Identification of the active triple-phase boundary of a non-Pt catalyst layer in fuel cells.

The rational design of non-Pt oxygen reduction reaction (ORR) catalysts and catalyst layers in fuel cells is largely impeded by insufficient knowledge of triple-phase boundaries (TPBs) in the micropore and mesopore ranges. Here, we developed a size-sensitive molecular probe method to resolve the TPB of Fe/N/C catalyst layers in these size ranges. More than 70% of the ORR activity was found to be contributed by the 0.8- to 2.0-nanometer micropores of Fe/N/C catalysts, even at a low micropore area fraction of 29%. Acid-alkaline interactions at the catalyst-polyelectrolyte interface deactivate the active sites in mesopores and macropores, resulting in inactive TPBs, leaving micropores without the interaction as the active TPBs. The concept of active and inactive TPBs provides a previously unidentified design principle for non-Pt catalyst and catalyst layers in fuel cells.

Structural Study of Sulfur-Added Carbon Nanohorns.

In the past few decades, nanostructured carbons (NCs) have been investigated for their interesting properties, which are attractive for a wide range of applications in electronic devices, energy systems, sensors, and support materials. One approach to improving the properties of NCs is to dope them with various heteroatoms. This work describes the synthesis and study of sulfur-added carbon nanohorns (S-CNH). Synthesis of S-CNH was carried out by modified chemical vapor deposition (m-CVD) using toluene and thiophene as carbon and sulfur sources, respectively. Some parameters such as the temperature of synthesis and carrier gas flow rates were modified to determine their effect on the properties of S-CNH. High-resolution scanning and transmission electron microscopy analysis showed the presence of hollow horn-type carbon nanostructures with lengths between 1 to 3 µm and, diameters that are in the range of 50 to 200 nm. Two types of carbon layers were observed, with rough outer layers and smooth inner layers. The surface textural properties are attributed to the defects induced by the sulfur intercalated into the lattice or bonded with the carbon. The XRD patterns and X-ray microanalysis studies show that iron serves as the seed for carbon nanohorn growth and iron sulfide is formed during synthesis.

Highly Active and Durable Single-Atom Tungsten-Doped NiS0.5 Se0.5 Nanosheet @ NiS0.5 Se0.5 Nanorod Heterostructures for Water Splitting.

Developing robust and highly active non-precious electrocatalysts for the hydrogen/oxygen evolution reaction (HER/OER) is crucial for the industrialization of hydrogen energy. In this study, a highly active and durable single-atom W-doped NiS0.5 Se0.5 nanosheet @ NiS0.5 Se0.5 nanorod heterostructure (W-NiS0.5 Se0.5 ) electrocatalyst is prepared. W-NiS0.5 Se0.5 exhibits excellent catalytic activity for the HER and OER with ultralow overpotentials (39 and 106 mV for the HER and 171 and 239 mV for the OER at 10 and 100 mA cm-2 , respectively) and excellent long-term durability (500 h), outperforming commercial precious-metal catalysts and many other previously reported transition-metal-based compounds (TMCs). The introduction of single-atom W delocalizes the spin state of Ni, which results in an increase in the Ni d-electron density. This causes the optimization of the adsorption/desorption process of H and a significant reduction in the adsorption free energy of the rate-determining step (O* → OOH*), thus accelerating the thermodynamics and kinetics of the HER and OER. This work provides a rational feasible strategy to design single-atom catalysts for water splitting and to develop advanced TMC electrocatalysts by regulating delocalized spin states.

Cause and Mitigation of Lithium-Ion Battery Failure-A Review.

Lithium-ion batteries (LiBs) are seen as a viable option to meet the rising demand for energy storage. To meet this requirement, substantial research is being accomplished in battery materials as well as operational safety. LiBs are delicate and may fail if not handled properly. The failure modes and mechanisms for any system can be derived using different methodologies like failure mode effects analysis (FMEA) and failure mode methods effects analysis (FMMEA). FMMEA is used in this paper as it helps to identify the reliability of a system at the component level focusing on the physics causing the observed failures and should thus be superior to the more data-driven FMEA approach. Mitigation strategies in LiBs to overcome the failure modes can be categorized as intrinsic safety, additional protection devices, and fire inhibition and ventilation. Intrinsic safety involves modifications of materials in anode, cathode, and electrolyte. Additives added to the electrolyte enhance the properties assisting in the improvement of solid-electrolyte interphase and stability. Protection devices include vents, circuit breakers, fuses, current interrupt devices, and positive temperature coefficient devices. Battery thermal management is also a protection method to maintain the temperature below the threshold level, it includes air, liquid, and phase change material-based cooling. Fire identification at the preliminary stage and introducing fire suppressive additives is very critical. This review paper provides a brief overview of advancements in battery chemistries, relevant modes, methods, and mechanisms of potential failures, and finally the required mitigation strategies to overcome these failures.

Growth Mechanism of Micro/Nano Metal Dendrites and Cumulative Strategies for Countering Its Impacts in Metal Ion Batteries: A Review.

Metal-ion batteries are capable of delivering high energy density with a longer lifespan. However, they are subject to several issues limiting their utilization. One critical impediment is the budding and extension of solid protuberances on the anodic surface, which hinders the cell functionalities. These protuberances expand continuously during the cyclic processes, extending through the separator sheath and leading to electrical shorting. The progression of a protrusion relies on a number of in situ and ex situ factors that can be evaluated theoretically through modeling or via laboratory experimentation. However, it is essential to identify the dynamics and mechanism of protrusion outgrowth. This review article explores recent advances in alleviating metal dendrites in battery systems, specifically alkali metals. In detail, we address the challenges associated with battery breakdown, including the underlying mechanism of dendrite generation and swelling. We discuss the feasible solutions to mitigate the dendrites, as well as their pros and cons, highlighting future research directions. It is of great importance to analyze dendrite suppression within a pragmatic framework with synergy in order to discover a unique solution to ensure the viability of present (Li) and future-generation batteries (Na and K) for commercial use.

Pillar-beam structures prevent layered cathode materials from destructive phase transitions.

Energy storage with high energy density and low cost has been the subject of a decades-long pursuit. Sodium-ion batteries are well expected because they utilize abundant resources. However, the lack of competent cathodes with both large capacities and long cycle lives prevents the commercialization of sodium-ion batteries. Conventional cathodes with hexagonal-P2-type structures suffer from structural degradations when the sodium content falls below 33%, or when the integral anions participate in gas evolution reactions. Here, we show a "pillar-beam" structure for sodium-ion battery cathodes where a few inert potassium ions uphold the layer-structured framework, while the working sodium ions could diffuse freely. The thus-created unorthodox orthogonal-P2 K0.4[Ni0.2Mn0.8]O2 cathode delivers a capacity of 194 mAh/g at 0.1 C, a rate capacity of 84% at 1 C, and an 86% capacity retention after 500 cycles at 1 C. The addition of the potassium ions boosts simultaneously the energy density and the cycle life.

On high-temperature evolution of passivation layer in Li-10 wt % Mg alloy via in situ SEM-EBSD.

Li-10 wt % Mg alloy (Li-10 Mg) is used as an anode material for a solid-state battery with excellent electrochemical performance and no evidence of dendrite formation during cycling. Thermal treatment of Li metal during manufacturing improves the interfacial contact between a Li metal electrode and solid electrolyte to achieve an all solid-state battery with increased performance. To understand the properties of the alloy passivation layer, this paper presents the first direct observation of its evolution at elevated temperatures (up to 325°C) by in situ scanning electron microscopy. We found that the morphology of the surface passivation layer was unchanged above the alloy melting point, while the bulk of the material below the surface was melted at the expected melting point, as confirmed by in situ electron backscatter diffraction. In situ heat treatment of Li-based materials could be a key method to improve battery performance.

Nanoscale assembling of graphene oxide with electrophoretic deposition leads to superior percolation network in Li-ion electrodes: TiNb2O7/rGO composite anodes.

In this paper, electrophoretic deposition (EPD) is shown to promote nanoscale assembling of graphene oxide (GO) enabling the fabrication of highly homogeneous, robust, and capacity fade resistant composite titanium niobate (TiNb2O7, TNO)/rGO anodes upon reductive annealing. Control tests revealed that EPD is superior to conventional PVDF-based casting in maximizing the performance benefits from using reduced GO in Li-ion electrode fabrication as is the case of TNO that is plagued with conductivity and capacity fading problems. In this particular study, we show that there is a synergy developed between GO and EPD with the former (1) stabilizing the EPD suspension, (2) acting as a flexible binder net that affords mechanical integrity during the volume expansion of TNO, (3) serving as a conductive filler, and (4) contributing to Li-ion storage via pseudocapacitance. As a consequence, a superior percolation network is developed. Thus while both EPD- and PVDF- built TNO/rGO composite anodes exhibited high initial capacities (∼350 and 318 mA h g-1) at 0.5 C cycling, respectively, their cycling behaviour was quite different with the latter experiencing high internal polarization and extended degradation. Post-mortem PEEM-XANES analysis clearly demonstrated a highly homogeneous mesostructure in the case of the EPD-built TNO/rGO anode vs. a highly segregated and dis-jointed rGO and TNO component clustering in the PVDF-built electrode.

Synthesis and Performance of MOF-Based Non-Noble Metal Catalysts for the Oxygen Reduction Reaction in Proton-Exchange Membrane Fuel Cells: A Review.

Hydrogen is widely regarded as a prime energy carrier for bridging the gap between renewable energy supply and demand. As the energy-generating component of the hydrogen cycle, affordable and reliable fuel cells are of key importance to the growth of the hydrogen economy. However, the use of scarce and costly Pt as an electrocatalyst for the oxygen reduction reaction (ORR) remains an issue to be addressed, and in this regard, metal-organic frameworks (MOFs) are viewed as promising non-noble alternatives because of their self-assembly capability and tunable properties. Herein, recent (2018-2020) works on MOF-based electrocatalysts containing N-doped C, Mn, Fe, Co, multiple metals, and multiple sites are reviewed and summarized with a focus on ORR activity, and the principal physicochemical properties and electrochemical performance of these catalysts realized using rotating electrodes are compared.

Direct observation of lithium metal dendrites with ceramic solid electrolyte.

Dendrite formation, which could cause a battery short circuit, occurs in batteries that contain lithium metal anodes. In order to suppress dendrite growth, the use of electrolytes with a high shear modulus is suggested as an ionic conductive separator in batteries. One promising candidate for this application is Li7La3Zr2O12 (LLZO) because it has excellent mechanical properties and chemical stability. In this work, in situ scanning electron microscopy (SEM) technique was employed to monitor the interface behavior between lithium metal and LLZO electrolyte during cycling with pressure. Using the obtained SEM images, videos were created that show the inhomogeneous dissolution and deposition of lithium, which induce dendrite growth. The energy dispersive spectroscopy analyses of dendrites indicate the presence of Li, C, and O elements. Moreover, the cross-section mapping comparison of the LLZO shows the inhomogeneous distribution of La, Zr, and C after cycling that was caused by lithium loss near the Li electrode and possible side reactions. This work demonstrates the morphological and chemical evolution that occurs during cycling in a symmetrical Li-Li cell that contains LLZO. Although the superior mechanical properties of LLZO make it an excellent electrolyte candidate for batteries, the further improvement of the electrochemical stabilization of the garnet-lithium metal interface is suggested.

Core hole screened electron energy loss calculations of beam damaged lithium fluoride.

A method of calculating the magnitude of the core hole screening of lithium materials is implemented for the simulation of Energy Loss Near Edge Structure (ELNES). ELNES is calculated for a range of lithium materials resulting in improved agreement between calculation and experiment. The technique uses linear response theory to relate the electron density to the core hole shielding contribution from the valence electrons in a crystal. This contribution is then implemented via a non-integer core hole in final state rule calculations.

High-Voltage Lithium-Ion Battery Using Substituted LiCoPO4: Electrochemical and Safety Performance of 1.2 Ah Pouch Cell.

A LiCoPO4-based high-voltage lithium-ion battery was fabricated in the format of a 1.2 Ah pouch cell that exhibited a highly stable cycle life at a cut-off voltage of 4.9 V. The high-voltage stability was achieved using a Fe-Cr-Si multi-ion-substituted LiCoPO4 cathode and lithium bis(fluorosulfonyl)imide in 1-methyl-1-propylpyrrolidinium bis(fluorosulfony)imide as the electrolyte. Due to the improved electrochemical stability at high voltage, the cell exhibited a stable capacity retention of 91% after 290 cycles without any gas evolution related to electrolyte decomposition at high voltage. In addition to improved cycling stability, the nominal 5 V LiCoPO4 pouch cell also exhibited excellent safety performance during a nail penetration safety test compared with a state-of-the-art lithium ion battery. Meanwhile, the thermal stabilities of the 1.2 Ah pouch cell as well as the delithiated LiCoPO4 were also studied by accelerating rate calorimetry (ARC), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and in situ X-ray diffraction (XRD) analyses and reported.

Lattice-Strain Engineering of Homogeneous NiS0.5 Se0.5 Core-Shell Nanostructure as a Highly Efficient and Robust Electrocatalyst for Overall Water Splitting.

Developing highly-efficient non-noble-metal electrocatalysts for water splitting is crucial for the development of clean and reversible hydrogen energy. Introducing lattice strain is an effective strategy to develop efficient electrocatalysts. However, lattice strain is typically co-created with heterostructure, vacancy, or substrate effects, which complicate the identification of the strain-activity correlation. Herein, a series of lattice-strained homogeneous NiSx Se1- x nanosheets@nanorods hybrids are designed and synthesized by a facile strategy. The NiS0.5 Se0.5 with ≈2.7% lattice strain exhibits outstanding activity for hydrogen and oxygen evolution reaction (HER/OER), affording low overpotentials of 70 and 257 mV at 10 mA cm-2 , respectively, as well as excellent long-term durability even at a large current density of 100 mA cm-2 (300 h), significantly superior to other benchmarks and the precious metal catalysts. Experimental and theoretical calculation results reveal that the generated lattice strain decreases the metal d-orbital overlap, leading to a narrower bandwidth and a closer d-band center toward the Fermi level. Thus, NiS0.5 Se0.5 possesses favorable H* adsorption kinetics for HER and lower energy barriers for OER. This work provides a new insight to regulate the lattice strain of advanced catalyst materials and further improve the performance of energy conversion technologies.

Phase Transformation of Doped LiCoPO4 during Galvanostatic Cycling.

In situ X-ray diffraction was employed to investigate the crystal structure changes in Cr/Si co-doped Li(Co,Fe)PO4 cathode material during a galvanostatic charge/discharge process at a slow rate of C/30. The evolution of the X-ray patterns revealed that the phase transformation between the Cr/Si-Li(Co,Fe)PO4 and Cr/Si-(Co,Fe)PO4 is a two-step process, which involves the formation of an intermediate compound of Cr/Si-Li0.62(Co,Fe)PO4 upon the extraction of Li ions from the pristine phase. Different from the previously reported two biphasic transition steps, the phase transformation of the Cr/Si-Li(Co,Fe)PO4 followed a solid solution and a biphasic reaction pathway at different stages of the delithiation/lithiation process, respectively.

Sulfide and Oxide Inorganic Solid Electrolytes for All-Solid-State Li Batteries: A Review.

Energy storage materials are finding increasing applications in our daily lives, for devices such as mobile phones and electric vehicles. Current commercial batteries use flammable liquid electrolytes, which are unsafe, toxic, and environmentally unfriendly with low chemical stability. Recently, solid electrolytes have been extensively studied as alternative electrolytes to address these shortcomings. Herein, we report the early history, synthesis and characterization, mechanical properties, and Li+ ion transport mechanisms of inorganic sulfide and oxide electrolytes. Furthermore, we highlight the importance of the fabrication technology and experimental conditions, such as the effects of pressure and operating parameters, on the electrochemical performance of all-solid-state Li batteries. In particular, we emphasize promising electrolyte systems based on sulfides and argyrodites, such as LiPS5Cl and ß-Li3PS4, oxide electrolytes, bare and doped Li7La3Zr2O12 garnet, NASICON-type structures, and perovskite electrolyte materials. Moreover, we discuss the present and future challenges that all-solid-state batteries face for large-scale industrial applications.

Comprehensive Review of Polymer Architecture for All-Solid-State Lithium Rechargeable Batteries.

Solid-state batteries are an emerging option for next-generation traction batteries because they are safe and have a high energy density. Accordingly, in polymer research, one of the main goals is to achieve solid polymer electrolytes (SPEs) that could be facilely fabricated into any preferred size of thin films with high ionic conductivity as well as favorable mechanical properties. In particular, in the past two decades, many polymer materials of various structures have been applied to improve the performance of SPEs. In this review, the influences of polymer architecture on the physical and electrochemical properties of an SPE in lithium solid polymer batteries are systematically summarized. The discussion mainly focuses on four principal categories: linear, comb-like, hyper-branched, and crosslinked polymers, which have been widely reported in recent investigations as capable of optimizing the balance between mechanical resistance, ionic conductivity, and electrochemical stability. This paper presents new insights into the design and exploration of novel high-performance SPEs for lithium solid polymer batteries.

Porous Carbon Membrane-Supported Atomically Dispersed Pyrrole-Type FeN4 as Active Sites for Electrochemical Hydrazine Oxidation Reaction.

The rational design of catalytically active sites in porous materials is essential in electrocatalysis. Herein, atomically dispersed Fe-Nx sites supported by hierarchically porous carbon membranes are designed to electrocatalyze the hydrazine oxidation reaction (HzOR), one of the key techniques in electrochemical nitrogen transformation. The high intrinsic catalytic activity of the Fe-Nx single-atom catalyst together with the uniquely mixed micro-/macroporous membrane support positions such an electrode among the best-known heteroatom-based carbon anodes for hydrazine fuel cells. Combined with advanced characterization techniques, electrochemical probe experiments, and density functional theory calculation, the pyrrole-type FeN4 structure is identified as the real catalytic site in HzOR.

Novel polymer coating for chemically absorbing CO2 for safe Li-ion battery.

Gas evolution in Li-ion batteries remains a barrier for the implementation of high voltage materials in a pouch cell format; the inflation of the pouch cell is a safety issue that can cause battery failure. In particular, for manganese-based materials employed for fabricating cathodes, the dissolution of Mn2+ in the electrolyte can accelerate cell degradation, and subsequently gas evolution, of which carbon dioxide (CO2) is a major component. We report on the utilization of a mixture of polymers that can chemically absorb the CO2, including the coating of aluminum foils, which serve as trapping sheets, introduced into two Ah pouch cells-based on a LiMnFePO4 (cathode) and a Li4Ti5O12 (anode). The pouch cells with trapping sheets experienced only an 8.0 vol% inflation (2.7 mmol CO2 per gram of polymers) as opposed to the 40 vol% inflation for the reference sample. Moreover, the cells were cycled for 570 cycles at 1 C and 45 °C before reaching 80% of their retention capacity.

Brief History of Early Lithium-Battery Development.

Lithium batteries are electrochemical devices that are widely used as power sources. This history of their development focuses on the original development of lithium-ion batteries. In particular, we highlight the contributions of Professor Michel Armand related to the electrodes and electrolytes for lithium-ion batteries.

Application of Magnetic Resonance Techniques to the In Situ Characterization of Li-Ion Batteries: A Review.

In situ magnetic resonance (MR) techniques, such as nuclear MR and MR imaging, have recently gained significant attention in the battery community because of their ability to provide real-time quantitative information regarding material chemistry, ion distribution, mass transport, and microstructure formation inside an operating electrochemical cell. MR techniques are non-invasive and non-destructive, and they can be applied to both liquid and solid (crystalline, disordered, or amorphous) samples. Additionally, MR equipment is available at most universities and research and development centers, making MR techniques easily accessible for scientists worldwide. In this review, we will discuss recent research results in the field of in situ MR for the characterization of Li-ion batteries with a particular focus on experimental setups, such as pulse sequence programming and cell design, for overcoming the complications associated with the heterogeneous nature of energy storage devices. A comprehensive approach combining proper hardware and software will allow researchers to collect reliable high-quality data meeting industrial standards.