Minimizing Undesired Side Reactions Induced by Nanoscale Conductive Carbon Enables Stable Cycling of Semi-Solid Li-Ion Full Batteries.

Semi-solid lithium-ion batteries (SSLIBs) based on "slurry-like" electrodes hold great promise to enable low-cost and sustainable energy storage. However, the development of the SSLIBs has long been hindered by the lack of high-performance anodes. Here the origin of low initial Coulombic efficiency (iCE, typically <60%) is elucidated in the graphite-based semi-solid anodes (in the non-flowing mode) and develop rational strategies to minimize the irreversible capacity loss. It is discovered that Ketjen black (KB), a nanoscale conductive additive widely used in SSLIB research, induces severe electrolyte decomposition during battery charge due to its large surface area and abundant surface defects. High iCEs up to 92% are achieved for the semi-solid graphite anodes by replacing KB with other low surface-area, low-defect conductive additives. A semi-solid full battery (LiFePO4 vs graphite, in the non-flowing mode) is further demonstrated with stable cycle performance over 100 cycles at a large areal capacity of 6 mAh cm-2 and a pouch-type semi-solid full cell that remains functional even when it is mechanically abused. This work demystifies the SSLIBs and provides useful physical insights to further improve their performance and durability.

Ultrafast Charge-Discharge Capable and Long-Life Na3.9 Mn0.95 Zr0.05 V(PO4 )3 /C Cathode Material for Advanced Sodium-Ion Batteries.

Na4 MnV(PO4 )3 /C (NMVP) has been considered an attractive cathode for sodium-ion batteries with higher working voltage and lower cost than Na3 V2 (PO4 )3 /C. However, the poor intrinsic electronic conductivity and Jahn-Teller distortion caused by Mn3+ inhibit its practical application. In this work, the remarkable effects of Zr-substitution on prompting electronic and Na-ion conductivity and also structural stabilization are reported. The optimized Na3.9 Mn0.95 Zr0.05 V(PO4 )3 /C sample shows ultrafast charge-discharge capability with discharge capacities of 108.8, 103.1, 99.1, and 88.0 mAh g-1 at 0.2, 1, 20, and 50 C, respectively, which is the best result for cation substituted NMVP samples reported so far. This sample also shows excellent cycling stability with a capacity retention of 81.2% at 1 C after 500 cycles. XRD analyses confirm the introduction of Zr into the lattice structure which expands the lattice volume and facilitates the Na+ diffusion. First-principle calculation indicates that Zr modification reduces the band gap energy and leads to increased electronic conductivity. In situ XRD analyses confirm the same structure evolution mechanism of the Zr-modified sample as pristine NMVP, however the strong ZrO bond obviously stabilizes the structure framework that ensures long-term cycling stability.

Design principles for self-forming interfaces enabling stable lithium-metal anodes.

The path toward Li-ion batteries with higher energy densities will likely involve use of thin lithium (Li)-metal anode (<50 µm thickness), whose cyclability today remains limited by dendrite formation and low coulombic efficiency (CE). Previous studies have shown that the solid-electrolyte interface (SEI) of the Li metal plays a crucial role in Li-electrodeposition and -stripping behavior. However, design rules for optimal SEIs are not well established. Here, using integrated experimental and modeling studies on a series of structurally similar SEI-modifying model compounds, we reveal the relationship between SEI compositions, Li deposition morphology, and CE and identify two key descriptors for the fraction of ionic compounds and compactness, leading to high-performance SEIs. We further demonstrate one of the longest cycle lives to date (350 cycles for 80% capacity retention) for a high specific-energy Li||LiCoO2 full cell (projected >350 watt hours [Wh]/kg) at practical current densities. Our results provide guidance for rational design of the SEI to further improve Li-metal anodes.

Establishment of a simplified score for predicting risk during intrahospital transport of critical patients: A prospective cohort study.

AIMS AND OBJECTIVES: To establish a simple score that enables nurses to quickly, conveniently and accurately identify patients whose condition may change during intrahospital transport. BACKGROUND: Critically ill patients may experience various complications during intrahospital transport; therefore, it is important to predict their risk before they leave the emergency department. The existing scoring systems were not developed for this population. DESIGN: A prospective cohort study. METHODS: This study used convenience sampling and continuous enrolment from 1 January, 2019, to 30 June, 2021, and 584 critically ill patients were included. The collected data included vital signs and any condition change during transfer. The STROBE checklist was used. RESULTS: The median age of the modelling group was 74 (62, 83) years; 93 (19.7%) patients were included in the changed group, and 379 (80.3%) were included in the stable group. The five independent model variables (respiration, pulse, oxygen saturation, systolic pressure and consciousness) were statistically significant (p < .05). The above model was simplified based on beta coefficient values, and each variable was assigned 1 point, for a total score of 0-5 points. The AUC of the simplified score in the modelling group was 0.724 (95% CI: 0.682-0.764); the AUC of the simplified score in the validation group (112 patients) was 0.657 (95% CI: 0.566-0.741). CONCLUSIONS: This study preliminarily established a simplified scoring system for the prediction of risk during intrahospital transport from the emergency department to the intensive care unit. It provides emergency nursing staff with a simple assessment tool to quickly, conveniently and accurately identify a patient's transport risk. RELEVANCE TO CLINICAL PRACTICE: This study suggested the importance of strengthening the evaluation of the status of critical patients before intrahospital transport, and a simple score was formed to guide emergency department nurses in evaluating patients.

High temperature proton exchange membrane fuel cells: progress in advanced materials and key technologies.

High temperature proton exchange membrane fuel cells (HT-PEMFCs) are one type of promising energy device with the advantages of fast reaction kinetics (high energy efficiency), high tolerance to fuel/air impurities, simple plate design, and better heat and water management. They have been expected to be the next generation of PEMFCs specifically for application in hydrogen-fueled automobile vehicles and combined heat and power (CHP) systems. However, their high-cost and low durability interposed by the insufficient performance of key materials such as electrocatalysts and membranes at high temperature operation are still the challenges hindering the technology's practical applications. To develop high performance HT-PEMFCs, worldwide researchers have been focusing on exploring new materials and the related technologies by developing novel synthesis methods and innovative assembly techniques, understanding degradation mechanisms, and creating mitigation strategies with special emphasis on catalysts for oxygen reduction reaction, proton exchange membranes and bipolar plates. In this paper, the state-of-the-art development of HT-PEMFC key materials, components and device assembly along with degradation mechanisms, mitigation strategies, and HT-PEMFC based CHP systems is comprehensively reviewed. In order to facilitate further research and development of HT-PEMFCs toward practical applications, the existing challenges are also discussed and several future research directions are proposed in this paper.

Insight into Ca-Substitution Effects on O3-Type NaNi1/3 Fe1/3 Mn1/3 O2 Cathode Materials for Sodium-Ion Batteries Application.

O3-type NaNi1/3 Fe1/3 Mn1/3 O2 (NaNFM) is well investigated as a promising cathode material for sodium-ion batteries (SIBs), but the cycling stability of NaNFM still needs to be improved by using novel electrolytes or optimizing their structure with the substitution of different elements sites. To enlarge the alkali-layer distance inside the layer structure of NaNFM may benefit Na+ diffusion. Herein, the effect of Ca-substitution is reported in Na sites on the structural and electrochemical properties of Na1-x Cax/2 NFM (x = 0, 0.05, 0.1). X-ray diffraction (XRD) patterns of the prepared Na1-x Cax/2 NFM samples show single α-NaFeO2 type phase with slightly increased alkali-layer distance as Ca content increases. The cycling stabilities of Ca-substituted samples are remarkably improved. The Na0.9 Ca0.05 Ni1/3 Fe1/3 Mn1/3 O2 (Na0.9 Ca0.05 NFM) cathode delivers a capacity of 116.3 mAh g-1 with capacity retention of 92% after 200 cycles at 1C rate. In operando XRD indicates a reversible structural evolution through an O3-P3-P3-O3 sequence of Na0.9 Ca0.05 NFM cathode during cycling. Compared to NaNMF, the Na0.9 Ca0.05 NFM cathode shows a wider voltage range in pure P3 phase state during the charge/discharge process and exhibits better structure recoverability after cycling. The superior cycling stability of Na0.9 Ca0.05 NFM makes it a promising material for practical applications in sodium-ion batteries.

Asymmetric Volcano Trend in Oxygen Reduction Activity of Pt and Non-Pt Catalysts: In Situ Identification of the Site-Blocking Effect.

Proper understanding of the major limitations of current catalysts for oxygen reduction reaction (ORR) is essential for further advancement. Herein by studying representative Pt and non-Pt ORR catalysts with a wide range of redox potential (Eredox) via combined electrochemical, theoretical, and in situ spectroscopic methods, we demonstrate that the role of the site-blocking effect in limiting the ORR varies drastically depending on the Eredox of active sites; and the intrinsic activity of active sites with low Eredox have been markedly underestimated owing to the overlook of this effect. Accordingly, we establish a general asymmetric volcano trend in the ORR activity: the ORR of the catalysts on the overly high Eredox side of the volcano is limited by the intrinsic activity; whereas the ORR of the catalysts on the low Eredox side is limited by either the site-blocking effect and/or intrinsic activity depending on the Eredox.

Metal and Metal Oxide Interactions and Their Catalytic Consequences for Oxygen Reduction Reaction.

Many industrial catalysts are composed of metal particles supported on metal oxides (MMO). It is known that the catalytic activity of MMO materials is governed by metal and metal oxide interactions (MMOI), but how to optimize MMO systems via manipulation of MMOI remains unclear, due primarily to the ambiguous nature of MMOI. Herein, we develop a Pt/NbOx/C system with tunable structural and electronic properties via a modified arc plasma deposition method. We unravel the nature of MMOI by characterizing this system under reactive conditions utilizing combined electrochemical, microscopy, and in situ spectroscopy. We show that Pt interacts with the Nb in unsaturated NbOx owing to the oxygen deficiency in the MMO interface, whereas Pt interacts with the O in nearly saturated NbOx, and further interacts with Nb when the oxygen atoms penetrate into the Pt cluster at elevated potentials. While the Pt-Nb interactions do not benefit the inherent activity of Pt toward oxygen reduction reaction (ORR), the Pt-O interactions improve the ORR activity by shortening the Pt-Pt bond distance. Pt donates electrons to NbOx in both Pt-Nb and Pt-O cases. The resultant electron eficiency stabilizes low-coordinated Pt sites, hereby stabilizing small Pt particles. This determines the two characteristic features of MMO systems: dispersion of small metal particles and high catalytic durability. These findings contribute to our understandings of MMO catalytic systems.

Experimental Proof of the Bifunctional Mechanism for the Hydrogen Oxidation in Alkaline Media.

Realization of the hydrogen economy relies on effective hydrogen production, storage, and utilization. The slow kinetics of hydrogen evolution and oxidation reaction (HER/HOR) in alkaline media limits many practical applications involving hydrogen generation and utilization, and how to overcome this fundamental limitation remains debatable. Here we present a kinetic study of the HOR on representative catalytic systems in alkaline media. Electrochemical measurements show that the HOR rate of Pt-Ru/C and Ru/C systems is decoupled to their hydrogen binding energy (HBE), challenging the current prevailing HBE mechanism. The alternative bifunctional mechanism is verified by combined electrochemical and in situ spectroscopic data, which provide convincing evidence for the presence of hydroxy groups on surface Ru sites in the HOR potential region and its key role in promoting the rate-determining Volmer step. The conclusion presents important references for design and selection of HOR catalysts.

Graphene-wrapped yolk-shell of silica-cobalt oxide as high-performing anode for lithium-ion batteries.

Silica (SiO2) shows promise as anode material for lithium-ion batteries due to its low cost, comparable lithium storage discharge potential and high theoretical capacity (approximately 1961 mA h g-1). However, it is plagued by issues of low electrochemical activity, low conductivity and severe volume expansion. To address these challenges, we initially coat SiO2 with CoO, followed by introducing SiO2@CoO into graphene sheets to fabricate an anode composite material (SiO2@CoO/GS) with uniformly dispersed particles and a 3D graphene wrapped yolk-shell structure. The coating of CoO on SiO2 converted the negative surface charge of SiO2 to positive, enabling effective electrostatic interactions between SiO2@CoO and graphene oxide sheets, which provided essential prerequisites for synthesizing composite materials with uniformly dispersed particles and good coating effects. Furthermore, the Co-metal formed during the charge-discharge process can act as a catalyst and electron transfer medium, activating the lithium storage activity of SiO2 and enhancing the conductivity of the electrode, conclusively achieving a higher lithium storage capacity. Ultimately, due to the activation of SiO2 by Co-metal during cycling and the excellent synergistic effect between SiO2@CoO and graphene, SiO2@CoO/GS delivers a high reversible capacity of 738 mA h g-1 after 500 cycles at 200 mA g-1. The product also demonstrates excellent rate performance with a reversible capacity of 206 mA h g-1 at a high specific current of 12.8 A g-1. The outstanding rate performance of SiO2@CoO/GS may be ascribed to the pseudo-capacitive contribution at high specific current upon cycling.

Stable Operation Induced by Plastic Crystal Electrolyte Used in Ni-Rich NMC811 Cathodes for Li-Ion Batteries.

The LiNi0.8Mn0.1Co0.1O2 (NMC811) cathode material has been of significant consideration owing to its high energy density for Li-ion batteries. However, the poor cycling stability in a carbonate electrolyte limits its further development. In this work, we report the excellent electrochemical performance of the NMC811 cathode using a rational electrolyte based on organic ionic plastic crystal N-ethyl-N-methyl pyrrolidinium bis(fluorosulfonyl)imide C2mpyr[FSI], with the addition of (1:1 mol) LiFSI salt. This plastic crystal electrolyte (PC) is a thick viscous liquid with an ionic conductivity of 2.3 × 10-3 S cm-1 and a high Li+ transference number of 0.4 at ambient temperature. The NMC811@PC cathode delivers a discharge capacity of 188 mA h g-1 at a rate of 0.2 C with a capacity retention of 94.5% after 200 cycles, much higher than that of using a carbonate electrolyte (54.3%). Moreover, the NMC811@PC cathode also exhibits a superior high-rate capability with a discharge capacity of 111.0 mA h g-1 at the 10 C rate. The significantly improved cycle performance of the NMC811@PC cathode can be attributed to the high Li+ conductivity of the PC electrolyte, the stable Li+ conductive CEI film, and the maintaining of particle integrity during long-term cycling. The admirable electrochemical performance of the NMC811|C2mpyr[FSI]:[LiFSI] system exhibits a promising application of the plastic crystal electrolyte for high voltage layered oxide cathode materials in advanced lithium-ion batteries.

Prussian blue/RGO with less coordinated water as superior cathode material for sodium-ion batteries.

A micro-cubic Prussian blue (PB) with less coordinated water is first developed by electron exchange between graphene oxide and PB. The obtained reduced graphene oxide-PB composite exhibited increased redox reactions of the Fe sites and delivered ultrahigh specific capacity of 163.3 mA h g-1 (30 mA g-1) as well as excellent cycle stability as a cathode in sodium-ion batteries.

Retraction: Prussian blue without coordinated water as a superior cathode for sodium-ion batteries.

Retraction of 'Prussian blue without coordinated water as a superior cathode for sodium-ion batteries' by Dezhi Yang et al., Chem. Commun., 2015, 51, 8181-8184, https://doi.org/10.1039/C5CC01180A.

Mg2+-Doping Constructed a Continuous and Homogeneous Cathode-Electrolyte Interphase Film on Na3.12Fe2.44(P2O7)2 with Superior and Stable High-Temperature Performance for Sodium-Ion Storage.

Sodium-ion batteries (SIBs) are on the verge of achieving practical applications, and the key is to find suitable electrode materials. The polyanionic iron-based material Na3.12Fe2.44(P2O7)2 (NFPO) possesses an open three-dimensional framework structure with good thermal stability and is regarded as an outstanding cathode material for SIBs. Nevertheless, its poor electrical conductivity, problems with erosion of electrolytes, and structural deterioration during cycling still need to be urgently addressed. Here, we first design a Mg2+-doped NFPO (NFPO-Mg) material with a dual-action effect. On the one hand, Mg2+ improves the intrinsic conductivity of the NFPO material, and on the other hand, Mg2+ promotes the formation of a homogeneous and stable cathode-electrolyte interphase film during the cycling process, which results in a superior rate performance and cycling stability. A capacity of 68.6 mAh g-1 was achieved at 50C (1C = 117.4 mAh g-1), and a capacity retention of 79.1% was maintained after 3000 cycles at 20C. More impressively, NFPO-Mg exhibits outstanding high-temperature electrochemical performance, with a capacity retention of 95.3% after 400 cycles at 10C at 60 °C (much higher than the 54.2% for the NFPO). This paper explores an effective method for improving the electrochemical performance of cathode materials, which may prove instrumental in guiding the design of more high-performance cathode materials in the future.

Structural and chemical evolution in layered oxide cathodes of lithium-ion batteries revealed by synchrotron techniques.

Rechargeable battery technologies have revolutionized electronics, transportation and grid energy storage. Many materials are being researched for battery applications, with layered transition metal oxides (LTMO) the dominating cathode candidate with remarkable electrochemical performance. Yet, daunting challenges persist in the quest for further battery developments targeting lower cost, longer lifespan, improved energy density and enhanced safety. This is, in part, because of the intrinsic complexity of real-world batteries, featuring sophisticated interplay among microstructural, compositional and chemical heterogeneities, which has motivated tremendous research efforts using state-of-the-art analytical techniques. In this research field, synchrotron techniques have been identified as a suite of effective methods for advanced battery characterization in a non-destructive manner with sensitivities to the lattice, electronic and morphological structures. This article provides a holistic overview of cutting-edge developments in synchrotron-based research on LTMO battery cathode materials. We discuss the complexity and evolution of LTMO's material properties upon battery operation and review recent synchrotron-based research works that address the frontier challenges and provide novel insights in this field. Finally, we formulate a perspective on future directions of synchrotron-based battery research, involving next-generation X-ray facilities and advanced computational developments.

A High-Rate, Durable Cathode for Sodium-Ion Batteries: Sb-Doped O3-Type Ni/Mn-Based Layered Oxides.

O3-Type layered oxides are widely studied as cathodes for sodium-ion batteries (SIBs) due to their high theoretical capacities. However, their rate capability and durability are limited by tortuous Na+ diffusion channels and complicated phase evolution during Na+ extraction/insertion. Here we report our findings in unravelling the mechanism for dramatically enhancing the stability and rate capability of O3-NaNi0.5Mn0.5-xSbxO2 (NaNMS) by substitutional Sb doping, which can alter the coordination environment and chemical bonds of the transition metal (TM) ions in the structure, resulting in a more stable structure with wider Na+ transport channels. Furthermore, NaNMS nanoparticles are obtained by surface energy regulation during grain growth. The synergistic effect of Sb doping and nanostructuring greatly reduces the ionic migration energy barrier while increasing the reversibility of the structural evolution during repeated Na+ extraction/insertion. An optimized NaNMS-1 electrode delivers a reversible capacity of 212.3 mAh g-1 at 0.2 C and 74.5 mAh g-1 at 50 C with minimal capacity loss after 100 cycles at a low temperature of -20 °C. Such electrochemical performance is superior to most of the reported layered oxide cathodes used in rechargeable SIBs.

Toward High-Performance Mg-S Batteries via a Copper Phosphide Modified Separator.

Magnesium-sulfur (Mg-S) batteries are emerging as a promising alternative to lithium-ion batteries, due to their high energy density and low cost. Unfortunately, current Mg-S batteries typically suffer from the shuttle effect that originates from the dissolution of magnesium polysulfide intermediates, leading to several issues such as rapid capacity fading, large overcharge, severe self-discharge, and potential safety concern. To address these issues, here we harness a copper phosphide (Cu3P) modified separator to realize the adsorption of magnesium polysulfides and catalyzation of the conversion reaction of S and Mg2+ toward stable cycling of Mg-S cells. The bifunctional layer with Cu3P confined in a carbon matrix is coated on a commercial polypropylene membrane to form a porous membrane with high electrolyte wettability and good thermal stability. Density functional theory (DFT) calculations, polysulfide permeability tests, and post-mortem analysis reveal that the catalytic layer can adsorb polysulfides, effectively restraining the shuttle effect and facilitating the reversibility of the Mg-S cells. As a result, the Mg-S cells can achieve a high specific capacity, fast rates (449 mAh g-1 at 0.1 C and 249 mAh g-1 at 1.0 C), and a long cycle life (up to 500 cycles at 0.5 C) and operate even at elevated temperatures.

Thermal-healing of lattice defects for high-energy single-crystalline battery cathodes.

Single-crystalline nickel-rich cathodes are a rising candidate with great potential for high-energy lithium-ion batteries due to their superior structural and chemical robustness in comparison with polycrystalline counterparts. Within the single-crystalline cathode materials, the lattice strain and defects have significant impacts on the intercalation chemistry and, therefore, play a key role in determining the macroscopic electrochemical performance. Guided by our predictive theoretical model, we have systematically evaluated the effectiveness of regaining lost capacity by modulating the lattice deformation via an energy-efficient thermal treatment at different chemical states. We demonstrate that the lattice structure recoverability is highly dependent on both the cathode composition and the state of charge, providing clues to relieving the fatigued cathode crystal for sustainable lithium-ion batteries.

Spray-dried assembly of 3D N,P-Co-doped graphene microspheres embedded with core-shell CoP/MoP@C nanoparticles for enhanced lithium-ion storage.

The advancement of novel synthetic approaches for micro/nanostructural manipulation of transition metal phosphide (TMP) materials with precisely controlled engineering is crucial to realize their practical use in batteries. Here, we develop a novel spray-drying strategy to construct three-dimensional (3D) N,P co-doped graphene (G-NP) microspheres embedded with core-shell CoP@C and MoP@C nanoparticles (CoP@C⊂G-NP, MoP@⊂G-NP). This intentional design shows a close correlation between the microstructural G-NP and chemistry of the core-shell CoP@C/MoP@C nanoparticle system that contributes towards their anode performance in lithium-ion batteries (LIBs). The obtained structure features a conformal porous G-NP framework prepared via the co-doping of heteroatoms (N,P) that features a 3D conductive highway that allows rapid ion and electron passage and maintains the overall structural integrity of the material. The interior carbon shell can efficiently restrain volume evolution and prevent CoP/MoP nanoparticle aggregation, providing excellent mechanical stability. As a result, the CoP@C⊂G-NP and MoP@⊂G-NP composites deliver high specific capacities of 823.6 and 602.9 mA h g-1 at a current density of 0.1 A g-1 and exhibit excellent cycling stabilities of 438 and 301 mA h g-1 after 500 and 800 cycles at 1 A g-1. The present work details a novel approach to fabricate core-shell TMPs@C⊂G-NP-based electrode materials for use in next-generation LIBs and can be expanded to other potential energy storage applications.

Multifunctional Catalyst CuS for Nonaqueous Rechargeable Lithium-Oxygen Batteries.

Copper sulfide with flower-like (f-CuS) and carambola-like (c-CuS) morphologies was successfully synthesized by a facile one-step solvothermal route with different surfactants. When employed as cathode catalysts for lithium-oxygen batteries (LOBs), f-CuS outperforms c-CuS in terms of oxygen electrochemistry, judging from the faster kinetics and the higher reversibility of oxygen reduction/oxidation reactions, as well as the better LOB performance. Moreover, an abnormal high-potential discharge plateau was observed in the discharge profile of the LOB. To understand the different performances of f-CuS and c-CuS and the abnormal high-potential plateau, theoretical calculations were conducted, based on which a mechanism was proposed and verified with experiments. On the whole, CuS can work as a multifunctional catalyst for promoting LOB performance, which means that the dissolved CuS in LiTFSI/TEGDME electrolyte can serve as a liquid catalyst by the redox couples of Cu(TFSI)2/Cu(TFSI)2-/Cu(TFSI)22-, in addition to the function as a traditional solid catalyst in the cathode.