Electrochemical Energy Conversion Devices Research Articles

A comprehensive review on developments and future perspectives of biopolymer‐based materials for energy storage

AbstractDriven by the escalating environmental impact of synthetic materials, there has been a growing focus on employing eco‐sustainable biomass‐derived biopolymers and native materials as a viable alternative to traditional energy storage applications. Biopolymer‐based energy devices, like batteries, supercapacitors, electrode materials, and ion‐exchange membranes, a novel and eco‐conscious approach, hold great potential for flexible and smart electrochemical energy storage and conversion devices, owing to their affordability, environmental sustainability, and biodegradability. This critical review outlines the sources and properties of biopolymers leading to energy storage and emphasizes their utilization in the energy sector. Despite their inherent constraints, biopolymers can be effectively leveraged when combined with other materials in composites. This collaborative approach not only refines their intrinsic physical attributes but also elevates the electrochemical performance of biologically active molecules. In this regard, bionanocomposites, a class of materials combining biopolymers and nanoparticles, have emerged as a promising greener alternative to conventional petroleum‐based polymers. Their biocompatibility, biodegradability, and antimicrobial properties have promoted their increased commercialization, thus paving the way for a more sustainable future. The review concludes by identifying and effectively addressing the limitations, challenges, and future perspectives of biopolymers in energy storage applications.

Shear Field-Controlled Synthesis of Nitrogen-Doped Carbon Nanochains Forest with High-Density sp3 Defects for Efficient CO2 Electroreduction Reaction.

Defect engineering and nitrogen doping being effective strategies for modulating the surface chemical state of the carbon matrix have been widely explored to promote the catalytic activity in the territory of electrochemical energy storage and conversion devices. However, the controllable synthesis of carbon material with high-density specific defects and high nitrogen doping is still full of challenges. Here, we first synthesize one-dimensional necklace-like nitrogen-doped carbon nanochains (N-CNCs) with abundant defects on carbon fiber paper (CFP) by chemical vapor deposition (CVD) method. The resultant nanostructures are a bunch of interconnected carbon spheres with a hollow structure at the internode and present the complete one-dimensional nanochain configuration. Specifically, the N-CNCs with a corrugated surface possesses high content of sp3 defects (31.2%) and nitrogen (23.6 at %). Combining finite element analysis and experimental results, it reveals that the robust shear field generated by etching gas releasing from thermal decomposition of melamine in situ modulates the CVD process via changing the size and force environment of the metal catalyst droplets for formation of N-CNCs. Benefiting from the high ratio of sp3/sp2 and nitrogen doped on the surface, the N-CNCs@CFP displays a superior electrocatalytic performance for CO2RR, delivering CO Faradaic efficiency of 95.9% and a current density of 23.2 mA cm-2 at -0.86 V vs RHE. This work provides promising synthesis strategy and some inspirations for construction of ultradense and specific defects coupling with nitrogen doping sites into carbon materials to achieve high-efficiency electrocatalysis applications.

An organic proton cage that is ultra-resistant to hydroxide-promoted degradation

Alkaline polymer membrane electrochemical energy conversion devices offer the prospect of using non-platinum group catalysts. However, their cationic functionalities are currently not sufficiently stable for vapor-phase applications, such as fuel cells. Herein, we report 1,6-diazabicyclo[4.4.4]tetradecan-1,6-ium (in-DBD), a cationic proton cage, that is orders of magnitude more resistant to hydroxide-promoted degradation than state-of-the-art organic cations under ultra-dry conditions and elevated temperature, and the first organic cation-hydroxide to persist at critically low hydration levels ( < 10% RH at 80 °C). This high stability against hydroxide-promoted degradation is due to the unique combination of endohedral protection and intra-bridgehead hydrogen bonding that prevents the removal of the inter-cavity proton and lowers the susceptibility to Hofmann elimination. We anticipate this discovery will facilitate a step-change in the advancement of materials and electrochemical devices utilizing anion-exchange membranes based on in-DBD that will enable stable operation under extreme alkaline conditions.

Anion exchange membranes derived from poly(ionic liquid) of poly(bis-piperidinium) and polybenzimidazole blends

Anion exchange membranes (AEMs) play a critical role in various environmentally friendly electrochemical energy conversion and storage devices such fuel cells, water electrolysis and flow batteries. Recently, AEMs based on ether-free ionomers or ionenes have attracted much attention due to their excellent alkaline stabilities, however normally suffering from multiple-step synthetic procedure, post-functionalization and the use of precious metal catalysts. In this study, we develop a facile method to synthesize bis-piperidinium main-chain poly(ionic liquid)s devoid of ether linkages through the nucleophilic reaction between a bis-piperidine monomer of 4,4′-trimethylene bis(1-methyl-piperidine) and various bifunctional alkyl or aryl bromides. Seven poly(ionic liquid)s of poly(bis-alkyl piperidinium) are subsequently blended with polybenzimidazole (PBI) to give mechanically robust and dimensionally stable AEMs. The membrane performances are readily adjusted by changing the chemical structure of poly(bis-alkyl piperidinium)s. The membrane based on the poly(bis-alkyl piperidinium) containing a flexible butylidene spacer chain achieves the highest Br- conductivity of 67 mS cm−1 at 80 °C, tensile strength of around 13 MPa at room temperature, and a superior alkaline stability in 1 mol/L KOH at 60 °C during 1250 h. Density functional theory calculations further support the enhanced alkaline stability of the piperidinium cation with alkyl group compared with the one with benzyl group.

Lattice Oxygen Redox Mechanisms in the Alkaline Oxygen Evolution Reaction

AbstractUnderstanding of fundamental mechanism and kinetics of the oxygen evolution reaction (OER) is pivotal for designing efficient OER electrocatalysts owing to its key role in electrochemical energy conversion devices. In the past few years, the lattice oxygen oxidation mechanism (LOM) arising from the anodic redox chemistry has attracted significant attention as it involves a direct O─O coupling and thus bypasses thermodynamic limitations in the traditional adsorbate evolution mechanism (AEM). Transition metal‐based oxyhydroxides are generally acknowledged as the real catalytic phase in alkaline media. In particular, their low‐dimensional layered structures offer sufficient structural flexibility to trigger the LOM. Herein, a comprehensive overview is provided for recent advances in anion redox from LOM‐based electrocatalysts. Based on analyses of electronic structure of electrocatalysts and LOM, a strategy is proposed to activate LOM. Possible identification techniques for corroboration of the oxygen redox are also reviewed. In addition, the structural reconstruction process induced by the LOM is focused and the importance of multiple in situ/operando characterizations is highlighted to unveil the structural and chemical origins of the LOM. To conclude, a prospect on the remaining challenges and future opportunities for LOM electrocatalysts is presented.

Medium-entropy perovskite Pr0.4Ba0.2Ca0.2La0.2Co0.2Fe0.8O3 as a promising bifunctional electrocatalyst for electrochemical energy conversion device

Reversible solid oxide cells (R-SOCs) are considered to be a promising energy conversion device that can achieve efficient conversion between fuel and electrical energy. However, there are still significant challenges in developing a promising bifunctional electrocatalyst as an electrode material for R-SOC devices. Here, a medium-entropy perovskite Pr0.4Ba0.2Ca0.2La0.2Co0.2Fe0.8O3 (PBCLCF) is designed to enhance the electrochemical oxidation and reduction activity. Under hydrogen atmosphere, cobalt metals are in situ exsolved from the perovskite structure, accompanied by partial phase transformation (denoted as R-PBCLCF). Characterizations show that PBCLCF and R-PBCLCF can increase the concentration of oxygen vacancies, thereby enhancing oxygen migration ability. Combined with electrochemical impedance spectroscopy (EIS) and distribution of relaxation times (DRT) analysis, the medium-entropy PBCLCF exhibits better oxygen reduction reaction (ORR) activity and R-PBCLCF shows better hydrogen oxidation reaction (HOR) activity. Furthermore, the oxygen dissociation is identified as the rate-determining step (RDS) in the ORR process, whereas the HOR process is dominated by the hydrogen adsorption and dissociation. The single cell with (R-)PBCLCF showcases remarkable reversible performance. When O2 is employed as the oxidant and H2 as the fuel, this cell achieves a maximum power density of 468.1 mW cm−2 in solid oxide fuel cell (SOFC) mode at 700 °C. Moreover, when O2 is employed as the oxidant and humidified H2 (30 %H2O) as the fuel, the current density of the cell in solid oxide electrolysis cell (SOEC) mode is −647.3 mA cm−2 at 1.3 V and 700 °C.

MAX Phase (Nb4 AlC3 ) For Electrocatalysis Applications.

In search for novel materials to replace noble metal-based electrocatalysts in electrochemical energy conversion and storage devices, special attention is given to a distinct class of materials, MAX phase that combines advantages of ceramic and metallic properties. Herein, Nb4 AlC3 MAX phase is prepared by a solid-state mixing reaction and characterized morphologically and structurally by transmission and scanning electron microscopy with energy-dispersive X-ray spectroscopy, nitrogen-sorption, X-ray diffraction analysis, X-ray photoelectron and Raman spectroscopy. Electrochemical performance of Nb4 AlC3 in terms of capacitance as well as for oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER) is evaluated in different electrolytes. The specific capacitance Cs of 66.4, 55.0, and 46.0 F g-1 at 5mV s-1 is determined for acidic, neutral and alkaline medium, respectively. Continuous cycling reveals high capacitance retention in three electrolyte media; moreover, increase of capacitance is observed in acidic and neutral media. The electrochemical impedance spectroscopyshowed a low charge transfer resistance of 64.76 Ω cm2 that resulted in better performance for HER in acidic medium (Tafel slope of 60mV dec-1 ). In alkaline media, the charge storage value in the double layer is 360 mF cm-2 (0.7V versus reversible hydrogen electrode) and the best ORR performance of the Nb4 AlC3 is achieved in this medium (Tafel slope of 126mV dec-1 ).

Complementary probes for the electrochemical interface.

The functions of electrochemical energy conversion and storage devices rely on the dynamic junction between a solid and a fluid: the electrochemical interface (EI). Many experimental techniques have been developed to probe the EI, but they provide only a partial picture. Building a full mechanistic understanding requires combining multiple probes, either successively or simultaneously. However, such combinations lead to important technical and theoretical challenges. In this Review, we focus on complementary optoelectronic probes and modelling to address the EI across different timescales and spatial scales - including mapping surface reconstruction, reactants and reaction modulators during operation. We discuss how combining these probes can facilitate a predictive design of the EI when closely integrated with theory.

Small but mighty: Empowering sodium/potassium‐ion battery performance with S‐doped SnO2 quantum dots embedded in N, S codoped carbon fiber network

AbstractSnO2 has been extensively investigated as an anode material for sodium‐ion batteries (SIBs) and potassium‐ion batteries (PIBs) due to its high Na/K storage capacity, high abundance, and low toxicity. However, the sluggish reaction kinetics, low electronic conductivity, and large volume changes during charge and discharge hinder the practical applications of SnO2‐based electrodes for SIBs and PIBs. Engineering rational structures with fast charge/ion transfer and robust stability is important to overcoming these challenges. Herein, S‐doped SnO2 (S–SnO2) quantum dots (QDs) (≈3 nm) encapsulated in an N, S codoped carbon fiber networks (S–SnO2–CFN) are rationally fabricated using a sequential freeze‐drying, calcination, and S‐doping strategy. Experimental analysis and density functional theory calculations reveal that the integration of S–SnO2 QDs with N, S codoped carbon fiber network remarkably decreases the adsorption energies of Na/K atoms in the interlayer of SnO2–CFN, and the S doping can increase the conductivity of SnO2, thereby enhancing the ion transfer kinetics. The synergistic interaction between S–SnO2 QDs and N, S codoped carbon fiber network results in a composite with fast Na+/K+ storage and extraordinary long‐term cyclability. Specifically, the S–SnO2–CFN delivers high rate capacities of 141.0 mAh g−1 at 20 A g−1 in SIBs and 102.8 mAh g−1 at 10 A g−1 in PIBs. Impressively, it delivers ultra‐stable sodium storage up to 10,000 cycles at 5 A g−1 and potassium storage up to 5000 cycles at 2 A g−1. This study provides insights into constructing metal oxide‐based carbon fiber network structures for high‐performance electrochemical energy storage and conversion devices.

Effects of Anions and Surface Structure on Pt Single Crystal Dissolution in Acidic Electrolytes

AbstractUnderstanding the mechanisms of Pt dissolution with well‐defined surfaces is vital for developing stable catalysts for electrochemical energy conversion devices such as fuel cells. This work investigates Pt dissolution from low‐index single crystals in perchlorate, sulfate, and methanesulfonate acid solutions by on‐line inductively coupled plasma mass spectrometry (ICP‐MS), and the results are correlated with surface X‐ray diffraction (SXRD) studies. The previously reported stability trend Pt(111)&gt;Pt(100)&gt;Pt(110) in HClO4 was confirmed for the other acids. The application of electrochemical protocols up to high potential values demonstrated that dissolution for Pt(100) increases to a lower extent than for the other planes. Dissolution is affected by the nature of the anion, especially for Pt(111), with the dissolution rate increasing in the order H2SO4&gt;MSA&gt;HClO4. This influence could be due to the interaction strength of the anion with Pt and its complexing ability or different ratios of the surface coverage of different oxide species. For Pt(111), SXRD measurements show different onset potentials for extraction in HClO4 and H2SO4, which can influence the dissolution processes. These results demonstrate that fundamental studies are necessary to improve the current knowledge about Pt dissolution and how to hinder it to a practical extent.

Surface Tailoring-Modulated Bifunctional Oxygen Electrocatalysis with CoP for Rechargeable Zn-Air Battery and Water Splitting.

The transition metal phosphide (TMP)-based functional electrocatalysts are very promising for the development of electrochemical energy conversion and storage devices including rechargeable metal-air batteries and water electrolyzer. Tuning the electrocatalytic activity of TMPs is one of the vital steps to achieve the desired performance of these energy devices. Herein, we demonstrate the modulation of the bifunctional oxygen electrocatalytic activity of nitrogen-doped carbon-encapsulated CoP (CoP@NC) nanostructures by surface tailoring with ultralow amount (0.56 atomic %) of Ru nanoparticles (2.5 nm). The CoP at the core and the Ru nanoparticles on the shell have a facile charge transfer interaction with the encapsulating NC. The strong coupling of Ru with CoP@NC boosts the electrocatalytic performance toward oxygen reduction (ORR), oxygen evolution (OER), and hydrogen evolution (HER) reactions. The surface-tailored catalyst requires only 35 mV to deliver the benchmark current density of 10 mA·cm-2 for HER. A small potential gap of 620 mV between ORR and OER is achieved, making the catalyst highly suitable for the development of rechargeable zinc-air batteries (ZABs). The homemade ZAB delivers a specific capacity of 780 mA·hgZn-1 and peak power density of 175 mW·cm-2 with a very small voltaic efficiency loss (1.1%) after 300 cycles. The two-electrode water splitting cell (CoP@NC-Ru||CoP@NC-Ru) delivers remarkably low cell voltage of 1.47 V at the benchmark current density. Stable current density of 25 mA·cm-2 for 25 h without any significant change is achieved. Theoretical studies support the charge transfer interaction-induced enhanced electrocatalytic activity of the surface-tailored nanostructure.

Beyond Small Molecular Cations: Elucidating the Alkaline Stability of Cationic Moieties at the Membrane Scale.

A major hindrance in the commercialization of alkaline polyelectrolyte-based electrochemical energy conversion devices is the development of durable anion exchange membranes (AEMs). Despite many alkali-stable cations that have been explored, the stability of these cationic moieties at the membrane scale is in the blind. Herein, we present a molecularly designed polyaromatic AEM with cationic moieties in an alternating manner to unbiasedly compare the alkaline stability of piperidinium and ammonium groups at the membrane state. Using nuclear magnetic resonance spectroscopy, we demonstrate that the pentyltrimethyl group is about 2-fold more stable than piperidinium within a polyaromatic scaffold, either in ex-situ alkaline soaking or in-situ cell operation. This finding challenges the judgment extrapolated from the stability trend of cations, that is, the piperidinium-functionalized AEM is more alkali-stable than the counterparts based on quaternary ammoniums. Moreover, the deterioration mechanism of piperidinium moiety after being embedded in polyaromatic backbone is rationalized by density functional theory.

Self-assembled monolayers for electrostatic electrocatalysis and enhanced electrode stability in thermogalvanic cells.

Waste heat is ubiquitous; as such, sustainable and long-lasting devices are required to convert it into more useful forms of energy that can make use of this abundant potential resource. Thermogalvanic cells (or thermocells) can use the thermoelectrochemical properties of redox couples to achieve this; entropy-driven redox reactions allow them to act as liquid thermoelectrics. However, excellent electrocatalysis at the electrode surface is required for optimum conversion efficiency. Serendipitous observation of Nafion-based electrocatalysis prompted the exploration of electrostatically charged self-assembled monolayers (SAMs) inside a thermocell. Both electrostatic electrocatalysis and improved electrode stability were observed; in an aqueous K3[Fe(CN)6]/K4[Fe(CN)6]-based cell, modification with (3-trimethylammonium bromide)thiopropane resulted in higher electrical power, and protection against [Fe(CN)6]3-/4--induced gold passivation, relative to bare gold. Molecular-based electrostatic electrocatalysis could be an alternative to precious metal-based nanomaterial electrocatalysis, and could be integrated with (nano)carbon-based electrodes to further enhance the ability of thermogalvanic and other electrochemical energy conversion devices, e.g. redox flow batteries.

Linking the ionomer film morphology and nanoscale oxygen transport properties in fuel cells

Transport processes are crucial for the performance of electrochemical energy conversion devices and attract wide attentions. This work focuses on the critical oxygen transport process in the ionomer electrolyte film on a Pt electrode, which highly limits the performance of low Pt-loading fuel cells. Reduction of oxygen transport resistance may be achieved by optimizing the ionomer film morphology. Therefore, the relationship between ionomer film morphology and oxygen transport characteristics is explored by altering ionomer side chain lengths in this work. The results show that the swollen structure with larger water agglomerates in the ionomer film with shorter ionomer side chains is detrimental to the formation of oxygen transport paths. However, the multilamellar structure with an alternating alignment of water agglomerates and PFSA ionomer agglomerates in the ionomer film with longer ionomer side chains has a larger water-PFSA interface, which provides more oxygen transport paths and thus reduces the oxygen transport resistance. This work inspires the novel design concept of the ionomer electrolyte film with low local oxygen transport resistance, i.e., enlarging the water-PFSA interface parallel to the oxygen transport direction via altering the ionomer material properties, which is valuable for the development of low Pt-loading fuel cells.

(Invited) Electrochemical Characterization of Catalyst/Ionomer Interfaces

Electrochemical energy conversion devices such as polymer-electrolyte fuel cells, water-splitting or carbon dioxide reduction electrolyzers, utilize ionically-conductive polymers (ionomers) in their electrode structure where an ionomer forms interfaces with the catalysts. The ionomers exist as nanometer-thick film to cover the catalyst particles and act as a binder while enabling the transport of active species necessary for the reactions. While the nature of species and operational environment differs across these devices, their overall efficiency and performance is influenced by the electrode architecture, where the interfaces and interactions between the ionomers and catalysts play an important role. In hydrogen technologies, for example, ionomer thin films bind the catalyst sites and carbon supports to facilitate transport of ionic (e.g. protons), liquid (water) and gaseous (e.g., oxygen) species under a nano-confined environment. Such confinement effects not only change the ionomer structure and properties, usually with a tendency to increase transport resistances, but also amplify the impact of the electrocatalyst-ionomer interactions in the electrodes, thereby reducing the catalyst activity. Thus, understanding the behavior of nano-confined ionomers and their interactions with the catalyst surfaces is key for mitigating the transport resistances in catalyst ionomers and improving the electrode performance and cell efficiency.This talk will provide insights into electrochemical characterization of catalyst ionomers by focusing on varying chemistries of perfluorosulfonated cation-exchange ionomers with additional examples of anion-exchange ionomers for emerging technologies. The hydration and transport properties of proton-exchange catalyst-ionomers will be examined with the effects of chemistry, processing and thickness (degree of confinement), along with their impact on the morphological changes governing the film function. Through a systematic variation of material chemistries and environmental parameters, primary factors impacting the structure-property relationship of catalyst ionomers are described along with a discussion of secondary factors altering the cation-anion interactions. Then, the interplay between the effects of chemistry and ion exchange (capacity) on modifying the transport function and the strength of ionomer-catalyst interactions will be presented. The results will be collated to elucidate the underlying origins of the transport resistances occurring in electrodes, and to develop materials and processing strategies for their mitigation for improved performance and efficiency in electrochemical energy devices.

Measuring three-dimensional bubble dynamics for hydrogen production via water electrolysis

The commercialization of mass hydrogen production via water electrolysis is presently limited by low operational current densities. The optimal performance of electrolysis cells is significantly influenced by the substantial formation and residence of bubbles at high current densities. Thus, it is crucial to design electrodes with the ability for rapid bubble discharge to ensure appropriate bubble management. However, the quantitative volumetric measurements required to determine the bubble discharge ability of an electrode are not yet sufficiently accurate. This paper describes a quantitative volumetric method that combines a stereoscopic shadowgraph imaging system with particle tracking velocimetry (PTV) to measure the three-dimensional position, size, and velocity of micrometer-sized bubbles. The proposed method successfully captures hydrogen bubbles larger than 30 μm bubbles in an alkaline water electrolyzer. Considering the different luminance patterns of small bubbles (r ≤ 4 pixels) and large bubbles (r &amp;gt; 4 pixels) in the current imaging system, a bubble-size adaptive detection algorithm is established based on the cascade correlation method to obtain the two-dimensional centroid coordinates and radius of the observed bubbles. The bubble size information is also introduced into a two-view PTV algorithm for retrieving the Lagrangian trajectory of each bubble. Both the bubble detection and PTV algorithms are validated using synthetic datasets. Once the bubble trajectories are resolved successfully, the three-dimensional bubble velocity is obtained, and the actual bubble sizes are further corrected using the depth information. Analysis of the trajectory and velocity components indicates the existence of lateral bubble motion, reflecting interactions among bubbles. The rise velocity is positively correlated with the bubble radius in two regions, respectively, and the deviation from the theoretical value reveals the influence of non-buoyancy factors. The proposed technique provides effective diagnostics of the three-dimensional dynamic characteristics of micrometer-sized bubbles and can be used to evaluate and design bubble management systems for various electrochemical energy conversion devices.

Experimental and Theoretical Analysis of Immersion Cooling of a Li-Ion Battery Module

Abstract Overheating of Li-ion cells and battery packs is an ongoing technological challenge for electrochemical energy conversion and storage, including in electric vehicles. Immersion cooling is a promising thermal management technique to address these challenges. This work presents experimental and theoretical analysis of the thermal and electrochemical impact of immersion cooling of a small module of Li-ion cells. Significant reduction in both surface and core temperature due to immersion cooling is observed, consistent with theoretical and simulation models developed here. However, immersion cooling is also found to result in a small but non-negligible increase in capacity fade of the cells. A number of hypotheses are formed and systematically tested through a comparison of experimental measurements with theoretical modeling and simulations. Electrochemical Impedance Spectroscopy measurements indicate that the accelerated cell aging due to immersion cooling is likely to be due to enhanced lithium plating. Therefore, careful consideration of the impact of immersion cooling on long-term performance may be necessary. The results presented in this work quantify both thermal and electrochemical impacts of a promising thermal management technique for Li-ion cells. These results may be of relevance for design and optimization of electrochemical energy conversion and storage systems.

Value‐Added Aqueous Metal‐Redox Bicatalyst Batteries

AbstractThe development and utilization of electrochemical energy conversion and storage devices can maximize intermittent renewable energy and balance environmental issues. Aqueous metal‐redox bicatalyst batteries, incorporating value‐added electro‐reduction reactions during discharge process at the cathode, are considered a particularly attractive alternative for simultaneous electricity generation and valuable chemical production. In this review, for the first time, a holistic and subtle description of value‐added metal‐redox bicatalyst batteries is made, focusing on recent efforts to optimize the energy conversion/chemical production‐involved cathodic discharging reactions, including CO2 reduction reaction (CO2RR), nitrogen reduction reaction (NRR), nitric oxide reduction reaction (NORR), nitrate reduction reaction (NO3−RR), nitrite reduction reaction (NO2−RR), hydrogen evolution reaction (HER), and acetylene reduction reaction (ARR). A macroscopic understanding of design principles in terms of anodes, cathodes, and reaction parameters is provided. Some mechanism explorations, feasibility analyses, technoeconomic assessments, device combinations, and associated comparisons are involved to deepen the understanding of different systems and evaluate their application prospects. Perspectives on and opportunities for future research directions are also outlined.

Tuning the surface electronic structure of noble metal aerogels to promote the electrocatalytic oxygen reduction

The sluggish kinetics of the oxygen reduction reaction (ORR) is the bottleneck for various electrochemical energy conversion devices. Regulating the electronic structure of electrocatalysts by ligands has received particular attention in deriving valid ORR electrocatalysts. Here, the surface electronic structure of Pt-based noble metal aerogels (NMAs) was modulated by various organic ligands, among which the electron-withdrawing ligand of 4-methylphenylene effectively boosted the ORR electrocatalysis. Theoretical calculations suggested the smaller energy barrier for the transformation of O* to OH* and downshift the d-band center of Pt due to the interaction between 4-methylphenylene and the surface metals, thus enhancing the ORR intrinsic activity. Both Pt3Ni and PtPd aerogels with 4-methylphenylene decoration performed significant enhancement in ORR activity and durability in different media. Remarkably, the 4-methylphenylene modified PtPd aerogel exhibited the higher half-wave potential of 0.952 V and the mass activity of 10.2 times of commercial Pt/C. This work explained the effect of electronic structure on ORR electrocatalytic properties and would promote functionalized NMAs as efficient ORR electrocatalysts.

Unravelling the trifunctional electrochemical properties of WSe2 nanosheets for self-powered hydrogen production

Two dimensional materials have received increasing recognition for their utility in electrochemical energy storage and conversion devices, as well as for self-powered systems. In this work, we are reporting the trifunctional electrochemical properties (such as energy-storage, hydrogen evolution reaction (HER) and oxygen evolution reaction (OER)) of WSe2 nanosheets (prepared by a solvothermal method) towards the development of a self-powered system for uninterrupted hydrogen (H2) production. First, we have examined the energy storage properties of the WSe2 nanosheets in the form of flexible solid-state supercapacitor (FSSC) that shows the presence of ion-intercalation pseudocapacitance in the WSe2 nanosheets. The fabricated WSe2 FSSC possess a high device capacitance, energy density, and power density with 119% capacitance retention over 5,000 cycles. Second, we explored the electrocatalytic properties of WSe2 nanosheets that indicated they possess effective HER and OER properties with low overpotential (115 mV for HER and 312 mV for OER), respectively. Finally, a proof-of-concept self-powered system comprising a solar cell, WSe2 FSSC, and lab-scale WSe2 electrolyzer (with a low overpotential of 1.604 V at 10 mA cm−2) was demonstrated to overcome the power fluctuation issues for effective and uninterrupted H2 production.