ABSTRACT
Effective water management is crucial for the optimal operation of low-temperature polymer electrolyte membrane fuel cells (PEMFCs). Excessive liquid water production can cause flooding in the gas diffusion electrodes and flow channels, limiting mass transfer and reducing PEMFC performance. To tackle this issue, a nature-inspired chemical engineering (NICE) approach has been adopted that takes cues from the integument structure of desert-dwelling lizards for passive water transport. By incorporating engraved, capillary microchannels into conventional flow fields, PEMFC performance improves significantly, including a 15% increase in maximum power density for a 25 cm2 cell and 13% for a 100 cm2 cell. Electro-thermal maps of the lizard-inspired flow field demonstrate a more uniform spatial distribution of current density and temperature than the conventional design. Neutron radiography provides evidence that capillary microchannels in the lizard-inspired flow field facilitate the efficient transport and removal of generated liquid water, thereby preventing blockages in the reactant channels. These findings present a universally applicable and highly efficient water management strategy for PEMFCs, with the potential for widespread practical implementation for other electrochemical devices.
ABSTRACT
Aqueous zinc-ion batteries (AZIBs) have experienced a rapid surge in popularity, as evident from the extensive research with over 30 000 articles published in the past 5 years. Previous studies on AZIBs have showcased impressive long-cycle stability at high current densities, achieving thousands or tens of thousands of cycles. However, the practical stability of AZIBs at low current densities (<1C) is restricted to merely 50-100 cycles due to intensified cathode dissolution. This genuine limitation poses a considerable challenge to their transition from the laboratory to the industry. In this study, leveraging density functional theory (DFT) calculations, an artificial interphase that achieves both hydrophobicity and restriction of the outward penetration of dissolved vanadium cations, thereby shifting the reaction equilibrium and suppressing the vanadium dissolution following Le Chatelier's principle, is described. The approach has resulted in one of the best cycling stabilities to date, with no noticeable capacity fading after more than 200 cycles (≈720 h) at 200 mA g-1 (0.47C). These findings represent a significant advance in the design of ultrastable cathodes for aqueous batteries and accelerate the industrialization of aqueous zinc-ion batteries.
ABSTRACT
Turning commercially available low-cost conducting carbon black materials into functional electrocatalytic electrode media using simple surface chemical modification is a highly attractive approach. This study reports on remarkably enhanced oxygen electrocatalytic activity of commercially available Ketjenblack (KB) by growing a non-precious cobalt metal-based zeolitic-imidazolate framework (ZIF-67) at room temperature in methanol solution followed by a mild thermolysis. The resulting Co@CoOx nanoparticle decorated nitrogen-doped KB derived from the optimized ZIF-67 : KB weight ratio of hybrid samples at 500-600 °C shows high performance for the oxygen reduction reaction (ORR) with impressive Eonset and E1/2 values of â¼0.90 and â¼0.83 V (vs. RHE), respectively in 0.1 M KOH electrolyte. Such ORR activity is comparable to, or better than many metal@metal-oxide-carbon based electrocatalysts synthesized under elevated carbothermal temperatures and using multicomponent/multistep chemical modification conditions. Therefore, a simple electrocatalyst design reported in this work is an efficient synthesis route that not only utilises earth-abundant carbon black but also comprises scalable room temperature synthesized ZIF-67 following mild thermolysis conditions under 600 °C.
ABSTRACT
The phase separation dynamics in graphitic anodes significantly affects lithium plating propensity, which is the major degradation mechanism that impairs the safety and fast charge capabilities of automotive lithium-ion batteries. In this study, we present comprehensive investigation employing operando high-resolution optical microscopy combined with non-equilibrium thermodynamics implemented in a multi-dimensional (1D+1D to 3D) phase-field modeling framework to reveal the rate-dependent spatial dynamics of phase separation and plating in graphite electrodes. Here we visualize and provide mechanistic understanding of the multistage phase separation, plating, inter/intra-particle lithium exchange and plated lithium back-intercalation phenomena. A strong dependence of intra-particle lithiation heterogeneity on the particle size, shape, orientation, surface condition and C-rate at the particle level is observed, which leads to early onset of plating spatially resolved by a 3D image-based phase-field model. Moreover, we highlight the distinct relaxation processes at different state-of-charges (SOCs), wherein thermodynamically unstable graphite particles undergo a drastic intra-particle lithium redistribution and inter-particle lithium exchange at intermediate SOCs, whereas the electrode equilibrates much slower at low and high SOCs. These physics-based insights into the distinct SOC-dependent relaxation efficiency provide new perspective towards developing advanced fast charge protocols to suppress plating and shorten the constant voltage regime.
ABSTRACT
For zinc-ion batteries (ZIBs), the non-uniform Zn plating/stripping results in a high polarization and low Coulombic efficiency (CE), hindering the large-scale application of ZIBs. Here, inspired by biomass seaweed plants, an anionic polyelectrolyte alginate acid (SA) was used to initiate the in situ formation of the high-performance solid electrolyte interphase (SEI) layer on the Zn anode. Attribute to the anionic groups of -COO- , the affinity of Zn2+ ions to alginate acid induces a well-aligned accelerating channel for uniform plating. This SEI regulates the desolvation structure of Zn2+ and facilitates the formation of compact Zn (002) crystal planes. Even under high depth of discharge conditions (DOD), the SA-coated Zn anode still maintains a stable Zn stripping/plating behavior with a low potential difference (0.114â V). According to the classical nucleation theory, the nucleation energy for SA-coated Zn is 97 % less than that of bare Zn, resulting in a faster nucleation rate. The Zn||Cu cell assembled with the SA-coated electrode exhibits an outstanding average CE of 99.8 % over 1,400 cycles. The design is successfully demonstrated in pouch cells, where the SA-coated Zn exhibits capacity retention of 96.9 % compared to 59.1 % for bare Zn anode, even under the high cathode mass loading (>10â mg/cm2 ).
ABSTRACT
It is widely accepted that the commercial application of lithium-sulfur batteries is inhibited by their short cycle life, which is primarily caused by a combination of Li dendrite formation and active material loss due to polysulfide shuttling. Unfortunately, while numerous approaches to overcome these problems have been reported, most are unscalable and hence further hinder Li-S battery commercialization. Most approaches suggested also only tackle one of the primary mechanisms of cell degradation and failure. Here, we demonstrate that the use of a simple protein, fibroin, as an electrolyte additive can both prevent Li dendrite formation and minimize active material loss to enable high capacity and long cycle life (up to 500 cycles) in Li-S batteries, without inhibiting the rate performance of the cell. Through a combination of experiments and molecular dynamics (MD) simulations, it is demonstrated that the fibroin plays a dual role, both binding to polysulfides to hinder their transport from the cathode and passivating the Li anode to minimize dendrite nucleation and growth. Most importantly, as fibroin is inexpensive and can be simply introduced to the cell via the electrolyte, this work offers a route toward practical industrial applications of a viable Li-S battery system.
ABSTRACT
Reduced graphene-oxide (RGO)-based electrodes in supercapacitors deliver high energy/power capacities compared to typical nanoporous carbon materials. However, extensive critical analysis of literature reveals enormous discrepancies (up to 250 F g-1 ) in the reported capacitance (variation of 100-350 F g-1 ) of RGO materials synthesized under seemingly similar methods, inhibiting an understanding of capacitance variation. Here, the key factors that control the capacitance performance of RGO electrodes are demonstrated by analyzing and optimizing various types of commonly applied electrode fabrication methods. Beyond usual data acquisition parameters and oxidation/reduction properties of RGO, a substantial difference of more than 100% in capacitance values (with change from 190 ± 20 to 340 ± 10 F g-1 ) is found depending on the electrode preparation method. For this demonstration, ≈40 RGO-based electrodes are fabricated from numerous distinctly different RGO materials via typically applied methods of solution (aqueous and organic) casting and compressed powders. The influence of data acquisition conditions and capacitance estimation practices are also discussed. Furthermore, by optimizing electrode processing method, a direct surface area governed capacitance relationship for RGO structures is revealed.
ABSTRACT
The growing interest in the development of next-generation net zero energy systems has led to the expansion of molybdenum disulfide (MoS2) research in this area. This activity has resulted in a wide range of manufacturing/synthesis methods, controllable morphologies, diverse carbonaceous composite structures, a multitude of applicable characterization techniques, and multiple energy applications for MoS2. To assess the literature trends, 37,347 MoS2 research articles from Web of Science were text scanned to classify articles according to energy application research and characterization techniques employed. Within the review, characterization techniques are grouped under the following categories: morphology, crystal structure, composition, and chemistry. The most common characterization techniques identified through text scanning are recommended as the base fingerprint for MoS2 samples. These include: scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. Similarly, XPS and Raman spectroscopy are suggested for 2H or 1T MoS2 phase confirmation. We provide guidance on the collection and presentation of MoS2 characterization data. This includes how to effectively combine multiple characterization techniques, considering the sample area probed by each technique and their statistical significance, and the benefit of using reference samples. For ease of access for future experimental comparison, key numeric MoS2 characterization values are tabulated and major literature discrepancies or currently debated characterization disputes are highlighted.
ABSTRACT
The zinc-ion battery is one of the promising candidates for next-generation energy storage devices beyond lithium technology due to the earth's abundance of Zn materials and their high volumetric energy density (5855 mA h cm-3). To date, the formation of Zn dendrites during charge-discharge cycling still hinders the practical application of zinc-ion batteries. It is, therefore, crucial to understand the formation mechanism of the zinc dendritic structure before effectively suppressing its growth. Here, the application of operando digital optical microscopy and in situ lab-based X-ray computed tomography (X-ray CT) is demonstrated to probe and quantify the morphologies of zinc electrodeposition/dissolution under multiple galvanostatic plating/stripping conditions in symmetric Zn||Zn cells. With the combined microscopy approaches, we directly observed the dynamic nucleation and subsequent growth of Zn deposits, the heterogeneous transportation of charged clusters/particles, and the evolution of 'dead' Zn particles via partial dissolution. Zn electrodeposition at the early stage is mainly attributed to activation, while the subsequent dendrite growth is driven by diffusion. The high current not only facilitates the formation of sharp dendrites with a larger mean curvature at their tips but also leads to dendritic tip splitting and the creation of a hyper-branching morphology. This approach offers a direct opportunity to characterize dendrite formation in batteries with a metal anode in the laboratory.
ABSTRACT
The electrochemical synthesis of hydrogen peroxide (H2 O2 ) via a two-electron (2 e- ) oxygen reduction reaction (ORR) process provides a promising alternative to replace the energy-intensive anthraquinone process. Herein, we develop a facile template-protected strategy to synthesize a highly active quinone-rich porous carbon catalyst for H2 O2 electrochemical production. The optimized PCC900 material exhibits remarkable activity and selectivity, of which the onset potential reaches 0.83â V vs. reversible hydrogen electrode in 0.1â M KOH and the H2 O2 selectivity is over 95 % in a wide potential range. Comprehensive synchrotron-based near-edge X-ray absorption fine structure (NEXAFS) spectroscopy combined with electrocatalytic characterizations reveals the positive correlation between quinone content and 2 e- ORR performance. The effectiveness of chair-form quinone groups as the most efficient active sites is highlighted by the molecule-mimic strategy and theoretical analysis.
ABSTRACT
Electrocatalytic oxygen reduction reaction (ORR) has been intensively studied for environmentally benign applications. However, insufficient understanding of ORR 2 e- -pathway mechanism at the atomic level inhibits rational design of catalysts with both high activity and selectivity, causing concerns including catalyst degradation due to Fenton reaction or poor efficiency of H2 O2 electrosynthesis. Herein we show that the generally accepted ORR electrocatalyst design based on a Sabatier volcano plot argument optimises activity but is unable to account for the 2 e- -pathway selectivity. Through electrochemical and operando spectroscopic studies on a series of CoNx /carbon nanotube hybrids, a construction-driven approach based on an extended "dynamic active site saturation" model that aims to create the maximum number of 2 e- ORR sites by directing the secondary ORR electron transfer towards the 2 e- intermediate is proven to be attainable by manipulating O2 hydrogenation kinetics.
ABSTRACT
Routine electrolyte additives are not effective enough for uniform zinc (Zn) deposition, because they are hard to proactively guide atomic-level Zn deposition. Here, based on underpotential deposition (UPD), we propose an "escort effect" of electrolyte additives for uniform Zn deposition at the atomic level. With nickel ion (Ni2+ ) additives, we found that metallic Ni deposits preferentially and triggers the UPD of Zn on Ni. This facilitates firm nucleation and uniform growth of Zn while suppressing side reactions. Besides, Ni dissolves back into the electrolyte after Zn stripping with no influence on interfacial charge transfer resistance. Consequently, the optimized cell operates for over 900â h at 1â mA cm-2 (more than 4 times longer than the blank one). Moreover, the universality of "escort effect" is identified by using Cr3+ and Co2+ additives. This work would inspire a wide range of atomic-level principles by controlling interfacial electrochemistry for various metal batteries.
ABSTRACT
Numerous layered materials are being recognized as promising candidates for high-performance alkali-ion battery anodes, but black phosphorus (BP) has received particular attention. This is due to its high specific capacity, due to a mixed alkali-ion storage mechanism (intercalation-alloying), and fast alkali-ion transport within its layers. Unfortunately, BP based batteries are also commonly associated with serious irreversible losses and poor cycling stability. This is known to be linked to alloying, but there is little experimental evidence of the morphological, mechanical, or chemical changes that BP undergoes in operational cells and thus little understanding of the factors that must be mitigated to optimize performance. Here the degradation mechanisms of BP alkali-ion battery anodes are revealed through operando electrochemical atomic force microscopy (EC-AFM) and ex situ spectroscopy. Among other phenomena, BP is observed to wrinkle and deform during intercalation but suffers from complete structural breakdown upon alloying. The solid electrolyte interphase (SEI) is also found to be unstable, nucleating at defects before spreading across the basal planes but then disintegrating upon desodiation, even above alloying potentials. By directly linking these localized phenomena with the whole-cell performance, we can now engineer stabilizing protocols for next-generation high-capacity alkali-ion batteries.
ABSTRACT
Proton exchange membrane fuel cells, consuming hydrogen and oxygen to generate clean electricity and water, suffer acute liquid water challenges. Accurate liquid water modelling is inherently challenging due to the multi-phase, multi-component, reactive dynamics within multi-scale, multi-layered porous media. In addition, currently inadequate imaging and modelling capabilities are limiting simulations to small areas (<1 mm2) or simplified architectures. Herein, an advancement in water modelling is achieved using X-ray micro-computed tomography, deep learned super-resolution, multi-label segmentation, and direct multi-phase simulation. The resulting image is the most resolved domain (16 mm2 with 700 nm voxel resolution) and the largest direct multi-phase flow simulation of a fuel cell. This generalisable approach unveils multi-scale water clustering and transport mechanisms over large dry and flooded areas in the gas diffusion layer and flow fields, paving the way for next generation proton exchange membrane fuel cells with optimised structures and wettabilities.
ABSTRACT
A stable cathode-electrolyte interface (CEI) is crucial for aqueous zinc-ion batteries (AZIBs), but it is less investigated. Commercial binder poly(vinylidene fluoride) (PVDF) is widely used without scrutinizing its suitability and cathode-electrolyte interface (CEI) in AZIBs. A water-soluble binder is developed that facilitated the in situ formation of a CEI protecting layer tuning the interfacial morphology. By combining a polysaccharide sodium alginate (SA) with a hydrophobic polytetrafluoroethylene (PTFE), the surface morphology, and charge storage kinetics can be confined from diffusion-dominated to capacitance-controlled processes. The underpinning mechanism investigates experimentally in both kinetic and thermodynamic perspectives demonstrate that the COO- from SA acts as an anionic polyelectrolyte facilitating the adsorption of Zn2+ ; meanwhile fluoride atoms on PTFE backbone provide hydrophobicity to break desolvation penalty. The hybrid binder is beneficial in providing a higher areal flux of Zn2+ at the CEI, where the Zn-Birnessite MnO2 battery with the hybrid binder exhibits an average specific capacity 45.6% higher than that with conventional PVDF binders; moreover, a reduced interface activation energy attained fosters a superior rate capability and a capacity retention of 99.1% in 1000 cycles. The hybrid binder also reduces the cost compared to the PVDF/NMP, which is a universal strategy to modify interface morphology.
ABSTRACT
Graphene-related materials are promising supports for electrocatalysts due to their stability and high surface area. Their innate surface chemistries can be controlled and tuned via functionalisation to improve the stability of both the carbon support and the metal catalyst. Functionalised graphenes were prepared using either aryl diazonium functionalisation or non-destructive chemical reduction, to provide groups adapted for platinum deposition. XPS and TGA-MS measurements confirmed the presence of polyethyleneglycol and sulfur-containing functional groups, and provided consistent values for the extent of the reactions. The deposited platinum nanoparticles obtained were consistently around 2 nm via reductive chemistry and around 4 nm via the diazonium route. Although these graphene-supported electrocatalysts provided a lower electrochemical surface area (ECSA), functionalised samples showed enhanced specific activity compared to a commercial platinum/carbon black system. Accelerated stress testing (AST) showed improved durability for the functionalised graphenes compared to the non-functionalised materials, attributed to edge passivation and catalyst particle anchoring.
ABSTRACT
Overcoming the slow oxygen reduction reaction (ORR) kinetics at the cathode of the hydrogen fuel cells requires the use of electrocatalysts containing expensive and scare platinum to achieve reasonable performance, hampering widespread use of the technology due to high material costs and sustainability issues. One option available to tackle this issue is to use new designs to create nanomaterials which achieve excellent electrocatalytic performances and long-lasting stabilities whilst using less platinum than is currently required. Reliably producing nanomaterials with predictable activities and stabilities using simple, safe, and scalable methods is an important research topic to the advancement of fuel cell technologies. The oxygen reduction reaction occurs at the surface of electrocatalytic materials, and since nanomaterial structures exhibit different catalytic activities, their shapes have a strong relationship to the final performance. Seed-mediated synthesis can be used to control the shape of materials with the aim of obtaining products with the most desirable surface properties for the ORR. This review summarized the current advancement of the synthesis of platinum-based ORR and provided the insights for the future development of this field.
ABSTRACT
In recent years, low-temperature polymer electrolyte fuel cells have become an increasingly important pillar in a zero-carbon strategy for curbing climate change, with their potential to power multiscale stationary and mobile applications. The performance improvement is a particular focus of research and engineering roadmaps, with water management being one of the major areas of interest for development. Appropriate characterisation tools for mapping the evolution, motion and removal of water are of high importance to tackle shortcomings. This article demonstrates the development of a 4D high-speed neutron imaging technique, which enables a quantitative analysis of the local water evolution. 4D visualisation allows the time-resolved studies of droplet formation in the flow fields and water quantification in various cell parts. Performance parameters for water management are identified that offer a method of cell classification, which will, in turn, support computer modelling and the engineering of next-generation flow field designs.
ABSTRACT
As the drive to improve the cost, performance characteristics and safety of lithium-ion batteries increases with adoption, one area where significant value could be added is that of battery diagnostics. This paper documents an investigation into the use of plasmonic-based optical fibre sensors, inserted internally into 1.4 Ah lithium-ion pouch cells, as a real time and in-situ diagnostic technique. The successful implementation of the fibres inside pouch cells is detailed and promising correlation with battery state is reported, while having negligible impact on cell performance in terms of capacity and columbic efficiency. The testing carried out includes standard cycling and galvanostatic intermittent titration technique (GITT) tests, and the use of a reference electrode to correlate with the anode and cathode readings separately. Further observations are made around the sensor and analyte interaction mechanisms, robustness of sensors and suggested further developments. These finding show that a plasmonic-based optical fibre sensor may have potential as an opto-electrochemical diagnostic technique for lithium-ion batteries, offering an unprecedented view into internal cell phenomena.
Subject(s)
Lithium , Optical Fibers , Electric Power Supplies , Electrodes , IonsABSTRACT
The electrode drying process (DP) is a crucial step in the lithium-ion battery manufacturing chain and plays a fundamental role in governing the performance of the cells. The DP is extremely complex, with the dynamics and their implication in the production of electrodes generally being poorly understood. To date, there is limited discussion of these processes in the literature due to the limitation of the existing in situ metrology. Here, ultrasound acoustic measurements are demonstrated as a promising tool to monitor the physical evolution of the electrode coating in situ. These observations are validated by gravimetric analysis to show the feasibility of the technique to monitor the DP and identify the three different drying stages. A possible application of this technique is to adjust the drying rates based upon the ultrasound readings at different drying stages and to speed up the drying time. These findings prove that this measurement can be used as a cost-effective and simple tool to provide characteristic diagnostics of the electrode, which can be applied in large-scale coating manufacturing.