Asymmetric Coordination of Iridium Single-atom IrN3 O Boosting Formic Acid Oxidation Catalysis.

Rational design of the proximal coordination of an active site to achieve its optimum catalytic activity is the ultimate goal in single-atom catalysis, but still challenging. Here, we report theoretical prediction and experimental realization of an asymmetrically coordinated iridium single-atom catalyst (IrN3 O) for the formic acid oxidation reaction (FAOR). Theoretical calculations reveal that the substitution of one or two nitrogen with more electronegative oxygen in the symmetric IrN4 motif splits and downshifts the Ir 5d orbitals with respect to the Fermi level, moderating the binding strength of key intermediates on IrN4-x Ox (x=1, 2) sites, especially that the IrN3 O motif shows ideal activity for FAOR with a near-zero overpotential. The as-designed asymmetric Ir motifs were realized by pyrolyzing Ir precursor with oxygen-rich glucose and nitrogen-rich melamine, exhibiting a mass activity of 25 and 87 times greater than those of state-of-the-art Pd/C and Pt/C, respectively.

Coordination Chemistry of Large-Sized Yttrium Single-Atom Catalysts for Oxygen Reduction Reaction.

Although being transition metals, the Fenton-inactive group 3-4 elements (Sc, Y, La, Ti, Zr, and Hf) can easily lose all the outermost s and d electrons, leaving behind ionic sites with nearly empty outermost orbitals that are stable but inactive for oxygen involved catalysis. Here, it is demonstrated that the dynamic coordination network can turn these commonly inactive ionic sites into platinum-like catalytic centers for the oxygen reduction reaction (ORR). Using density functional theory calculations, a macrocyclic ligand coordinated yttrium single-atom (YN4 ) moiety is identified, which is originally ORR inactive because of the too strong binding of hydroxyl intermediate, while it can be activated by an axial ligand X through the covalency competition between YX and YOH bonds. Strikingly, it is also found that the binding force of the axially coordinated ligand is an effective descriptor, and the chlorine ligand is screened out with an optimal binding force that behaves self-adaptively to facilitate each ORR intermediate steps by dynamically changing its YCl covalency. These experiments validate that the as-designed YN4 -Cl moieties embedded within the carbon framework exhibit a high half-wave potential (E1/2 = 0.85 V) in alkaline media, the same as that of the commercial Pt/C catalyst .

Metalloid-Cluster Ligands Enabling Stable and Active FeN4 -Ten Motifs for the Oxygen Reduction Reaction.

In nature, the oxygen reduction reaction (ORR) is catalyzed by cytochrome P450 (CYP) enzymes containing heme iron centers with an axial thiolate ligand (FeN4 -S), which are among the most finely developed catalysts by natural selection. However, the exceptional ORR activity and selectivity of CYP enzymes originate from their non-rigid and self-adaptive coordination network with molecular ligands, which sacrifices the stability of the active motifs under electrochemical reaction conditions. Here, a design strategy to circumvent this dilemma by incorporating Fe-N4 motifs into carbon matrices instead of the protein scaffold and replacing the axial molecular thiolate ligand with a stable tellurium cluster (Ten ) is demonstrated. Theoretical calculations indicate a moderate interaction between Fe 3d and Te 5p orbitals once n > 2, allowing the FeTe bond to dynamically change its strength to adaptively facilitate the intermediate steps during the ORR process, which renders FeN4 -Ten active sites with superior ORR activity. This adaptive behavior mimics the conformational dynamics of an enzyme during the reaction, but retains the stability nature as a heterogeneous catalyst. The experiments validate that the as-designed catalyst with a characterized FeN4 -Ten structure outperforms the commercial Pt/C catalyst both on activity and stability.

Tilting and twisting in a novel perovzalate, K3NaMn(C2O4)3.

In the title compound, the oxalate ligand simultaneously bridges both Mn-centred and Na-centred octahedra to produce a unique 'doubly-interpenetrated' perovskite-like lattice with an unconventional octahedral tilt system. In turn, the coordination requirements of the oxalate ligand lead to a rare 'twisted' conformation.

Recent Advances and Perspectives on Calcium-Ion Storage: Key Materials and Devices.

The urgent demand for cost-effective energy storage devices for large-scale applications has led to the development of several beyond-lithium energy storage systems (EESs). Among them, calcium-ion batteries (CIBs) are attractive due to abundant calcium resources, excellent volumetric and gravimetric capacities of Ca metal anode, and potential high energy density coming from the multivalent feature of Ca-ion. Therefore, the exploration of CIBs electrode materials and the construction of CIBs devices are gaining increasing research interest. Relevant publications cover a wide range of materials by both theoretical and experimental investigations, whereas the performances of rocking-chair CIBs have been unsatisfactory. Meanwhile, multi-ion strategies using more than one ion as the charge carrier have been demonstrated to be feasible and promising options in realizing room temperature CIBs. The summary and reflection of previous studies would provide useful information for future exploration and optimization. In this circumstance, this paper overviews the reported CIBs electrode materials, including both anode and cathode, and presents the latest progress of multi-ion strategies in CIBs. Fundamental challenges, potential solutions, and opportunities are accordingly proposed, mimicking other more mature EESs. This review may promote the development of electrode materials and accelerate the construction of low-cost and high-performance CIBs.

A fluoroxalate cathode material for potassium-ion batteries with ultra-long cyclability.

Potassium-ion batteries are a compelling technology for large scale energy storage due to their low-cost and good rate performance. However, the development of potassium-ion batteries remains in its infancy, mainly hindered by the lack of suitable cathode materials. Here we show that a previously known frustrated magnet, KFeC2O4F, could serve as a stable cathode for potassium ion storage, delivering a discharge capacity of ~112 mAh g-1 at 0.2 A g-1 and 94% capacity retention after 2000 cycles. The unprecedented cycling stability is attributed to the rigid framework and the presence of three channels that allow for minimized volume fluctuation when Fe2+/Fe3+ redox reaction occurs. Further, pairing this KFeC2O4F cathode with a soft carbon anode yields a potassium-ion full cell with an energy density of ~235 Wh kg-1, impressive rate performance and negligible capacity decay within 200 cycles. This work sheds light on the development of low-cost and high-performance K-based energy storage devices.

Strategies towards Low-Cost Dual-Ion Batteries with High Performance.

Rocking-chair based lithium-ion batteries (LIBs) have extensively applied to consumer electronics and electric vehicles (EVs) for solving the present worldwide issues of fossil fuel exhaustion and environmental pollution. However, due to the growing unprecedented demand of LIBs for commercialization in EVs and grid-scale energy storage stations, and a shortage of lithium and cobalt, the increasing cost gives impetus to exploit low-cost rechargeable battery systems. Dual-ion batteries (DIBs), in which both cations and anions are involved in the electrochemical redox reaction, are one of the most promising candidates to meet the low-cost requirements of commercial applications, because of their high working voltage, excellent safety, and environmental friendliness compared to conventional rocking-chair based LIBs. However, DIB technologies are only at the stage of fundamental research and considerable effort is required to improve the energy density and cycle life further. We review the development history and current situation, and discuss the reaction kinetics involved in DIBs, including various anionic intercalation mechanism of cathodes, and the reactions at the anodes including intercalation and alloying to explore promising strategies towards low-cost DIBs with high performance.

An oxalate cathode for lithium ion batteries with combined cationic and polyanionic redox.

The growing demand for advanced lithium-ion batteries calls for the continued development of high-performance positive electrode materials. Polyoxyanion compounds are receiving considerable interest as alternative cathodes to conventional oxides due to their advantages in cost, safety and environmental friendliness. However, polyanionic cathodes reported so far rely heavily upon transition-metal redox reactions for lithium transfer. Here we show a polyanionic insertion material, Li2Fe(C2O4)2, in which in addition to iron redox activity, the oxalate group itself also shows redox behavior enabling reversible charge/discharge and high capacity without gas evolution. The current study gives oxalate a role as a family of cathode materials and suggests a direction for the identification and design of electrode materials with polyanionic frameworks.

Potassium Dual-Ion Hybrid Batteries with Ultrahigh Rate Performance and Excellent Cycling Stability.

Potassium-ion batteries (KIBs) are regarded as a potential alternative battery technology to conventional lithium-ion batteries owing to their low potential, natural abundance, and the low cost of potassium. However, sluggish reaction kinetic of the much larger K+ ions leads to low rate capability and poor cycling performance of KIBs, restricting KIB's practical applications. Herein, we propose a novel full battery called a potassium dual-ion hybrid battery (KDHB) by employing an absorption-type hierarchical porous carbon as the anode material and an anion intercalation-type expanded graphite (EG) as the cathode material. Owing to the hybrid mechanism of the battery and capacitive reaction, the KDHB exhibits superior rate performance with a high capacity of 82 mA h g-1 even at a high current density of 3 A g-1 with negligible capacity decay. Moreover, the KDHB exhibits excellent cycling performance with 74.2% capacity retention after 2000 cycles at 1 A g-1, which is so far the best performance of the reported KDIBs.

A Novel Potassium-Ion-Based Dual-Ion Battery.

In this work, combining both advantages of potassium-ion batteries and dual-ion batteries, a novel potassium-ion-based dual-ion battery (named as K-DIB) system is developed based on a potassium-ion electrolyte, using metal foil (Sn, Pb, K, or Na) as anode and expanded graphite as cathode. When using Sn foil as the anode, the K-DIB presents a high reversible capacity of 66 mAh g-1 at a current density of 50 mA g-1 over the voltage window of 3.0-5.0 V, and exhibits excellent long-term cycling performance with 93% capacity retention for 300 cycles. Moreover, as the Sn foil simultaneously acts as the anode material and the current collector, dead load and dead volume of the battery can be greatly reduced, thus the energy density of the K-DIB is further improved. It delivers a high energy density of 155 Wh kg-1 at a power density of 116 W kg-1 , which is comparable with commercial lithium-ion batteries. Thus, with the advantages of environmentally friendly, cost effective, and high energy density, this K-DIB shows attractive potential for future energy storage application.

A Novel and Generalized Lithium-Ion-Battery Configuration utilizing Al Foil as Both Anode and Current Collector for Enhanced Energy Density.

A novel battery configuration based on an aluminum foil anode and a conventional cathode is developed. The aluminum foil plays a dual role as both the active anode material and the current collector, which enhances the energy density of the packaged battery, and reduces the production cost. This generalized battery configuration has high potential for application in next-generation lithium-ion batteries.

Carbon-Coated Porous Aluminum Foil Anode for High-Rate, Long-Term Cycling Stability, and High Energy Density Dual-Ion Batteries.

A 3D porous Al foil coated with a uniform carbon layer (pAl/C) is prepared and used as the anode and current collector in a dual-ion battery (DIB). The pAl/C-graphite DIB demonstrates superior cycling stability and high rate performance, achieving a highly reversible capacity of 93 mAh g-1 after 1000 cycles at 2 C over the voltage range of 3.0-4.95 V. In addition, the DIB could achieve an energy density of ≈204 Wh kg-1 at a high power density of 3084 W kg-1 .