Regulating Electron Filling and Orbital Occupancy of Anti-Bonding States of Transition Metal Nitride Heterojunction for High Areal Capacity Lithium-Sulfur Full Batteries.

The commercialization of lithium-sulfur (Li-S) battery is seriously hindered by the shuttle behavior of lithium (Li) polysulfide, slow conversion kinetics, and Li dendrite growth. Herein, a novel hierarchical p-type iron nitride and n-type vanadium nitride (p-Fe2 N/n-VN) heterostructure with optimal electronic structure, confined in vesicle-like N-doped nanofibers (p-Fe2 N/n-VN⊂PNCF), is meticulously constructed to work as "one stone two birds" dual-functional hosts for both the sulfur cathode and Li anode. As demonstrated, the d-band center of high-spin Fe atom captures more electrons from V atom to realize more π* and moderate σ* bond electron filling and orbital occupation; thus, allowing moderate adsorption intensity for polysulfides and more effective d-p orbital hybridization to improve reaction kinetics. Meanwhile, this unique structure can dynamically balance the deposition and transport of Li on the anode; thereby, more effectively inhibiting Li dendrite growth and promoting the formation of a uniform solid electrolyte interface. The as-assembled Li-S full batteries exhibit the conspicuous capacities and ultralong cycling lifespan over 2000 cycles at 5.0 C. Even at a higher S loading (20 mg cm-2 ) and lean electrolyte (2.5 µL mg-1 ), the full cells can still achieve an ultrahigh areal capacity of 16.1 mAh cm-2 after 500 cycles at 0.1 C.

A restricted dynamic surface self-reconstruction toward high-performance of direct seawater oxidation.

The development of highly efficient electrocatalysts for direct seawater splitting with bifunctionality for inhibiting anodic oxidation reconstruction and selective oxygen evolution reactions is a major challenge. Herein, we report a direct seawater oxidation electrocatalyst that achieves long-term stability for more than 1000 h at 600 mA/cm2@η600 and high selectivity (Faraday efficiency of 100%). This catalyst revolves an amorphous molybdenum oxide layer constructed on the beaded-like cobalt oxide interface by atomic layer deposition technology. As demonstrated, a new restricted dynamic surface self-reconstruction mechanism is induced by the formation a stable reconstructed Co-Mo double hydroxide phase interface layer. The device assembled into a two-electrode flow cell for direct overall seawater electrolysis maintained at 1 A/cm2@1.93 V for 500 h with Faraday efficiency higher than 95%. Hydrogen generation rate reaches 419.4 mL/cm2/h, and the power consumption (4.62 KWh/m3 H2) is lower than that of pure water (5.0 KWh/m3 H2) at industrial current density.

Long Cycle Life for Rechargeable Lithium Battery using Organic Small Molecule Dihydrodibenzo[c,h][2,6]naphthyridine-5,11-dione as a Cathode after Isoindigo Pigment Isomerization.

Sustainability and adaptability in structural design of the organic cathodes present promises for applications in alkali metal ion batteries. Nevertheless, a formidable challenge lies in their high solubility in organic electrolytes, particularly for small molecular materials, impeding cycling stability and high capacity. This study focuses on the design and synthesis of organic small molecules, the isomers of (E)-5,5'-difluoro-[3,3'-biindolinylidene]-2,2'-dione (EFID) and 3,9-difluoro-6,12-dihydrodibenzo [c, h][2,6]naphthyridine-5,11-dione (FBND). While EFID, characterized by a less π-conjugated structure, exhibits subpar cycling stability in lithium-ion batteries (LIBs), intriguingly, another isomer, FBND, demonstrates exceptional capacity and cycling stability in LIBs. FBND delivers a remarkable capacity of 175 mAh g-1 at a current density of 0.05 A g-1 and maintains excellent cycling stability over 2000 cycles, retaining 90% of its initial capacity. Furthermore, an in-depth examination of redox reactions and storage mechanisms of FBND are conducted. The potential of FBND is also explored as an anode in lithium-ion batteries (LIBs) and as a cathode in sodium-ion batteries (SIBs). The FBND framework, featuring extended π-conjugated molecules with an imide structure compared to EFID, proves to be an excellent material template to develop advanced organic small molecular cathode materials for sustainable batteries.

Distinguished Roles of Nitrogen-Doped Sp2 and Sp3 Hybridized Carbon on Extraordinary Supercapacitance in Acidic Aqueous Electrolyte.

The acidic aqueous supercapacitors have been found to deliver appealing capacitive properties due to fast ion diffusion caused by the applied smallest size of hydrion. However, their practical applications are largely inhibited by the narrow electrochemical stability window of water (1.23 V). Herein, A nitrogen-enriched porous carbon materials (RNOPCs) is reported, consisting of varied nitrogen doping bonded on sp2 and sp3 carbon sites, which are capable of stimulating a wider potential window up to 1.4 V and thus resulting in a great enhancement of capacitive performance in aqueous acidic electrolytes. Together with the improved electrical conductivity and preferable hydrion diffusion, RNOPCs exhibit an ultrahigh volumetric capacitance (1084 F cm-3) in 0.5 M H2SO4. Besides, a fully packed RNOPCs-based symmetrical supercapacitor can deliver a high gravimetric and volumetric energy density of 31.8 Wh Kg-1 and 54.3 Wh L-1 respectively, approaching those of lead acid batteries (25-35 Wh Kg-1). The first-principles calculations reveal that the lone pair electrons of the doped nitrogen can be delocalized on its neighboring carbon atoms, improving charge uptakes and overpotentials. Such facile and scale-up production of carbon-based supercapacitors can bridge the gap of energy density between traditional supercapacitors and batteries in aqueous electrolytes.

Nitrogen Plasma Activates CoMn-Layered Double Hydroxides for Superior Electrochemical Oxygen Evolution.

Bimetallic layered double hydroxide is considered an ideal electrocatalytic material. However, due to the poor electrical conductivity of the bimetallic layered structure, obtaining highly active and stable catalysts through facile regulation strategies remains a great challenge. Herein, we use a simple corrosion strategy and nitrogen plasma technology to convert cobalt-based metal-organic frameworks into nitrogen-doped CoMn bimetallic layered double hydroxides (CoMn-LDH). Under the condition of regulating the local coordination environment of the catalytic active site and the presence of rich oxygen vacancy defects, N@CoMn-LDH/CC generates a low overpotential of 219 mV at 10 mA cm-2, which exceeds that of the commercial RuO2 catalyst. Density functional theory calculation shows that nitrogen doping improves the adsorption energy of the Mn site for oxygen evolution intermediates and reduces the reaction energy barrier of the Co site. Meanwhile, experiments and theoretical calculations verify that the mechanism of nitrogen doping regulating the oxygen evolution reaction (OER) follows the lattice oxygen oxidation mechanism, avoiding the collapse of the structure caused by catalyst reconstruction, thus improving the stability of oxygen evolution. This work provides a new simple strategy for the preparation of catalysts for a superior electrocatalytic oxygen evolution reaction.

High-Efficiency Oxygen Evolution Reaction: Controllable Reconstruction of Surface Interface.

The precatalyst undergoes surface reconstruction during the oxygen evolution reaction (OER) process, and the reconstituted material is the one that really plays a catalytic role. However, the degree of surface reconstruction seriously affects the catalytic performance. For this reason, it is important to establish the link between the degree of reconstruction and catalytic activity based on a deep understanding of the OER mechanism for the rational design of high-performance OER electrocatalysts. Here, the reaction mechanism of OER is briefly introduced, the competition between adsorbate evolution mechanism (AEM) mechanism and lattice oxygen-mediated mechanism (LOM) mechanism is discussed, and several activity descriptors of OER reaction are summarized. The strategies to realize OER controllable surface reconstruction are emphatically introduced, including ion leaching, element doping, regulating catalyst size, heterogeneous structure engineering, and self-reconstruction. A mechanistic perspective is emphasized to understand the relationship between dynamic surface reconstruction and electronic structure. Controlled reconfiguration of OER surface can break the limitation of proportional relationship brought by traditional AEM mechanism, also can realize the switching between AEM mechanism and LOM mechanism, thus realizing ultra-low overpotential. This review will provide some reference for surface controllable reconstruction of OER transition metal-based catalysts and reasonable development of ideal catalytic performance.

Modifying charge transfer between rhodium and ceria for boosted hydrogen oxidation reaction in alkaline electrolyte.

Sluggish kinetics of hydrogen oxidation reaction (HOR) in alkaline solution has restricted the rapid development of hydrogen economy. Constructing catalyst with metal-oxide heterostructures can enhance HOR performance; however, little studies concentrate on charge transfer between them, and the corresponding effects on reactions remain unclear. Herein, we report charge-transfer-adjustable CeO2/Rh interfaces uniformly dispersed on multiwalled carbon nanotube (CNT), which exhibit excellent alkaline HOR performance. Results confirm that the charge transfer from Rh to CeO2 could be conveniently tuned via thermal treatment. Consequently, the adsorption free energies of H* in Rh sites and OH* adsorption strength in CeO2 could be adjusted, as corroborated by density functional theory study. The optimized CeO2/Rh interfaces exhibit an exchange current density and a mass-specific kinetic current of 0.53 mA cmPGM-2 and 830 A gPGM-1 at an overpotential of 50 mV, respectively, which surpasses most of the advanced noble-metal-based electrocatalysts. This work provides a new insight of harnessing charge transfer of heterostructure to enhance catalytic activities.

Bivalent Cobalt as Efficient Catalyst Intercalation Layer Improves Polysulfide Conversion in Lithium-Sulfur Batteries.

Herein, we investigated in detail the effect of metal valences in different cobalt-based organic framework compounds on the kinetics of sulfur reaction in lithium-sulfur batteries (LSBs). On this basis, two organic framework compounds of zeolite-imidazole-based cobalt organic framework compound (Co-ZIF) and tetrakis(4-benzoic acid) porphyrinato-CoIII chloride [Co-TBP(III)] with different valences were constructed as the functional intercalation separators of LSBs, and explored the effects of different valences on improving the reaction kinetics of polysulfides and inhibiting the shuttle effect. Experiments and theoretical calculations prove that CoII exhibits the best catalytic activity. This is mainly due to the fact that +2 valence shows a strong adsorption energy for polysulfides and a higher Fermi level compared with +3 valence, thus improving the efficiency of the rapid catalytic conversion of sulfur species. As expected, the discharge specific capacity of Co-ZIF as the catalytic layer of the LSBs reached 772.7 mAh g-1 at a high current density of 5 C. More importantly, the initial specific capacity is 839.6 mAh g-1 at high current 3 C, and after 720 cycles, the attenuation rate of per cycle is only 0.092 %, and the coulombic efficiency remains above 92 %.

Flexible, Permeable, and Recyclable Liquid-Metal-Based Transient Circuit Enables Contact/Noncontact Sensing for Wearable Human-Machine Interaction.

The past several years have witnessed a rapid development of intelligent wearable devices. However, despite the splendid advances, the creation of flexible human-machine interfaces that synchronously possess multiple sensing capabilities, wearability, accurate responsivity, sensitive detectivity, and fast recyclability remains a substantial challenge. Herein, a convenient yet robust strategy is reported to craft flexible transient circuits via stencil printing liquid metal conductor on the water-soluble electrospun film for human-machine interaction. Due to the inherent liquid conductor within porous substrate, the circuits feature high-resolution, customized patterning viability, attractive permeability, excellent electroconductivity, and superior mechanical stability. More importantly, such circuits display appealing noncontact proximity capabilities while maintaining compelling tactile sensing performance, which is unattainable by traditional systems with compromised contact sensing. As such, the flexible circuit is utilized as wearable sensors with practical multifunctionality, including information transfer, smart identification, and trajectory monitoring. Furthermore, an intelligent human-machine interface composed of the flexible sensors is fabricated to realize specific goals such as wireless object control and overload alarm. The transient circuits are quickly and efficiently recycled toward high economic and environmental values. This work opens vast possibilities of generating high-quality flexible and transient electronics for advanced applications in soft and intelligent systems.

Flower-Like NiS2 /WS2 Heterojunction as Polysulfide/sulfide Bidirectional Catalytic Layer for High-Performance Lithium-Sulfur Batteries.

The slow sulfur oxidation-reduction kinetics are one of the key factors hindering the widespread use of lithium-sulfur batteries (LSBs). Herein, flower-shaped NiS2 -WS2 heterojunction as the functional intercalation of LSBs is successfully prepared, and effectively improved the reaction kinetics of sulfur. Flower-like nanospheres composed of ultra-thin nanosheets (≤10 nm) enhance quickly transfer of mass and charge. Meanwhile, the heterostructures simultaneously serve as an electron receptor and a donor, thereby simultaneously accelerating the bidirectional catalytic activity of reduction and oxidation reactions in the LSBs. In addition, the adsorption experiment, chemical state analysis of elements before and after the reaction and theoretical calculation have effectively verified that NiS2 -WS2 heterojunction nanospheres optimize the adsorption capacity and bidirectional catalytic effect of polysulfides. The results show that the initial discharge capacity of NiS2 -WS2 functional intercalation is as high as 1518.7 mAh g-1 at 0.2 C. Even at a high current density of 5 C, it still shows a discharge specific capacity of 615.7 mAh g-1 , showing excellent rate performance. More importantly, the capacity is 258.9 mAh g-1 after 1500 cycles at 5 C, and the attenuation per cycle is only 0.039%, and the Coulomb efficiency remains above 95%.

High Pseudocapacitance-Driven CoC2 O4 Electrodes Exhibiting Superior Electrochemical Kinetics and Reversible Capacities for Lithium-Ion and Lithium-Sulfur Batteries.

In this study, cuboid-like anhydrous CoC2 O4 particles (CoC2 O4 -HK) are synthesized through a potassium citrate-assisted hydrothermal method, which possess well-crystallized structure for fast Li+ transportation and efficient Li+ intercalation pseudocapacitive behaviors. When being used in lithium-ion batteries, the as-prepared CoC2 O4 -HK delivers a high reversible capacity (≈1360 mAh g-1 at 0.1 A g-1 ), good rate capability (≈650 mAh g-1 at 5 A g-1 ) and outstanding cycling stability (835 mAh g-1 after 1000 cycles at 1 A g-1 ). Characterizations illustrate that the Li+ -intercalation pseudocapacitance dominates the charge storage of CoC2 O4 -HK electrode, together with the reversible reaction of CoC2 O4 +2Li+ +2e- →Co+Li2 C2 O4 on discharging and charging. In addition, CoC2 O4 -HK particles are also used together with carbon-sulfur composite materials as the electrocatalysts for lithium-sulfur (Li-S) battery, which displays a gratifying sulfur electrochemistry with a high reversibility of 1021.5 mAh g-1 at 2 C and a low decay rate of 0.079% per cycle after 500 cycles. The density functional theory (DFT) calculations show that CoC2 O4 /C can regulate the adsorption-activation of reaction intermediates and therefore boost the catalytic conversion of polysulfides. Therefore, this work presents a new prospect of applying CoC2 O4 as the high-performance electrode materials for rechargeable Li-ion and Li-S batteries.

Tuning the Interface of Co1-xS/Co(OH)F by Atomic Replacement Strategy toward High-Performance Electrocatalytic Oxygen Evolution.

The construction of heterostructures is one of the most promising strategies for engineering interfaces of catalysts to perform high-efficiency oxygen evolution reaction (OER). However, accurately tuning heterostructures' interface during operation remains a challenge. Herein, we fabricated the needled-like heterostructure Co1-xS/Co(OH)F supported on flexible carbon fiber cloth via an atomic substitution strategy, in which sulfur atoms are simultaneously grafted into F vacancies after the partial removal of F atoms from Co(OH)F during the electrodeposition, thus achieving the growth of cobalt sulfide on the interface of Co(OH)F. This electrocatalyst with such design exhibits the following advantages: (1) The lattice distortion caused by atomic substitution leads to the increase of active sites; (2) Co1-xS constructed on the surface of Co(OH)F by the atomic replacement strategy optimizes the adsorption (OH-) and desorption (O2) energy in the OER process; (3) the needle-like structure possesses the tip-enhanced local electric field effect. As a result, the Co1-xS/Co(OH)F/CC catalyst exhibits very high OER catalytic performance with an overpotential of 269 mV at a current density of 10 mA cm-2 and a Tafel slope of 71 mV dec-1. The asymmetric electrode shows superior catalytic activity and stability in overall water splitting. The catalytic mechanism of these highly efficient Co1-xS/Co(OH)F/CC catalysts was investigated via DFT theoretical calculations and ex situ characterizations. This atomic substitution strategy displays universality for other transition metal sulfides (metal = Ni, Mn, Cu).

A Review on the Construction of Carbon-Based Metal Compound Composite Cathode Materials for Room Temperature Sodium-Sulfur Batteries.

Room temperature sodium-sulfur batteries are one of the most attractive energy storage systems due to their low cost, environmental friendliness, and ultra-high energy density. However, due to the inherent slow redox kinetics and the shuttle of polysulfides, the road of room temperature sodium-sulfur batteries to practical application is still full of difficulties. As a sulfur cathode, which is directly related to battery performance, a lot of research efforts have been devoted to it and many strategies have been proposed to solve the shuttle effect problem of sulfur cathodes. This paper analyzes the existing problems and solutions of sodium-sulfur batteries, mainly discusses and summarizes the research progress of constructing carbon-based cathode materials for sodium-sulfur batteries, and expounds the current research popular from two main directions. That is to construct advanced cathode materials based on two mechanisms of adsorption and electrocatalysis. Finally, the research direction of advanced sodium-sulfur batteries is prospected.

Hydroxylated Multi-Walled Carbon Nanotubes Covalently Modified with Tris(hydroxypropyl) Phosphine as a Functional Interlayer for Advanced Lithium-Sulfur Batteries.

We have successfully constructed a new type of intercalation membrane material by covalently grafting organic tris(hydroxypropyl)phosphine (THPP) molecules onto hydroxylated multi-walled carbon nanotubes (CNT-OH) as a functional interlayer for the advanced LSBs. The as-assembled interlayer has been demonstrated to be responsible for the fast conversion kinetics of polysulfides, the inhibition of polysulfide shuttle effect, as well as the formation of a stable solid electrolyte interphase(SEI) layer. By means of spectroscopic and electrochemical analysis, we further found THPP plays a key role in accelerating the conversion of polysulfides into low-ordered lithium sulfides and suppressing the loss of polysulfides, thus rendering the as-designed lithium-sulfur battery in this work a high capacity, excellent rate performance and long-term stability. Even at low temperatures, the capacity decay rate was only 0.036 % per cycle for 1700 cycles.

Challenges of layer-structured cathodes for sodium-ion batteries.

As the most promising alternative to lithium-ion batteries (LIBs), sodium-ion batteries (SIBs) still face many issues that hinder their large-scale commercialization. Layered transition metal oxide cathodes have attracted widespread attention owing to their large specific capacity, high ionic conductivity, and feasible preparation conditions. However, their electrochemical properties are usually limited by the irreversible phase transition and harsh storage conditions caused by humidity sensitivity. Recently, tremendous efforts have been devoted to solving these issues toward advanced high-performance layered oxide cathodes. Herein, we summarize these remaining challenges of layered oxide cathodes and the corresponding modification strategies such as the variations in chemical compositions, the architecture of (nano)micro-structures, surface engineering, and the regulation of phase compositions. We hope that the understanding presented in this review can provide useful guidance to developing high-performance layer-structured cathode materials for advanced SIBs.

Toward High-Performance Lithium-Sulfur Batteries: Efficient Anchoring and Catalytic Conversion of Polysulfides Using P-Doped Carbon Foam.

Rational design of the sulfur cathode structure enables effective adsorption of polysulfides and accelerates the sulfur reduction reaction, which is of great significance to the practical application of lithium-sulfur batteries. Here, P-doped carbon foam (PCF) as a sulfur host for the lithium-sulfur battery cathode was successfully synthesized by a facile strategy. The tailored hierarchical pore structure combined with P doping not only facilitates Li+ diffusion but also enhances the adsorption and accelerates the catalytic conversion of lithium polysulfides, thus significantly improving lithium storage performance of the PCF/S cathode.

A T-shaped gate tunneling field effect transistor with negative capacitance, super-steep subthreshold swing.

With the development of semiconductor technology, the size of traditional metal oxide semiconductor field effect transistor devices continues to decrease, but it cannot meet the requirements of high performance and low power consumption. Low power tunneling field effect transistor (TFET) has gradually become the focus of researchers. This paper proposes a novel T-shaped gate TFET based on the silicon with the negative capacitance (NC-TGTFET). On the basis of TGTFET, ferroelectric material (HZO) is used as gate dielectric. The simulation results show that, compared with the traditional TGTFET, the opening order and sensitivity of the two tunneling junctions are different. The influences of thickness and the doping concentration of pocket and ferroelectric material properties on the characteristics of NC-TGTFET is also discussed by Sentaurus simulation tool. Furthermore, the negative capacitance of ferroelectric material makes NC-TGTFET have a very steep subthreshold swing (18.32 mV/dec) at the range of drain current from 1 × 10-15to 1 × 10-7Aµm-1. And the on-state current (Vg= 0.5 V,Vd= 0.5 V) is 1.52 × 10-6Aµm-1.

In situ organic solvent-free synthesis of a novel red emitting Mn4+ doped KRbGeF6 phosphor at the room temperature.

Red emitting phosphors of Mn4+ doped fluorides are in high demand because the high color purities of phosphors make them potentially useful white light-emitting diodes (WLEDs) as backlights of electronic devices. We herein report an efficient red emitting phosphor KRbGeF6 : Mn4+ (KRGF : Mn) that was prepared by an in situ one-pot ion-exchange method at room temperature without organic solvents or HF. Homogenous mixtures of the starting materials with a stoichiometric KRGF : Mn ratio were partly dissolved in various acid solutions, and [MnF6]2- and [GeF6]2- successively underwent ion exchange under stirring. More importantly, in situ recrystallization of KRGF : Mn occurred simultaneously in solution with water as a solvent. Evidently, the formation of stable KRGF : Mn crystals propels the processes of dissolution and ion exchange. We also investigated the effect of inorganic acids on the resultant phases and photoluminescence properties of KRGF : Mn. The red phosphor KRGF : Mn prepared in HCl solution shows the highest luminescence intensity with an yield of 80%.

Strategic Atomic Layer Deposition and Electrospinning of Cobalt Sulfide/Nitride Composite as Efficient Bifunctional Electrocatalysts for Overall Water Splitting.

Reported herein is comprehensive study of a highly active and stable cobalt catalyst for overall water splitting. This composite SFCNF/Co1- x S@CoN, consisting of S-doped flexible carbon nanofiber (SFCNF) matrix, Co1- x S nanoparticles, and CoN coatings, is prepared by integration of electrospinning and atomic layer deposition (ALD) technique. Representative results include the following: 1) ultrathin CoN layer is deposited by ALD on the surface of flexible substrate without any sacrifice of SFCNF and Co1- x S; 2) the composite exhibits strong electrocatalytic activity in both acidic and basic solutions. The overpotentials of hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) are 20 and 180 mV, respectively, at a current density of 10 mA cm-2 in basic medium. A small Tafel slope of 54.4 mV dec-1 is observed in 0.5 m H2 SO4 electrolyte; 3) tested as overall water splitting electrode, the composite records a current density of 10 mA cm-2 at a relative low cell voltage of 1.58 V and long-term stability for 20 h at a current density of up to 50 mA cm-2 . The superior performance for overall water splitting is probably attributed to the synergistic effect of Co1- x S and ALD CoN. Specifically, implementation of ALD can be extended to innovate nanostructured materials for overall water splitting and even other renewable energy aspects.

Radially Inwardly Aligned Hierarchical Porous Carbon for Ultra-Long-Life Lithium-Sulfur Batteries.

Rational design of hollow micro- and/or nano-structured cathodes as sulfur hosts has potential for high-performance lithium-sulfur batteries. However, their further commercial application is hindered because infusing sulfur into hollow hosts is hard to control and the interactions between high loading sulfur and electrolyte are poor. Herein, we designed hierarchical porous hollow carbon nanospheres with radially inwardly aligned supporting ribs to mitigate these problems. Such a structure could aid the sulfur infusion and maximize sulfur utilization owing to the well-ordered pore channels. This highly organized internal carbon skeleton can also enhance the electronic conductivity. The hollow carbon nanospheres with further nitrogen-doping as the sulfur host material exhibit good capacity and excellent cycling performance (0.044 % capacity degradation per each cycle for 1000 cycles).