Superior sodiophilicity and molecule crowding of crown ether boost the electrochemical performance of all-climate sodium-ion batteries.

Sodium-ion batteries (SIBs) as one of the promising alternatives to lithium-ion batteries have achieved remarkable progress in the past. However, the all-climate performance is still very challenging for SIBs. Herein, 15-Crown-5 (15-C-5) is screened as an electrolyte additive from a number of ether molecules theoretically. The good sodiophilicity, high molecule rigidity, and bulky size enable it to reshape the solvation sheath and promote the anion engagement in the solvated structures by molecule crowding. This change also enhances Na-ion transfer, inhibits side reactions, and leads to a thin and robust solid-electrolyte interphase. Furthermore, the electrochemical stability and operating temperature windows of the electrolyte are extended. These profits improve the electrochemical performance of SIBs in all climates, much better than the case without 15-C-5. This improvement is also adopted to µ-Sn, µ-Bi, hard carbon, and MoS2. This work opens a door to prioritize the potential molecules in theory for advanced electrolytes.

Routes to high-performance layered oxide cathodes for sodium-ion batteries.

Sodium-ion batteries (SIBs) are experiencing a large-scale renaissance to supplement or replace expensive lithium-ion batteries (LIBs) and low energy density lead-acid batteries in electrical energy storage systems and other applications. In this case, layered oxide materials have become one of the most popular cathode candidates for SIBs because of their low cost and comparatively facile synthesis method. However, the intrinsic shortcomings of layered oxide cathodes, which severely limit their commercialization process, urgently need to be addressed. In this review, inherent challenges associated with layered oxide cathodes for SIBs, such as their irreversible multiphase transition, poor air stability, and low energy density, are systematically summarized and discussed, together with strategies to overcome these dilemmas through bulk phase modulation, surface/interface modification, functional structure manipulation, and cationic and anionic redox optimization. Emphasis is placed on investigating variations in the chemical composition and structural configuration of layered oxide cathodes and how they affect the electrochemical behavior of the cathodes to illustrate how these issues can be addressed. The summary of failure mechanisms and corresponding modification strategies of layered oxide cathodes presented herein provides a valuable reference for scientific and practical issues related to the development of SIBs.

Molten-Salt Electrochemical-Assisted Synthesis of the CeO2-OV@GC Composite-Supported Pt Clusters with a Pt-O-Ce Structure for the Oxygen Reduction Reaction.

Highly active and robust Pt-based electrocatalysts for an oxygen reduction reaction (ORR) are of crucial significance for the development of proton exchange membrane fuel cells (PEMFCs). Herein, the high-loading and well-dispersive Pt clusters on graphitic carbon-supported CeO2 with abundant oxygen vacancies (PtAC/CeO2-OV@GC) were successfully fabricated by a molten-salt electrochemical-assisted method. The bonding of Pt with the highly electronegative O induces charge redistribution through the Pt-O-Ce structure, thus reducing the adsorption energies of oxygen-containing species. Such a PtAC/CeO2-OV@GC electrocatalyst exhibits a greatly enhanced ORR performance with a mass activity of 0.41 ± 0.02 A·mg-1Pt at 0.9 V versus a reversible hydrogen electrode, which is 2.7 times the value of a commercial Pt/C catalyst and shows negligible activity decay after 20000 cycles of accelerated degradation tests. It is anticipated that this work will provide enlightening guidance on the controllable synthesis and rational design of high-performance Pt-based electrocatalysts for PEMFCs.

A Holistic Additive Protocol Steers Dendrite-Free Zn(101) Orientational Electrodeposition.

Orientation guidance has shown its cutting edges in electrodeposition modulation to promote Zn anode stability toward commercialized standards. Nevertheless, large-scale orientational deposition is handicapped by the competition between Zn-ion reduction and mass transfer. Herein, a holistic electrolyte additive protocol is put forward via incorporating bio-derived dextrin molecules into a zinc sulfate electrolyte bath. Electrochemical tests in combination with molecular dynamics simulations demonstrate the alleviation of concentration polarization throughout accelerating Zn2+ diffusion and retarding their reduction. The predominant (101) texture on inert current collectors (i.e., Cu, Ti, and stainless steel) and (101)/(002) textures on Zn foils afford homogeneous electrical field distribution, which is contributed by the work difference to form the 2D nucleus and the adsorption of dextrin molecules, respectively. Consequently, the symmetric cell harvests a longevous cycling lifespan of over 4000 h at 0.5 mA cm-2 /0.5 mAh cm-2 while the Zn@Cu electrode sustains for 240 h at a high depth of discharge of 40%.

Recent progress and strategic perspectives of inorganic solid electrolytes: fundamentals, modifications, and applications in sodium metal batteries.

Solid-state electrolytes (SEs) have attracted overwhelming attention as a promising alternative to traditional organic liquid electrolytes (OLEs) for high-energy-density sodium-metal batteries (SMBs), owing to their intrinsic incombustibility, wider electrochemical stability window (ESW), and better thermal stability. Among various kinds of SEs, inorganic solid-state electrolytes (ISEs) stand out because of their high ionic conductivity, excellent oxidative stability, and good mechanical strength, rendering potential utilization in safe and dendrite-free SMBs at room temperature. However, the development of Na-ion ISEs still remains challenging, that a perfect solution has yet to be achieved. Herein, we provide a comprehensive and in-depth inspection of the state-of-the-art ISEs, aiming at revealing the underlying Na+ conduction mechanisms at different length scales, and interpreting their compatibility with the Na metal anode from multiple aspects. A thorough material screening will include nearly all ISEs developed to date, i.e., oxides, chalcogenides, halides, antiperovskites, and borohydrides, followed by an overview of the modification strategies for enhancing their ionic conductivity and interfacial compatibility with Na metal, including synthesis, doping and interfacial engineering. By discussing the remaining challenges in ISE research, we propose rational and strategic perspectives that can serve as guidelines for future development of desirable ISEs and practical implementation of high-performance SMBs.

A Dual Organic Solvent Zn-Ion Electrolyte Enables Highly Stable Zn Metal Batteries.

Aqueous zinc (Zn) batteries have been regarded as an alternative to lithium-ion batteries due to their high abundance, low cost, and higher intrinsic safety. However, the low Zn plating/stripping reversibility, Zn dendrite growth, and continuous water consumption have hindered the practical application of aqueous Zn anodes. Herein, a hydrous organic Zn-ion electrolyte based on a dual organic solvent, namely hydrated Zn(BF4)2 zinc salt dissolved in dimethyl carbonate (DMC) and vinyl carbonate (EC) solvents [denoted as Zn(BF4)2/DMC/EC], can address these problems, which not only inhibits the side reactions but also promotes uniform Zn plating/stripping through the formation of a stable solid state interface layer and Zn2+-EC/2DMC pairs. This electrolyte enables the Zn electrode to stably undergo >700 cycles at a rate of 1 mA cm-2 with a Coulombic efficiency of 99.71%. Moreover, the full cell paired with V2O5 also demonstrates excellent cycling stability without capacity decay at 1 A g-1 after 1600 cycles.

Boosted Mg-CO2 Batteries by Amine-Mediated CO2 Capture Chemistry and Mg2+ -Conducting Solid-electrolyte Interphases.

Mg-CO2 battery has been considered as an ideal system for energy conversion and CO2 fixation. However, its practical application is significantly limited by the poor reversibility and sluggish kinetics of CO2 cathode and Mg anode. Here, a new amine mediated chemistry strategy is proposed to realize a highly reversible and high-rate Mg-CO2 battery in conventional electrolyte. Judiciously combined experimental characterization and theoretical computation unveiled that the introduced amine could simultaneously modify the reactant state of CO2 and Mg2+ to accelerate CO2 cathodic reactions on the thermodynamic-kinetic levels and facilitate the formation of Mg2+ -conductive solid-electrolyte interphase (SEI) to enable highly reversible Mg anode. As a result, the Mg-CO2 battery exhibits boosted stable cyclability (70 cycles, more than 400 h at 200 mA g-1 ) and high-rate capability (from 100 to 2000 mA g-1 with 1.5 V overpotential) even at -15 °C. This work opens a newly promising avenue for advanced metal-CO2 batteries.

Electric Double Layer Regulator Design through a Functional Group Assembly Strategy towards Long-Lasting Zinc Metal Batteries.

Regulating the electric double layer (EDL) structure of the zinc metal anode by using electrolyte additives is an efficient way to suppress interface side reactions and facilitate uniform zinc deposition. Nevertheless, there are no reports investigating the proactive design of EDL-regulating additives before the start of experiments. Herein, a functional group assembly strategy is proposed to design electrolyte additives for modulating the EDL, thereby realizing a long-lasting zinc metal anode. Specifically, by screening ten common functional groups, N, N-dimethyl-1H-imidazole-1-sulfonamide (IS) is designed by assembling an imidazole group, characterized by its high adsorption capability on the zinc anode, and a sulfone group, which exhibits strong binding with Zn2+ ions. Benefiting from the adsorption functionalization of the imidazole group, the IS molecules occupy the position of H2O in the inner Helmholtz layer of the EDL, forming a molecular protective layer to inhibit H2O-induced side reactions. Meanwhile, the sulfone group in IS, acting as a binding site to Zn2+, promotes the de-solvation of Zn2+ ions, facilitating compact zinc deposition. Consequently, the utilization of IS significantly extending the cycling stability of Zn||Zn and Zn||NaV3O8 ⋅ 1.5H2O full cell. This study offers an innovative approach to the design of EDL regulators for high-performance zinc metal batteries.

Scalable Precise Nanofilm Coating and Gradient Al Doping Enable Stable Battery Cycling of LiCoO2 at 4.7†V.

The quest for smart electronics with higher energy densities has intensified the development of high-voltage LiCoO2 (LCO). Despite their potential, LCO materials operating at 4.7 V faces critical challenges, including interface degradation and structural collapse. Herein, we propose a collective surface architecture through precise nanofilm coating and doping that combines an ultra-thin LiAlO2 coating layer and gradient doping of Al. This architecture not only mitigates side reactions, but also improves the Li+ migration kinetics on the LCO surface. Meanwhile, gradient doping of Al inhibited the severe lattice distortion caused by the irreversible phase transition of O3-H1-3-O1, thereby enhanced the electrochemical stability of LCO during 4.7 V cycling. DFT calculations further revealed that our approach significantly boosts the electronic conductivity. As a result, the modified LCO exhibited an outstanding reversible capacity of 230 mAh g-1 at 4.7 V, which is approximately 28 % higher than the conventional capacity at 4.5 V. To demonstrate their practical application, our cathode structure shows improved stability in full pouch cell configuration under high operating voltage. LCO exhibited an excellent cycling stability, retaining 82.33 % after 1000 cycles at 4.5 V. This multifunctional surface modification strategy offers a viable pathway for the practical application of LCO materials, setting a new standard for the development of high-energy-density and long-lasting electrode materials.

Defect-Healing Induced Monoclinic Iron-Based Prussian Blue Analogs as High-Performance Cathode Materials for Sodium-Ion Batteries.

Prussian blue analogs (PBAs) have attracted wide interest as a class of ideal cathodes for rechargeable sodium-ion batteries due to their low cost, high theoretical capacity, and facile synthesis. Herein, a series of highly crystalline Fe-based PBAs (FeHCF) cubes, where HCF stands for the hexacyanoferrate, is synthesized via a one-step pyrophosphate-assisted co-precipitation method. By applying this proposed facile crystallization-controlled method to slow down the crystallization process and suppress the defect content of the crystal framework of the PBAs, the as-prepared materials demonstrate high crystallization and a sodium-rich induced rhombohedral phase. As a result, the as prepared FeHCF can deliver a high specific capacity of up to 152.0 mA h g-1 (achieving ≈90% of its theoretical value) and an excellent rate capability with a high-capacity retention ratio of 88% at 10 C, which makes it one of the most competitive candidates among the cathodes reported regarding both capacity and rate performance. A highly reversible three-phase-transition sodium-ion storage mechanism has been revealed via multiple in situ techniques. Furthermore, the full cells fabricated with as-prepared cathode and commercial hard carbon anode exhibit excellent compatibility which shows great prospects for application in the large-scale energy storage systems.

Key Roles of Interfacial OH- ion Distribution on Proton Coupled Electron Transfer Kinetics Toward Urea Oxidation Reaction.

Enhancing alkaline urea oxidation reaction (UOR) activity is essential to upgrade renewable electrolysis systems. As a core step of UOR, proton-coupled electron transfer (PCET) determines the overall performance, and accelerating its kinetic remains a challenge. In this work, a newly raised electrocatalyst of NiCoMoCuOx Hy with derived multi-metal co-doping (oxy)hydroxide species during electrochemical oxidation states is reported, which ensures considerable alkaline UOR activity (10/500 mA cm-2 at 1.32/1.52 V vs RHE, respectively). Impressively, comprehensive studies elucidate the correlation between the electrode-electrolyte interfacial microenvironment and the electrocatalytic urea oxidation behavior. Specifically, NiCoMoCuOx Hy featured with dendritic nanostructure creates a strengthened electric field distribution. This structural factor prompts the local OH- enrichment in electrical double layer (EDL), so that the dehydrogenative oxidation of the catalyst is directly reinforced to facilitate the subsequent PCET kinetics of nucleophilic urea, resulting in high UOR performance. In practical utilization, NiCoMoCuOx Hy -driven UOR coupled cathodic hydrogen evolution reaction (HER) and carbon dioxide reduction reaction (CO2 RR), and harvested high value-added products of H2 and C2 H4 , respectively. This work clarifies a novel mechanism to improve electrocatalytic UOR performance through structure-induced interfacial microenvironment modulation.

Nonionic Surfactant-Assisted In Situ Generation of Stable Passivation Protective Layer for Highly Stable Aqueous Zn Metal Anodes.

A highly stable interface for aqueous rechargeable Zn batteries is of importance to inhibit the growth of Zn dendrites and suppress the side reactions. In this work, we have developed a stable honeycomb-like ZnO passivation protective layer on the Zn surface, which is in situ generated with the assistance of a nonionic surfactant additive (polyethylene glycol tert-octylphenyl ether, denoted as PEGTE). The ZnO passivation layer can facilitate the uniform distribution of the electric field, guiding the uniform deposition of Zn2+ and inhibit the generation of dendrites. As a result, the symmetric cell using the electrolyte with PEGTE shows an excellent performance at high areal capacity, reflected by stable cycling for over 2400 h at 5 mAh/cm2 and 1300 h at 10 mAh/cm2. The full cell paired with V2O5 demonstrates a long lifespan for more than 600 cycles at a low negative/positive capacity ratio.

Synchronous Dual Electrolyte Additive Sustains Zn Metal Anode with 5600†h Lifespan.

Despite conspicuous merits of Zn metal anodes, the commercialization is still handicapped by rampant dendrite formation and notorious side reaction. Manipulating the nucleation mode and deposition orientation of Zn is a key to rendering stabilized Zn anodes. Here, a dual electrolyte additive strategy is put forward via the direct cooperation of xylitol (XY) and graphene oxide (GO) species into typical zinc sulfate electrolyte. As verified by molecular dynamics simulations, the incorporated XY molecules could regulate the solvation structure of Zn2+ , thus inhibiting hydrogen evolution and side reactions. The self-assembled GO layer is in favor of facilitating the desolvation process to accelerate reaction kinetics. Progressive nucleation and orientational deposition can be realized under the synergistic modulation, enabling a dense and uniform Zn deposition. Consequently, symmetric cell based on dual additives harvests a highly reversible cycling of 5600 h at 1.0 mA cm-2 /1.0 mAh cm-2 .

Electrostatic Shielding Boosts Electrochemical Performance of Alloy-Type Anode Materials of Sodium-Ion Batteries.

The applications of alloy-type anode materials for Na-ion batteries are always obstructed by enormous volume variation upon cycles. Here, K+ ions are introduced as an electrolyte additive to improve the electrochemical performance via electrostatic shielding, using Sn microparticles (µ-Sn) as a model. Theoretical calculations and experimental results indicate that K+ ions are not incorporated in the electrode, but accumulate on some sites. This accumulation slows down the local sodiation at the "hot spots", promotes the uniform sodiation and enhances the electrode stability. Therefore, the electrode maintains a high specific capacity of 565 mAh g-1 after 3000 cycles at 2 A g-1 , much better than the case without K+ . The electrode also remains an areal capacity of ≈3.5 mAh cm-2 after 100 cycles. This method does not involve time-consuming preparation, sophisticated instruments and expensive reagents, exhibiting the promising potential for other anode materials.

Dual-Atom Support Boosts Nickel-Catalyzed Urea Electrooxidation.

Nickel-based catalysts have been regarded as one of the most promising electrocatalysts for urea oxidation reaction (UOR), however, their activity is largely limited by the inevitable self-oxidation reaction of Ni species (NSOR) during the UOR. Here, we proposed an interface chemistry modulation strategy to trigger the occurrence of UOR before the NSOR via constructing a 2D/2D heterostructure that consists of ultrathin NiO anchored Ru-Co dual-atom support (Ru-Co DAS/NiO). Operando spectroscopic characterizations confirm this unique triggering mechanism on the surface of Ru-Co DAS/NiO. Consequently, the fabricated catalyst exhibits outstanding UOR activity with a low potential of 1.288 V at 10 mA cm-2 and remarkable long-term durability for more than 330 h operation. DFT calculations and spectroscopic characterizations demonstrate that the favorable electronic structure induced by this unique heterointerface endows the catalyst energetically more favorable for the UOR than the NSOR.

A Disordered Rubik's Cube-Inspired Framework for Sodium-Ion Batteries with Ultralong Cycle Lifespan.

Sodium-ion batteries (SIBs) with fast-charge capability and long lifespan could be applied in various sustainable energy storage systems, from personal devices to grid storage. Inspired by the disordered Rubik's cube, here, we report that the high-entropy (HE) concept can lead to a very substantial improvement in the sodium storage properties of hexacyanoferrate (HCF). An example of HE-HCF has been synthesized as a proof of concept, which has achieved impressive cycling stability over 50 000 cycles and an outstanding fast-charging capability up to 75 C. Remarkable air stability and all-climate performance are observed. Its quasi-zero-strain reaction mechanism and high sodium diffusion coefficient have been measured and analyzed by multiple in situ techniques and density functional theory calculations. This strategy provides new insights into the development of advanced electrodes and provides the opportunity to tune electrochemical performance by tailoring the atomic composition.

Lattice Distortion and H-passivation in Pure Carbon Electrocatalysts for Efficient and Stable Two-electron Oxygen Reduction to H2 O2.

The exploration of inexpensive and efficient catalysts for oxygen reduction reaction (ORR) is crucial for chemical and energy industries. Carbon materials have been proved promising with different catalysts enabling 2 and 4e- ORR. Nevertheless, their ORR activity and selectivity is still complex and under debate in many cases. Many structures of these active carbon materials are also chemically unstable for practical implementations. Unlike the well-discussed structures, this work presents a strategy to promote efficient and stable 2e- ORR of carbon materials through the synergistic effect of lattice distortion and H-passivation (on the distorted structure). We show how these structures can be formed on carbon cloth, and how the reproducible chemical adsorption can be realized on these structures for efficient and stable H2 O2 production. The work here gives not only new understandings on the 2e- ORR catalysis, but also the robust catalyst which can be directly used in industry.

Homologous Nitrogen-Doped Hierarchical Carbon Architectures Enabling Compatible Anode and Cathode for Potassium-Ion Hybrid Capacitors.

Potassium-ion hybrid capacitors (PIHCs) have been considered as an emerging device to render grid-scale energy storage. Nevertheless, the sluggish kinetics at the anode side and limited capacity output at the cathode side remain daunting challenges for the overall performances of PIHCs. Herein, an exquisite "homologous strategy" to devise multi-dimensional N-doped carbon nanopolyhedron@nanosheet anode and activated N-doped hierarchical carbon cathode targeting high-performance PIHCs is reported. The anode material harnessing a dual-carbon structure and the cathode candidate affording a high specific surface area (2651 m2 g-1 ) act in concert with a concentrated ether-based electrolyte, resulting in an excellent half cell performance. The related storage mechanism is systematically revealed by in situ electrokinetic characterizations. More encouragingly, the thus-derived PIHC full cell demonstrates a favorable energy output (157 Wh kg-1 ), showing distinct advantages over the state-of-the-art PIHC counterparts.

Recent Progress on Fe-Based Single/Dual-Atom Catalysts for Zn-Air Batteries.

As one of the most competitive candidates for large-scale energy storage, zinc-air batteries (ZABs) have attracted great attention due to their high theoretical specific energy density, low toxicity, high abundance, and high safety. It is highly desirable but still remains a huge challenge, however, to achieve cheap and efficient electrocatalysts to promote their commercialization. Recently, Fe-based single-atom and dual-atom catalysts (SACs and DACs, respectively) have emerged as powerful candidates for ZABs derived from their maximum utilization of atoms, excellent catalytic performance, and low price. In this review, some fundamental concepts in the field of ZABs are presented and the recent progress on the reported Fe-based SACs and DACs is summarized, mainly focusing on the relationship between structure and performance at the atomic level, with the aim of providing helpful guidelines for future rational designs of efficient electrocatalysts with atomically dispersed active sites. Finally, the great advantages and future challenges in this field of ZABs are also discussed.

Highly Stable Lithium/Sodium Metal Batteries with High Utilization Enabled by a Holey Two-Dimensional N-Doped TiNb2O7 Host.

Lithium/sodium metal batteries have attracted enormous attention as promising candidates for high-energy storage devices. However, their practical applications are impeded by the growth of dendrites upon Li/Na plating. Here, we report that holey 2D N-doped TiNb2O7 (N-TNO) nanosheets with high electroactive surface area and large amounts of lithiophilic/sodiophilic sites can effectively regulate Li/Na deposition as an interfacial layer, leading to an excellent cycling stability. The N-TNO interfacial layer enables the Li||Li symmetric cell to sustain stable electrodeposition over 1000 h as well as the Na||Na cell to stably cycle for 2400 h at 1 mA cm-2 and 3 mA h cm-2 with a depth of discharge as high as 50%. The full cells of the Li/Na anodes based on the N-TNO layer paired with the LiFePO4 and NaTi2(PO4)3 cathodes, respectively, show a very stable cycling over 1000 cycles at a negative-to-positive electrode capacity (N/P) ratio up to 3.