Highly Reversible Sodium-ion Storage in A Bifunctional Nanoreactor Based on Single-atom Mn Supported on N-doped Carbon over MoS2 Nanosheets.

Conversion-type electrode materials have gained massive research attention in sodium-ion batteries (SIBs), but their limited reversibility hampers practical use. Herein, we report a bifunctional nanoreactor to boost highly reversible sodium-ion storage, wherein a record-high reversible degree of 85.65% is achieved for MoS2 anodes. Composed of nitrogen-doped carbon-supported single atom Mn (NC-SAMn), this bifunctional nanoreactor concurrently confines active materials spatially and catalyzes reaction kinetics. In-situ/ex-situ characterizations including spectroscopy, microscopy, and electrochemistry, combined with theoretical simulations containing density functional theory and molecular dynamics, confirm that the NC-SAMn nanoreactors facilitate the electron/ion transfer, promote the distribution and interconnection of discharging products (Na2S/Mo), and reduce the Na2S decomposition barrier.As a result, the nanoreactor-promoted MoS2 anodes exhibit ultra-stable cycling with a capacity retention of 99.86% after 200 cycles in the full cell. This work demonstrates the superiority of bifunctional nanoreactors with two-dimensional confined and catalytic effects, providing a feasible approach to improve the reversibility for a wide range of conversion-type electrode materials, thereby enhancing the application potential for long-cycled SIBs.

Anion-Reinforced Solvation Structure Enables Stable Operation of Ether-Based Electrolyte in High-Voltage Potassium Metal Batteries.

Electrolytes with anion-dominated solvation are promising candidates to achieve dendrite-free and high-voltage potassium metal batteries. However, it's challenging to form anion-reinforced solvates at low salt concentrations. Herein, we construct an anion-reinforced solvation structure at a moderate concentration of 1.5 M with weakly coordinated cosolvent ethylene glycol dibutyl ether. The unique solvation structure accelerates the desolvation of K+, strengthens the oxidative stability to 4.94 V and facilitates the formation of inorganic-rich and stable electrode-electrolyte interface. These enable stable plating/stripping of K metal anode over 2200 h, high capacity retention of 83.0 % after 150 cycles with a high cut-off voltage of 4.5 V in K0.67MnO2//K cells, and even 91.5 % after 30 cycles under 4.7 V. This work provides insight into weakly coordinated cosolvent and opens new avenues for designing ether-based high-voltage electrolytes.

Electrolyte-Induced Morphology Evolution to Boost Potassium Storage Performance of Perylene-3,4,9,10-tetracarboxylic Dianhydride.

Organic materials have attracted extensive attention for potassium-ion batteries due to their flexible structure designability and environmental friendliness. However, organic materials generally suffer from unavoidable dissolution in aprotic electrolytes, causing an unsatisfactory electrochemical performance. Herein, we designed a weakly solvating electrolyte to boost the potassium storage performance of perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA). The electrolyte induces an in situ morphology evolution and achieves a nanowire structure. The weakly dissolving capability of ethylene glycol diethyl ether-based electrolyte and unique nanowire structure effectively avoid the dissolution of PTCDA. As a result, PTCDA shows excellent cycling stability (a capacity retention of 89.1% after 2000 cycles) and good rate performance (70.3 mAh g-1 at 50C). In addition, experimental detail discloses that the sulfonyl group plays a key role in inducing morphology evolution during the charge/discharge process. This work opens up new opportunities in electrolyte design for organic electrodes and illuminates further developments of potassium-ion batteries.

Weakly Coordinating Diluent Modulated Solvation Chemistry for High-Performance Sodium Metal Batteries.

Diluents have been extensively employed to overcome the disadvantages of high viscosity and sluggish kinetics of high-concentration electrolytes, but generally do not change the pristine solvation structure. Herein, a weakly coordinating diluent, hexafluoroisopropyl methyl ether (HFME), is applied to regulate the coordination of Na+ with diglyme and anion and form a diluent-participated solvate. This unique solvation structure promotes the accelerated decomposition of anions and diluents, with the construction of robust inorganic-rich electrode-electrolyte interphases. In addition, the introduction of HFME reduces the desolvation energy of Na+, improves ionic conductivity, strengthens the antioxidant, and enhances the safety of the electrolyte. As a result, the assembled Na||Na symmetric cell achieves a stable cycle of over 1800 h. The cell of Na||P'2-Na0.67MnO2 delivers a high capacity retention of 87.3 % with a high average Coulombic efficiency of 99.7 % after 350 cycles. This work provides valuable insights into solvation chemistry for advanced electrolyte engineering.

Mo-doped PdCu nanoparticles as high-performance catalysts for oxygen reduction reactions.

The instability of palladium-based binary alloys hinders their wide application in the oxygen reduction processes. Here, we prepared Mo-doped PdCu nanoparticles with controllable dopant content and valence. Further research has revealed that Mo, particularly Mo5+, may effectively suppress the oxidation of Pd and Cu, optimize the oxygen binding of Pd, and increase catalytic activity and stability. In particular, Mo-PdCu-1/C with the highest Mo5+ content shows the best oxygen reduction reaction (ORR) mass activity (1.20 A mg-1Pd), which is 4.8 times higher than that of PdCu/C. It also exhibits outstanding stability, retaining 80.8% of the original mass activity after 20 000 cycles. This study clearly explains the mechanism by which Mo doping affects the performance and provides a reference for further optimization of catalyst performance for fuel cell industrialization.

A High-Power Aqueous Zinc-Organic Radical Battery with Tunable Operating Voltage Triggered by Selected Anions.

In contrast to traditional rechargeable rock-chair metal-ion batteries, dual-ion batteries (DIBs) involve redox reactions with anions rather than cations in p-type cathodes. In principle, regulating the electrochemical performance of the DIB by different anion species is highly feasible. Herein, the anion effect on the electrochemical performance of a DIB, the aqueous Zn- organic radical battery (Zn-ORB), consisting of a poly(2,2,6,6tetramethylpiperidinyloxy-4-yl vinyl ether) cathode and a Zn anode, was investigated by DFT calculations. SO4 2- , CF3 SO3 - , and ClO4 - with different molecular electrostatic potential values were selected as anion models. DFT calculations revealed that a stronger electrostatic interaction of the anion with the organic radical resulted in a higher operating voltage of the Zn-ORB, which was consistent with experimental results. These results bring new insight into the redox chemistry of p-type organic radicals with anions and will promote the development of high-power aqueous Zn-ORBs as well as inspire more investigations into the anion effect towards novel battery designs.

A Hybrid Na//K+-Containing Electrolyte//O2 Battery with High Rechargeability and Cycle Stability.

Na-O2 and K-O2 batteries have attracted extensive attention in recent years. However, the parasitic reactions involving the discharge product of NaO2 or K anode with electrolytes and the severe Na or K dendrites plague their rechargeability and cycle stability. Herein, we report a hybrid Na//K+-containing electrolyte//O2 battery consisting of a Na anode, 1.0 M of potassium triflate in diglyme, and a porous carbon cathode. Upon discharging, KO2 is preferentially produced via oxygen reduction in the cathode with Na+ stripped from the Na anode, and reversely, the KO2 is electrochemically decomposed with Na+ plated back onto the anode. The new reaction pathway can circumvent the parasitic reactions involving instable NaO2 and active K anode, and alternatively, the good stability and conductivity of KO2 and stable Na stripping/plating in the presence of K+ enable the hybrid battery to exhibit an average discharge/charge voltage gap of 0.15 V, high Coulombic efficiency of >96%, and superior cycling stability of 120 cycles. This will pave a new pathway to promote metal-air batteries.

A nonaqueous potassium-ion hybrid capacitor enabled by two-dimensional diffusion pathways of dipotassium terephthalate.

Nonaqueous potassium-ion hybrid capacitors (KIHCs) are faced with limited redox reaction kinetics of electrodes for accommodation of large-sized K+. Here, dipotassium terephthalate (K2TP) is applied as an organic negative electrode to provide comparable reaction kinetics with a non-faradaic activated carbon (AC) positive electrode to boost the electrochemical performance of KIHCs. It is revealed that the large exchange current density and fast two-dimensional (2D) diffusion pathways of K+ in K2TP determined by density functional theory (DFT) calculations ensure its fast redox reaction and transport kinetics. The as-constructed KIHC presents both high energy and power densities of 101 W h kg-1 and 2160 W kg-1 based on the mass of the two electrodes (41.5 W h kg-1 and 885.2 W kg-1 based on the mass of the two electrodes and electrolyte), respectively, and a superior capacity retention of 97.7% after 500 cycles. The excellent electrochemical performance is attributed to the fast kinetics, good structural flexibility, and small volume change (9.4%) of K2TP upon K+ insertion/extraction, and its good compatibility with the AC positive electrode in 1,2-dimethoxyethane (DME)-based electrolyte. This will promote application of organic materials in hybrid capacitors and the development of KIHCs.

Sodium-Ion Hybrid Capacitor of High Power and Energy Density.

Sodium-ion hybrid capacitors (NHCs) have been attracting research interest in recent years. However, NHCs suffer from slower redox reaction kinetics of electrodes as compared to non-Faradaic capacitive counterparts. Herein, a high-performance NHC using porous NaBi as anode, activated carbon (AC) as cathode, and 1.5 M of NaPF6 in diglyme as electrolyte is reported. In a charging process, Na+ is inserted into NaBi to form Na3Bi, and PF6 - is stored in the electric double layers of the AC cathode; in a reverse process, the Na3Bi is desodiated to NaBi and eventually Bi, and the adsorbed PF6 - is released into the electrolyte in the first cycle. The NHC exhibits a capacity of ∼298 mA h gBi -1, capacity retention of 98.6% after 1000 cycles at 2 A gBi -1, and Coulombic efficiency of >99.4%. The achievable power and energy density are as high as 11.1 kW kgtotal -1 and 106.5 W h kgtotal -1, respectively. The superior electrochemical performance is ascribed to the gradually formed three-dimensional (3D) porous and stable networks of the anode, ensuring its comparable fast reaction kinetics and cycle stability to the AC cathode.

3D Porous Tin Created by Tuning the Redox Potential Acts as an Advanced Electrode for Sodium-Ion Batteries.

Sodium-ion batteries (SIBs) have attracted significant research interest for large-scale electric energy storage. However, anodes with good rate capability and long cycle life are still lacking. Here, a three-dimensional (3D) porous Sn on Cu foil (Sn/Cu) is prepared by tuning the redox potential of Cu+ /Cu with a ligand of thiourea to trigger the replacement reaction between Cu and Sn2+ . The as-synthesized Sn/Cu is used as an integrated porous electrode and can be directly applied as an advanced freestanding electrode for SIBs. Such a unique structure can efficiently relieve the strain caused by sodiation/desodiation and benefit penetration of the electrolyte and diffusion of Na+ . This is a merit of its large reversible capacity of about 700 mAh g-1 at 2500 mA g-1 for 400 cycles. A full battery of Sn/Cu//Na3 (VO0.5 )2 (PO4 )3 F2 is constructed, which presents a high energy density of 311.7 Wh kg-1 and long lifespan of 200 cycles. This facile synthesis strategy and good electrochemical performance will encourage more investigations into structure design of functional materials.

A Microporous Covalent-Organic Framework with Abundant Accessible Carbonyl Groups for Lithium-Ion Batteries.

A key challenge faced by organic electrodes is how to promote the redox reactions of functional groups to achieve high specific capacity and rate performance. Here, we report a two-dimensional (2D) microporous covalent-organic framework (COF), poly(imide-benzoquinone), via in situ polymerization on graphene (PIBN-G) to function as a cathode material for lithium-ion batteries (LIBs). Such a structure favors charge transfer from graphene to PIBN and full access of both electrons and Li+ ions to the abundant redox-active carbonyl groups, which are essential for battery reactions. This enables large reversible specific capacities of 271.0 and 193.1 mAh g-1 at 0.1 and 10 C, respectively, and retention of more than 86 % after 300 cycles. The discharging/charging process successively involves 8 Li+ and 2 Li+ in the carbonyl groups of the respective imide and quinone groups. The structural merits of PIBN-G will trigger more investigations into the designable and versatile COFs for electrochemistry.

A Porous Network of Bismuth Used as the Anode Material for High-Energy-Density Potassium-Ion Batteries.

Potassium-ion batteries (KIBs) are plagued by a lack of materials for reversible accommodation of the large-sized K+ ion. Herein we present, the Bi anode in combination with the dimethoxyethane-(DME) based electrolyte to deliver a remarkable capacity of ca. 400 mAh g-1 and long cycle stability with three distinct two-phase reactions of Bi↔ KBi2 ↔K3 Bi2 ↔K3 Bi. These are ascribed to the gradually developed three-dimensional (3D) porous networks of Bi, which realizes fast kinetics and tolerance of its volume change during potassiation and depotassiation. The porosity is linked to the unprecedented movement of the surface Bi atoms interacting with DME molecules, as suggested by DFT calculations. A full KIB of Bi//DME-based electrolyte//Prussian blue of K0.72 Fe[Fe(CN)6 ] is demonstrated to present large energy density of 108.1 Wh kg-1 with average discharge voltage of 2.8 V and capacity retention of 86.5 % after 350 cycles.

Atomic-scaled cobalt encapsulated in P,N-doped carbon sheaths over carbon nanotubes for enhanced oxygen reduction electrocatalysis under acidic and alkaline media.

A one-step in situ nanoconfined pyrolysis strategy was developed to anchor highly active single Co atoms on the P,N-doped porous carbon@carbon nanotube coaxial nanocables (Co-P,N-CNT), which exhibit remarkable enhanced ORR electrocatalytic activity in both acidic and alkaline media.

Cation-Deficient Spinel ZnMn2O4 Cathode in Zn(CF3SO3)2 Electrolyte for Rechargeable Aqueous Zn-Ion Battery.

Rechargeable aqueous Zn-ion batteries are attractive cheap, safe and green energy storage technologies but are bottlenecked by limitation in high-capacity cathode and compatible electrolyte to achieve satisfactory cyclability. Here we report the application of nonstoichiometric ZnMn2O4/carbon composite as a new Zn-insertion cathode material in aqueous Zn(CF3SO3)2 electrolyte. In 3 M Zn(CF3SO3)2 solution that enables ∼100% Zn plating/stripping efficiency with long-term stability and suppresses Mn dissolution, the spinel/carbon hybrid exhibits a reversible capacity of 150 mAh g-1 and a capacity retention of 94% over 500 cycles at a high rate of 500 mA g-1. The remarkable electrode performance results from the facile charge transfer and Zn insertion in the structurally robust spinel featuring small particle size and abundant cation vacancies, as evidenced by combined electrochemical measurements, XRD, Raman, synchrotron X-ray absorption spectroscopy, FTIR, and NMR analysis. The results would enlighten and promote the use of cation-defective spinel compounds and trifluoromethanesulfonic electrolyte to develop high-performance rechargeable zinc batteries.

Template-free synthesis of porous graphitic carbon nitride/carbon composite spheres for electrocatalytic oxygen reduction reaction.

Porous graphitic carbon nitride/carbon composite spheres were synthesized using melamine and cyanuric acid, and glucose as the carbon nitride and carbon precursor, respectively. The 3D hierarchical composites efficiently catalyzed the oxygen reduction reaction with an onset potential of 0.90 V and a kinetic current density of 23.92 mA cm(-2). These merit their promising applications in fuel cells and metal-air batteries.

Chemical etching of manganese oxides for electrocatalytic oxygen reduction reaction.

Mixed-valent MnO(x) (1 < x < 2) was selectively synthesized by chemically etching MnO and Mn2O3 with ceric ammonium nitrate. The obtained MnO(x) exhibited greatly enhanced electrocatalytic activity toward the oxygen reduction reaction (ORR) as compared to the corresponding pristine oxides.