Enhanced Oxygen Accumulation for a Hydrophobic Cathode in Lean-Oxygen Seawater Batteries.

The unsatisfactory oxygen reduction reaction (ORR) kinetics caused by the inherent lean-oxygen marine environment brings low power density for metal-dissolved oxygen seawater batteries (SWBs). In this study, we propose a seawater/electrode interfacial engineering strategy by constructing a hydrophobic coating to realize enhanced mass transfer of dissolved oxygen for the fully immersed cathode of SWBs. Accumulation of dissolved oxygen from seawater to the catalyst is particularly beneficial for improving the ORR performance under lean-oxygen conditions. As a result, SWB assembled with a hydrophobic cathode achieved a power density of up to 2.32 mW cm-2 and sustained discharge at 1.3 V for 250 h. Remarkably, even in environments with an oxygen concentration of 4 mg L-1, it can operate at a voltage approximately 100 mV higher than that of an unmodified SWB. The introduction of a hydrophobic interface enhances the discharge voltage and power of SWBs by improving interfacial oxygen mass transfer, providing new insights into improving the underwater ORR performance for practical SWBs.

Switching Hydrophobic Interface with Ionic Valves for Reversible Zinc Batteries.

Developing hydrophobic interface has proven effective in addressing dendrite growth and side reactions during zinc (Zn) plating in aqueous Zn batteries. However, this solution inadvertently impedes the solvation of Zn2+ with H2O and subsequent ionic transport during Zn stripping, leading to insufficient reversibility. Herein, an adaptive hydrophobic interface that can be switched "on" and "off" by ionic valves to accommodate the varying demands for interfacial H2O during both the Zn plating and stripping processes, is proposed. This concept is validated using octyltrimethyl ammonium bromide (C8TAB) as the ionic valve, which can initiatively establish and remove a hydrophobic interface in response to distinct electric-field directions during Zn plating and stripping, respectively. Consequently, the Zn anode exhibits an extended cycling life of over 2500 h with a high Coulombic efficiency of ≈99.8%. The full cells also show impressive capacity retention of over 85% after 1 000 cycles at 5 A g-1. These findings provide a new insight into interface design for aqueous metal batteries.

Engineering catalytic defects via molecular imprinting for high energy Li-S pouch cells.

Heterogeneous catalysis promises to accelerate sulfur-involved conversion reactions in lithium-sulfur batteries. Solid-state Li2S dissociation remains as the rate-limiting step because of the weakly matched solid-solid electrocatalysis interfaces. We propose an electrochemically molecular-imprinting strategy to have a metal sulfide (MS) catalyst with imprinted defects in positions from which the pre-implanted Li2S has been electrochemically removed. Such tailor-made defects enable the catalyst to bind exclusively to Li atoms in Li2S reactant and elongate the Li-S bond, thus decreasing the reaction energy barrier during charging. The imprinted Ni3S2 catalyst shows the best activity due to the highest defect concentration among the MS catalysts examined. The Li2S oxidation potential is substantially reduced to 2.34 V from 2.96 V for the counterpart free of imprinted vacancies, and an Ah-level pouch cell is realized with excellent cycling performance. With a lean electrolyte/sulfur ratio of 1.80 µL mgS -1, the cell achieves a benchmarkedly high energy density beyond 500 Wh kg-1.

High-Entropy Catalysis Accelerating Stepwise Sulfur Redox Reactions for Lithium-Sulfur Batteries.

Catalysis is crucial to improve redox kinetics in lithium-sulfur (Li-S) batteries. However, conventional catalysts that consist of a single metal element are incapable of accelerating stepwise sulfur redox reactions which involve 16-electron transfer and multiple Li2Sn (n = 2-8) intermediate species. To enable fast kinetics of Li-S batteries, it is proposed to use high-entropy alloy (HEA) nanocatalysts, which are demonstrated effective to adsorb lithium polysulfides and accelerate their redox kinetics. The incorporation of multiple elements (Co, Ni, Fe, Pd, and V) within HEAs greatly enhances the catalytically active sites, which not only improves the rate capability, but also elevates the cycling stability of the assembled batteries. Consequently, HEA-catalyzed Li-S batteries achieve a high capacity up to 1364 mAh g-1 at 0.1 C and experience only a slight capacity fading rate of 0.054% per cycle over 1000 cycles at 2 C, while the assembled pouch cell achieves a high specific capacity of 1192 mAh g-1. The superior performance of Li-S batteries demonstrates the effectiveness of the HEA catalysts with maximized synergistic effect for accelerating S conversion reactions, which opens a way to catalytically improving stepwise electrochemical conversion reactions.

Both Resilience and Adhesivity Define Solid Electrolyte Interphases for a High Performance Anode.

Solid electrolyte interphases (SEIs) are sought to protect high-capacity anodes, which suffer from severe volume changes and fast degradations. The previously proposed effective SEIs were of high strength yet abhesive, inducing a yolk-shell structure to decouple the rigid SEI from the anode for accommodating the volume change. Ambivalently, the interfacial void-evolved electro-chemo-mechanical vulnerabilities become inherent defects. Here, we establish a new rationale for SEIs that resilience and adhesivity are both requirements and pioneer a design of a resilient yet adhesive SEI (re-ad-SEI), integrated into a conjugated surface bilayer structure. The re-ad-SEI and its protected particles exhibit excellent stability almost free from the thickening of SEI and the particle pulverization during cycling. More promisingly, the dynamically bonded intact SEI-anode interfaces enable a high-efficiency ion transport and provide a unique mechanical confinement effect for structural integrity of anodes. The high Coulombic efficiency (>99.8%), excellent cycling stability (500 cycles), and superior rate performance have been demonstrated in microsized Si-based anodes.

High yield electrosynthesis of oxygenates from CO using a relay Cu-Ag co-catalyst system.

As a sustainable alternative to fossil fuel-based manufacture of bulk oxygenates, electrochemical synthesis using CO and H2O as raw materials at ambient conditions offers immense appeal. However, the upscaling of the electrosynthesis of oxygenates encounters kinetic bottlenecks arising from the competing hydrogen evolution reaction with the selective production of ethylene. Herein, a catalytic relay system that can perform in tandem CO capture, activation, intermediate transfer and enrichment on a Cu-Ag composite catalyst is used for attaining high yield CO-to-oxygenates electrosynthesis at high current densities. The composite catalyst Cu/30Ag (molar ratio of Cu to Ag is 7:3) enables high efficiency CO-to-oxygenates conversion, attaining a maximum partial current density for oxygenates of 800 mA cm-2 at an applied current density of 1200 mA cm-2, and with 67 % selectivity. The ability to finely control the production of ethylene and oxygenates highlights the principle of efficient catalyst design based on the relay mechanism.

Consummating ion desolvation in hard carbon anodes for reversible sodium storage.

Hard carbons are emerging as the most viable anodes to support the commercialization of sodium-ion (Na-ion) batteries due to their competitive performance. However, the hard carbon anode suffers from low initial Coulombic efficiency (ICE), and the ambiguous Na-ion (Na+) storage mechanism and interfacial chemistry fail to give a reasonable interpretation. Here, we have identified the time-dependent ion pre-desolvation on the nanopore of hard carbons, which significantly affects the Na+ storage efficiency by altering the solvation structure of electrolytes. Consummating the pre-desolvation by extending the aging time, generates a highly aggregated electrolyte configuration inside the nanopore, resulting in negligible reductive decomposition of electrolytes. When applying the above insights, the hard carbon anodes achieve a high average ICE of 98.21% in the absence of any Na supplementation techniques. Therefore, the negative-to-positive capacity ratio can be reduced to 1.02 for full cells, which enables an improved energy density. The insight into hard carbons and related interphases may be extended to other battery systems and support the continued development of battery technology.

Engineering Triple-Phase Interfaces around the Anode toward Practical Alkali Metal-Air Batteries.

Alkali metal-air batteries (AMABs) promise ultrahigh gravimetric energy densities, while the inherent poor cycle stability hinders their practical application. To address this challenge, most previous efforts are devoted to advancing the air cathodes with high electrocatalytic activity. Recent studies have underlined the solid-liquid-gas triple-phase interface around the anode can play far more significant roles than previously acknowledged by the scientific community. Besides the bottlenecks of uncontrollable dendrite growth and gas evolution in conventional alkali metal batteries, the corrosive gases, intermediate oxygen species, and redox mediators in AMABs cause more severe anode corrosion and structural collapse, posing greater challenges to the stabilization of the anode triple-phase interface. This work aims to provide a timely perspective on the anode interface engineering for durable AMABs. Taking the Li-air battery as a typical example, this critical review shows the latest developed anode stabilization strategies, including formulating electrolytes to build protective interphases, fabricating advanced anodes to improve their anti-corrosion capability, and designing functional separator to shield the corrosive species. Finally, the remaining scientific and technical issues from the prospects of anode interface engineering are highlighted, particularly materials system engineering, for the practical use of AMABs.

Phenothiazine Derivatives as Small-Molecule Organic Cathodes with Adjustable Dropout Voltage and Cycle Performance.

Compared with conventional inorganic materials, organic electrodes are competitive candidates for secondary battery cathodes due to their resourcefulness, environmental friendliness, and cost-effectiveness. Much effort is devoted at the level of chemical structure, while ignoring the impact of molecular aggregation on battery behavior. Herein, this work designs a series of organic molecules with two electrochemically active phenothiazine groups linked by different lengths of alkyl chain to regulate molecular symmetry and crystallinity. The results emphasize the equally important role of molecular aggregation and chemical structure for battery performance. Among them, 2PTZ-C7H14|Li cell exhibits the most impressive cycle and rate performance. At the high rate of 50 C, it can still deliver a capacity of 63.4 mA h g-1 and 74.5% capacity retention after 10 000 cycles. Besides, the dropout voltage of 2PTZ-C9H18|Li cell is only 52 mV, which is among the lowest reported for lithium-organic batteries to the best of the author's knowledge.

Proton is Essential or Not: A Fresh Look on Pseudocapacitive Energy Storage of PANI Composites.

Protonation has been considered essential for the pseudocapacitive energy storage of polyaniline (PANI) for years, as proton doping in PANI chains not only activates electron transport pathways, but also promotes the proceeding of redox reactions. Rarely has the ability for PANI of storing energy without protonation been investigated, and it remains uncertain whether PANI has pseudocapacitive charge storage properties in an alkaline electrolyte. Here, this work first demonstrates the pseudocapacitive energy storage for PANI without protonation using a PANI/graphene composite as a model material in an alkaline electrolyte. Using in situ Raman spectroscopy coupled with electrochemical quartz crystal microbalance (EQCM) measurements, this work determines the formation of -N= group over potential on a PANI chain and demonstrates the direct contribution of OH- in the nonprotonation type of oxidation reactions. This work finds that the PANI/graphene composite in an alkaline electrolyte has excellent cycling stability with a wider operation voltage of 1 V as well as a slightly higher specific capacitance than that in an acidic electrolyte. The findings provide a new perspective on pseudocapacitive energy storage of PANI-based composites, which will influence the selection of electrolytes for PANI materials and expand their application in energy storage fields.

Fluorinating All Interfaces Enables Super-Stable Solid-State Lithium Batteries by In Situ Conversion of Detrimental Surface Li2CO3.

Li-stuffed battery materials intrinsically have surface impurities, typically Li2CO3, which introduce severe kinetic barriers and electrochemical decay for a cycling battery. For energy-dense solid-state lithium batteries (SSLBs), mitigating detrimental Li2CO3 from both cathode and electrolyte materials is required, while the direct removal approaches hardly avoid Li2CO3 regeneration. Here, a decarbonization-fluorination strategy to construct ultrastable LiF-rich interphases throughout the SSLBs by in situ reacting Li2CO3 with LiPF6 at 60 °C is reported. The fluorination of all interfaces effectively suppresses parasitic reactions while substantially reducing the interface resistance, producing a dendrite-free Li anode with an impressive cycling stability of up to 7000 h. Particularly, transition metal dissolution associated with gas evolution in the cathodes is remarkably reduced, leading to notable improvements in battery rate capability and cyclability at a high voltage of 4.5 V. This all-in-one approach propels the development of SSLBs by overcoming the limitations associated with surface impurities and interfacial challenges.

Molecular catalysts with electronic axial stretching for high-performance lean-oxygen seawater batteries.

A dissolved-oxygen seawater battery (SWB) can generate electricity by reducing dissolved oxygen and sacrificing the metal anode at different depths and temperatures in the ocean, acting as the basic unit of spatially underwater energy networks for future maritime exploration. However, most traditional oxygen reduction reaction (ORR) catalysts are out of work at such ultralow dissolved oxygen concentration. Here, we proposed that the electronic axial stretching of the catalyst is essentially responsible for enhancing the catalyst's sensitivity to dissolved oxygen. By modulating the lattice of iron phthalocyanine (FePc) as a model catalyst, the unique electronic axial stretching in the z-direction of planar FePc molecules was realized to achieve a boosted adsorption and electron transfer and result in a much improved ORR activity in lean-oxygen seawater environment. The peak power density of a homemade SWB using a practical carbon brush electrode decorated by the FePc is estimated to be as high as 3 W L-1. These results provide inspiring insights into the interaction between the catalyst and complicated seawater environment, and propose the electronic axial stretching as an effective indicator for the rational design of catalysts to be used in extremely lean-oxygen environment.

Toward High Performance Anodes for Sodium-Ion Batteries: From Hard Carbons to Anode-Free Systems.

Sodium-ion batteries (SIBs) have been deemed to be a promising energy storage technology in terms of cost-effectiveness and sustainability. However, the electrodes often operate at potentials beyond their thermodynamic equilibrium, thus requiring the formation of interphases for kinetic stabilization. The interfaces of the anode such as typical hard carbons and sodium metals are particularly unstable because of its much lower chemical potential than the electrolyte. This creates more severe challenges for both anode and cathode interfaces when building anode-free cells to achieve higher energy densities. Manipulating the desolvation process through the nanoconfining strategy has been emphasized as an effective strategy to stabilize the interface and has attracted widespread attention. This Outlook provides a comprehensive understanding about the nanopore-based solvation structure regulation strategy and its role in building practical SIBs and anode-free batteries. Finally, guidelines for the design of better electrolytes and suggestions for constructing stable interphases are proposed from the perspective of desolvation or predesolvation.

Production of gas-releasing electrolyte-replenishing Ah-scale zinc metal pouch cells with aqueous gel electrolyte.

Aqueous zinc batteries are ideal candidates for grid-scale energy storage because of their safety and low-cost aspects. However, the production of large-format aqueous Zn batteries is hindered by electrolyte consumption, hydrogen gas evolution and accumulation, and Zn dendrites growth. To circumvent these issues, here we propose an "open" pouch cell design for large-format production of aqueous Zn batteries, which can release hydrogen gas and allow the refilling of the electrolyte components consumed during cell cycling. The cell uses a gel electrolyte containing crosslinked kappa (k)-carrageenan and chitosan. It bonds water molecules and hinders their side reaction with Zn, preventing electrolyte leakage and fast evaporation. As a proof-of-concept, we report the assembly and testing of a Zn | |ZnxV2O5·nH2O multi-layer "open" pouch cell using the carrageenan/chitosan gel electrolyte, which delivers an initial discharge capacity of 0.9 Ah and 84% capacity retention after 200 cycles at 200 mA g‒1, 370 kPa and 25 °C.

Collective photothermal bending of flexible organic crystals modified with MXene-polymer multilayers as optical waveguide arrays.

The performance of any engineering material is naturally limited by its structure, and while each material suffers from one or multiple shortcomings when considered for a particular application, these can be potentially circumvented by hybridization with other materials. By combining organic crystals with MXenes as thermal absorbers and charged polymers as adhesive counter-ionic components, we propose a simple access to flexible hybrid organic crystal materials that have the ability to mechanically respond to infrared light. The ensuing hybrid organic crystals are durable, respond fast, and can be cycled between straight and deformed state repeatedly without fatigue. The point of flexure and the curvature of the crystals can be precisely controlled by modulating the position, duration, and power of thermal excitation, and this control can be extended from individual hybrid crystals to motion of ordered two-dimensional arrays of such crystals. We also demonstrate that excitation can be achieved over very long distances (>3 m). The ability to control the shape with infrared light adds to the versatility in the anticipated applications of organic crystals, most immediately in their application as thermally controllable flexible optical waveguides for signal transmission in flexible organic electronics.

A Self-Deoxidizing Electrolyte Additive Enables Highly Stable Aqueous Zinc Batteries.

In aqueous zinc (Zn) batteries, the Zn anode suffers from severe corrosion reactions and consequent dendrite growth troubles that cause fast performance decay. Herein, we uncover the corrosion mechanism and confirm that the dissolved oxygen (DO) other than the reputed proton is a principal origin of Zn corrosion and by-product precipitates, especially during the initial battery resting period. In a break from common physical deoxygenation methods, we propose a chemical self-deoxygenation strategy to tackle the DO-induced hazards. As a proof of concept, sodium anthraquinone-2-sulfonate (AQS) is introduced to aqueous electrolytes as a self-deoxidizing additive. As a result, the Zn anode sustains a long-term cycling of 2500 h at 0.5 mA cm-2 and over 1100 h at 5 mA cm-2 together with a high Coulombic efficiency up to 99.6 %. The full cells also show a high capacity retention of 92 % after 500 cycles. Our findings provide a renewed understanding of Zn corrosion in aqueous electrolytes and also a practical solution towards industrializing aqueous Zn batteries.

Hydroiodic-Acid-Initiated Dense yet Porous Ti3 C2 Tx MXene Monoliths toward Superhigh Areal Energy Storage.

The assembly of 3D structured materials from 2D units paves a royal road for building thick and dense electrodes, which are long sought after for practical energy-storage devices. 2D transitional metal carbides (MXene) are promising for this due to their capabilities of solution-based assembly and intrinsic high density, yet face huge challenges in yielding high areal capacitance electrodes owing to the absence of porous ion-transport paths. Here, a gelation-densification process initiated by hydroiodide acids (HI) is proposed, where the protons break the electrostatic balance of MXene nanosheets to trigger gelation, while HI serves as a spacer to prevent nanosheets from restacking during capillary shrinkage. More promising, the controlled evaporation of reductive HI leaves superiorly shrinking yet porous network for ion transport, and the produced monoliths exhibit a high density of 2.74 g cm-3 and an unprecedented areal capacitance of 18.6 F cm-2 .

A Zn-based catalyst with high oxygen reduction activity and anti-poisoning property for stable seawater batteries.

Seawater batteries (SWBs) are a key part of the future underwater energy network for maritime safety and resource development due to their high safety, long lifespan, and eco-friendly nature. However, the complicated seawater composition and pollution, such as the S2-, usually poison the catalyst and lead to the degradation of the battery performance. Here, Zn single-atom catalysts (SACs) were demonstrated as effective oxygen reduction reaction catalysts with high anti-poisoning properties by density functional theory calculation and the Zn SACs anchoring on an N, P-doped carbon substrate (Zn-SAC@PNC) was synthesized by a one-pot strategy. Zinc active sites ensure the anti-poisoning property toward S2-, and N, P-doped carbon helps improve the activity. Therefore, Zn-SAC@PNC exhibits superior activity (E1/2: 0.87 V, Tafel slope: 69.5 mV dec-1) compared with Pt/C and shows a lower decay rate of the voltage after discharge in lean-oxygen natural seawater. In the presence of S2-, Zn-SAC@PNC can still maintain its original catalytic activity, which ensures the stable operation of SWBs in the marine environment with sulfur-based pollutants. This study provides a new strategy to design and develop efficient cathode materials for SWBs.

Folic Acid-Derived Low-dimensional carbons for efficient oxidative dehydrogenation of ethylbenzene.

The oxidative dehydrogenation (ODH) of alkane is one of the most attractive routes in alkane production because of its favourable thermodynamic characteristic. Nitrogen-doped nanocarbons have demonstrated great potential in this reaction due to its cost-effective, high catalytic activity and stability. However, the influence of nitrogen on the catalytic properties of carbon materials is poorly understood due to the complexities of surface oxygen and nitrogen functional groups. Here we derive the performance descriptor that account for the nitrogen-dependent carbocatalysis in ODH reaction. To achieve this, we designed a set of nitrogen-doped nanocarbon materials with tunable nitrogen species by hydrothermal carbonization (HTC) treatment of the biomass folic acid (FA), which are applied in ODH of ethylbenzene. Among them, FA-180-1000 catalyst can achieve high ethylbenzene conversion (up to ∼62 %) and styrene selectivity (∼87 %), outperforming other HTC carbon-based catalysts. Structural characterizations and kinetic analyses revealed that nitrogen doping strongly interferes the charge polarization of CO site via electron transfer between CO, and nitrogen (mainly pyridine nitrogen and graphitic nitrogen) thus enhancing the reactivity of CO. Furthermore, the induction period during reaction process can be shortened by applying of sulfuric acid-assisted HTC method for constructing nitrogen-doped carbon catalyst with low crystallinity. The present work provides new insights into the contribution of nitrogen doping to the ODH reaction of carbon nanocatalysts, as well as guidance for the rational design of carbon catalysts for the conversion of hydrocarbons to high-value chemicals.

A Permselective Coating Protects Lithium Anode toward a Practical Lithium-Sulfur Battery.

Lithium metal is a desirable anode for high-energy density lithium-sulfur (Li-S) batteries. However, its reliability is severely limited by dendrite growth and side reactions with polysulfides, which are yet challenging to solve simultaneously. Herein, we report a protective layer that works the same way as the ion-permselective cell membrane, yielding a corrosion-resistant and dendrite-free Li metal anode specially for Li-S batteries. A self-limited assembly of octadecylamine together with Al3+ ions on a Li metal anode surface produces a dense, stable yet thin layer with ionic conductive Al-Li alloy uniformly embedded in it, which prevents the passage of polysulfides but regulates the penetrated Li ion flux for uniform Li deposition. As a result, the assembled batteries show excellent cycling stability even with a high sulfur-loaded cathode, suggesting a straightforward but promising strategy to stabilize highly active anodes for practical applications.