Electron Sponge Effect by Dynamic-Regulated Electron Self-Flow toward Coupled Electrochemical Ammonia Synthesis.

A dynamic-regulated Pd-Fe-N electrocatalyst was effectively constructed with electron-donating and back-donating effects, which serves as an efficient engineering strategy to optimize the electrocatalytic activity. The designed PdFe3/FeN features a comprehensive electrocatalytic performance toward the nitrogen reduction reaction (NRR, yield rate of 29.94 µg h-1 mgcat-1 and FE of 38.43% at -0.2 V vs RHE) and oxygen evolution reaction (OER, 308 mV at 100 mA cm-2). Combining in situ ATR-FTIR, XAS, and DFT results, the role of the interstitial-N-dopant-induced electron sponge effect has been significantly elucidated in strengthening the electrocatalytic NRR process. Specifically, the introduction of a N dopant, an electron acceptor, initiates the generation of robust Lewis-acidic Fe sites, facilitating free N2 capture and bonding. Simultaneously, after NH3 adsorption, the N dopant can back-donate electrons to Fe sites, strengthening the NH3 deportation through weakening the Lewis acidity of Fe centers. Besides, the electron-deficient Fe sites contribute to the reconstruction of FeOOH, the real active species during the OER, which accelerates the four-electron reaction kinetics. This research offers a perspective on electrocatalyst design, potentially facilitating the evolution of advanced material engineering for efficient electrocatalytic synthesis and energy storage.

Constructing Cyclic Hydrogen Bonding to Suppress Side Reactions and Dendrite Formation on Zinc Anodes.

The high electrochemical reactivity of H2O molecules and zinc metal results in severe side reactions and dendrite formation on zinc anodes. Here we demonstrate that these issues can be addressed by using N-hydroxymethylacetamide (NHA) as additives in 2 M ZnSO4 electrolytes. The addition of NHA molecules, acting as both a hydrogen bond donor and acceptor, enables the formation of cyclic hydrogen bonding with H2O molecules. This interaction disrupts the existing hydrogen bonding networks between H2O molecules, hindering proton transport, and containing H2O molecules within the cyclic hydrogen bonding structure to prevent deprotonation. Additionally, NHA molecules show a preference for adsorption on the (101) crystal surface of zinc metal. This preferential adsorption reduces the surface energy of the (101) plane, facilitating the homogeneous Zn deposition along the (101) direction. Thus, the NHA enables Zn||Zn symmetric cell with a cycle lifespan of 1100 hours at 5 mA cm-2 and Zn||Cu asymmetric cell with a high Coulombic efficiency over 99.5%. Moreover, the NHA-modified Zn||AC zinc ion hybrid capacitor is capable of sustaining 15000 cycles at 2 A g-1. This electrolyte additive engineering presents a promising strategy to enhance the performance and broaden the application potential of zinc metal-based energy storage devices.

Ultrathin carbon film as ultrafast rechargeable cathode for hybrid sodium dual-ion capacitor.

The development of electrochemical energy storage devices has a decisive impact on clean renewable energy. Herein, novel ultrafast rechargeable hybrid sodium dual-ion capacitors (HSDICs) were designed by using ultrathin carbon film (UCF) as the cathode material. The UCF is synthesized by a simple low temperature catalytic route followed by an acid leaching process. UCF owns a large adsorption interface and number of additional active sites, which is due to the nitrogen doping. In addition, there exists several short-range order carbons on the surface of UCF, which are beneficial for anionic storage. An ultrafast rechargeable remarkable performance, remarkable anion hybrid storage capability and outstanding structure stability is fully tapped employing UCF as cathode for HSDICs. The electrochemical performance of UCF in a half-cell system at the operating voltage between 1.0 and 4.8 V, achieving an admirable specific discharge capacity of 358.52 mAh·g-1at 500 mA·g-1, and a high capacity retention ratio of 98.42% after cycling 2500 times at 1000 mA·g-1, respectively. Besides, with the support ofex-situTEM and EDS mapping, the structural stability principle and anionic hybrid storage mechanism of UCF electrode are investigated in depth. In the full-cell system, HSDICs with the UCF as cathode and hard carbon as anode also presents a super-long cycle stability (80.62% capacity retention ratio after cycling 1300 times at 1000 mA·g-1).

Ambient Electrochemical Ammonia Synthesis: From Theoretical Guidance to Catalyst Design.

Ammonia, a vital component in the synthesis of fertilizers, plastics, and explosives, is traditionally produced via the energy-intensive and environmentally detrimental Haber-Bosch process. Given its considerable energy consumption and significant greenhouse gas emissions, there is a growing shift toward electrocatalytic ammonia synthesis as an eco-friendly alternative. However, developing efficient electrocatalysts capable of achieving high selectivity, Faraday efficiency, and yield under ambient conditions remains a significant challenge. This review delves into the decades-long research into electrocatalytic ammonia synthesis, highlighting the evolution of fundamental principles, theoretical descriptors, and reaction mechanisms. An in-depth analysis of the nitrogen reduction reaction (NRR) and nitrate reduction reaction (NitRR) is provided, with a focus on their electrocatalysts. Additionally, the theories behind electrocatalyst design for ammonia synthesis are examined, including the Gibbs free energy approach, Sabatier principle, d-band center theory, and orbital spin states. The review culminates in a comprehensive overview of the current challenges and prospective future directions in electrocatalyst development for NRR and NitRR, paving the way for more sustainable methods of ammonia production.

A Tough Monolithic-Integrated Triboelectric Bioplastic Enabled by Dynamic Covalent Chemistry.

Electronic waste is a growing threat to the global environment and human health, raising particular concerns. Triboelectric devices synthesized from sustainable and degradable materials are a promising electronic alternative, but the mechanical mismatch at the interface between the polymer substrate and the electrodes remains unresolved in practical applications. This study uses the sulfhydryl silanization reaction and the chemical selectivity and site specificity of the thiol-disulfide exchange reaction in dynamic covalent chemistry to prepare a tough monolithic-integrated triboelectric bioplastic. The stress is dissipated by covalent bond adaptation to the interface interaction, which makes the polymer dielectric layer to the conductive layer have a good interface adhesion effect (220.55 kPa). The interfacial interlocking of the polymer substrate with the conductive layer gives the triboelectric bioplastic excellent tensile strength (87.4 MPa) and fracture toughness (33.3 MJ m-3). Even when subjected to a tension force of 10 000 times its weight, it still maintains a stable triboelectric output with no visible cracks. This study provides new insights into the design of reliable and environmentally friendly self-powered devices, which is significant for the development of flexible wearable electronics.

Layer-Structured Multitransition-Metal Oxide Cathode Materials for Potassium-Ion Batteries with Long Cycling Lifespan and Superior Rate Capability.

Manganese (Mn)-based layer-structured transition metal oxides are considered as excellent cathode materials for potassium ion batteries (KIBs) owing to their low theoretical cost and high voltage plateau. The energy density and cycling lifetime, however, cannot simultaneously satisfy the basic requirements of the market for energy storage systems. One of the primary causes results from the complex structural transformation and transition metal migration during the ion intercalation and deintercalation process. The orbital and electronic structure of the octahedral center metal element plays an important role for maintaining the octahedral structural integrity and improving the K+ diffusivity by the introduced heterogeneous [Me-O] chemical bonding. A multitransition metal oxide, P3-type K0.5Mn0.85Co0.05Fe0.05Al0.05O2 (KMCFAO), was synthesized and employed as a cathode material for KIBs. Beneficial from the larger layer spacing for K+ to better accommodate and effectively preventing the irreversible structural transformation in the insertion/extraction process, it can reach a superior capacity retention up to 96.8% after 300 cycles at a current density of 500 mA g-1. The full cell of KMCFAO//hard carbon exhibits an encouraging promising energy density of 113.8 W h kg-1 at 100 mA g-1 and a capacity retention of 72.6% for 500 cycles.

Green, efficient extraction of bamboo hemicellulose using freeze-thaw assisted alkali treatment.

The premise of high value utilization of lignocellulosic biomass is effective separation of hemicellulose. In this paper, the extraction of bamboo hemicellulose using freeze-thaw assisted alkali treatment (FAT) was studied. The effect of alkali concentration, alkali treatment time, freezing temperature, and freeze-thaw time on the main components was studied. Bamboo was frozen at -30 °C for 12 h, thawed at room temperature, and then treated at 75 °C for 90 min with 7.0% alkali. The extraction rate of hemicellulose was as high as 64.71%. The purity of hemicellulose samples using conventional AT decreased from 82.63% to 78.56%. Hemicellulose with the same yield as that of conventional alkali treatment was obtained by further reducing the alkali concentration. The purity of hemicellulose samples increased from 82.63% to 89.45%. It had a higher purity, higher molecular weight, and lower polydispersity. A new, green and efficient alkaline extraction method for hemicellulose was developed.

Organic phosphomolybdate: a high capacity cathode for potassium ion batteries.

Homogeneous tetra-n-butylammonium phosphomolybdate (TBAPM) nanoparticles with an inter-connected structure were synthesized via a facile soft chemical route and firstly introduced into potassium ion batteries. The obtained novel TBAPM cathode delivers a high capacity of 232 mA h g-1 at 20 mA g-1 and shows slight decay during the subsequent cycle.

Effect of Pre-Corrected pH on the Carbohydrate Hydrolysis of Bamboo during Hydrothermal Pretreatment.

To confirm the prospects for application of pre-corrected pH hydrothermal pretreatment in biorefineries, the effects of pH on the dissolution and degradation efficiency of carbohydrates were studied. The species composition of the hydrolysate was analyzed using high efficiency anion exchange chromatography and UV spectroscopy. The result showed that the greatest balance between the residual solid and total dissolved solids was obtained at pH 4 and 170 °C. Maximum recovery rates of cellulose and lignin were as expected, whereas hemicellulose had the least recovery rate. The hemicellulose extraction rate was 42.19%, and the oligomer form accounted for 93.39% of the product. The physicochemical properties of bamboo with or without pretreatment was characterized. Compared with the traditional hydrothermal pretreatment, the new pretreatment bamboo has higher fiber crystallinity and thermal stability. In the pretreatment process, the fracture of ß-aryl ether bond was inhibited and the structural dissociation of lignin was reduced. The physicochemical properties of bamboo was protected while the hemicellulose was extracted efficiently. It provides theoretical support for the efficient utilization of all components of woody biomass.

Plum pudding model inspired KVPO4F@3DC as high-voltage and hyperstable cathode for potassium ion batteries.

The investigation on the cathode material of potassium ion batteries (PIBs), one of the most promising alternatives to lithium ion batteries, is of great significance. Potassium vanadium fluorophosphate (KVPO4F) with a high working voltage is an appealing cathode candidate for PIBs, while the poor cycling performance and low electronic conductivity dramatically hinder the application. Herein, a plum pudding model inspired three-dimensional amorphous carbon network modified KVPO4F composite (KVPO4F@3DC) is successfully designed in this study to tackle these problems. In the composite, KVPO4F particles are homogeneously wrapped by a layer of amorphous carbon and bridged by cross-linked large area carbon sheets. As the cathode for PIBs, the KVPO4F@3DC composite exhibits a high average operating voltage about 4.10 V with a super-high discharge capacity of 102.96 mAh g-1 at 20 mA g-1. An excellent long cycle stability with a capacity retention of 85.4% over 550 cycles at 500 mA g-1 is achieved. In addition, it maintains 83.6% of its initial capacity at 50 mA g-1 after 100 cycles at 55 °C. The design of KVPO4F@3DC with plum pudding structure provides facilitative electron conductive network and stable electrode/electrode interface for electrode, successfully innovating an ultra-stable and high-performance cathode material for potassium ion batteries.

Rational Design of a Polyimide Cathode for a Stable and High-Rate Potassium-Ion Battery.

Potassium has similar chemical characteristics compared with lithium while it is more abundant and of low cost, resulting in widespread research attention on potassium-ion batteries (PIBs). Developing organic polymer cathodes has garnered extensive attention because of their merits of environmental friendship and structure diversity, while confronted with inferior cycle stability and low rate performance. In this paper, we utilize the low-cost graphite nanosheets to stabilize polyimide (PI@G) for PIBs. Additionally, the potassium storage mechanism of PI@G was further evaluated; the highly reversible chemical bonds (C═O) of PI@G are responsible to its long-term stability. Consequently, the PI@G exhibits a maximal capacity of 142 mA h g-1 at the current density of 100 mA g-1 and maintains a capacity of 118 mA h g-1 after 500 cycles (corresponding to a capacity fade of 0.034% per cycle). Moreover, the full battery based on the PI@G cathode also reveals promisingly electrochemical performance. This study may have great significance to the application prospect of the organic cathode for PIBs.

Sb-MOFs derived Sb nanoparticles@porous carbon for high performance potassium-ion batteries anode.

Reasonable design of Sb-based nanomaterials, which can alleviate volume expansion, agglomeration and pulverization, is meaningful for PIBs. We used Sb-MOFs as precursors to perfectly and controllably embed uniform Sb nanoparticles (∼19 nm) into porous carbon networks through simple carbonization strategies and achieved excellent electrochemical performance for PIBs.

Graphene Armored with a Crystal Carbon Shell for Ultrahigh-Performance Potassium Ion Batteries and Aluminum Batteries.

Graphene is of great significance in energy storage devices. However, a graphene-based electrode is difficult to use in direct applications due to the large surface area and flexibility, which leads to the excessive consumption of electrolyte, low Coulombic efficiency, and electrode shedding behaviors. Herein, a special crystal carbon@graphene microsphere (CCGM) composite was successfully synthesized. The scalable carbonaceous microsphere composite displays a small specific surface area and a superior structure stability. As a potassium ion battery electrode in a half-cell, CCGM delivers an initial capacity of 297.89 mAh g-1 with a high Coulombic efficiency of about 99%. It achieves an excellent cyclic stability with no capacity loss after 1250 cycles at the low current density of 100 mA g-1 with a long performing period of more than one year. As the cathode for an aluminum battery, a reversible specific capacity of 99.1 mAh g-1 at 1000 mA g-1 is obtained. CCGM delivers a long cycle performance of about 10 000 cycles at 4000 mA g-1 with a capacity retention of nearly 100%. Our design provides a fresh thought for the improvement of graphene-based materials, and it will greatly facilitate the application of graphene in the field of energy storage.

Nature of Bimetallic Oxide Sb2MoO6/rGO Anode for High-Performance Potassium-Ion Batteries.

Potassium-ion batteries (KIBs) are one of the most appealing alternatives to lithium-ion batteries, particularly attractive in large-scale energy storage devices considering the more sufficient and lower cost supply of potassium resources in comparison with lithium. To achieve more competitive KIBs, it is necessary to search for anode materials with a high performance. Herein, the bimetallic oxide Sb2MoO6, with the presence of reduced graphene oxide, is reported as a high-performance anode material for KIBs in this study, achieving discharge capacities as high as 402 mAh g-1 at 100 mA g-1 and 381 mAh g-1 at 200 mA g-1, and reserving a capacity of 247 mAh g-1 after 100 cycles at a current density of 500 mA g-1. Meanwhile, the potassiation/depotassiation mechanism of this material is probed in-depth through the electrochemical characterization, operando X-ray diffraction, transmission electron microscope, and density functional theory calculation, successfully unraveling the nature of the high-performance anode and the functions of Sb and Mo in Sb2MoO6. More importantly, the phase development and bond breaking sequence of Sb2MoO6 are successfully identified, which is meaningful for the fundamental study of metal-oxide based electrode materials for KIBs.

In Situ Alloying Strategy for Exceptional Potassium Ion Batteries.

We report an in situ alloying strategy for obtaining homogeneous (Bi,Sb) alloy nanoparticles from (Bi,Sb)2S3 nanotubes for the exceptional anode of potassium ion batteries (KIBs). The operando X-ray diffraction results, along with transmission electron microscopy and energy-dispersive X-ray spectroscopy mappings, successfully reveal the phase evolution of this material, which is (Bi,Sb)2S3 → (Bi,Sb) → K(Bi,Sb) → K3(Bi,Sb) during the initial discharge and K3(Bi,Sb) → K(Bi,Sb) → (Bi,Sb) in the charging process. The in situ alloying strategy produces a synergistic effect and brings an outstanding electrochemical performance. It achieves ultrahigh discharge capacities of 611 mAh g-1 at 100 mA g-1 (0.135C) and 300 mAh g-1 at 1000 mA g-1 (1.35C) and retains a capacity as high as 353 mAh g-1 after 1000 cycles at 500 mA g-1 (0.675C) with a Coulombic efficiency close to 100%. In addition, the KIBs full cell, which is composed of this anode and a perylenetetracarboxylic dianhydride cathode, reaches an initial discharge capacity as high as 276 mAh g-1 at 500 mA g-1 and maintains 207 mAh g-1 after 100 cycles.

Carbon Nanoscrolls for Aluminum Battery.

This design provides a scalable route for in situ synthesizing of special carbon nanoscrolls as the cathode for an aluminum battery. The frizzy architectures are generated by a few graphene layers convoluting into the hollow carbon scroll, possessing rapid electronic transportation channels, superior anion storage capability, and outstanding ability of accommodating a large volume expansion during the cycling process. The electrochemical performance of the carbon nanoscroll cathode is fully tapped, displaying an excellent reversible discharge capacity of 104 mAh g-1 at 1000 mA g-1. After 55 000 cycles, this cathode retains a superior reversible specific capacity of 101.24 mAh g-1 at an ultrafast rate of 50 000 mA g-1, around 100% of the initial capacity, which demonstrates a superior electrochemical performance. In addition, anionic storage capability and structural stability are discussed in detail. The battery capacity under a wide temperature range from -80 to 120 °C is examined. At a low temperature of -25 °C, the battery delivers a discharge capacity of 62.83 mAh g-1 after 10 000 cycles, obtaining a capacity retention near 100%. In addition, it achieves a capacity of 99.5 mAh g-1 after 4000 cycles at a high temperature of 80 °C, with a capacity retention close to 100%. The carbon nanoscrolls possess an outstanding ultrafast charging/variable discharging rate performance surpassing all the batteries previously reported, which are highly promising for being applied in energy storage fields.

Ultrastable Potassium Storage Performance Realized by Highly Effective Solid Electrolyte Interphase Layer.

Potassium ion-batteries (PIBs) have attracted tremendous attention recently due to the abundance of potassium resources and the low standard electrode potential of potassium. Particularly, the solid-electrolyte interphase (SEI) in the anode of PIBs plays a vital role in battery security and battery cycling performance due to the highly reactive potassium. However, the SEI in the anode for PIBs with traditional electrolytes is mainly composed of organic compositions, which are highly reactive with air and water, resulting in inferior cycle performance and safety hazards. Herein, a highly stable and effective inorganic SEI layer in the anode is formed with optimized electrolyte. As expected, the PIBs exhibit an ultralong cycle performance over 14 000 cycles at 2000 mA g-1 and an ultrahigh average coulombic efficiency over 99.9%.

Molybdenum Disulfide-Coated Lithium Vanadium Fluorophosphate Anode: Experiments and First-Principles Calculations.

To develop a new anode material to meet the increasing demands of lithium-ion battery, MoS2 is used for the first time to modify the C/LiVPO4 F anode to improve its lithium-storage performance between 3 and 0.01 V. Morphological observations reveal that the MoS2 -modified C/LiVPO4 F particles (M-LVPF) are wrapped by an amorphous carbon as interlayer and layered MoS2 as external surface. Charge-discharge tests show that M-LVPF delivers a high reversible capacity of 308 mAh g(-1) at 50 mA g(-1) . After 300 cycles at 1.0 A g(-1) , a capacity retention of 98.7 % is observed. Moreover, it exhibits high rate capability with a specific capacity of 199 mAh g(-1) at 1.6 A g(-1) . Electrochemical impedance spectroscopy tests indicate that the lithium-ion diffusion and charge-exchange reaction at the surface of M-LVPF are greatly enhanced. First-principles calculations for the MoS2 (001)/C/LiVPO4 F (010) system demonstrate that the absorption of MoS2 on C/LiVPO4 F is exothermic and spontaneous and that the electron transfer at the MoS2 -absorbed C/LiVPO4 F surface is enhanced.