Cycling Performance Research Articles

Nickel-molybdenum bimetallic sulfide decorated biomass derived carbon support for high performance asymmetric supercapacitor application

Biomass - derived carbon electrode material with a porous structure is widely used in supercapacitor applications, which can improve electron transfer and shorter ion diffusion pathways. In this work, the garlic peel biomass carbon (GPBC), NiMo3S4(NMS) and garlic peel biomass carbon decorated with NiMo3S4 (GPBC/NMS) composite were prepared through a in situ two-step hydrothermal method. The synthesized materials were characterized by X-ray diffraction (XRD) and field emission scanning electron microscopy (FE-SEM), energy dispersive x-ray spectroscopy (EDS), Transmission electron microscopy techniques (TEM), Raman spectroscopy and Brunauer-Emmett-Teller (BET) techniques were used to analyze the structure, morphology and specific surface areas and X-ray photoelectron spectroscopy (XPS). The prepared bimetallic metal sulfide on a biomass - derived carbon namely the GPBC/NMS composite is used in supercapacitor application. The GPBC/NMS composite electrode exhibits good cycle performance with high specific capacity of 304C/g at current density of 1 A/g in a 3 M KOH electrolyte solution. The electrochemical performance of the GPBC/NMS//GPBC asymmetric supercapacitor device produces an excellent energy density 45.5 Wh kg−1 at a power density of 1125 W kg−1 in the 1.6 V operating potential window. The GPBC/NMS//GPBC also exhibits 93 % retention of its initial capacitance after the 10,000 GCD cycle performance. The above results demonstrate a new way of developing high performance electrode materials for energy storage applications.

Exploring Microstructure Variations and Hydrogen Storage Characteristics in TiVNbCrNi High-Entropy Alloys with Different Ni Incorporation

In recent years, high-entropy alloys (HEAs), as a novel class of hydrogen storage materials, have been deemed highly promising due to their extensive compositional tunability and the unique high entropy effects. This study aims to enhance the comprehensive hydrogen storage performance of the TiVNbCr-based HEA by introducing Ni. The effects of Ni addition on the microstructural evolution of the alloy and its impact on activation properties, hydrogen absorption and desorption kinetics, thermodynamics, and cycling performance under the complex physicochemical environment of multiple principal elements was systematically investigated. The findings indicate that Ni addition shortens the activation incubation period of the alloy but more Ni reduces the intrinsic hydrogen absorption kinetics. In the Ti25V30Nb10Cr33Ni2 alloy, a high reversible hydrogen storage capacity of up to 2.2 wt% at room temperature was achieved, surpassing most of the currently reported body-centered cubic (BCC)-structured high-entropy hydrogen storage alloys. Furthermore, the influence of Ni on the alloy's hydrogen desorption kinetics and cycling hydrogenation performance was studied. Results from 110 cycles of testing reveal that the introduction of Ni-induced Laves phases can act to relax stress, thereby reducing strain accumulation during the hydrogen absorption and desorption cycling process. This could provide guidance for the design of high-entropy hydrogen storage alloys with extended cycling lifetimes.

Deciphering fundamental mechanism of different-type diluents on manipulating interfacial chemistry toward lithium metal anode

The growth of dendrites on lithium metal anode is troublesome because it induces irreversible capacity loss and safety hazards. Formulating localized high-concentration electrolytes (LHCEs) is an alternative solution to satisfy these challenges. However, the role of diluents in tailoring interfacial chemistry remains to be explicated. Herein, we decipher the direct relationship between different-type diluents and Li-coordinated solvation at the molecular scale. Compare to hydrofluoroethers (HFE), the “active” difluoro ethylene carbonate (DFEC) delivers a pronounced interaction with Li+ and 1, 2-dimethoxyethane (DME) molecule, resulting in a compressed but more accumulated aggregates (AGGs) solvation shell, assisting in the expected chemical nature of SEI with defluorination of DFEC. Consequently, DFEC-based LHCEs (D-LHCEs) realize a record-long lifespan over 3000 h with dendrite-free at 1 mA cm−2 and outstanding dendrite tolerance even under 3 mA cm−2 in symmetric cells. The assembled full cells with D-LHCEs outperform a superior capacity retention of ∼86.83 % with average CE of ∼99.42 % after 500 cycles at 0.5C and the remarkable cycling performance even under harsh conditions (including pouch cells or with controlled N/P of 1.8) in 4.45 V-level Li||LiCoO2 cells. This work highlights the decisive role of diluents in pursuing high-efficiency electrolytes for high-energy Li metal batteries.

Layer effects on MXenes electrode and it applied to silicon composite structures

Despite the very high capacity of Si (4200mAh g−1), the widespread application of Si anodes has been hampered by drastic volume changes (up to 300 %) during cycling, leading to electrical contact losses and thus a sharp drop in capacity as the cycle life is shortened. Here we present a class of layered MXene/Si electrodes, which consist of nano-Si embedded in the interlayers of MXene to form a coupling effect, which can inhibit the huge volume change of Si during cycling. Therefore, layered MXene/Si has a highly reversible capacity, much improved cycling performance and excellent mechanical properties. First-principles calculations reveal the excellent electronic conductivity and good diffusion ability of layered MXene/Si, confirming the rapid storage of Li ions. This study provides useful information for the development and production of anode materials with high energy density and good mechanical properties.

Cyclic performance of RC frame joints with drilled openings

The construction industry commonly employs reinforced concrete (RC) beams with utility pipe openings to facilitate the passage of pipes through structures. These openings can be made through pre-construction or post-construction processes. Pre-construction openings in RC members are included in the design, and in most cases, designers include reinforcements around the opening to deal with the stress concentration and failure mechanism caused by the presence of the opening. However, post-construction or drilled openings are added after the structure is built, potentially disrupting established load paths, and developing stress concentrations that are not anticipated by the designer. In this study, three-dimensional nonlinear numerical finite element models (FEM) models were developed and validated according to four sets of experimental data. These models formed the basis for a parametric study exploring different design parameters. Parameters such as the width and depth of the specimen and the size of the opening were investigated. The results suggest that the presence of the opening leads to a brittle behavior and a sudden drop in the strength and stiffness of the specimen after the ultimate load. Increasing the depth of the beam results in more brittle behavior in specimens with openings and decreased the drift ratio where the specimen failed by up to 75%. However, increasing the width of the specimen increases the ductility of these specimens. Finally, opening size was found to lead the specimen to behave more brittle in all cases, and decrease the maximum drift ratio from 5% to 1.5%, and decrease the load capacity in 1.5% drift ratio by up to 61%. This study will help engineers and designers to understand the effect of beam-column joints with post-construction openings under cyclic loading, whether these openings are intentional or by human error.

Laser-Scribed Battery Electrodes for Ultrafast Zinc-Ion Energy Storage.

Aqueous Zn batteries are promising for large-scale energy storage applications but are plagued by the lack of high-performance cathode materials that enable high specific capacity, ultrafast charging, and outstanding cycling stability. In this work, we design a laser-scribed nano-vanadium oxide (LNVO) cathode that can simultaneously achieve these properties. Our material stores charge through Faradaic redox reactions on/near the surface at fast rates owing to the small grain size (2-6nm) of vanadium oxide and interpenetrating three-dimensional (3D) graphene network, displaying a surface-controlled capacity contribution (90%-98%). Multiple characterization techniques unambiguously reveal that zinc and hydronium ions co-insert with minimal LNVO lattice change upon cycling. As a result, we demonstrate that a high specific capacity of 553 mAh g-1 can be achieved by the LNVO/Zn system at 0.1 A g-1 , and an impressive 264 mAh g-1 capacity can be retained at 100 A g-1 with a 10 s charge/discharge cycle, showing excellent rate capability. The LNVO/Zn is also capable of reaching >90% capacity retention after 3,000 cycles at a high rate of 30 A g-1, as well as achieving both high energy (369Wh kg-1) and power densities (56,306W kg-1). Moreover, the LNVO cathode retains its excellent cycling performance when integrated into quasi-solid-state pouch cells, further demonstrating mechanical stability and its potential for practical application in wearable and grid-scale applications. This article is protected by copyright. All rights reserved.

Mo4/3B2Tx induced hierarchical structure and rapid reaction dynamics in MoS2 anode for superior sodium storage

Molybdenum sulfide (MoS2) with large layer distance and high theoretical capacity has been identified as one of the most promising anodes for sodium ion batteries, but the poor intrinsic conductivity and severe structural agglomeration restricted its diffusion kinetic and specific capacity. In this work, the synergistic effect of heterogeneous interface and Na2S adsorption/conversion active sites was employed to construct Mo4/3B2Tx-MoS2@C composites using a self-assembly and calcination strategy. Theoretical calculation and experimental results demonstrated that the charge transfer and interface between Mo4/3B2Tx and MoS2 along with the 3D hydrangea-like structure improved the intrinsic conductivity and provided fast ion diffusion channels, boosting the electrochemical kinetics; while the favorable adsorption of Na2S and weakened Na-S bond at Mo4/3B2Tx-Mo interface optimized the recombination energies of Mo-S bond, accelerating the ion diffusion and enhancing the electrochemical reversibility. In addition, the copious sulfur vacancies provided additional active sites for ion storage, ameliorating the electrochemical capacity. As expected, the novel Mo4/3B2Tx-MoS2@C electrode delivered a satisfactory rate capacity (340.6 mAh g−1 at 1 A g−1) and durable cyclic performance (267.2 mAh g−1 after 600 cycles at 2 A g−1). When paring with Na3V2(PO4)3, the Mo4/3B2Tx-MoS2@C||Na3V2(PO4)3 full cell exhibited high energy densities of 234.0 and 131.7 Wh kg−1 at 215.7 W kg−1 and 4.4 kW kg−1, respectively. The proposed synergistic strategy of heterogeneous interface and Na2S adsorption/conversion active sites provided a new guidance for the rational design of transitional metal sulfide anodes for sodium ion batteries.

Granulation of Lithium-Ion Sieves Using Biopolymers: A Review

The high demand for lithium (Li) relates to clean, renewable storage devices and the advent of electric vehicles (EVs). The extraction of Li ions from aqueous media calls for efficient adsorbent materials with various characteristics, such as good adsorption capacity, good selectivity, easy isolation of the Li-loaded adsorbents, and good recovery of the adsorbed Li ions. The widespread use of metal-based adsorbent materials for Li ions extraction relates to various factors: (i) the ease of preparation via inexpensive and facile templation techniques, (ii) excellent selectivity for Li ions in a matrix, (iii) high recovery of the adsorbed ions, and (iv) good cycling performance of the adsorbents. However, the use of nano-sized metal-based Lithium-ion sieves (LISs) is limited due to challenges associated with isolating the loaded adsorbent material from the aqueous media. The adsorbent granulation process employing various binding agents (e.g., biopolymers, synthetic polymers, and inorganic materials) affords composite functional particles with modified morphological and surface properties that support easy isolation from the aqueous phase upon adsorption of Li ions. Biomaterials (e.g., chitosan, cellulose, alginate, and agar) are of particular interest because their structural diversity renders them amenable to coordination interactions with metal-based LISs to form three-dimensional bio-composite materials. The current review highlights recent progress in the use of biopolymer binding agents for the granulation of metal-based LISs, along with various crosslinking strategies employed to improve the mechanical stability of the granules. The study reviews the effects of granulation and crosslinking on adsorption capacity, selectivity, isolation, recovery, cycling performance, and the stability of the LISs. Adsorbent granulation using biopolymer binders has been reported to modify the uptake properties of the resulting composite materials to varying degrees in accordance with the surface and textural properties of the binding agent. The review further highlights the importance of granulation and crosslinking for improving the extraction process of Li ions from aqueous media. This review contributes to manifold areas related to industrial application of LISs, as follows: (1) to highlight recent progress in the granulation and crosslinking of metal-based adsorbents for Li ions recovery, (2) to highlight the advantages, challenges, and knowledge gaps of using biopolymer-based binders for granulation of LISs, and finally, (3) to catalyze further research interest into the use of biopolymer binders and various crosslinking strategies to engineer functional composite materials for application in Li extraction industry. Properly engineered extractants for Li ions are expected to offer various cost benefits in terms of capital expenditure, percent Li recovery, and reduced environmental footprint.

Enhancing Performance and Longevity of Solid-State Zinc-Iodine Batteries with Fluorine-Rich Solid Electrolyte Interphase

Abstract Rechargeable zinc-iodine (ZnI2) batteries have gained popularity within the realm of aqueous batteries due to their inherent advantages, including natural abundance, intrinsic safety, and high theoretical capacity. However, challenges persist in their practical applications, notably battery swelling and vulnerability in aqueous electrolytes, primarily linked to the hydrogen evolution reaction and zinc dendrite growth. To address these challenges, this study presents an innovative approach by designing an all-solid-state ZnI2 battery featuring a solid perfluoropolyether (PFPE)-based polymer electrolyte. The results demonstrate the formation of a solid electrolyte interphase (SEI) layer on zinc, promoting horizontal zinc growth, mitigating dendrite penetration, and enhancing battery cycle life. Moreover, the solid electrolyte hinders the iodine ion shuttle effect, reducing zinc foil corrosion. Symmetric batteries employing this electrolyte demonstrate excellent cycle performance, maintaining stability for approximately 5000 hours at room temperature, while all-solid-state ZnI2 batteries exhibit over 7000 cycles with a capacity retention exceeding 72.2%. This work offers a promising pathway to achieving reliable energy storage in solid-state ZnI2 batteries and introduces innovative concepts for flexible and wearable zinc batteries.

Inclusion of Anion Additives in the Inner Solvation Shell to Regulate the Composition of Solid Electrolyte Interphase

AbstractAn innovative approach to electrolyte engineering in carbonate electrolytes is introduced by incorporating high donor number dual anion additives into the conventional electrolyte system (1 M NaPF6 EC:PC). The active engagement of anions in the primary solvation shell effectively hinders the reduction of solvent molecules by reducing the Lowest Unoccupied Molecular Orbital (LUMO) of Na+‐solvent‐anion complex as compared to the LUMO of pure solvents or Na+‐solvent complex. The participation of anions leads to the formation of a thinner and an inorganic‐rich Solid Electrolyte Interphase on the hard carbon anode enhancing Initial Coulombic Efficiency and significantly improving its kinetics. Moreover, the system with dual anion additives exhibits oxidative stability up to 4.5 V, effectively mitigating the undesired side reactions at high voltage operation of the layered sodium nickel manganese oxide cathode. The addition of dual anion additives proves instrumental in suppressing structural degradation and transition metal dissolution during the long cycling performance of the layered oxide cathode in a sodium‐ion full cell. The synergistic effects of this dual anion additive added electrolyte on both the anode and the cathode ultimately ensured prolonged cycling of the sodium‐ion full cell. The electrolyte engineering approach outlined in this study opens the door to advancing next‐generation high‐voltage sodium batteries.

High Selenium Loading in Vertically Aligned Porous Carbon Framework with Visualized Fast Kinetics for Enhanced Lithium/Sodium Storage

AbstractLithium/sodium–selenium (Li/Na–Se) batteries with high volumetric specific capacity are considered promising as next‐generation battery technologies. However, their practical application is hindered by challenges such as low Se loading in cathodes and the polyselenides shuttle effect. To address these challenges, a new Se host is introduced in the form of a free‐standing N, O co‐doped vertically aligned porous carbon framework decorated with a carbon nanotube forest (VCF‐CNTs), allowing for high mass loading of up to 16 mg cm−2. The low‐tortuosity Se@VCF‐CNTs architecture facilitates rapid lithiation/sodiation kinetics, while the CNT forests in vertical microchannels enhance efficient Se loading and serve as a multi‐layer fence to prevent undesired polyselenide shuttling. Consequently, the Se@VCF‐CNTs cathode displays a significant areal capacity of 10.3 mAh cm−2 at 0.1 C with a Se loading of 16 mg cm−2 for Li–Se batteries, exceeding that of commercial lithium ion batteries (4.0 mAh cm−2). In Na–Se batteries, the Se@VCF‐CNTs electrode with a Se loading of 5 mg cm−2 exhibits a discharge capacity of 436 mAh g−1 after 200 cycles, proving its consistent cycling performance. This study enriches the field of knowledge concerning high‐loading Se‐based battery systems, offering a promising avenue for enhancing energy density in the field.

Heterogeneous MoS2 Nanosheets on Porous TiO2 Nanofibers toward Fast and Reversible Sodium-Ion Storage.

2D layered molybdenum disulfide (MoS2) has garnered considerable attention as an attractive electrode material in sodium-ion batteries (SIBs), but sluggish mass transfer kinetic and capacity fading make it suffer from inferior cycle capability. Herein, hierarchical MoS2 nanosheets decorated porous TiO2 nanofibers (MoS2 NSs@TiO2 NFs) with rich oxygen vacancies are engineered by microemulsion electrospinning method and subsequent hydrothermal/heat treatment. The MoS2 NSs@TiO2 NFs improves ion/electron transport kinetic and long-term cycling performance through distinctive porous structure and heterogeneous component. Consequently, the electrode exhibits excellent long-term Na storage capacity (298.4mAhg-1 at 5Ag-1 over 1100 cycles and 235.6mAhg-1 at 10Ag-1 over 7200 cycles). Employing Na3V2(PO4)3 as cathode, the full cell maintains a desirable capacity of 269.6mAhg-1 over 700 cycles at 1.0Ag-1. The stepwise intercalation-conversion and insertion/extraction endows outstanding Na+ storage performance, which yields valuable insight into the advancement of fast-charging and long-cycle life SIBs anode materials.

Vitrified Metal-Organic Framework Composite Electrolyte Enabling Dendrite-Free and Long-Lifespan Solid-State Lithium Metal Batteries.

Solid-state lithium metal batteries (LMBs) are still plagued with low ionic conductivity and inferior interfacial contact, which hinder their practical implementation. Herein, a quasi-solid-state composite electrolyte, poly(1,3-dioxolane) (PDOL)/glassy ZIF-62 (PGZ) with fast ion transport and intimate interface contact, is fabricated via in situ polymerization. The in situ polymerization of DOL in an electrolyte matrix not only improves the exterior interface between electrolyte/electrode but also optimizes the inner interfaces among glassy particles, rendering PGZ as an uninterrupted ionic conductor. Moreover, PGZ inherits the superior ionic conductivity and the robust dendrite prohibition of glassy MOFs originating from their grain-boundary-free nature, isotropy, and abundant groups containing N species. As expected, our proposed PGZ exhibits a prominent ionic conductivity of 6.3 × 10-4 S cm-1 at 20 °C. Li|PGZ|LiFePO4 delivers an outstanding rate performance (103 mAh g-1 at 4C) and a stable cycling capacity (118 mAh g-1 at 1C over 1000 cycles). PGZ also presents excellent low-temperature cycling performance with 75 mAh g-1 for 480 cycles at -20 °C and excellent flame retardance. Even at a high loading of 12.1 mg cm-2, it can still discharge at 140 mAh g-1 for 100 cycles. Hence, PGZ prepared via in situ polymerization holds enormous prospects as a solid-state electrolyte for high-performance and safe LMBs.

Facile Fabrication of Large-Area CuO Flakes for Sodium-Ion Energy Storage Applications

CuO is recognized as a promising anode material for sodium-ion batteries because of its impressive theoretical capacity of 674 mAh g−1, derived from its multiple electron transfer capabilities. However, its practical application is hindered by slow reaction kinetics and rapid capacity loss caused by side reactions during discharge/charge cycles. In this work, we introduce an innovative approach to fabricating large-area CuO and CuO@Al2O3 flakes through a combination of magnetron sputtering, thermal oxidation, and atomic layer deposition techniques. The resultant 2D CuO flakes demonstrate excellent electrochemical properties with a high initial reversible specific capacity of 487 mAh g−1 and good cycling stability, which are attributable to their unique architectures and superior structural durability. Furthermore, when these CuO flakes are coated with an ultrathin Al2O3 layer, the integration of the 2D structures with outer nanocoating leads to significantly enhanced electrochemical properties. Notably, even after 70 rate testing cycles, the CuO@Al2O3 materials maintain a high capacity of 525 mAh g−1 at a current density of 50 mA g−1. Remarkably, at a higher current density of 2000 mA g−1, these materials still achieve a capacity of 220 mAh g−1. Moreover, after 200 cycles at a current density of 200 mA g−1, a high charge capacity of 319 mAh g−1 is sustained. In addition, a full cell consisting of a CuO@Al2O3 anode and a NaNi1/3Fe1/3Mn1/3O2 cathode is investigated, showcasing remarkable cycling performance. Our findings underscore the potential of these innovative flake-like architectures as electrode materials in high-performance sodium-ion batteries, paving the way for advancements in energy storage technologies.

Dual-Site Doping in Transition Metal Oxide Cathode Enables High-Voltage Stability of Na-Ion Batteries.

Designing cathode materials that effectively enhancing structural stability under high voltage is paramount for rationally enhancing energy density and safety of Na-ion batteries. This study introduces a novel P2-Na0.73K0.03Ni0.23Li0.1Mn0.67O2 (KLi-NaNMO) cathode through dual-site synergistic doping of K and Li in Na and transition metal (TM) layers. Combining theoretical and experimental studies, this study discovers that Li doping significantly strengthens the orbital overlap of Ni (3d) and O (2p) near the Fermi level, thereby regulates the phase transition and charge compensation processes with synchronized Ni and O redox. The introduction of K further adjusts the ratio of Nae and Naf sites at Na layer with enhanced structural stability and extended lattice space distance, enabling the suppression of TM dissolution, achieving a single-phase transition reaction even at a high voltage of 4.4V, and improving reaction kinetics. Consequently, KLi-NaNMO exhibits a high capacity (105 and 120 mAh g-1 in the voltage of 2-4.2V and 2-4.4V at 0.1 C, respectively) and outstanding cycling performance over 300 cycles under 4.2 and 4.4V. This work provides a dual-site doping strategy to employ synchronized TM and O redox with improved capacity and high structural stability via electronic and crystal structure modulation.

Incorporating Sodium-Conductive Polymeric Interfacial Adhesive with Inorganic Solid-State Electrolytes for Quasi-Solid-State Sodium Metal Batteries.

Inorganic solid-state electrolytes have attracted enormous attention due to their potential safety, increased energy density, and long cycle-life benefits. However, their application in solid-state batteries is limited by unstable electrode-electrolyte interface, poor point-to-point physical contact, and low utilization of metallic anodes. Herein, interfacial engineering based on sodium (Na)-conductive polymeric solid-state interfacial adhesive is studied to improve interface stability and optimize physical contacts, constructing a robust organic-rich solid electrolyte interphaselayer to prevent dendrite-induced crack propagation and security issues. The interfacial adhesive strategy significantly increases the room-temperature critical current density of inorganic Na-ion conductors from 0.8 to 3.2mAcm-2 and markedly enhances the cycling performance of solid-state batteries up to 500 cycles, respectively. Particularly, the Na3V2(PO4)3-based full solid-state batteries with high cathode loading of 10.16mgcm-2 also deliver an excellent cycling performance, further realizing the stable operation of solid-state laminated pouch cells. The research provides fundamental perspectives into the role of interfacial chemistry and takes the field a step closer to realizing practical solid-state batteries.

Inhibiting Residual Solvent Induced Side Reactions in Vinylidene Fluoride-Based Polymer Electrolytes Enables Ultra-Stable Solid-State Lithium Metal Batteries.

Residual solvents in vinylidene fluoride (VDF)-based solid polymer electrolytes (SPEs) have been recognized as responsible for their high ionic conductivity. However, side reactions by the residual solvents with the lithium (Li) metal induce poor stability, which has been long neglected. This study proposes a strategy to achieve a delicate equilibrium between ion conduction and electrode stability for VDF-based SPEs. Specifically, 2,2,2-trifluoro-N,N-dimethylacetamide (FDMA) is developed as the nonside reaction solvent for poly(vinylidene fluoride-co-hexafluoropropylene) (PVHF)-based SPEs, achieving both high ionic conductivity and significantly improved electrochemical stability. The developed FDMA solvent fosters the formation of a stable solid electrolyte interphase (SEI) through interface reactions with Li metal, effectively mitigating side reactions and dendrite growth on the Li metal electrode. Consequently, the Li||Li symmetric cells and Li||LiFePO4 cells demonstrate excellent cycling performance, even under limited Li (20µm thick) supply and high-loading cathodes (>10mg cm-2, capacity >1 mAh cm-2) conditions. The stable Li||LiCoO2 cells operation with a cutoff voltage of 4.48V indicates the high-voltage stability of the developed SPE. This study offers valuable insights into the development of advanced VDF-based SPEs for enhanced lithium metal battery performance and longevity.

Synergetic Dual-Additive Electrolyte Enables Highly Stable Performance in Sodium Metal Batteries.

Sodium (Na)-metal batteries (SMBs) are considered one of the most promising candidates for the large-scale energy storage market owing to their high theoretical capacity (1,166 mAh g-1) and the abundance of Na raw material. However, the limited stability of electrolytes still hindered the application of SMBs. Herein, sulfolane (Sul) and vinylene carbonate (VC) are identified as effective dual additives that can largely stabilize propylene carbonate (PC)-based electrolytes, prevent dendrite growth, and extend the cycle life of SMBs. The cycling stability of the Na/NaNi0.68Mn0.22Co0.1O2 (NaNMC) cell with this dual-additive electrolyte is remarkably enhanced, with a capacity retention of 94% and a Coulombic efficiency (CE) of 99.9% over 600 cycles at a 5 C (750mA g-1) rate. The superior cycling performance of the cells can be attributed to the homogenous, dense, and thin hybrid solid electrolyte interphase consisting of F- and S-containing species on the surface of both the Na metal anode and the NaNMC cathode by adding dual additives. Such unique interphases can effectively facilitate Na-ion transport kinetics and avoid electrolyte depletion during repeated cycling at a very high rate of 5 C. This electrolyte design is believed to result in further improvements in the performance of SMBs.

Core–Double-Shell TiO2@Fe3O4@C Microspheres with Enhanced Cycling Performance as Anode Materials for Lithium-Ion Batteries

Due to the volume expansion effect during charge and discharge processes, the application of transition metal oxide anode materials in lithium-ion batteries is limited. Composite materials and carbon coating are often considered feasible improvement methods. In this study, three types of TiO2@Fe3O4@C microspheres with a core–double-shell structure, namely TFCS (TiO2@Fe3O4@C with 0.0119 g PVP), TFCM (TiO2@Fe3O4@C with 0.0238 g PVP), and TFCL (TiO2@Fe3O4@C with 0.0476 g PVP), were prepared using PVP (polyvinylpyrrolidone) as the carbon source through homogeneous precipitation and high-temperature carbonization methods. After 500 cycles at a current density of 2 C, the specific capacities of these three microspheres are all higher than that of TiO2@Fe2O3 with significantly improved cycling stability. Among them, TFCM exhibits the highest specific capacity of 328.3 mAh·g−1, which was attributed to the amorphous carbon layer effectively mitigating the capacity decay caused by the volume expansion of iron oxide during charge and discharge processes. Additionally, the carbon coating layer enhances the electrical conductivity of the TiO2@Fe3O4@C materials, thereby improving their rate performance. Within the range of 100 to 1600 mA·g−1, the capacity retention rates for TiO2@Fe2O3, TFCS, TFCM, and TFCL are 27.2%, 35.2%, 35.9%, and 36.9%, respectively. This study provides insights into the development of new lithium-ion battery anode materials based on Ti and Fe oxides with the abundance and environmental friendliness of iron, titanium, and carbon resources in TiO2@Fe3O4@C microsphere anode materials, making this strategy potentially applicable.

Stabilizing Zinc Hexacyanoferrate Cathode by Low Contents of Cs Cations for Aqueous Zn-Ion Batteries.

Exploring cathode materials with excellent electrochemical performance is crucial for developing rechargeable aqueous zinc ion batteries (RAZIBs). Zinc hexacyanoferrate (ZnHCF), a promising candidate of cathode materials for RAZIBs, suffers from severe electrochemical instability issues. This work reports using low contents of alkaline metal cations as electrolyte additives to improve the cycle performance of ZnHCF. The cations with large sizes, particularly Cs+, changes the intercalation chemistry of ZnHCF in RAZIBs. During cycling, Cs+ cations co-inserted into ZnHCF stabilize the host structure. Meanwhile, a stable phase of CsZn[Fe(CN)6] forms on the ZnHCF cathode, suppressing the loss of active materials through dissolution. ZnHCF gradually converts to an electrochemically inert Zn-rich phase during long-term cycling in aqueous electrolyte, leading to irreversible capacity loss. Introducing Cs+ in the electrolyte inhibits this conversion reaction, resulting in the extended lifespan. Owing to these advantages, the capacity retention rate of ZnHCF/Zn full batteries increases from the original 7.0% to a high value of 54.6% in the electrolyte containing 0.03 M of Cs2SO4 after 300 cycles at 0.25 A∙g-1. This research provides an in-depth understanding of the electrochemical behavior of ZnHCF in aqueous zinc electrolyte, beneficial for further optimizing ZnHCF and other metal hexacyanoferrates.