In-situ Ultrafast Construction of Zinc Tungstate Interface Layer for Highly Reversible Zinc Anodes.

Constructing artificial solid electrolyte interface on the Zn anode surface is recognized as an appealing method to inhibit zinc dendrites and side reactions, whereas the current techniques are complex and time-consuming. Here, a robust and zincophilic zinc tungstate (ZnWO4) layer has been in situ constructed on the Zn anode surface (denoted as ZWO@Zn) by an ultrafast chemical solution reaction. Comprehensive characterizations and theoretical calculations demonstrate that the ZWO layer can effectively modulate the interfacial electric field distribution and promote the Zn2+ uniform diffusion, thus facilitating the uniform Zn2+ nucleation and suppressing zinc dendrites. Besides, ZWO layer can prevent direct contact between the Zn/water and increase the hydrogen evolution reaction overpotential to eliminate side reactions. Consequently, the in-situ constructed ZWO layer facilitates remarkable reversibility in the ZWO@Zn||Ti battery, achieving an impressive Coulombic efficiency of 99.36% under 1.0 mA cm-2, unprecedented cycling lifespan exceeding 1800 h under 1.0 mA cm-2 in ZWO@Zn||ZWO@Zn battery, and a steady and reliable operation of the overall ZWO@Zn||VS2 battery. The work provides a simple, low cost, and ultrafast pathway to crafting protective layers for driving advancements in aqueous zinc-metal batteries.

Freestanding Ammonium Vanadate Composite Cathodes with Lattice Self-Regulation and Ion Exchange for Long-Lasting Ca-Ion Batteries.

Calcium-ion batteries (CIBs) have emerged as a promising alternative for electrochemical energy storage. The lack of high-performance cathode materials severely limits the development of CIBs. Vanadium oxides are particularly attractive as cathode materials for CIBs, and preinsertion chemistry is often used to improve their calcium storage performance. However, the room temperature cycling lifespan of vanadium oxides in organic electrolytes still falls short of 1000 cycles. Here, based on preinsertion chemistry, the cycling life of vanadium oxides is further improved by integrated electrode and electrolyte engineering. Utilizing a tailored Ca electrolyte, the constructed freestanding (NH4)2V6O16·1.35H2O@graphene oxide@carbon nanotube (NHVO-H@GO@CNT) composite cathode achieves a 305 mAh g-1 high capacity and 10 000 cycles record-long life. Additionally, for the first time, a Ca-ion hybrid capacitor full cell is assembled and delivers a capacity of 62.8 mAh g-1. The calcium storage mechanism of NHVO-H@GO@CNT based on a two-phase reaction and the exchange of NH4 + and Ca2+ during cycling are revealed. The lattice self-regulation of V─O layers is observed and the layered vanadium oxides with Ca2+ pillars formed by ion exchange exhibit higher capacity. This work provides novel strategies to enhance the calcium storage performance of vanadium oxides via integrated structural design of electrodes and electrolyte modification.

Suppressed Dissolution of Fluorine-rich SEI Enables Highly Reversible Zinc Metal Anodes for Stable Aqueous Zinc-ion Batteries.

The instability of the solid electrolyte interface (SEI) is a critical challenge for the zinc metal anodes, leading to an erratic electrode/electrolyte interface and hydrogen evolution reaction (HER), ultimately resulting in anode failure. This study uncovers that the fluorine species dissolution is the root cause of SEI instability. To effectively suppress the F- dissolution, an introduction of low-polarity molecule, 1,4-thioxane (TX), is proposed, which reinforces the stability of the fluorine-rich SEI. Moreover, the TX molecule has a strong affinity for coordinating with Zn2+ and adsorbing at the electrode/electrolyte interface, thereby diminishing the activity of local water and consequently impeding SEI dissolution. The robust fluorine-rich SEI layer promotes the high durability of the zinc anode in repeated plating/stripping cycles, while concurrently suppressing HER and enhancing Coulombic efficiency. Furthermore, the Zn||KVOH full cell exhibits excellent capacity retention, averaging 6.8 mAh cm-2 with 98% retention after 400 cycles, even at high loading with a lean electrolyte. This work offers a novel perspective on SEI dissolution as a key factor in anode failure, providing valuable insights for the electrolyte design in energy storage devices.

Atomically dispersed asymmetric cobalt electrocatalyst for efficient hydrogen peroxide production in neutral media.

Electrochemical hydrogen peroxide (H2O2) production (EHPP) via a two-electron oxygen reduction reaction (2e- ORR) provides a promising alternative to replace the energy-intensive anthraquinone process. M-N-C electrocatalysts, which consist of atomically dispersed transition metals and nitrogen-doped carbon, have demonstrated considerable EHPP efficiency. However, their full potential, particularly regarding the correlation between structural configurations and performances in neutral media, remains underexplored. Herein, a series of ultralow metal-loading M-N-C electrocatalysts are synthesized and investigated for the EHPP process in the neutral electrolyte. CoNCB material with the asymmetric Co-C/N/O configuration exhibits the highest EHPP activity and selectivity among various as-prepared M-N-C electrocatalyst, with an outstanding mass activity (6.1 × 105 A gCo-1 at 0.5 V vs. RHE), and a high practical H2O2 production rate (4.72 mol gcatalyst-1 h-1 cm-2). Compared with the popularly recognized square-planar symmetric Co-N4 configuration, the superiority of asymmetric Co-C/N/O configurations is elucidated by X-ray absorption fine structure spectroscopy analysis and computational studies.

Induced Anionic Functional Group Orientation-Assisted Stable Electrode-Electrolyte Interphases for Highly Reversible Zinc Anodes.

Dendrite growth and other side-reaction problems of zinc anodes in aqueous zinc-ion batteries heavily affect their cycling lifespan and Coulombic efficiency, which can be effectively alleviated by the application of polymer-based functional protection layer on the anode. However, the utilization rate of functional groups is difficult to improve without destroying the polymer chain. Here, a simple and well-established strategy is proposed by controlling the orientation of functional groups (─SO3H) to assist the optimization of zinc anodes. Depending on the electrostatic effect, the surface-enriched ─SO3H groups increase the ionic conductivity and homogenize the Zn2+ flux while inhibiting anionic permeation. This approach avoids the destruction of the polymer backbone by over-sulfonation and amplifies the effect of functional groups. Therefore, the modified sulfonated polyether ether ketone (H-SPEEK) coating-optimized zinc anode is capable of longtime stable zinc plating/stripping, and moreover an enhanced cycling steadiness under high current densities is also detected in a series of Zn batteries with different cathode materials, which achieved by the inclusion of H-SPEEK coating without causing any harmful effects on the electrolyte and cathode. This work provides an easy and efficient approach to further optimize the plating/stripping of cations on metal electrodes, and sheds lights on the scale-up of high-performance aqueous zinc-ion battery technology.

Rational Design of an In-Situ Polymer-Inorganic Hybrid Solid Electrolyte Interphase for Realising Stable Zn Metal Anode under Harsh Conditions.

The in-depth understanding of the composition-property-performance relationship of solid electrolyte interphase (SEI) is the basis of developing a reliable SEI to stablize the Zn anode-electrolyte interface, but it remains unclear in rechargeable aqueous zinc ion batteries. Herein, a well-designed electrolyte based on 2 M Zn(CF3SO3)2-0.2 M acrylamide-0.2 M ZnSO4 is proposed. A robust polymer (polyacrylamide)-inorganic (Zn4SO4(OH)6.xH2O) hybrid SEI is in situ constructed on Zn anodes through controllable polymerization of acrylamide and coprecipitation of SO4 2- with Zn2+ and OH-. For the first time, the underlying SEI composition-property-performance relationship is systematically investigated and correlated. The results showed that the polymer-inorganic hybrid SEI, which integrates the high modulus of the inorganic component with the high toughness of the polymer ingredient, can realize high reversibility and long-term interfacial stability, even under ultrahigh areal current density and capacity (30 mA cm-2~30 mAh cm-2). The resultant Zn||NH4V4O10 cell also exhibits excellent cycling stability. This work will provide a guidance for the rational design of SEI layers in rechargeable aqueous zinc ion batteries.

Rational Design of Organic Electrocatalysts for Hydrogen and Oxygen Electrocatalytic Applications.

Efficient electrocatalysts are pivotal for advancing green energy conversion technologies. Organic electrocatalysts, as cost-effective alternatives to noble-metal benchmarks, have garnered attention. However, the understanding of the relationships between their properties and electrocatalytic activities remains ambiguous. Plenty of research articles regarding low-cost organic electrocatalysts started to gain momentum in 2010 and have been flourishing recently though, a review article for both entry-level and experienced researchers in this field is still lacking. This review underscores the urgent need to elucidate the structure-activity relationship and design suitable electrode structures, leveraging the unique features of organic electrocatalysts like controllability and compatibility for real-world applications. Organic electrocatalysts are classified into four groups: small molecules, oligomers, polymers, and frameworks, with specific structural and physicochemical properties serving as activity indicators. To unlock the full potential of organic electrocatalysts, five strategies are discussed: integrated structures, surface property modulation, membrane technologies, electrolyte affinity regulation, and addition of anticorrosion species, all aimed at enhancing charge efficiency, mass transfer, and long-term stability during electrocatalytic reactions. The review offers a comprehensive overview of the current state of organic electrocatalysts and their practical applications, bridging the understanding gap and paving the way for future developments of more efficient green energy conversion technologies.

Langmuir-Blodgett Film Formed by Amphiphilic Molecules for Facile and Rapid Construction of Zinc-Iodine Cell.

Zinc-iodine batteries (ZIBs) are promising candidates for ecofriendly, safe, and low-cost energy storage systems, but polyiodide shuttling and the complex cathode fabrication procedures have severely hindered their broader commercial usage. Herein, a protocol is developed using phospholipid-like oleylamine molecules for scalable production of Langmuir-Blodgett films, which allows the facile preparation of ZIB cathodes in less than 1 min. The resulting inhomogeneous cathode allows for the continuous conversion of iodine. Moreover, the amine group of the oleylamine molecule at the cathode is capable of producing [OA*I+]I3- charge-transfer complexes with iodine, which facilitates the rapid migration of iodine and results in a highly reversible iodine conversion process. Consequently, the as-prepared ZIBs can deliver over 2000 cycles at 0.5 mA cm-2 with a capacity retention of 75.3%. This work presents a novel, straightforward, and efficient method for the rapid construction of ZIBs.

Integrated energy storage and CO2 conversion using an aqueous battery with tamed asymmetric reactions.

Developing a CO2-utilization and energy-storage integrated system possesses great advantages for carbon- and energy-intensive industries. Efforts have been made to developing the Zn-CO2 batteries, but access to long cycling life and low charging voltage remains a grand challenge. Here we unambiguously show such inefficiencies originate from the high-barrier oxygen evolution reaction on charge, and by recharging the battery via oxidation of reducing molecules, Faradaic efficiency-enhanced CO2 reduction and low-overpotential battery regeneration can be simultaneously achieved. Showcased by using hydrazine oxidation, our battery demonstrates a long life over 1000 hours with a charging voltage as low as 1.2 V. The low charging voltage and formation of gaseous product upon hydrazine oxidation are the key to stabilize the catalyst over cycling. Our findings suggest that by fundamentally taming the asymmetric reactions, aqueous batteries are viable tools to achieve integrated energy storage and CO2 conversion that is economical, highly energy efficient, and scalable.

Inhibition of Vanadium Cathodes Dissolution in Aqueous Zn-Ion Batteries.

Aqueous zinc-ion batteries (AZIBs) have experienced a rapid surge in popularity, as evident from the extensive research with over 30 000 articles published in the past 5 years. Previous studies on AZIBs have showcased impressive long-cycle stability at high current densities, achieving thousands or tens of thousands of cycles. However, the practical stability of AZIBs at low current densities (<1C) is restricted to merely 50-100 cycles due to intensified cathode dissolution. This genuine limitation poses a considerable challenge to their transition from the laboratory to the industry. In this study, leveraging density functional theory (DFT) calculations, an artificial interphase that achieves both hydrophobicity and restriction of the outward penetration of dissolved vanadium cations, thereby shifting the reaction equilibrium and suppressing the vanadium dissolution following Le Chatelier's principle, is described. The approach has resulted in one of the best cycling stabilities to date, with no noticeable capacity fading after more than 200 cycles (≈720 h) at 200 mA g-1 (0.47C). These findings represent a significant advance in the design of ultrastable cathodes for aqueous batteries and accelerate the industrialization of aqueous zinc-ion batteries.

Industrial Waste Derived Separators for Zn-Ion Batteries Achieve Homogeneous Zn(002) Deposition Through Low Chemical Affinity Effects.

Designing a cost-effective and multifunctional separator that ensures dendrite-free and stable Zn metal anode remains a significant challenge. Herein, a multifunctional cellulose-based separator is presented consisting of industrial waste-fly ash particles and cellulose nanofiber using a facile solution-coating method. The resulting fly ash-cellulose (FACNF) separators enable a high ion conductivity (5.76 mS cm-1 ) and low desolvation energy barrier of hydrated Zn2+ . These features facilitate fast ion transfer kinetics and inhibit water-induced side reactions. Furthermore, experimental results and theoretical simulations confirm that the presence of fly ash particles in FACNF separators effectively accommodate the preferential deposition of Zn(002) planes, due to the weak chemical affinity between Zn(002) plane and fly ash, to mitigate dendrite formation and growth. Consequently, the utilization of FACNF separators causes an impressive cycling performance in both Zn||Zn symmetric cells (1600 h at 2 mA cm-2 /1 mAh cm-2 ) and Zn||(NH4 )2 V10 O25 (NVO) full cells (4000 cycles with the capacity retention of 92.1% at 5 A g-1 ). Furthermore, the assembled pouch cells can steadily support digital thermometer over two months without generating gas and volume expansion. This work provides new insights for achieving crystallographic uniformity in Zn anodes and realizing cost-effective and long-lasting aqueous zinc-ion batteries (AZIBs).

Nanowires Framework Supported Porous Lotus-Carbon Anode Boosts Lithium-Ion and Sodium-Ion Batteries.

The novel design of carbon materials with stable nanoarchitecture and optimized electrical properties featuring simultaneous intercalation of lithium ions (Li+ ) and sodium ions (Na+ ) is of great significance for the superb lithium- sodium storage capacities. Biomass-derived carbon materials with affluent porosity have been widely studied as anodes for lithium-ion batteries (LIBs) and sodium-ion batteries (SIBs). However, it remains unexplored to further enhance the stability and utilization of the porous carbon skeleton during cycles. Here, a lotus stems derived porous carbon (LPC) with graphene quantum dots (GQDs) and intrinsic carbon nanowires framework (CNF) is successfully fabricated by a self-template method. The LPC anodes show remarkable Li+ and Na+ storage performance with ultrahigh capacity (738 mA h g-1 for LIBs and 460 mA h g-1 for SIBs at 0.2 C after 300 cycles, 1C≈372 mA h g-1 ) and excellent long-term stability. Structural analysis indicates that the CNFs-supported porous structure and internal GQDs with excellent electrical conductivity contribute significantly to the dominant capacitive storage mechanism in LPC. This work provides new perspectives for developing advanced carbon-based materials for multifunctional batteries with improved stability and utilization of porous carbon frameworks during cycles.

Ammonium fluoride additive-modified interphase chemistry stabilizes zinc anodes in aqueous electrolytes.

Herein, ammonium fluoride is reported as an additive within 1 M ZnSO4 aqueous electrolyte to improve zinc anodes. The as-formed electrostatic shielding layer and ZnF2-rich solid-state interphase layer can jointly inhibit side reactions and dendrite growth. Consequently, symmetric Zn‖Zn cells, asymmetric Zn‖Cu cells and Zn‖MnO2 cells with the additives present dramatically enhanced performance in comparison to the ones with pure ZnSO4 electrolyte counterparts. This work proposes a facile but effective method to achieve highly reversible zinc anodes.

Trimetallic MOF-derived CoFeNi/Z-P NC nanocomposites as efficient catalysts for oxygen evolution reaction.

We used sodium hydroxide-mediated approach and tannic acid etching to prepare hollow structured trimetallic MOF-derived CoFeNi/Z-P NC nanocomposites. Remarkably, the resulting CoFeNi/Z-P NC nanocomposites have large specific surface area and mesoporous structure, making their active sites more accessible and mass transfer more effective. More complex trimetallic components provide greater possibilities for further improving electrocatalytic performance. The CoFeNi/Z-P NC nanocomposites demonstrate notable enhancements for the OER, and 10 mA cm-2 current density is achieved at a low overpotential of 244 mV, with a low Tafel slope of 66.2 mV dec-1 and have good stability in alkaline solutions. In addition, as a cathode material for overall alkaline water splitting, CoFeNi/Z-P NC is better than RuO2 with longer cycling stability.

The glass transition in the high-density amorphous Zn/Co-ZIF-4.

The high-density amorphous phases (HDAs) of bimetallic zeolitic imidazolate frameworks (Zn/Co-ZIF-4) were prepared. The temperature dependence of the isobaric heat capacity (Cp) of ZIF-4 HDAs was measured to determine the glass transition temperature (Tg) of HDAs. The Tg non-linearly decreases with the molar ratio R, where R is Co/(Co + Zn), indicating the presence of a mixed-metal node effect. This effect arises from the non-linear increase of the degree of configurational freedom in the HDA as R increases. The degree of configurational freedom is inversely correlated with the network connectivity, which is, in turn, affected by variations in the MN4 (M: Zn or Co; N: nitrogen) tetrahedral symmetry in the ZIF-4 HDA. Overall, this work offers valuable insights into the glass transition of metal-organic frameworks.

"Mn-locking" effect by anionic coordination manipulation stabilizing Mn-rich phosphate cathodes.

High-voltage cathodes with high power and stable cyclability are needed for high-performance sodium-ion batteries. However, the low kinetics and inferior capacity retention from structural instability impede the development of Mn-rich phosphate cathodes. Here, we propose light-weight fluorine (F) doping strategy to decrease the energy gap to 0.22 eV from 1.52 eV and trigger a "Mn-locking" effect-to strengthen the adjacent chemical bonding around Mn as confirmed by density functional theory calculations, which ensure the optimized Mn ligand framework, suppressed Mn dissolution, improved structural stability and enhanced electronic conductivity. The combination of in situ and ex situ techniques determine that the F dopant has no influence on the Na+ storage mechanisms. As a result, an outstanding rate performance up to 40C and an improved cycling stability (1000 cycles at 20C) are achieved. This work presents an effective and widely available light-weight anion doping strategy for high-performance polyanionic cathodes.

Bio-Inspired Polyanionic Electrolytes for Highly Stable Zinc-Ion Batteries.

For zinc-ion batteries (ZIBs), the non-uniform Zn plating/stripping results in a high polarization and low Coulombic efficiency (CE), hindering the large-scale application of ZIBs. Here, inspired by biomass seaweed plants, an anionic polyelectrolyte alginate acid (SA) was used to initiate the in situ formation of the high-performance solid electrolyte interphase (SEI) layer on the Zn anode. Attribute to the anionic groups of -COO- , the affinity of Zn2+ ions to alginate acid induces a well-aligned accelerating channel for uniform plating. This SEI regulates the desolvation structure of Zn2+ and facilitates the formation of compact Zn (002) crystal planes. Even under high depth of discharge conditions (DOD), the SA-coated Zn anode still maintains a stable Zn stripping/plating behavior with a low potential difference (0.114 V). According to the classical nucleation theory, the nucleation energy for SA-coated Zn is 97 % less than that of bare Zn, resulting in a faster nucleation rate. The Zn||Cu cell assembled with the SA-coated electrode exhibits an outstanding average CE of 99.8 % over 1,400 cycles. The design is successfully demonstrated in pouch cells, where the SA-coated Zn exhibits capacity retention of 96.9 % compared to 59.1 % for bare Zn anode, even under the high cathode mass loading (>10 mg/cm2 ).

Surface passivation for highly active, selective, stable, and scalable CO2 electroreduction.

Electrochemical conversion of CO2 to formic acid using Bismuth catalysts is one the most promising pathways for industrialization. However, it is still difficult to achieve high formic acid production at wide voltage intervals and industrial current densities because the Bi catalysts are often poisoned by oxygenated species. Herein, we report a Bi3S2 nanowire-ascorbic acid hybrid catalyst that simultaneously improves formic acid selectivity, activity, and stability at high applied voltages. Specifically, a more than 95% faraday efficiency was achieved for the formate formation over a wide potential range above 1.0 V and at ampere-level current densities. The observed excellent catalytic performance was attributable to a unique reconstruction mechanism to form more defective sites while the ascorbic acid layer further stabilized the defective sites by trapping the poisoning hydroxyl groups. When used in an all-solid-state reactor system, the newly developed catalyst achieved efficient production of pure formic acid over 120 hours at 50 mA cm-2 (200 mA cell current).

Recent Advances in Ultralow-Pt-Loading Electrocatalysts for the Efficient Hydrogen Evolution.

Hydrogen production from water electrolysis provides a green and sustainable route. Platinum (Pt)-based materials have been regarded as efficient electrocatalysts for the hydrogen evolution reaction (HER). However, the large-scale commercialization of Pt-based catalysts suffers from the high cost. Therefore, ultralow-Pt-loading electrocatalysts, which can reach the balance of low cost and high HER performance, have attracted much attention. In this review, representative promising synthetic strategies, including wet chemistry, annealing, electrochemistry, photochemistry, and atomic layer deposition are summarized. Further, the interaction between different electrocatalyst components (transition metals and their derivatives) and Pt is discussed. Notably, this interaction can effectively accelerate the kinetics of the HER, enhancing the catalytic activity. At last, current challenges and future perspectives are briefly discussed.

Enhanced Luminescence of Dye-Decorated ZIF-8 Composite Films via Controllable D-A Interactions for White Light Emission.

Metal-organic frameworks (MOFs) constructed by metal ions/clusters and organic linkers are used to encapsulate fluorescent guest species with aggregation-caused quenching (ACQ) effects to enhance fluorescence properties due to their porous structures and high specific surface areas. However, there would be a problem of matching between MOF pores and guest molecules' sizes. In this paper, amorphous ZIF-8 was modified by carboxyl functional groups (H3BTC-ZIF-8) via introducing the 1,2,4-benzenetricarbonic acid (H3BTC) ligand into the ZIF-8 sol system. Moreover, H3BTC-ZIF-8 was used for the loading of organic fluorescent dyes rhodamine 6G (R6G) and coumarin 151 (C151) to prepare R6G/C151/H3BTC-ZIF-8 composite films. A white-light-emitting composite film (R6G/C151/H3BTC-ZIF-8) with CIE coordinates of (0.323, 0.347) was successfully prepared by compounding fluorescent dyes (R6G and C151) with H3BTC-modified ZIF-8, whose photoluminescence quantum yield (PLQY) can reach 64.0%. It was higher than the PLQY of the composite films prepared by crystalline ZIF-8 (40.2%) or amorphous ZIF-8 without H3BTC (48.0%) compounded with the same concentrations of dyes. The fluorescence enhancement was probably attributed to an increased amount of active sites of H3BTC-modified ZIF-8 interacting with dyes C151 and R6G. This can form hydrogen bonds between H3BTC-ZIF-8 and C151, and weak electron donor-acceptor (D-A) interactions between H3BTC-ZIF-8 and R6G molecules, respectively, thus enhancing the interactions between dyes and ZIF-8 and reducing the ACQ effect existing between dye molecules. Therefore, this strategy could provide an important guidance to develop white-light-emissive materials.