Cu-N Synergism Regulation to Enhance Anionic Redox Reversibility and Activity of Li- and Mn-Rich Layered Oxides Cathode.

Anionic redox chemistry enables extraordinary capacity for Li- and Mn-rich layered oxides (LMROs) cathodes. Unfortunately, irreversible surface oxygen evolution evokes the pernicious phase transition, structural deterioration, and severe electrode-electrolyte interface side reaction with element dissolution, resulting in fast capacity and voltage fading of LMROs during cycling and hindering its commercialization. Herein, a redox couple strategy is proposed by utilizing copper phthalocyanine (CuPc) to address the irreversibility of anionic redox. The Cu-N synergistic effect of CuPc could not only inhibit surface oxygen evolution by reducing the peroxide ion O2 2- back to lattice oxygen O2-, but also enhance the reaction activity and reversibility of anionic redox in bulk to achieve a higher capacity and cycling stability. Moreover, the CuPc strategy suppresses the interface side reaction and induces the forming of a uniform and robust LiF-rich cathode electrolyte, interphase (CEI) to significantly eliminate transition metal dissolution. As a result, the CuPc-enhanced LMRO cathode shows superb cycling performance with a capacity retention of 95.0% after 500 long-term cycles. This study sheds light on the great effect of N-based redox couple to regulate anionic redox behavior and promote the development of high energy density and high stability LMROs cathode.

Electron Manipulation and Surface Reconstruction of Bimetallic Iron-Nickel Phosphide Nanotubes for Enhanced Alkaline Water Electrolysis.

Developing high-efficiency and stable bifunctional electrocatalysts for water splitting remains a great challenge. Herein, NiMoO4 nanowires as sacrificial templates to synthesize Mo-doped NiFe Prussian blue analogs are employed, which can be easily phosphorized to Mo-doped Fe2xNi2(1-x)P nanotubes (Mo-FeNiP NTs). This synthesis method enables the controlled etching of NiMoO4 nanowires that results in a unique hollow nanotube architecture. As a bifunctional catalyst, the Mo-FeNiP NTs present lower overpotential and Tafel slope of 151.3 (232.6) mV at 100 mA cm-2 and 76.2 (64.7) mV dec-1 for HER (OER), respectively. Additionally, it only requires an ultralow cell voltage of 1.47 V to achieve 10 mA cm-2 for overall water splitting and can steadily operate for 200 h at 100 mA cm-2. First-principles calculations demonstrate that Mo doping can effectively adjust the electron redistribution of the Ni hollow sites to optimize the hydrogen adsorption-free energy for HER. Besides, in situ Raman characterization reveals the dissolving of doped Mo can promote a rapid surface reconstruction on Mo-FeNiP NTs to dynamically stable (Fe)Ni-oxyhydroxide layers, serving as the actual active species for OER. The work proposes a rational approach addressed by electron manipulation and surface reconstruction of bimetallic phosphides to regulate both the HER and OER activity.

Recent Advances in Understanding of the Singlet Oxygen in Energy Storage and Conversion.

Singlet oxygen (term symbol 1 Δg , hereafter 1 O2 ), a reactive oxygen species, has recently attracted increasing interest in the field of rechargeable batteries and electrocatalysis and photocatalysis. These sustainable energy conversion and storage technologies are of vital significance to replace fossil fuels and promote carbon neutrality and finally tackle the energy crisis and climate change. Herein, the recent progresses of 1 O2 for energy storage and conversion is summarized, including physical and chemical properties, formation mechanisms, detection technologies, side reactions in rechargeable batteries and corresponding inhibition strategies, and applications in electrocatalysis and photocatalysis. The formation mechanisms and inhibition strategies of 1 O2 in particular aprotic lithium-oxygen (Li-O2 ) batteries are highlighted, and the applications of 1 O2 in photocatalysis and electrocatalysis is also emphasized. Moreover, the confronting challenges and promising directions of 1 O2 in energy conversion and storage systems are discussed.

Polymeric Electronic Shielding Layer Enabling Superior Dendrite Suppression for All-Solid-State Lithium Batteries.

LiBH4 is one of the most promising candidates for use in all-solid-state lithium batteries. However, the main challenges of LiBH4 are the poor Li-ion conductivity at room temperature, excessive dendrite formation, and the narrow voltage window, which hamper practical application. Herein, we fabricate a flexible polymeric electronic shielding layer on the particle surfaces of LiBH4. The electronic conductivity of the primary LiBH4 is reduced by 2 orders of magnitude, to 1.15 × 10-9 S cm-1 at 25 °C, due to the high electron affinity of the electronic shielding layer; this localizes the electrons around the BH4- anions, which eliminates electronic leakage from the anionic framework and leads to a 68-fold higher critical electrical bias for dendrite growth on the particle surfaces. Contrary to the previously reported work, the shielding layer also ensures fast Li-ion conduction due to the fast-rotational dynamics of the BH4- species and the high Li-ion (carrier) concentration on the particle surfaces. In addition, the flexibility of the layer guarantees its structural integrity during Li plating and stripping. Therefore, our LiBH4-based solid-state electrolyte exhibits a high critical current density (11.43 mA cm-2) and long cycling stability of 5000 h (5.70 mA cm-2) at 25 °C. More importantly, the electrolyte had a wide operational temperature window (-30-150 °C). We believe that our findings provide a perspective with which to avoid dendrite formation in hydride solid-state electrolytes and provide high-performance all-solid-state lithium batteries.

Experimentally validated design principles of heteroatom-doped-graphene-supported calcium single-atom materials for non-dissociative chemisorption solid-state hydrogen storage.

Non-dissociative chemisorption solid-state storage of hydrogen molecules in host materials is promising to achieve both high hydrogen capacity and uptake rate, but there is the lack of non-dissociative hydrogen storage theories that can guide the rational design of the materials. Herein, we establish generalized design principle to design such materials via the first-principles calculations, theoretical analysis and focused experimental verifications of a series of heteroatom-doped-graphene-supported Ca single-atom carbon nanomaterials as efficient non-dissociative solid-state hydrogen storage materials. An intrinsic descriptor has been proposed to correlate the inherent properties of dopants with the hydrogen storage capability of the carbon-based host materials. The generalized design principle and the intrinsic descriptor have the predictive ability to screen out the best dual-doped-graphene-supported Ca single-atom hydrogen storage materials. The dual-doped materials have much higher hydrogen storage capability than the sole-doped ones, and exceed the current best carbon-based hydrogen storage materials.

Inorganic All-Solid-State Sodium Batteries: Electrolyte Designing and Interface Engineering.

Inorganic all-solid-state sodium batteries (IASSSBs) are emerged as promising candidates to replace commercial lithium-ion batteries in large-scale energy storage systems due to their potential advantages, such as abundant raw materials, robust safety, low price, high-energy density, favorable reliability and stability. Inorganic sodium solid electrolytes (ISSEs) are an indispensable component of IASSSBs, gaining significant attention. Herein, this review begins by discussing the fundamentals of ISSEs, including their ionic conductivity, mechanical property, chemical and electrochemical stabilities. It then presents the crystal structures of advanced ISSEs (e.g., ß/ß''-alumina, NASICON, sulfides, complex hydride and halide electrolytes) and the related issues, along with corresponding modification strategies. The review also outlines effective approaches for forming intimate interfaces between ISSEs and working electrodes. Finally, current challenges and critical perspectives for the potential developments and possible directions to improve interfacial contacts for future practical applications of ISSEs are highlighted. This comprehensive review aims to advance the understanding and development of next-generation rechargeable IASSSBs.

Functional dissection of KATP channel structures reveals the importance of a conserved interface.

ATP-sensitive potassium channels (KATP) are inhibited by ATP but activated by Mg-ADP, coupling the intracellular ATP/ADP ratio to the potassium conductance of the plasma membrane. Although there has been progress in determining the structure of KATP, the functional significance of the domain-domain interface in the gating properties of KATP channels remains incompletely understood. In this study, we define the structure of KATP as two modules: KATPcore and SURABC. Based on this model, we identified two functionally important interfaces between these two modules, namely interface I and interface II. Further structure-guided mutagenesis experiments indicate that destabilizing interface II by deleting ECL3 on the SUR1 subunit impairs KNtp-independent Mg-ADP activation, demonstrating the essential role of intramolecular interactions between KATPcore and SURABC in Mg-ADP activation. Additionally, interface II is functionally conserved between SUR1 and SUR2, and the hydrophobic residue F351 on ECL3 of SUR1 is crucial for maintaining the stability of this interface.

Phase Transition Liquid Metal Enabled Emerging Biomedical Technologies and Applications.

Phase change materials that can absorb or release large amounts of heat during phase transition, play a critical role in many important processes, including heat dissipation, thermal energy storage, and solar energy utilization. In general, phase change materials are usually encapsulated in passive modules to provide assurance for energy management. The shape and mechanical changes of these materials are greatly ignored. An emerging class of phase change materials, liquid metals (LMs) have attracted significant interest beyond thermal management, including in transformable robots, flexible electronics, soft actuators, and biomedicine. Interestingly, the melting point of LM is highly tunable around body temperature, allowing it to experience considerable stiffness change when interacting with human organisms during solid-liquid change, which brings about novel phenomena, applied technologies, and therapeutic methods, such as mechanical destruction of tumors, neural electrode implantation technique, and embolization therapy. This review focuses on the technology, regulation, and application of the phase change process along with diverse changes of LM to facilitate emerging biomedical applications based on the influences of mechanical stiffness change and versatile regulation strategies. Typical applications will also be categorized and summarized. Lastly, the advantages and challenges of using the unique and reversible process for biomedicine will be discussed.

Lithium aluminum hydride Li3AlH6: new insight into the anode material for liquid-state lithium-ion batteries.

Metal hydrides have been demonstrated as one of the promising high-capacity anode materials for Li-ion batteries. Herein, we report the electrochemical properties and lithium storage mechanism of a Li-rich complex metal hydride (Li3AlH6). Li3AlH6 exhibits a lithiation capacity of ∼1729 mAh/g with a plateau potential of ∼0.33 V vs. Li+/Li at the first discharge cycle. Experimental results demonstrate that Li3AlH6 is converted into LiH and LiAl in the initial electrochemical lithiation process. In addition, Li3AlH6 also possesses a good cycling stability that 71 % of the second discharge capacity is retained after 20 cycles. More importantly, the cycling performance of Li3AlH6 can be improved to 100 cycles via adjusting electrolyte composition. This study provides a new approach for developing the lithium storage properties of anode materials for Li-ion batteries.

Oxygen Defect Engineering toward Zero-Strain V2O2.8@Porous Reticular Carbon for Ultrastable Potassium Storage.

Potassium-ion batteries (KIBs) are promising candidates for large-scale energy storage devices due to their high energy density and low cost. However, the large potassium-ion radius leads to its sluggish diffusion kinetics during intercalation into the lattice of the electrode material, resulting in electrode pulverization and poor cycle stability. Herein, vanadium trioxide anodes with different oxygen vacancy concentrations (V2O2.9, V2O2.8, and V2O2.7 determined by the neutron diffraction) are developed for KIBs. The V2O2.8 anode is optimal and exhibits excellent potassium storage performance due to the realization of expanded interlayer spacing and efficient ion/electron transport. In situ X-ray diffraction indicates that V2O2.8 is a zero-strain anode with a volumetric strain of 0.28% during the charge/discharge process. Density functional theory calculations show that the impacts of oxygen defects are embodied in reducing the band gap, increasing electron transfer ability, and lowering the diffusion energy barriers for potassium ions. As a result, the electrode of nanosized V2O2.8 embedded in porous reticular carbon (V2O2.8@PRC) delivers high reversible capacity (362 mAh g-1 at 0.05 A g-1), ultralong cycling stability (98.8% capacity retention after 3000 cycles at 2 A g-1), and superior pouch-type full-cell performance (221 mAh g-1 at 0.05 A g-1). This work presents an oxygen defect engineering strategy for ultrastable KIBs.

In-situ synthesis of porous Na3V2(PO4)3 with stable VOC bridge bonding by hard template method.

Low electronic conductivity and poor properties at high rate have hindered the application of Na3V2(PO4)3 (NVP). Herein, a facile synthesis of NVP with porous carbon skeleton is proposed. Specifically, Na2CO3 and glucose, acting as hard templates, are introduced to the precursors after initial firing stage, and Na2CO3 particles are removed by flushing after the final heatment. Due to the thermal conductivity of Na2CO3, the secondary addition of glucose can generate distinctive graphitized porous carbon skeleton, which bonds well with the amorphous carbon coating to construct stable and conductive network. The porous construction can alleviate the stress and strain caused by the current impact through deformation. Furthermore, ex-situ EIS reveals the highly conductive carbon skeleton can significantly reduce the surface resistance and result in an increase of effective voltage to promote the de-intercalation of Na+. Moreover, the ex-situ X-ray photoelectron spectroscopy (XPS) at different potentials confirms the stabilized existence of VOC bonds. Benefiting from the unique carbon skeleton, the PC-NVP releases capacity of 116.9 mAh g-1 at 0.1C. Even at 120C, PC-NVP still exhibits a high capacity of 84.7 mAh g-1, retaining a value of 41.3 mAh g-1 after 16,000 cycles, corresponding to a low decay rate of 0.0032% per cycle.

In-Situ-Generated Electron-Blocking LiH Enabling an Unprecedented Critical Current Density of Over 15 mA cm-2 for Solid-State Hydride Electrolytes.

LiBH4 is a promising solid-state electrolyte (SE) due to its thermodynamic stability to Li. However, poor Li-ion conductivities at room temperature, low oxidative stabilities, and severe dendrite growth hamper its application. In this work, a partial dehydrogenation strategy is adopted to in situ generate an electronic blocking layer dispersed of LiH, addressing the above three issues simultaneously. The electrically insulated LiH reduces the electronic conductivity by two orders of magnitude, leading to a 32.0-times higher critical electrical bias for dendrite growth on the particle surfaces than that of the counterpart. Additionally, this layer not only promotes the Li-ion conductance by stimulating coordinated rotations of BH4 - and B12 H12 2- , contributing to a Li-ion conductivity of 1.38 × 10-3 S cm-1 at 25 °C, but also greatly enhances oxidation stability by localizing the electron density on BH4 - , extending its voltage window to 6.0 V. Consequently, this electrolyte exhibits an unprecedented critical current density (CCD) of 15.12 mA cm-2 at 25 °C, long-term Li plating and stripping stability for 2700 h, and a wide temperature window for dendrite inhibition from -30 to 150 °C. Its Li-LiCoO2 cell displays high reversibility within 3.0-5.0 V. It is believed that this work provides a clear direction for solid-state hydride electrolytes.

Lithium Azides Induced SnS Quantum Dots for Ultra-Fast and Long-Term Sodium Storage.

Tin sulfide (SnS) is an attractive anode for sodium ion batteries (NIBs) because of its high theoretical capacity, while it seriously suffers from the inherently poor conductivity and huge volume variation during the cycling process, leading to inferior lifespan. To intrinsically maximize the sodium storage of SnS, herein, lithium azides (LiN3 )-induced SnS quantum dots (QDs) are first reported using a simple electrospinning strategy, where SnS QDs are uniformly distributed in the carbon fibers. Taking the advantage of LiN3 , which can effectively prevent the growth of crystal nuclei during the thermal treatment, the well-dispersed SnS QDs performs superior Na+ transfer kinetics and pseudocapacitive when used as an anode material for NIBs. The 3D SnS quantum dots embedded uniformly in N-doped nanofibers (SnS QDs@NCF) electrodes display superior long cycling life-span (484.6 mAh g-1 after 5800 cycles at 2 A g-1 and 430.9 mAh g-1 after 7880 cycles at 10 A g-1 ), as well as excellent rate capability (422.3 mAh g-1 at 20 A g-1 ). This fabrication of transition metal sulfides QDs composites provide a feasible strategy to develop NIBs with long life-span and superior rate capability to pave its practical implementation.

2D Layered Materials for Fast-Charging Lithium-Ion Battery Anodes.

The development of electric vehicles has received worldwide attention in the background of reducing carbon emissions, wherein lithium-ion batteries (LIBs) become the primary energy supply systems. However, commercial graphite-based anodes in LIBs currently confront significant difficulty in enduring ultrahigh power input due to the slow Li+ transport rate and the low intercalation potential. This will, in turn, cause dramatic capacity decay and lithium plating. The 2D layered materials (2DLMs) recently emerge as new fast-charging anodes and hold huge promise for resolving the problems owing to the synergistic effect of a lower Li+ diffusion barrier, a proper Li+ intercalation potential, and a higher theoretical specific capacity with using them. In this review, the background and fundamentals of fast-charging for LIBs are first introduced. Then the research progress recently made for 2DLMs used for fast-charging anodes are elaborated and discussed. Some emerging research directions in this field with a short outlook on future studies are further discussed.

Construction of Inorganic/Organic Hybrid Layer for Stable Na Metal Anode Operated under Wide Temperatures.

Sodium metal battery is supposed to be a propitious technology for high-energy storage application owing to the advantages of natural abundance and low cost. Unfortunately, the uncontrollable dendrite growth critically hampers its practical implementation. Herein, an inorganic/organic hybrid layer of NaF/CF/CC on the surface of Na foil (IOHL-Na) is designed and synthesized through the in situ reaction of polyvinylidene fluoride (PVDF) and metallic sodium. This protective layer possesses satisfactory Young's modulus, good kinetic property, and sodiophilicity, which can distinctly stabilize Na metal anode. As a result, the symmetric IOHL-Na cell achieves a lifespan of 770 h at 1 mAh cm-2 /1 mA cm-2 in carbonate electrolyte. The assembled full battery of IOHL-Na||Na3 V2 (PO4 )3 delivers a high discharge capacity of 85 mAh g-1 at 10 C after 600 cycles under ambient temperature. Furthermore, the IOHL-Na||Na3 V2 (PO4 )3 cell still can steadily operate at 10 C for 600 cycles at 55 °C. And when testing at an ultralow temperature of -40 °C, the full cell achieves 40 mAh g-1 at 0.5 C with a prolonged lifespan of 450 cycles. This work offers a new approach to protect the metal sodium anode without dendrite growth under wide temperatures.

Multi-Scale Structure Engineering of ZnSnO3 for Ultra-Long-Life Aqueous Zinc-Metal Batteries.

Suppressing the severe water-induced side reactions and uncontrolled dendrite growth of zinc (Zn) metal anodes is crucial for aqueous Zn-metal batteries to achieve ultra-long cyclic lifespans and promote their practical applications. Herein, a concept of multi-scale (electronic-crystal-geometric) structure design is proposed to precisely construct the hollow amorphous ZnSnO3 cubes (HZTO) for optimizing Zn metal anodes. In situ gas chromatography demonstrates that Zn anodes modified by HZTO (HZTO@Zn) can effectively inhibit the undesired hydrogen evolution. The pH stabilization and corrosion suppression mechanisms are revealed via operando pH detection and in situ Raman analysis. Moreover, comprehensive experimental and theoretical results prove that the amorphous structure and hollow architecture endow the protective HZTO layer with strong Zn affinity and rapid Zn2+ diffusion, which are beneficial for achieving the ideal dendrite-free Zn anode. Accordingly, excellent electrochemical performances for the HZTO@Zn symmetric battery (6900 h at 2 mA cm-2 , 100 times longer than that of bare Zn), HZTO@Zn||V2 O5 full battery (99.3% capacity retention after 1100 cycles), and HZTO@Zn||V2 O5 pouch cell (120.6 Wh kg-1 at 1 A g-1 ) are achieved. This work with multi-scale structure design provides significant guidance to rationally develop advanced protective layers for other ultra-long-life metal batteries.

Molecular Engineering on Solvation Structure of Carbonate Electrolyte toward Durable Sodium Metal Battery at -40 °C.

Carbonate electrolytes have excellent chemical stability and high salt solubility, which are ideally practical choice for achieving high-energy-density sodium (Na) metal battery at room temperature. However, their application at ultra-low temperature (-40 °C) is adversely affected by the instability of solid electrolyte interphase (SEI) formed by electrolyte decomposition and the difficulty of desolvation. Here, we designed a novel low-temperature carbonate electrolyte by molecular engineering on solvation structure. The calculations and experimental results demonstrate that ethylene sulfate (ES) reduces the sodium ion desolvation energy and promotes the forming of more inorganic substances on the Na surface, which promote ion migration and inhibit dendrite growth. At -40 °C, the Na||Na symmetric battery exhibits a stable cycle of 1500 hours, and the Na||Na3 V2 (PO4 )3 (NVP) battery achieves 88.2 % capacity retention after 200 cycles.

Water-Stabilized Vanadyl Phosphate Monohydrate Ultrathin Nanosheets toward High Voltage Al-Ion Batteries.

Al ion batteries (AIBs) are attracting considerable attention owing to high volumetric capacity, low cost, and high safety. However, the strong electrostatic interaction between Al3+ and host lattice leads to discontented cycling life and inferior rate capability. Herein, a new strategy of employing water molecules contained VOPO4 ·H2 O to boost Al3+ migration via the charge shielding effect of water is reported. It is revealed that VOPO4 ·H2 O with water lubrication effect and smaller steric hindrance owns high capacity and fast Al3+ diffusion, while the loss of unstable water upon cycling leads to a rapid performance degradation. To address this problem, ultrathin VOPO4 ·H2 O@MXene nanosheets are fabricated via the formed TiOV bond between VOPO4 ·H2 O and MXene. The MXene aided exfoliation results in enhanced VOwater bond strength between H2 O and VOPO4 that endows the obtained composite with strong water holding ability, contributing to the extraordinary cycling stability. Consequently, the VOPO4 ·H2 O@MXene delivers a high discharge potential of 1.8 V and maintains discharge capacities of 410 and 374.8 mAh g-1 after 420 and 2000 cycles at the current densities of 0.5 and 1.0 A g-1 , respectively. This work provides a new understanding of water-contained AIBs cathodes and vital guidance for developing high-performance AIBs.

Optimizing the Fermi Level of a 3D Current Collector with Ni3 S2 /Ni3 P Heterostructure for Dendrite-Free Sodium-Metal Batteries.

Rechargeable sodium-metal batteries (RSMBs) with high energy density and low cost are attracting extensive attention as promising energy-storage technologies. However, the poor cyclability and safety issues caused by unstable solid electrolyte interphase (SEI) structure and dendrite issues limit their practical application. Herein, it is theoretically predicted that constructing the Ni3 S2 /Ni3 P heterostructure with high work function can lower the Fermi energy level, and therefore effectively suppressing continuous electrolyte decomposition derived from the electron-tunneling effect after long-term sodiation process. Furthermore, the Ni3 S2 /Ni3 P heterostructure on 3D porous nickel foam (Ni3 S2 /Ni3 P@NF) is experimentally fabricated as an advanced Na-anode current collector. The seamless Ni3 S2 /Ni3 P heterostructure not only offers abundant active sites to induce uniform Na+ deposition and enhance ion-transport kinetics, but also facilitates the formation of stable SEI for dendrite-free sodium anode, which are confirmed by cryogenic components transmission electron microscopy tests and in situ spectroscopy characterization. As a result, the Na-composite anode (Ni3 S2 /Ni3 P@NF@Na) delivers stable plating/stripping process of 5000 h and high average Coulombic efficiency of 99.7% over 2500 cycles. More impressively, the assembled sodium-ion full cell displays ultralong cycle life of 10 000 cycles at 20 C. The strategy of stabilizing the sodium-metal anode gives fundamental insight into the potential construction of advanced RSMBs.

Topologically Porous Heterostructures for Photo/Photothermal Catalysis of Clean Energy Conversion.

As a straightforward way to fix solar energy, photo/photothermal catalysis with semiconductor provides a promising way to settle the energy shortage and environmental crisis in many fields, especially in clean energy conversion. Topologically porous heterostructures (TPHs), featured with well-defined pores and mainly composed by the derivatives of some precursors with specific morphology, are a major part of hierarchical materials in photo/photothermal catalysis and provide a versatile platform to construct efficient photocatalysts for their enhanced light absorption, accelerated charges transfer, improved stability, and promoted mass transportation. Therefore, a comprehensive and timely review on the advantages and recent applications of the TPHs is of great importance to forecast the potential applications and research trend in the future. This review initially demonstrates the advantages of TPHs in photo/photothermal catalysis. Then the universal classifications and design strategies of TPHs are emphasized. Besides, the applications and mechanisms of photo/photothermal catalysis in hydrogen evolution from water splitting and COx hydrogenation over TPHs are carefully reviewed and highlighted. Finally, the challenges and perspectives of TPHs in photo/photothermal catalysis are also critically discussed.