hierarchical architectures have been applied during catalyst synthesis to enhance the surface area and accessibility, thereby improving mass transfer and catalytic OER efficiency. Strategies including doping, substrate invitation, soft/hard templating has been utilized to accelerate mass transfer as well as the ion/electron conduction efficiency for the overall improvement of OER performance of the catalysts. These developments underline the critical role of advanced material design in achieving high‐performance OER catalysts and highlight the potential of TM‐based materials in cost‐effective and scalable applications.

Molten Salt-Assisted Synthesis of Catalysts for Energy Conversion.

A breakthrough in manufacturing procedures often enables people to obtain the desired functional materials. For the field of energy conversion, designing and constructing catalysts with high cost-effectiveness is urgently needed for commercial requirements. Herein, the molten salt-assisted synthesis (MSAS) strategy is emphasized, which combines the advantages of traditional solid and liquid phase synthesis of catalysts. It not only provides sufficient kinetic accessibility, but effectively controls the size, morphology, and crystal plane features of the product, thus possessing promising application prospects. Specifically, the selection and role of the molten salt system, as well as the mechanism of molten salt assistance are analyzed in depth. Then, the creation of the catalyst by the MSAS and the electrochemical energy conversion related application are introduced in detail. Finally, the key problems and countermeasures faced in breakthroughs are discussed and look forward to the future. Undoubtedly, this systematical review and insights here will promote the comprehensive understanding of the MSAS and further stimulate the generation of new and high efficiency catalysts.

Nanocarbons-Based Trifunctional Electrocatalysts for Overall Water Splitting and Metal-Air Batteries: Metal-Free and Hybrid Electrocatalysts.

Trifunctional electrocatalysts, an exciting class of materials that can simultaneously catalyze hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR), can significantly enhance the performance and economic viability of electrochemical energy storage and conversion technologies such as water-splitting electrolyzers, metal-air batteries, fuel cells and their integrated devices. Such multifunctional electrocatalysts encompass multiple active sites that can simultaneously catalyze two or more different electrochemical reactions and are feasible routes for addressing global energy and environmental challenges. This review accounts for nanocarbons-based trifunctional electrocatalysts reported for electrolyzers, metal-air batteries and integrated electrolyzer-battery systems, providing a practical perspective. Metal-free and hybrid (hybrids of nanocarbons and transition metals/compounds) trifunctional electrocatalysts are covered. Given the growing importance of green technologies, we discuss biomass-derived carbon-based trifunctional electrocatalysts separately. The collective information provided in the review could help researchers derive more effective and durable trifunctional electrocatalysts suitable for commercial use.

Building aluminium-air battery on waste paper for DIY learning

Abstract Environmental sustainability and the effective use of renewable resources are critical subjects that need to be integrated into our educational systems through practical, hands-on learning. This paper focuses on the fabrication of aluminium-air batteries using waste materials, providing an innovative and cost-effective DIY approach to energy storage education. Utilizing aluminium from food packaging and graphite from pencils, this study demonstrates the construction and functionality of an aluminium-air battery to run an LED, highlighting its potential applications in educational settings and low-cost energy solutions. The paper aims to inspire the adoption of environmentally friendly practices and enhance students’ understanding of electrochemical energy conversion through accessible and engaging DIY projects.

Ni-incorporated N-doped graphitic carbon derived from pomegranate peel biowaste as an efficient OER and HER electrocatalyst for sustainable water splitting

The electrochemical energy conversion process must develop effective, long-lasting, and reasonably priced bifunctional electrocatalysts for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). In this work, we present a simple, sustainable, economical, and scalable method for the preparation of stable and useful nickel nanoparticles on highly porous graphitic carbon doped with nitrogen. Direct pyrolysis followed by carbonization was used to create robust catalysts at different temperatures in an environment containing nitrogen (N2). The carbon material generated at 600 °C (Ni@NPC-600) shows greater electrochemical efficiency when compared to other catalysts. The synthesized electroactive catalyst Ni@NPC-600 requires a less overpotential 280 mV (114 mV dec−1) for OER and 151 mV (98 mV dec−1) to conduct a HER at 10 mA cm−2 in 1 M KOH. The active catalyst Ni@NPC-600 shows long-lasting robustness over 90 h with a current loss of <3.33 % and <4.9 % for OER and HER respectively. In addition, the overall water disintegration of Ni@NPC-600/NF//Ni@NPC-600/NF was achieved at 1.51 V with a continuous evolution of H2 and O2 at the cathode and anode respectively for approximately 150 h of prolonged robustness with a current reduction of < 4.6 %.

Sulfur vacancy riched pure 2H phase VS2 for efficient electrocatalytic hydrogen evolution

Vanadium disulfide (VS2), a typical metallic layered transition metal chalcogenide (TMC), has been widely concerned for its high electrical conductivity and reactivity in electrochemical energy storage and conversion applications. The 2H phase VS2 is expected to exhibit high electrocatalytic activity and be more stable for hydrogen evolution reaction (HER) than the 1T phase structure. But at present, there still lacks a facile method to prepare pure 2H phase VS2. Herein, we successfully prepared pure 2H–VS2 through a simple one-step low-temperature hydrothermal method. We have investigated the effect of the hydrothermal reaction conditions (including the proportion of raw materials and hydrothermal reaction temperatures) on the phase composition and microstructure. Under the optimal condition of 140°C-24 h with a vanadium sulfur ratio of 1:5, a nano-flower-like 2H–VS2 material with high crystallinity and rich sulfur vacancy defects was obtained. Leveraging these structural advantages, as a demonstration, the product exhibits excellent electrocatalytic HER activity (with η10 of 181 mV, Tafel slope of 52 mV dec−1, and J0 of 67.9 × 10−3 mA cm−2) and stability (it can continuously produce hydrogen for 20 h at a current density of 50 mA cm−2 with ultra-small increased potential of less than 5 mV). This work provides a new way for constructing atomic vacancy defects in layered TMCs for efficient electrocatalysis and is also expected to promote the research of the basic properties of high phase purity TMCs.

Engineered Two-Dimensional Transition Metal Dichalcogenides for Energy Conversion and Storage.

Designing efficient and cost-effective materials is pivotal to solving the key scientific and technological challenges at the interface of energy, environment, and sustainability for achieving NetZero. Two-dimensional transition metal dichalcogenides (2D TMDs) represent a unique class of materials that have catered to a myriad of energy conversion and storage (ECS) applications. Their uniqueness arises from their ultra-thin nature, high fractions of atoms residing on surfaces, rich chemical compositions featuring diverse metals and chalcogens, and remarkable tunability across multiple length scales. Specifically, the rich electronic/electrical, optical, and thermal properties of 2D TMDs have been widely exploited for electrochemical energy conversion (e.g., electrocatalytic water splitting), and storage (e.g., anodes in alkali ion batteries and supercapacitors), photocatalysis, photovoltaic devices, and thermoelectric applications. Furthermore, their properties and performances can be greatly boosted by judicious structural and chemical tuning through phase, size, composition, defect, dopant, topological, and heterostructure engineering. The challenge, however, is to design and control such engineering levers, optimally and specifically, to maximize performance outcomes for targeted applications. In this review we discuss, highlight, and provide insights on the significant advancements and ongoing research directions in the design and engineering approaches of 2D TMDs for improving their performance and potential in ECS applications.

Porous Transport Layers with Laser Micropatterning for Enhanced Mass Transport in PEM Water Electrolyzers.

Efficient electrochemical energy conversion technologies, such as fuel cells and water electrolyzers, require high current densities to lower the capital cost for large-scale commercialization but are often limited by mass transport. In this study, we demonstrated exceptional electrochemical performances in proton electrolyte membrane water electrolyzers (PEMWEs) creating micropatterned pore channels in the porous transport layer (MPC PTL) using a picosecond laser. This approach yielded an impressive performance of 1.82 V @ 2 A·cm-2, which is better than commercial PTL of 1.90 V @ 2 A cm-2. The significant performance enhancement is attributed to the micropatterned porous channel structure, facilitating the efficient expulsion of oxygen bubbles and input of reactant water. This work provides valuable insights for the design of PTL responsible for biphasic transport in electrochemical energy conversion technologies.

Diurnal humidity cycle driven selective ion transport across clustered polycation membrane

The ability to manipulate the flux of ions across membranes is a key aspect of diverse sectors including water desalination, blood ion monitoring, purification, electrochemical energy conversion and storage. Here we illustrate the potential of using daily changes in environmental humidity as a continuous driving force for generating selective ion flux. Specifically, self-assembled membranes featuring channels composed of polycation clusters are sandwiched between two layers of ionic liquids. One ionic liquid layer is kept isolated from the ambient air, whereas the other is exposed directly to the environment. When in contact with ambient air, the device showcases its capacity to spontaneously produce ion current, with promising power density. This result stems from the moisture content difference of ionic liquid layers across the membrane caused by the ongoing process of moisture absorption/desorption, which instigates selective transmembrane ion flux. Cation flux across the polycation clusters is greatly inhibited because of intensified charge repulsion. However, anions transport across polycation clusters is amplified. Our research underscores the potential of daily cycling humidity as a reliable energy source to trigger ion current and convert it into electrical current.

Protonic conduction on oxide surfaces—role and applications in electrochemical energy conversion

Abstract Protonic conduction on surfaces of oxides has over the last two decades drawn attention for its possible utilisation in electrolytes for energy conversion at low temperatures and for its roles in enhancement of catalytic activity. This has led to deeper investigation and increased understanding of the phenomenon and development of quantifiable models. Along with this has emerged apparent demonstrations of use of such conduction in low-drain fuel cells as well as acknowledgement of the role of surface protonic conduction in electrodes for solid-state electrochemical and photoelectrochemical cells. Here is provided a brief review and elaboration of the fundamentals of the interaction of water and hydrogen with oxide surfaces, and models for the resulting protonic conduction in chemisorbed and physisorbed layers. We finally discuss aspects of surface protonic conduction in a range of applications, including sensors, catalysis, and electrochemical and photoelectrochemical energy conversion.

Investigating the impact of various etching agents on Ti3C2Tx MXene synthesis for electrochemical energy conversion

MXenes represent a revolutionary class of two-dimensional (2D) materials that have garnered significant attention due to their unique properties, including excellent electrical conductivity, and remarkable mechanical strength. This study investigates the influence of different etching agents on the synthesis of MXenes for electrochemical energy conversion applications, particularly in methanol oxidation reactions (MOR). Morphological characterization, particle distribution and sizing, elemental analysis, and surface chemistry assessments were conducted using field emission scanning electron microscopy (FESEM), elemental mapping, transmission electron microscopy (TEM), x-ray diffraction (XRD), and x-ray photoelectron spectroscopy (XPS). Electrochemical techniques such as cyclic voltammetry (CV), electrochemical active surface area (ECSA), Tafel analysis, electrochemical impedance spectroscopy (EIS), and long-term stability assessment were employed. The study reveals that PtRu/MXene synthesized with the FeF3/HCl etching route exhibits the highest ECSA value and peak current density, being 12.3 times and 3.63 times higher than those achieved via the LiF/HCl etching route. The kinetic rate, tolerance to catalyst poisoning and long-term stability also show the better results for this etching route. These findings suggest promising potential for PtRu/MXene_FeF3/HCl as an effective anodic electrocatalyst in direct methanol fuel cell (DMFC) applications.

Hydrogels and Aerogels for Versatile Photo-/Electro-Chemical and Energy-Related Applications.

The development of photo-/electro-chemical and flexible electronics has stimulated research in catalysis, informatics, biomedicine, energy conversion, and storage applications. Gels (e.g., aerogel, hydrogel) comprise a range of polymers with three-dimensional (3D) network structures, where hydrophilic polyacrylamide, polyvinyl alcohol, copolymers, and hydroxides are the most widely studied for hydrogels, whereas 3D graphene, carbon, organic, and inorganic networks are widely studied for aerogels. Encapsulation of functional species with hydrogel building blocks can modify the optoelectronic, physicochemical, and mechanical properties. In addition, aerogels are a set of nanoporous or microporous 3D networks that bridge the macro- and nano-world. Different architectures modulate properties and have been adopted as a backbone substrate, enriching active sites and surface areas for photo-/electro-chemical energy conversion and storage applications. Fabrication via sol-gel processes, module assembly, and template routes have responded to professionalized features and enhanced performance. This review presents the most studied hydrogel materials, the classification of aerogel materials, and their applications in flexible sensors, batteries, supercapacitors, catalysis, biomedical, thermal insulation, etc.

Unraveling the Mechanism of Covalent Organic Frameworks-Based Functional Separators in High-Energy Batteries.

Covalent organic frameworks (COFs) are promising porous materials due to their high specific surface area, adjustable structure, highly ordered nanochannels, and abundant functional groups, which brings about wide applications in the field of gas adsorption, hydrogen storage, optics, and so forth. In recent years, COFs have attracted considerable attention in electrochemical energy storage and conversion. Specifically, COF-based functional separators are ideal candidates for addressing the ionic transport-related issues in high-energy batteries, such as dendritic formation and shuttle effect. Therefore, it is necessary to make a comprehensive understanding of the mechanism of COFs in functional separators. In this review, the advantages, applications as well as synthesis of COFs are firstly presented. Then, the mechanism of COFs in functional separators for high-energy batteries is summarized in detail, including pore channels regulating ionic transport, functional groups regulating ionic transport, adsorption effect, and catalytic effect. Finally, the application prospect of COFs-based separators in high-energy batteries is proposed. This review may provide new insights into the design of functional separators for advanced electrochemical energy storage and conversion systems.

In-Situ Sulfuration of CoAl Metal-Organic Framework for Enhanced Supercapacitor Properties.

Designing efficient electrode materials is necessary for supercapacitors but remains highly challenging. Herein, cobalt sulfide with crystalline/amorphous heterophase (denoted as Co(Al)S) derived from an Al metal-organic framework was constructed by ion exchange/acid etching and subsequent sulfidation strategy. It was found that rational sulfidation by adjusting the sulfur source concentration to a suitable level was favorable to form a 3D nanosheet-interconnected network architecture with a large specific surface area, which promoted ion/electron transport and charge separation. Benefiting from the features of the unique network structure and heterophase accompanied by aluminum, nitrogen and carbon coordinated in amorphous phase, the optimal Co(Al)S(10) exhibited a high specific capacity (1791.8 C g-1 at 1 A g-1), an outstanding rate capability and an excellent cycling stability. Furthermore, the as-assembled Co(Al)S//AC device afforded an energy density of 72.3 Wh kg-1 at a power density of 750 W kg-1, verifying that the Co(Al)S was a promising material for energy storage devices. The developed scheme is expected to promote the application of MOF-derived electrode materials in electrochemical energy storage and conversion fields.

Enhanced catalytic activity of novel sea urchin-like spinel for advanced electrochemical energy conversion

Through precise morphological engineering, novel sea urchin-like spinel NiCo2O4 (NCO) was successfully synthesized and thoroughly investigated as a bifunctional electrode for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). In contrast to traditional NCO, the distinctive scattered nanofiber microstructure of NCO prepared via hydrothermal at 100 ℃ (HT100) increases the specific surface area, introduces more oxygen vacancies, reduces the bandgap, enhances the diffusion, adsorption, and dissociation processes of oxygen molecules, thereby promoting rapid electron transfer and augmenting the number of active sites for both ORR and OER. At 800 °C, under the ORR model, NCO-HT100 exhibits an impressive output performance of 920 mW cm−2, surpassing traditional NCO by 47.8 %. Simultaneously, under the OER model, NCO-HT100 achieves a current density of 134.29 mA cm−2. Compared with conventional NCO, sea urchin-like NCO-HT100 displays lower Tafel slopes and overpotentials in alkaline solution at room temperature, indicating superior OER performance. These findings highlight that the sea urchin-like NCO-HT100 stands out as an advanced bifunctional electrode material for both ORR and OER. The insights gained from this research provide pivotal guidance for the future development of multifunctional electrode materials in energy conversion device applications.

(Invited) Computational Models of Proton-Coupled Electron Transfer in Energy Conversion and Storage

Proton-coupled electron transfer (PCET) is a fundamental class of chemical reactions that is central to many electrochemical energy conversion and storage processes. In this talk, I will discuss recent theoretical model development for interfacial and intermolecular PCET reactions. First, I will describe a rate constant model for the reaction between reduced anatase TiO2 surfaces and a 4-MeO-TEMPO nitroxyl radical. The rate constants are modeled using vibronically nonadiabatic PCET theory, where the transferring proton and electron are treated quantum mechanically. Hybrid functional periodic density functional theory (DFT) calculations are used to derive model parameters such as driving forces, reorganization energies, and proton vibrational wavefunctions. This modeling strategy highlights the role of inner-sphere bond reorganization and excited vibronic states on the PCET reactivity of metal oxides. Next, I will show how similar computational approaches can be used to predict whether electrochemical PCET is likely to proceed through concerted electron–proton transfer or sequential electron transfer and proton transfer steps. Using PCET reactions between redox-active quinones and functionalized imidazole bases as an example, mechanistic predictions are informed by DFT-calculated potential energy surfaces. These PCET modeling strategies have broad applicability to kinetic studies of electrochemical energy conversion and storage processes.

Modeling Interfacial Proton-Coupled Electron Transfer Reactions Involving Imidazolium Proton Donors

Proton-coupled electron transfer (PCET) is an elementary reaction that plays a pivotal role in various electrochemical energy conversion and storage processes. PCET reactions involving nonaqueous proton donors are of interest for applications in energy storage such as redox flow batteries, as well as in CO2 and O2 reduction catalysis. Yet, there remains much to be understood about the molecular reactivity of these systems. In this talk, I will describe periodic density functional theory (DFT) studies of interfacial PCET reactions involving different imidazolium proton donors on Pt(111) electrode surfaces.The imidazole conjugate bases adsorb strongly to the electrode surface; however, this adsorption behavior varies with isomers that feature distinct proton positions and with different functional substituent groups. Because the adsorption of imidazole conjugate bases could affect reactivity, these models are used as a foundation to understand the intrinsic PCET kinetics of these systems. The Volmer and Heyrovsky steps of hydrogen evolution reaction are two of the most basic heterogeneous electrochemical PCET reactions and are therefore chosen as model interfacial PCET reactions in this study. Potential-dependent reaction energies and activation barriers are calculated using the charge extrapolation method, where the electrode potential is tuned by modifying proton coverage for different-sized unit cells. This approach is used to develop relationships between PCET reaction thermodynamics and kinetics through Brønsted–Evans–Polanyi (BEP) relationships for different imidazoles, where BEP slopes are analogs to charge transfer coefficients in the Butler–Volmer equation. Investigating reaction parameters influencing charge transfer kinetics at the electrode-electrolyte interface is crucial for designing efficient energy storage systems, impacting overall device performance. These studies show trends in the kinetic behavior of different functionalized imidazoles, which can aid in the design of catalytic and energy storage systems.