Single-Crystalline Cathodes for Advanced Li-Ion Batteries: Progress and Challenges.

Single-crystalline cathodes are the most promising candidates for high-energy-density lithium-ion batteries (LIBs). Compared to their polycrystalline counterparts, single-crystalline cathodes have advantages over liquid-electrolyte-based LIBs in terms of cycle life, structural stability, thermal stability, safety, and storage but also have a potential application in solid-state LIBs. In this review, the development history and recent progress of single-crystalline cathodes are reviewed, focusing on properties, synthesis, challenges, solutions, and characterization. Synthesis of single-crystalline cathodes usually involves preparing precursors and subsequent calcination, which are summarized in the details. In the following sections, the development issues of single-crystalline cathodes, including kinetic limitations, interfacial side reactions, safety issues, reversible planar gliding and micro-cracking, and particle size distribution and agglomeration, are systematically analyzed, followed by current solutions and characterization techniques. Finally, this review is concluded with proposed research thrusts for the future development of single-crystalline cathodes.

High-Performance Zinc-Air Batteries Based on Bifunctional Hierarchically Porous Nitrogen-Doped Carbon.

Active and durable bifunctional electrocatalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) on the cathode are required for high-performance rechargeable metal-air batteries. Herein, the synthesis of hierarchically porous nitrogen-doped carbon (HPNC) with bifunctional oxygen electrocatalysis for Zn-air batteries is reported. The HPNC catalyst possesses a large surface area of 1459 m2 g-1 and exhibits superior electrocatalytic activity toward ORR and OER simultaneously with a low OER/ORR overpotential of 0.62 V, taking the difference between the potential at 10 mA cm-2 for OER and half-wave potential for ORR in 0.1 m KOH. Adopting HPNC as the air cathode, primary and rechargeable Zn-air batteries are fabricated. The primary batteries demonstrate a high open-circuit potential of 1.616 V, a specific capacity of 782.7 mAh gZn -1 and a superb peak power density of 201 mW cm-2 . The rechargeable batteries can be cycled stably for over 360 cycles or 120 h at the current density of 5 mA cm-2 . As elucidated by density functional theory, N-doping is preferred on defective sites with pentagon configuration and on the edge in the form of pyridinic-N-type. The high content of these two motifs in HPNC leads to the superior ORR and OER activities, respectively.

Investigation of non-precious metal cathode catalysts for direct borohydride fuel cells.

Borohydride crossover in anion exchange membrane (AEM) based direct borohydride fuel cells (DBFCs) impairs their performance and induces cathode catalyst poisoning. This study evaluates three non-precious metal catalysts, namely LaMn0.5Co0.5O3 (LMCO) perovskite, MnCo2O4 (MCS) spinel, and Fe-N-C, for their application as cathode catalysts in DBFCs. The rotating disk electrode (RDE) testing shows significant borohydride tolerance of MCS. Moreover, MCS has exhibited exceptional stability in accelerated durability tests (ADTs), with a minimal reduction of 10 mV in half-wave potential. DFT calculations further reveal that these catalysts predominantly adsorb over , unlike commercial Pt/C which preferentially adsorbs . In DBFCs, MCS can deliver a peak power density of 1.5 W cm-2, and a 3% voltage loss after a 5 hours durability test. In contrast, LMCO and Fe-N-C have exhibited significantly lower peak power density and stability. The analysis of the TEM, XRD, and XPS results before and after the single-cell stability tests suggests that the diminished stability of LMCO and Fe-N-C catalysts is due to catalyst detachment from carbon supports, resulting from the nanoparticle aggregation during the high-temperature preparation process. Such findings suggest that MCS can effectively mitigate the fuel crossover challenge inherent in DBFCs, thus enhancing its viability for practical application.

Generative Artificial Intelligence for Designing Multi-Scale Hydrogen Fuel Cell Catalyst Layer Nanostructures.

Multiscale design of catalyst layers (CLs) is important to advancing hydrogen electrochemical conversion devices toward commercialized deployment, which has nevertheless been greatly hampered by the complex interplay among multiscale CL components, high synthesis cost and vast design space. We lack rational design and optimization techniques that can accurately reflect the nanostructure-performance relationship and cost-effectively search the design space. Here, we fill this gap with a deep generative artificial intelligence (AI) framework, GLIDER, that integrates recent generative AI, data-driven surrogate techniques and collective intelligence to efficiently search the optimal CL nanostructures driven by their electrochemical performance. GLIDER achieves realistic multiscale CL digital generation by leveraging the dimensionality-reduction ability of quantized vector-variational autoencoder. The powerful generative capability of GLIDER allows the efficient search of the optimal design parameters for the Pt-carbon-ionomer nanostructures of CLs. We also demonstrate that GLIDER is transferable to other fuel cell electrode microstructure generation, e.g., fibrous gas diffusion layers and solid oxide fuel cell anode. GLIDER is of potential as a digital tool for the design and optimization of broad electrochemical energy devices.

Improving Interfacial Adhesion of Graphite/Epoxy Composites by Surface Functionalization.

Graphite/epoxy resin (G/EP) composites are extensively utilized in bipolar plates for fuel cells owing to their outstanding electrical and mechanical properties. However, the mechanical strength of these composites declines notably due to the inadequate bonding interface between graphite and epoxy resin. To address this issue, we used molecular dynamics (MD) simulations to study the influence of graphite surface functionalization on the interfacial structures of composites. The results of this study revealed that the functionalization of the graphite surface led to an increase in the interface thickness of the composite. This phenomenon can be attributed to the interdiffusion and hydrogen bond formation between functionalized graphite and epoxy molecular chains. And all four types of functional groups demonstrated a promoting effect on the adsorption process. Additionally, the adsorption and contact angle results provided further evidence that the adsorption rate of graphite to the epoxy resin significantly improved after functionalization. These findings contribute to a more comprehensive understanding of the microscopic process of forming interfaces in G/EP composites. In addition, these insights provide valuable guidance for improving the interface bonding of composite bipolar plates, which can ultimately increase their mechanical strength.

Rational Design of Atomically Dispersed Metal Site Electrocatalysts for Oxygen Reduction Reaction.

Future renewable energy supply and a cleaner Earth greatly depend on various crucial catalytic reactions for the society. Atomically dispersed metal site electrocatalysts (ADMSEs) have attracted tremendous research interest and are considered as the next-generation promising oxygen reduction reaction (ORR) electrocatalysts due to the maximum atom utilization efficiency, tailorable catalytic sites, and tunable electronic structures. Despite great efforts have been devoted to the development of ADMSEs, the systematic summary for design principles of high-efficiency ADMSEs is not sufficiently highlighted for ORR. In this review, the authors first summarize the fundamental ORR mechanisms for ADMSEs, and further discuss the intrinsic catalytic mechanism from the perspective of theoretical calculation. Then, the advanced characterization techniques to identify the active sites and effective synthesis methods to prepare catalysts for ADMSEs are also showcased. Subsequently, a special emphasis is placed on effective strategies for the rational design of the advanced ADMSEs. Finally, the present challenges to be addressed in practical application and future research directions are also proposed to overcome the relevant obstacles for developing high-efficiency ORR electrocatalysts. This review aims to provide a deeper understanding for catalytic mechanisms and valuable design principles to obtain the advanced ADMSEs for sustainable energy conversion and storage techniques.

A Super Uniform Hydrophobic Gas Diffusion Layer for a Proton Exchange Membrane Fuel Cell.

The design and optimization of the gas diffusion layer (GDL) play a crucial role in the improvement of proton exchange membrane fuel cell performance. Hydrophobic treatment of a GDL is an important method for facilitating mass transfer, while conventional Teflon treatment is not uniform and leads to an increase in ohmic and heat resistance. Herein, a homogeneous molecular hydrophobic GDL was prepared by liquid phase synthesis, and a two-dimensional non-isothermal model was developed to investigate the transfer mechanism. The peak power density of cells with the GDL described above was improved by 46% compared to that of the conventional GDL. The ohmic and mass transport resistance decreased by 15% and 52%, respectively, under a current density of 1 A cm-2 using the uniform hydrophobic GDL. The simulation results proved that the uniform hydrophobic GDL eliminates the hydrophilic dots, which prevents the formation of water pools and reduces the resistance to gas flow. The water saturation of the conventional GDL reaches 0.19 at a current density of 1 A cm-2, and the saturation of a modified GDL under the same conditions is only 0.13. A dimensionless parameter, Tf, is proposed to characterize the resistance of oxygen diffusion. In conclusion, molecular-level uniform hydrophobic treatment can effectively reduce the ohmic and mass transfer resistance of a GDL and effectively improve the performance of fuel cells.

Effects of Electrostatic Force and Network Structure on the Stability of Proton-Exchange Membrane Fuel Cell Catalyst Ink.

The stability of the catalyst slurry of a proton-exchange membrane fuel cell (PEMFC) is of great significance to its large-scale production and commercialization. In this study, three kinds of slurries with different stabilities were prepared using different probe ultrasonic powers. The influence of electrostatic force and network structure on slurry stability was also studied. In addition, the catalyst layer (CL) and membrane electrode assembly (MEA) were further tested to determine the relationship between slurry stability, CL, and MEA performance. The results showed that the slurry prepared with 600 W dispersion power had the least agglomeration on day 12, which is due to the clusters in the slurry having the smallest average particle size and the largest surface area, thereby allowing them to absorb the most Nafion and have the largest electrostatic force to inhibit agglomeration. However, the slurry with 1200 W dispersion power had the least sedimentation after 9.4 days because the strength of the network structure in the slurry strengthened the most, resulting in a significant increase in viscosity and inhibition of sedimentation. Electrochemical tests showed that the MEA gradually exhibited worse electrical performance and higher impedance due to the agglomeration of catalyst particles caused by the standing process. Altogether, this study provides insights to better understand and regulate the stability of catalyst slurries.

Effect of Microstructural Damage on the Thermomechanical Properties of Electrodes in Proton Exchange Membrane Fuel Cells.

Advanced functional materials composed of multiple nanoscale phases, including pores and interfaces, have been extensively applied in the fields of new energy, architecture, and aerospace. However, insufficient knowledge of the thermomechanical properties resulting from material failures, such as interfacial delamination and porosity deformations, which limit the durability and lifetime of these materials, has hindered their further application, demanding a deeper understanding of microstructural changes. Based on the fuel cell electrode, we explore a multiscale prediction model that correlates the atomic interactions between interfaces with a microscopic thermomechanical model to illuminate the effects of interface binding characteristics on the materials' mechanical response and heat conduction mechanisms. Compared with experimental measurements and theoretical calculations at the macroscopic scale, our model excels in predicting the initiation and propagation of interfacial debonding and the thermal conductivity of the electrode, with the resistance factors for the interface, pores, and cracks taken into consideration. This work provides guidance for designing robust electrodes resistant to thermomechanical failure and serves as a reference method for predicting damage in heterogeneous porous materials.

Influence of Degassing Treatment on the Ink Properties and Performance of Proton Exchange Membrane Fuel Cells.

Degradation occurs in catalyst inks because of the catalytic oxidation of the solvent. Identification of the generation process of impurities and their effects on the properties of HSC ink and LSC ink is crucial in mitigating them. In this study, gas chromatography-mass spectrometry (GC-MS) and cyclic voltammetry (CV) showed that oxidation of NPA and EA was the primary cause of impurities such as acetic acid, aldehyde, propionic acid, propanal, 1,1-dipropoxypropane, and propyl propionate. After the degassing treatment, the degradation of the HSC ink was suppressed, and the concentrations of acetic acid, propionic acid, and propyl propionate plummeted from 0.0898 wt.%, 0.00224 wt.%, and 0.00046 wt.% to 0.0025 wt.%, 0.0126 wt.%, and 0.0003 wt.%, respectively. The smaller particle size and higher zeta potential in the degassed HSC ink indicated the higher utilization of Pt, thus leading to optimized mass transfer in the catalyst layer (CL) during working conditions. The electrochemical performance test result shows that the MEA fabricated from the degassed HSC ink had a peak power density of 0.84 W cm-2, which was 0.21 W cm-2 higher than that fabricated from the normal HSC ink. However, the introduction of propionic acid in the LSC ink caused the Marangoni flux to inhibit the coffee ring effect and promote the uniform deposition of the catalyst. The RDE tests indicated that the electrode deposited from the LSC ink with propionic acid possessed a mass activity of 84.4 mA∙mgPt-1, which was higher than the 60.5 mA∙mgPt-1 of the electrode deposited from the normal LSC ink.