Carbon Energy最新文献

Compared to traditional liquid electrolyte batteries, solid metal batteries offer advantages such as a wide operating temperature range, high energy density, and improved safety, making them a promising energy storage technology. Solid electrolytes, as the core components of solid-state batteries, are key factors in advancing solid-state battery technology. Among various solid electrolytes, Na super ionic conductor (NASICON)-type solid electrolytes exhibit high ionic conductivity (10⁻³ S·cm⁻¹), a wide electrochemical window, and good thermal stability, providing room for the development of high energy-density solid metal batteries. Since the discovery of NASICON-type solid electrolytes in 1976, interest in their use in all-solid-state battery development has grown significantly. In this review, we comprehensively analyze the common features of NASICON lithium-ion conductors and NASICON sodium-ion conductors, review the historical development of NASICON-type solid electrolytes, systematically summarize the transport mechanisms of metal cations in NASICON-type solid electrolytes, discuss the latest strategies for enhancing ionic conductivity, elaborate on the latest methods for improving mechanical stability and interface stability, and point out the requirements of high energy density devices for NASICON-type solid electrolytes as well as three types of in situ characterization techniques for interfaces. Finally, we highlight the challenges and potential solutions for the future development of NASICON-type solid electrolytes and solid-state metal batteries.

Salination of solutions of salinity gradient releases large-scale clean and renewable energy, which can be directly and efficiently transformed into electrical energy using ion-selective nanofluidic channel membranes. However, conventional ion-selective membranes are typically either cation- or anion-selective. A pH-switchable system capable of dual cation and anion transport along with salt gradient energy harvesting properties has not been demonstrated in ion-selective membranes. Here, we constructed an amphoteric heterolayer metal–organic framework (MOF) membrane with subnanochannels modified with carboxylic and amino functional groups. The amphoteric MOF-composite membrane, AAO/aUiO-66-(COOH)₂/UiO-66-NH₂, exhibits pH-tuneable ion conduction and achieves osmotic energy conversion of 7.4 and 5.7 W/m² in acidic and alkaline conditions, respectively, using a 50-fold salt gradient. For different anions but the same cation diffusion transport, the amphoteric membrane produces an outstanding I⁻/CO₃²⁻ selectivity of ~4160 and an osmotic energy conversion of ~133.5 W/m². The amphoteric membrane concept introduces a new pathway to explore the development of ion transport and separation technologies and their application in osmotic energy-conversion devices and flow batteries.

The high chloride (Cl) concentration in seawater presents a critical challenge for hydrogen production via seawater electrolysis by deactivating catalysts through active site passivation, highlighting the need for catalyst innovation. Herein, in situ boron-doped Co₂P/CoP (B-Co_xP) ultrathin nanosheet arrays are prepared as high-performance bifunctional electrocatalysts for seawater decomposition. Density functional theory (DFT) simulations, comprehensive characterizations, and in-situ analyses reveal that boron doping enhances electron density around Co centers, induces lattice distortions, and significantly elevates catalytic activity and durability. Moreover, boron doping reduces *Cl retention time at active sites—defined as the DFT-derived residence time of adsorbed Cl intermediates based on their adsorption energies—effectively mitigating Cl-induced poisoning. In a three-electrode system, B-Co_xP achieves exceptional bifunctional performance with overpotentials of 11 mV for hydrogen evolution reaction and 196 mV for oxygen evolution reaction to deliver 10 and 50 mA·cm^–2, respectively—a result that showcases its superior bifunctional properties surpassing noble metal-based counterparts. In an alkaline electrolyzer, it delivers 1.56 A·cm^–2 at 2.87 V for seawater electrolysis with outstanding stability over 500 h, preserving active site integrity via boron's robust protective role. This study defines a paradigm for designing advanced seawater electrolysis catalysts through a strategic in-situ doping approach.

Front cover image: Lithium-sulfur (Li-S) batteries hold great promise for high-energy-density storage, but their practical performance is hindered by sluggish lithium polysulfide (LiPS) conversion kinetics. To address this issue, in the article numbered e270043, Yang et al. successfully synthesized ultrafine truncated octahedral titanium dioxide nanocrystals (P-O_v-TiO₂) with specific {101} crystal faces, phosphorus doping, and oxygen vacancies under mild conditions. The oxygen vacancies significantly enhance the electron enrichment and charge transfer ability by adjusting the electronic structure; phosphorus doping effectively optimize the d-band center of the catalyst, further strengthening the titanium-sulfur interaction at the {101} crystal faces. This dual-defect engineering enables the exposed {101} crystal faces to exhibit excellent chemical adsorption capacity and catalytic performance. The assembled lithium-sulfur battery using P-O_v-TiO₂ as the separator modification achieves a high specific capacity of 895 mAh g^-1 at 5 C and exhibites a minimal decay rate of 0.14% per cycle over 200 cycles. Additionally, the lithium-sulfur pouch battery delivers a high capacity of 1004 mAh g^-1 under a 0.1 C current density in a low electrolyte condition. This research provides important theoretical basis and new ideas for designing efficient catalysts suitable for lithium-sulfur battery applications.

Back cover image: Layered manganese dioxide (δ-MnO₂) cathodes for aqueous zinc-ion batteries offer high capacity but suffer from sluggish Zn²⁺ diffusion and severe manganese dissolution. In article number e70014, Ding et al. engineer a dual-functional δ-MnO₂ cathode modified with 2-methylimidazole. This synergistic molecular design combines pre-intercalation to expand interlayer spacing (accelerating Zn²⁺ diffusion) and surface coating to form stabilizing Mn–N bonds (suppressing Mn²⁺ dissolution), achieving exceptional capacity and cycling stability.

Polarization-dependent loss is important to the highly electromagnetic wave absorption (EWA) performance. Recently, metal–N_x moieties have been discovered to trigger polarization loss, but the physical origin and other possible related loss mechanisms still need to be deeply explored. In this article, we reveal that the FeN₄ moiety from iron phthalocyanine (FePc) can coordinate with Ti₃C₂T_x through Ti–OH groups, inducing dipole polarization and synchronous magnetic modulation in Fe/TiO₂/Ti₃C₂T_x composites. Interestingly, using the enhanced electric dipole moment and increased number of unpaired electrons in Fe atoms, the dipole polarization loss and possible magnetic response can be rapidly confirmed and evaluated. As a result, the minimum reflection loss (RL_min) of Fe/TiO₂/Ti₃C₂T_x composites reaches −67.12 dB at 6.72 GHz with a thickness of 3.32 mm. This study elaborates the EWA mechanism based on the atomic scale, and provides a new idea to design efficient EWA materials.

The efficient storage and application of sustainable solar energy has drawn significant attention from both academic and industrial points of view. However, most developed catalytic materials still suffer from insufficient mass diffusion and unsatisfactory durability due to the lack of interconnected and regulatable porosity. Developing catalytic architectures with engineered active sites and prominent stability through rational synthesis strategies has become one of the core projects in solar-driven applications. The unique properties of mesoporous silicas render them among the most valuable functional materials for industrial applications, such as high specific surface area, regulatable porosity, adjustable surface properties, tunable particle sizes, and great thermal and mechanical stability. Mesoporous silicas serve as structural templates or catalytic supports to enhance light harvesting via the scattering effect and provide large surface areas for active site generation. These advantages have been widely utilized in solar applications, including hydrogen production, CO₂ conversion, photovoltaics, biomass utilization, and pollutant degradation. To achieve the specific functionalities and desired activity, various types of mesoporous silicas from different synthesis methods have been customized and synthesized. Moreover, morphology regulation and component modification strategies have also been performed to endow mesoporous silica-based materials with unprecedented efficiency for solar energy storage and utilization. Nevertheless, reviews about synthesis, morphology regulation, and component modification strategies for mesoporous silica-based catalyst design in solar-driven applications are still limited. Herein, the latest progress concerning mesoporous silica-based catalysis in solar-driven applications is comprehensively reviewed. Synthesis principles, formation mechanisms, and rational functionalities of mesoporous silica are systematically summarized. Some typical catalysts with impressive activities in different solar-driven applications are highlighted. Furthermore, challenges and future potential opportunities in this study field are also discussed and proposed. This present review guides the design of mesoporous silica catalysts for efficient solar energy management for solar energy storage and conversion applications.

Full-manganese (Mn) Li-rich materials have gained attention owing to the limited availability of cobalt- or nickel-based cathodes commonly used in batteries, which greatly restricts their potential for large-scale application. However, their practical implementation is hindered by the rapid voltage/capacity decay during cycling and the long-standing problem of redox kinetics due to their poor ionic conductivity based on the ordered honeycomb structure. In this study, the kinetic and thermodynamic properties of intralayer disordered and ordered Li-rich full-Mn-based cathode materials were compared, demonstrating that the disordered $��\; ��R�\; �\overline{3}�\; �m��$ Li_0.6[Li_0.2Mn_0.8]O₂ (D-LMO) delivers a significant advantage of rate capability over the ordered $��\; ��C�\; �2�\; �/�\; �m��$ Li_0.6[Li_0.2Mn_0.8]O₂ (O-LMO). Meanwhile, the D-LMO keeps superior capacity retention of up to 99% after 50 cycles under 25 mA g⁻¹. In comparsion, the capacity retention of the O-LMO drops to just 70%, and its average discharge voltage is 0.2 V lower than that of the D-LMO. Herein, we conducted systematic density functional theory (DFT) simulations, focusing on the electronic structure modulation governing the voltage platform between the ordered and disordered phases. The ab initio molecular dynamics (AIMD) results indicated that the energy of the intralayer disordered structure fluctuates around the equilibrium position without any abrupt drops, demonstrating excellent stability. This study enhances the understanding of intralayer disordered full-Mn Li-rich material and provides insights into the design of low-cost, high-performance cathode materials for Li-ion batteries.

The development of human industry inevitably leads to excessive carbon dioxide (CO₂) emissions. It can cause critical ecological consequences, primarily global warming and ocean acidification. In this regard, close attention is paid to the carbon capture, utilization, and storage concept. The key component of this concept is the catalytic conversion of CO₂ into valuable chemical compounds and fuels. Light olefins are one of the most industrially important chemicals, and their sustainable production via CO₂ hydrogenation could be a prospective way to reach carbon neutrality. Fe-based materials are widely recognized as effective thermocatalysts and photothermal catalysts for that process thanks to their low cost, high activity, and good stability. This review critically examines the most recent progress in the development and optimization of Fe-based catalysts for CO₂ hydrogenation into light olefins. Particular attention is paid to understanding the roles of catalyst composition, structural properties, and promoters in enhancing catalytic activity, selectivity, and stability.

Lead (Pb)–zinc (Zn) slags contain large amounts of Pb, causing irreversible damage to the environment. Therefore, developing an effective strategy to extract Pb from Pb–Zn slags and convert them into a renewable high-value catalyst not only solves the energy crisis but also reduces environmental pollution. Herein, we present a viable strategy to recycle Pb and iron (Fe) from Pb–Zn slags for the fabrication of efficient methylammonium lead tri-iodide (r-MAPbI₃) piezocatalysts with single-atom Fe–N₄ sites. Intriguingly, atomically dispersed Fe sites from Pb–Zn slags, which coordinated with N in the neighboring four CH₃NH₃ to form the FeN₄ configuration, were detected in the as-obtained r-MAPbI₃ by synchrotron X-ray absorption spectroscopy. The introduction of Fe single atoms amplified the polarization of MAPbI₃ and upshifted the d-band center of MAPbI₃. This not only enhanced the piezoelectric response of MAPbI₃ but also promoted the proton transfer during the hydrogen evolution process. Due to the decoration of Fe single atoms, r-MAPbI₃ showed a pronounced H₂ yield of 322.4 μmol g⁻¹ h⁻¹, which was 2.52 times that of MAPbI₃ synthesized using commercially available reagents. This simple yet robust strategy to manufacture MAPbI₃ piezocatalysts paves a novel way to the large-scale and value-added consumption of Pb-containing waste residues.