Boosting the sodium storage performance of iron selenides by a synergetic effect of vacancy engineering and spatial confinement

Recently, iron selenides have been considered as one of the most promising candidates for the anodes of sodium-ion batteries (SIBs) due to their cost-effectiveness and high theoretical capacity; however, their practical application is limited by poor conductivity, large volume variation and slow reaction kinetics during electrochemical reactions. In this work, spatially dual-carbon-confined Vₛₑ-Fe₃Se₄₋ₓSₓ/FeSe₂₋ₓSₓ nanohybrids with abundant Se vacancies (Vₛₑ-Fe₃Se₄₋ₓSₓ/FeSe₂₋ₓSₓ@NSC@rGO) are constructed via anion doping and carbon confinement engineering. The three-dimensional crosslinked carbon network composed of the nitrogen-doped carbon support derived from polyacrylic acid (PAA) and reduced graphene enhances the electronic conductivity, provides abundant channels for ion/electron transfer, ensures the structure integrity, and alleviates the agglomeration, pulverization and volume change of active material during the chemical reactions. Moreover, the introduction of S into iron selenides induces a large number of Se vacancies and regulates the electron density around iron atoms, synergistically improving the conductivity of the material and reducing the Na+ diffusion barrier. Based on the aforementioned features, the as-synthesized Vₛₑ-Fe₃Se₄₋ₓSₓ/FeSe₂₋ₓSₓ@NSC@rGO electrode possesses excellent electrochemical properties, exhibiting the satisfactory specific capacity of 630.1 mA h g−¹ after 160 cycles at 0.5 A/g and the reversible capacity of 319.8 mA h g−¹ after 500 cycles at 3 A/g with the low-capacity attenuation of 0.016 % per cycle. This investigation provides a feasible approach to develop high-performanc

Critical roles of multiphase coexistence in boosting piezo-catalytic activity of BaTiO3-based piezoelectric ceramics

Recently, piezocatalysis induced by perovskite ferroelectric ceramics has widely been favored as a possible fascinating strategy for water remediation due to its low cost, simplicity and feasibility. Herein, a strategy of three-ferroelectric-phase coexistence is proposed to boost the piezocatalytic performance of BaTiO3-based ceramics by introducing Ca(Sn0.5Zr0.5)O3 into BaTiO3. The piezocatalysts of (1-x)BaTiO3–xCa(Sn0.5Zr0.5)O3 ceramics were prepared by a high-temperature solid-phase method. The phase structure, microstructure, electrical properties and catalytic performance of ceramics were comprehensively studied. As x increases from 0 to 0.10, the ceramics undergo the phase evolution from single tetragonal phase to multiphase (coexistence of rhombic, orthorhombic, and tetragonal phases). It is found that the phase structure of the ceramics plays a critical role in enhancing the piezocatalytic activity. The pure BaTiO3 exhibits the tetragonal (T) phase with few spontaneous polarization directions and high polarization rotational energy barrier, resulting in poor catalytic performance and low piezoelectricity. With the coexistence of rhombic (R), orthorhombic (O) and tetragonal (T) phases, the ceramic with x = 0.1 exhibits the increased spontaneous polarization directions and low polarization rotational energy barrier, leading to excellent catalytic performance and high piezoelectricity. Especially, for the ceramics with x = 0.10, the degradation rates of rhodamine B (RhB), methylene blue (MB) and methyl orange (MO) under ultrasonication reach 97 %, 93 % and 73 %, respectively. In addition, the influencing factors of piezocatalytic degradation of RhB and the catalytic mechanism are investigated. This work proposes an environmentally friendly piezoelectric material for improving the water environment and a strategy for improving the catalytic activity of BaTiO3-based lead-free piezoelectric materials

Heterogeneous engineering and carbon confinement strategy to synergistically boost the sodium storage performance of transition metal selenides

Transition metal selenides (TMSs) stand out as a promising anode material for sodium-ion batteries (SIBs) owing to their natural resources and exceptional sodium storage capacity. Despite these advantages, their practical application faces challenges, such as poor electronic conductivity, sluggish reaction kinetics and severe agglomeration during electrochemical reactions, hindering their effective utilization. Herein, the dual-carbon-confined CoSe /FeSe @NC@C nanocubes with heterogeneous structure are synthesized using ZIF-67 as the template by ion exchange, resorcin-formaldehyde (RF) coating, and subsequent in situ carbonization and selenidation. The N-doped porous carbon promotes rapid electrolyte penetration and minimizes the agglomeration of active materials during charging and discharging, while the RF-derived carbon framework reduces the cycling stress and keeps the integrity of the material structure. More importantly, the built-in electric field at the heterogeneous boundary layer drives electron redistribution, optimizing the electronic structure and enhancing the reaction kinetics of the anode material. Based on this, the nanocubes of CoSe /FeSe @NC@C exhibits superb sodium storage performance, delivering a high discharge capacity of 512.6 mA h g at 0.5 A g after 150 cycles and giving a discharge capacity of 298.2 mA h g at 10 A g with a CE close to 100.0 % even after 1000 cycles. This study proposes a viable method to synthesize advanced anodes for SIBs by a synergy effect of heterogeneous interfacial engineering and a carbon confinement strategy. [Abstract copyright: Copyright © 2024 The Authors. Published by Elsevier Inc. All rights reserved.

Multilevel spatial confinement of transition metal selenides porous microcubes for efficient and stable potassium storage

Recently, potassium-ion batteries (PIBs) have been considered as one of the most promising energy storage systems; however, the slow kinetics and large volume variation induced by the large radius of potassium ions (K+) during chemical reactions lead to inferior structural stability and weak electrochemical activity for most potassium storage anodes. Herein, a multilevel space confinement strategy is proposed for developing zinc-cobalt bimetallic selenide (ZnSe/Co0.85Se@NC@C@rGO) as high-efficient anodes for PIBs by in-situ carbonizing and subsequently selenizing the resorcinol-formaldehyde (RF)-coated zeolitic imidazolate framework-8/zeolitic imidazolate framework-67 (ZIF-8/ZIF-67) encapsulated into 2D graphene. The highly porous carbon microcubes derived from ZIF-8/ZIF-67 and carbon shell arising from RF provide rich channels for ion/electron transfer, present a rigid skeleton to ensure the structural stability, offer space for accommodating the volume change, and minimize the agglomeration of active material during the insertion/extraction of large-radius K+. In addition, the three-dimensional (3D) carbon network composed of graphene and RF-derived carbon-coated microcubes accelerates the electron/ion transfer rate and improves the electrochemical reaction kinetics of the material. As a result, the as-synthesized ZnSe/Co0.85Se@NC@C@rGO as the anode of PIBs possesses the excellent rate capability of 203.9 mA h g−1 at 5 A g−1 and brilliant long-term cycling performance of 234 mA h g−1 after 2,000 cycles at 2 A g−1. Ex-situ X-ray diffraction (Ex-situ XRD) diffraction reveals that the intercalation/de-intercalation of K+ proceeds through the conversion-alloying reaction. The proposed strategy based on the spatial confinement engineering is highly effective to construct high-performance anodes for PIBs

Trace alcohol ether electrolytes with dual-site hydrogen bonds and modulated solvation structures for ultralong-life zinc-ion batteries

Aqueous zinc-ion batteries (AZIBs) are highly regarded for their affordability, stability, safety, and eco-friendliness. Nevertheless, their practical application is hindered by severe side reactions and the formation of zinc (Zn) protrusions on the Zn metal anode surface. In this study, we employ tetrahydrofuran alcohol (THFA), an efficient and cost-effective alcohol ether electrolyte, to mitigate these issues and achieve ultralong-life AZIBs. Theoretical calculations and experimental findings demonstrate that THFA acts as both a hydrogen bonding donor and acceptor, effectively anchoring H2O molecules through dual-site hydrogen bonding. This mechanism restricts the activity of free water molecules. Moreover, the two oxygen (O) atoms in THFA serve as dual solvation sites, enhancing the desolvation kinetics of [Zn(H2O)6]2+ and improving the deposition dynamics of Zn2+ ions. As a result, even trace amounts of THFA significantly suppress adverse reactions and the formation of Zn dendrites, enabling highly reversible Zn metal anodes for ultralong-life AZIBs. Specifically, a Zn-based symmetric cell containing 2 % THFA achieves an ultralong cycle life of 8,800 h at 0.5 mA cm−2/0.5 mAh cm−2, while a Zn//VO2 full cell containing 2 % THFA maintains a remarkable 80.03 % capacity retention rate at 5 A g−1 over 2,000 cycles. This study presents a practical strategy to develop dendrite-free, cost-effective, and highly efficient aqueous energy storage systems by leveraging alcohol ether compounds with dual-site hydrogen bonding capabilities

Optimizing interplanar spacing, oxygen vacancies and micromorphology via lithium-ion pre-insertion into ammonium vanadate nanosheets for advanced cathodes in aqueous zinc-ion batteries

Ammonium vanadates, featuring an N─H···O hydrogen bond network structure between NH4+ and V─O layers, have become popular cathode materials for aqueous zinc-ion batteries (AZIBs). Their appeal lies in their multi-electron transfer, high specific capacity, and facile synthesis. However, a major drawback arises as Zn2+ ions tend to form bonds with electronegative oxygen atoms between V─O layers during cycling, leading to irreversible structural collapse. Herein, Li+ pre-insertion into the intermediate layer of NH4V4O10 is proposed to enhance the electrochemical activity of ammonium vanadate cathodes for AZIBs, which extends the interlayer distance of NH4V4O10 to 9.8 Å and offers large interlaminar channels for Zn2+ (de)intercalation. Moreover, Li+ intercalation weakens the crystallinity, transforms the micromorphology from non-nanostructured strips to ultrathin nanosheets, and increases the level of oxygen defects, thus exposing more active sites for ion and electron transport, facilitating electrolyte penetration, and improving electrochemical kinetics of electrode. In addition, the introduction of Li+ significantly reduces the bandgap by 0.18 eV, enhancing electron transfer in redox reactions. Leveraging these unique advantages, the Li+ pre-intercalated NH4V4O10 cathode exhibits a high reversible capacity of 486.1 mAh g−1 at 0.5 A g−1 and an impressive capacity retention rate of 72% after 5,000 cycles at 5 A g−1

Modulating solvated structure of Zn2+ and inducing surface crystallography by a simple organic molecule with abundant polar functional groups to synergistically stabilize zinc metal anodes for long-life aqueous zinc-ion batteries

Aqueous zinc-ion batteries (AZIBs) have attracted significant attention owing to their inherent security, low cost, abundant zinc (Zn) resources and high energy density. Nevertheless, the growth of zinc dendrites and side reactions on the surface of Zn anodes during repeatedly plating/stripping shorten the cycle life of AZIBs. Herein, a simple organic molecule with abundant polar functional groups, 2,2,2-trifluoroether formate (TF), has been proposed as a high-efficient additive in the ZnSO4 electrolyte to suppress the growth of Zn dendrites and side reaction during cycling. It is found that TF molecules can infiltrate the solvated sheath layer of the hydrated Zn2+ to reduce the number of highly chemically active H2O molecules owing to their strong binding energy with Zn2+. Simultaneously, TF molecules can preferentially adsorb onto the Zn surface, guiding the uniform deposition of Zn2+ along the crystalline surface of Zn(0 0 2). This dual action significantly inhibits the formation of Zn dendrites and side reactions, thus greatly extending the cycling life of the batteries. Accordingly, the Zn//Cu asymmetric cell with 2 % TF exhibits stable cycling for more than 3,800 cycles, achieving an excellent average Columbic efficiency (CE) of 99.81 % at 2 mA cm−2/1 mAh cm−2. Meanwhile, the Zn||Zn symmetric cell with 2 % TF demonstrates a superlong cycle life exceeding 3,800 h and 2,400 h at 2 mA cm−2/1 mAh cm−2 and 5 mA cm−2/2.5 mAh cm−2, respectively. Simultaneously, the Zn//VO2 full cell with 2 % TF possesses high initial capacity (276.8 mAh/g) and capacity retention (72.5 %) at 5 A/g after 500 cycles. This investigation provides new insights into stabilizing Zn metal anodes for AZIBs through the co-regulation of Zn2+ solvated structure and surface crystallography

Structure and electrical properties of K0.5Na0.5NbO3–LiSbO3 lead-free piezoelectric ceramics

Lead-free piezoelectric ceramics (1−x)K₀.₅Na ₀.₅NbO₃-xLiSbO₃have been fabricated by a conventional ceramic sintering technique. The results of x-ray diffraction suggest that Liᐩ and Sb⁵ᐩ diffuse into the K₀.₅Na₀.₅NbO₃lattices to form a solid solution with a perovskite structure. The ceramics can be well sintered at 1070–1110 ℃ . The introduction of LiSbO₃into the Na₀.₅K₀.₅NbO₃solid solution decreases slightly the paraelectric cubic-ferroelectric tetragonal phase transition temperature (Tᴄ) , but greatly shifts the ferroelectric tetragonal-ferroelectric orthorhombic phase transition (T[sub O–F]) to room temperature. Coexistence of the orthorhombic and tetragonal phases is formed at 0.05< x <0.07 at room temperature, leading to a significant enhancement of the piezoelectric properties. For the ceramic with x=0.06, the piezoelectric properties become optimum: piezoelectric constant d₃₃=212 pC/N, planar and thickness electromechanical coupling factors kP =46% and kt=47%, respectively, remanent polarization Pᵣ=15.0 μC/cm², coercive field Ec=1.74 kV/mm, and Curie temperature Tᴄ=358 °C.Department of Applied PhysicsAuthor name used in this publication: K. W. KwokAuthor name used in this publication: K. H. LamAuthor name used in this publication: H. L. W. Cha