通讯机构：
[Jiang, Y; Zhang, JJ ] S;[Chen, ZY ; Duan, JF] C;Changsha Univ Sci & Technol, Sch Mat Sci & Engn, Changsha 410114, Peoples R China.;Shanghai Univ, Sch Environm & Chem Engn, Shanghai Key Lab Atom Control & Applicat Inorgan 2, Shanghai 200444, Peoples R China.
关键词：
hard carbon anodes;pore structure modulation;sodium ion batteries;sodium storage mechanism;ultramicropores
摘要：
Regulating the microstructure of hard carbon (HC) anodes has emerged as a popular strategy to enhance the application potential of sodium-ion batteries (SIBs). However, the low platform capacity and inferior rate property remain significant barriers to their further development. Herein, HC materials with abundant ultramicropores (0.3-0.8 nm) are prepared employed epoxy resin and zinc acetate as precursors. Benefiting from the abundant hydroxyl and epoxy groups, the synergistic generation of simple aromatic free radicals and the precipitated ZnO promote the cross-linking between precursor molecules during the first-step pyrolysis, alter the twisting and folding of carbon layers during high-temperature calcniantion, thereby precisely regulating the micropore structure of HC. Owing to its abundant ultramicropore structure and the boosted Na + transfer dynamics, the optimal anode demonstrates a superior plateau capacity of 256.2 mAh g −1 at 30 mA g −1 (408.0 mAh g −1 reversible capacity) and rate capability of 317.0 mAh g −1 at 1 A g −1 , outperforming most other resin-derived carbon materials. In situ Raman combined with in situ XRD testing results demonstrate that the well-designed HC presents a typical “adsorption-intercalation-pore filling” sodium storage mechanism. This work provides a theoretical basis and experimental guidance for high-performance HC derived from epoxy resin, which is essential for advancements in SIBs.
关键词：
Domestic waste incineration fly ash;Ceramic foams;Flexural strength;Heavy metal leaching;Thermal phase transition model
摘要：
In this study, ceramic foams were prepared from domestic waste incineration fly ash. The physical and mechanical properties of ceramic foams were studied systematically. The bulk density, open porosity, water absorption rate was 3.04 g/cm 3 , 1.01 %, and 4.04 %, respectively. Especially, the flexural strength was 20.63 MPa, the thermal conductivity was 0.2721 W/(m K) (25 °C) and the heavy metal leaching concentration was 0.5442 mg/L (Pb). By analyzing the thermal phase transition of sintering process for ceramic foams, the thermal phase transition model during the sintering process of high-calcium and low-silicon domestic waste incineration fly ash-based ceramic foams is discussed. Therefore, the use of fly ash from domestic waste incineration to prepare ceramic foams can turn waste into treasure and realize the resource utilization of fly ash.
In this study, ceramic foams were prepared from domestic waste incineration fly ash. The physical and mechanical properties of ceramic foams were studied systematically. The bulk density, open porosity, water absorption rate was 3.04 g/cm 3 , 1.01 %, and 4.04 %, respectively. Especially, the flexural strength was 20.63 MPa, the thermal conductivity was 0.2721 W/(m K) (25 °C) and the heavy metal leaching concentration was 0.5442 mg/L (Pb). By analyzing the thermal phase transition of sintering process for ceramic foams, the thermal phase transition model during the sintering process of high-calcium and low-silicon domestic waste incineration fly ash-based ceramic foams is discussed. Therefore, the use of fly ash from domestic waste incineration to prepare ceramic foams can turn waste into treasure and realize the resource utilization of fly ash.
摘要：
Micro-nanobubbles (MNBs), as an emerging environmental-friendly technology, have shown great potential in enhancing advanced oxidation processes for water treatment. This study innovatively integrated MNBs with a biochar-supported cobalt-iron catalyst (CoFe/BC) and persulfate (PDS) system, creating a novel synergistic approach for tetracycline (TC) degradation. The CoFe/BC+PDS+MNB system achieved 95.63% TC degradation efficiency under optimized conditions (50 mg/L catalyst, 30 mg/L TC, 400 mg/L PDS), outperforming the conventional system with half the catalyst. While CO 3 2- and HCO 3 - inhibited TC degradation, NO 3 - , H 2 PO 4 - , and humic acid showed minimal interference. Mechanistic studies revealed that singlet oxygen ( 1 O 2 ), sulfate radicals (SO 4 •- ), and hydroxyl radicals (•OH) were the primary reactive species. MNBs facilitated electron transfer between dissolved oxygen (DO) and CoFe/BC, while bubble collapse generated localized •OH hotspots. Electrostatic attraction between MNBs and CoFe/BC under acidic conditions (pH 3-6.2) improved DO conversion efficiency, while MNB stability at neutral-alkaline pH ensured sustained degradation (>91% at pH 7-9). Despite pH sensitivity, the synergistic effect maintained efficient degradation across a broad pH range. This study demonstrates the potential of MNBs integration in persulfate-based advanced oxidation processes for water treatment applications.
Micro-nanobubbles (MNBs), as an emerging environmental-friendly technology, have shown great potential in enhancing advanced oxidation processes for water treatment. This study innovatively integrated MNBs with a biochar-supported cobalt-iron catalyst (CoFe/BC) and persulfate (PDS) system, creating a novel synergistic approach for tetracycline (TC) degradation. The CoFe/BC+PDS+MNB system achieved 95.63% TC degradation efficiency under optimized conditions (50 mg/L catalyst, 30 mg/L TC, 400 mg/L PDS), outperforming the conventional system with half the catalyst. While CO 3 2- and HCO 3 - inhibited TC degradation, NO 3 - , H 2 PO 4 - , and humic acid showed minimal interference. Mechanistic studies revealed that singlet oxygen ( 1 O 2 ), sulfate radicals (SO 4 •- ), and hydroxyl radicals (•OH) were the primary reactive species. MNBs facilitated electron transfer between dissolved oxygen (DO) and CoFe/BC, while bubble collapse generated localized •OH hotspots. Electrostatic attraction between MNBs and CoFe/BC under acidic conditions (pH 3-6.2) improved DO conversion efficiency, while MNB stability at neutral-alkaline pH ensured sustained degradation (>91% at pH 7-9). Despite pH sensitivity, the synergistic effect maintained efficient degradation across a broad pH range. This study demonstrates the potential of MNBs integration in persulfate-based advanced oxidation processes for water treatment applications.
期刊：
Chemical Engineering Journal,2025年504:158517 ISSN：1385-8947
通讯作者：
Ou, X;Fu, Chaochao;Shen, JX;Bai, MH
作者机构：
[Zhang, Zhi; Zhu, Wenqi; Liao, Tong; Zhang, Dongsheng] Hunan Univ Arts & Sci, Coll Chem & Mat Engn, Hunan Prov Key Lab Water Treatment Funct Mat, Changde 415000, Peoples R China.;[Gao, Shuai; Zhang, Zhi; Ou, Xing] Cent South Univ, Engn Res Ctr Minist Educ Adv Battery Mat, Sch Met & Environm, Changsha 410083, Peoples R China.;[Guo, Haipeng] Feng Fan Co LTD, Baoding 071002, Peoples R China.;[Fu, Chaochao; Wang, Yi; Shen, Jixue; Fu, CC] Hebei Univ, Hebei Technol Innovat Ctr Lightweight New Energy V, Sch Qual & Tech Supervis, Baoding 071002, Peoples R China.;[Bai, Maohui] Changsha Univ Sci & Technol, Coll Mat Sci & Engn, Changsha 410004, Peoples R China.
通讯机构：
[Shen, JX ; Fu, CC] H;[Bai, MH ; Ou, X ] C;Cent South Univ, Engn Res Ctr Minist Educ Adv Battery Mat, Sch Met & Environm, Changsha 410083, Peoples R China.;Hebei Univ, Hebei Technol Innovat Ctr Lightweight New Energy V, Sch Qual & Tech Supervis, Baoding 071002, Peoples R China.;Changsha Univ Sci & Technol, Coll Mat Sci & Engn, Changsha 410004, Peoples R China.
关键词：
Interfacial chemistry;Elevated temperature;High-voltage;Lithium-ion pouch full cell;Multicomponent additives
摘要：
The interfacial chemistry influenced by electrolyte components, including lithium salts, solvents, and additives, has attracted significant attention for its critical role in advancing high-performance lithium-ion batteries (LIBs). However, the instability of interfacial interactions between traditional electrolytes and electrodes presents a major obstacle to achieving optimal LIB performance, especially in conditions of high temperature and cut-off voltage. This work introduces an interfacial engineering method utilizing a combination of additives − specifically, fluoroethylene carbonate, ethylene sulfate, and propane sultone (referred to as FDP) − to enhance the conventional carbonate electrolyte for applications in high-voltage and high-temperature LIBs. These additives effectively adjust the interactions between lithium ions and solvents, reducing desolvation energy, thereby decreasing gas evolution, mitigating extensive solvent decomposition, and promoting the formation of a thin, uniform, low-impedance elastic interfacial film on both the anode and cathode. Noteworthy results include a 97.3 % capacity retention at 4.4 V over 250 cycles at 45 °C in a 1.7 Ah-level single crystal LiNi0.6Co0.1Mn0.3O2 (SC-NCM613)||graphite pouch full cell incorporating FDP additives. This interfacial engineering approach facilitated by these multicomponent additives presents a highly promising and practical pathway for achieving long-lasting high-voltage and high-temperature LIBs.
The interfacial chemistry influenced by electrolyte components, including lithium salts, solvents, and additives, has attracted significant attention for its critical role in advancing high-performance lithium-ion batteries (LIBs). However, the instability of interfacial interactions between traditional electrolytes and electrodes presents a major obstacle to achieving optimal LIB performance, especially in conditions of high temperature and cut-off voltage. This work introduces an interfacial engineering method utilizing a combination of additives − specifically, fluoroethylene carbonate, ethylene sulfate, and propane sultone (referred to as FDP) − to enhance the conventional carbonate electrolyte for applications in high-voltage and high-temperature LIBs. These additives effectively adjust the interactions between lithium ions and solvents, reducing desolvation energy, thereby decreasing gas evolution, mitigating extensive solvent decomposition, and promoting the formation of a thin, uniform, low-impedance elastic interfacial film on both the anode and cathode. Noteworthy results include a 97.3 % capacity retention at 4.4 V over 250 cycles at 45 °C in a 1.7 Ah-level single crystal LiNi0.6Co0.1Mn0.3O2 (SC-NCM613)||graphite pouch full cell incorporating FDP additives. This interfacial engineering approach facilitated by these multicomponent additives presents a highly promising and practical pathway for achieving long-lasting high-voltage and high-temperature LIBs.
摘要：
The catalyst-free growth of vertically oriented graphene (VG) networks with growth rate of about 5 nm/min on commercial aluminum (Al) foil via radio frequency plasma-enhanced chemical vapor deposition (RF-PECVD) is reported. The effects of process parameters, including precursor type and deposition temperature, on VG synthesis were systematically investigated. The deposition temperature plays a decisive role in the formation of VGs, while the precursor primarily influences growth rate and crystallinity. VGs were synthesized using either ethylene (C 2 H 4 ) or propylene (C 3 H 6 ) as precursors, but formation does not occur at lower temperatures (e.g., 500 °C). Precursors that effectively generate carbon dimers and exhibit a higher H:C ratio are more favorable for achieving VGs with high growth rates and superior crystallinity. Furthermore, we proposed a deposition mechanism that encompasses both the growth of VGs on the Al foil surface and the diffusion of carbon atoms into the Al foil. The growth process of VGs follows three distinct stages: the formation of buffer carbon nanoislands, nucleation, and subsequent growth. X-ray photoelectron spectroscopy (XPS) revealed the chemical interactions between carbon, Al x O y , and metallic Al at the interface, resulting in a diffusion layer and an interface layer between the VG layer and the underlying Al substrate.
The catalyst-free growth of vertically oriented graphene (VG) networks with growth rate of about 5 nm/min on commercial aluminum (Al) foil via radio frequency plasma-enhanced chemical vapor deposition (RF-PECVD) is reported. The effects of process parameters, including precursor type and deposition temperature, on VG synthesis were systematically investigated. The deposition temperature plays a decisive role in the formation of VGs, while the precursor primarily influences growth rate and crystallinity. VGs were synthesized using either ethylene (C 2 H 4 ) or propylene (C 3 H 6 ) as precursors, but formation does not occur at lower temperatures (e.g., 500 °C). Precursors that effectively generate carbon dimers and exhibit a higher H:C ratio are more favorable for achieving VGs with high growth rates and superior crystallinity. Furthermore, we proposed a deposition mechanism that encompasses both the growth of VGs on the Al foil surface and the diffusion of carbon atoms into the Al foil. The growth process of VGs follows three distinct stages: the formation of buffer carbon nanoislands, nucleation, and subsequent growth. X-ray photoelectron spectroscopy (XPS) revealed the chemical interactions between carbon, Al x O y , and metallic Al at the interface, resulting in a diffusion layer and an interface layer between the VG layer and the underlying Al substrate.
作者机构：
[Guo, Xueyi; Guo, XY; Liao, Hanxiao] Cent South Univ, Sch Met & Environm, Changsha 410083, Peoples R China.;[Tong, Jiaxin; Tan, Pengfei; Pan, Jun; Liao, Hanxiao; He, Xiaorong; Tan, PF] Cent South Univ, State Key Lab Powder Met, Changsha 410083, Peoples R China.;[Chen, Kejun] Changsha Univ Sci & Technol, Coll Mat Sci & Engn, Changsha 410114, Peoples R China.;[Wang, Xin] Univ Wollongong, Fac Engn & Informat Sci, Wollongong, NSW 2500, Australia.;[Pan, Jun; Liu, Feng] Yunnan Precious Met Lab Co Ltd, Kunming 650106, Yunnan, Peoples R China.
通讯机构：
[Guo, XY ; Pan, J ; Tan, PF] C;Cent South Univ, Sch Met & Environm, Changsha 410083, Peoples R China.;Cent South Univ, State Key Lab Powder Met, Changsha 410083, Peoples R China.;Yunnan Precious Met Lab Co Ltd, Kunming 650106, Yunnan, Peoples R China.
摘要：
Nickel-iron (NiFe) materials with flexible structure and component have shown all-right potency for the alkaline oxygen evolution reaction (OER) due to their low reaction barriers. However, most of NiFe catalysts suffer from inferior electrocatalytic stability induced by unfavorable Fe dissolution. Herein, the selective sulfuration of FeOOH/Ni(OH)2 (NiFe) is developed to construct a reliable Fe & horbar;S interaction in FeOOH/Ni3S2/Ni(OH)2 (NiFeS) composite and subsequently restrain the Fe dissolution, realizing durable OER stability. X-ray absorption spectroscopy and theoretical calculations demonstrate that the strong Fe & horbar;S interaction affords more electrons to metal sites, thereby stabilizing Fe sites. Meanwhile, the tailored Fe sites with shortened interatomic distance are conducive to inducing double lattice oxygen mechanism (dLOM) for further improving OER activity. Consequently, NiFeS displays a seven-fold improvement of OER stability and a decreased overpotential compared to NiFe. Moreover, the anion exchange membrane water electrolysis (AEMWE) cell using NiFeS as anode presents an impressive durability for 300 h with negligible attenuation of 0.26 mV h & horbar;1 at 1.0 A cm & horbar;2 at 60 degrees C. This work provides a new approach to conquer the Fe leakage in NiFe catalysts and enhance the catalytic stability, escorting for their industrial application.
关键词：
3D ordered gyroid substrate;Bubble behavior;High current decoupled hydrogen and oxygen evolution;High current water electrolysis
摘要：
The conversion of renewable energy sources with relatively large energy fluctuations into hydrogen represents a crucial aspect of energy storage. Nevertheless, the direct water electrolysis process is known to require excessive instantaneous energy consumption and high cost. Two-step alkaline water electrolysis is regarded as a secure and effective method of generating hydrogen from renewable energy sources when compared to direct water electrolysis. Here we propose a two-step alkaline water electrolysis using nickel–cobalt based hydroxide (Ni 0.9 Co 0.1 (OH) 2 ) as a redox mediator, and a high-performance bifunctional catalyst as gas evolution electrodes (GEE). The substrates for the GEE were prepared using 3D printing and then loaded with in-situ grown Ru-doped MoS 2 /NiFe-LDH hierarchical heterostructure catalysts (MS-NiFe-Ru-3D). The oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) of the MS-NiFe-Ru-3D catalyst can reach up to 500 mA cm −2 at 300 and 250 mV overpotentials, respectively. It can meet the requirement of high catalyst performance for two-step alkaline water electrolysis. The direct water electrolysis using the bifunctional MS-NiFe-Ru-3D catalyst only requires a voltage of 1.85 V at 500 mA cm −2 with minimal attenuation over 300 h. For the two-step alkaline water electrolysis using MS-NiFe-Ru-3D as bifunctional catalysts and Ni 0.9 Co 0.1 (OH) 2 as redox mediator, only 1.70 V and 0.27 V were required for HER and OER at 500 mA cm −2 , respectively. This work offers a promising avenue for the efficient conversion of renewable secondary energy sources into hydrogen.
The conversion of renewable energy sources with relatively large energy fluctuations into hydrogen represents a crucial aspect of energy storage. Nevertheless, the direct water electrolysis process is known to require excessive instantaneous energy consumption and high cost. Two-step alkaline water electrolysis is regarded as a secure and effective method of generating hydrogen from renewable energy sources when compared to direct water electrolysis. Here we propose a two-step alkaline water electrolysis using nickel–cobalt based hydroxide (Ni 0.9 Co 0.1 (OH) 2 ) as a redox mediator, and a high-performance bifunctional catalyst as gas evolution electrodes (GEE). The substrates for the GEE were prepared using 3D printing and then loaded with in-situ grown Ru-doped MoS 2 /NiFe-LDH hierarchical heterostructure catalysts (MS-NiFe-Ru-3D). The oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) of the MS-NiFe-Ru-3D catalyst can reach up to 500 mA cm −2 at 300 and 250 mV overpotentials, respectively. It can meet the requirement of high catalyst performance for two-step alkaline water electrolysis. The direct water electrolysis using the bifunctional MS-NiFe-Ru-3D catalyst only requires a voltage of 1.85 V at 500 mA cm −2 with minimal attenuation over 300 h. For the two-step alkaline water electrolysis using MS-NiFe-Ru-3D as bifunctional catalysts and Ni 0.9 Co 0.1 (OH) 2 as redox mediator, only 1.70 V and 0.27 V were required for HER and OER at 500 mA cm −2 , respectively. This work offers a promising avenue for the efficient conversion of renewable secondary energy sources into hydrogen.
摘要：
Physical reservoir computing (RC) mimics the brain's capacity for temporal processing by mapping inputs into high-dimensional feature spaces. This biologically inspired approach offers advantages in terms of training efficiency and real-time performance. To enhance physical RC's accuracy, nonlinear and dynamic responses are essential to distinguish complex time-series input data. Here, we present a sodium-doped perovskite memristor-based RC system that capitalizes on the synergistic effects of photovoltaic and photogating to induce nonlinear and high-dimensional dynamics. By precisely controlling the sodium doping concentration, we achieve a wide range of distinct conductance states (16 levels), enabling the system to effectively process diverse temporal patterns. We demonstrate the system’s capabilities across a range of computational tasks, achieving a 92.11 % accuracy in image recognition and a low normalized root-mean-square error (NRMSE) of 0.056 in temporal Hénon map prediction. Our findings demonstrate the potential for future development of high-performance memristor-based RC systems, particularly those capable of handling complex temporal tasks.
Physical reservoir computing (RC) mimics the brain's capacity for temporal processing by mapping inputs into high-dimensional feature spaces. This biologically inspired approach offers advantages in terms of training efficiency and real-time performance. To enhance physical RC's accuracy, nonlinear and dynamic responses are essential to distinguish complex time-series input data. Here, we present a sodium-doped perovskite memristor-based RC system that capitalizes on the synergistic effects of photovoltaic and photogating to induce nonlinear and high-dimensional dynamics. By precisely controlling the sodium doping concentration, we achieve a wide range of distinct conductance states (16 levels), enabling the system to effectively process diverse temporal patterns. We demonstrate the system’s capabilities across a range of computational tasks, achieving a 92.11 % accuracy in image recognition and a low normalized root-mean-square error (NRMSE) of 0.056 in temporal Hénon map prediction. Our findings demonstrate the potential for future development of high-performance memristor-based RC systems, particularly those capable of handling complex temporal tasks.
摘要：
Understanding the relationship between deformation behaviors and mechanisms is significant for the processing and application of metastable β titanium alloys. Here we aim to investigate and evaluate the abnormal yield strength and strain softening of a Ti-15.1Mo-2.77Nb-3.1Al-0.21Si alloy at room temperature. This alloy exhibits a high yield strength of 970 MPa, followed by the continuous stress drop behavior in the entire engineering strains (or true strains of 0.018 ∼ 0.056). Digital image correlation (DIC) reveals that the flow stress drop results from local strain softening associated with a local increase in strain rate, instead of Lüders strain. The pinning between dislocations and Si atoms as well as other interstitial atoms at and near grain boundaries is mainly responsible for the high yield strength. Subsequently, dislocations originating from grain boundaries can easily slip in a planar pattern along the {110} 〈111〉 slip systems, resulting in a continuous stress drop. In addition, both the low density of dislocations within β grains and large grain size also provide favorable conditions for dislocation slip over a long distance. This study reveals the mechanisms of both high yield strength and strain softening in the metastable β Ti alloys.
Understanding the relationship between deformation behaviors and mechanisms is significant for the processing and application of metastable β titanium alloys. Here we aim to investigate and evaluate the abnormal yield strength and strain softening of a Ti-15.1Mo-2.77Nb-3.1Al-0.21Si alloy at room temperature. This alloy exhibits a high yield strength of 970 MPa, followed by the continuous stress drop behavior in the entire engineering strains (or true strains of 0.018 ∼ 0.056). Digital image correlation (DIC) reveals that the flow stress drop results from local strain softening associated with a local increase in strain rate, instead of Lüders strain. The pinning between dislocations and Si atoms as well as other interstitial atoms at and near grain boundaries is mainly responsible for the high yield strength. Subsequently, dislocations originating from grain boundaries can easily slip in a planar pattern along the {110} 〈111〉 slip systems, resulting in a continuous stress drop. In addition, both the low density of dislocations within β grains and large grain size also provide favorable conditions for dislocation slip over a long distance. This study reveals the mechanisms of both high yield strength and strain softening in the metastable β Ti alloys.
关键词：
Ti 2 AlNb alloy;Diffusion bonding;Post heat treatment;Phase transformation;Mechanical properties
摘要：
Diffusion-bonded Ti2AlNb-based alloys commonly present a low strength compared with the deformed or aged ones. In this study, the post heat treatment including solution and aging treatments is proposed to optimize the microstructure, contributing to strength improvement and appropriate ductility sacrifice. An available method by the introduction of fine size (both 20-100 nm) and a high fraction (59.7% and 13.7%) of O and alpha(2) phases using both solution at 1000 degrees C for 1 h and aging at 750 degrees C for 5 h can result in excellent tensile strength (992 MPa and 858 MPa) at room temperature and 650 degrees C, respectively, which increases 5.3% and 44.5% than that of as-received sample. The aging treatment can contribute to lamellar O and alpha(2) grains precipitated from the B2 parent, which results in limited dislocation slip systems and slip spaces to resist plastic deformation. Moreover, the crack propagation and fracture surfaces are also comparatively analyzed to reveal the fracture behaviors in the samples with high and low strength. This study can provide a new method for the mechanical property optimization of the welded Ti2AlNb alloys.
摘要：
Herein, we report Co 3 S 4 @Zn 0.5 Co 0.5 Mn 2 O 4 (CS-ZCMO) nanocomposites formed by etching a ZnCo metal–organic framework (ZnCo-ZIF) precursor to form the Zn 0.5 Co 0.5 Mn 2 O 4 spinel structure and compositing it with Co 3 S 4 . This ZIF-derived nanosheet constitutes a reticular structure that enhances the interfacial contact with electrolyte ions and exhibits excellent electrochemical properties. With CS-ZCMO as electrode materials for a supercapacitor, the specific capacitance reached 3006 F/g at a current density of 1 A/g. The assembled CS-ZCMO//active carbon all-solid-state asymmetric supercapacitor (ASC) provided a specific capacitance of 212.3 F/g at a current density of 1 A/g and an energy density of 75.4 Wh/kg at a power density of 800 W/kg. Furthermore, the integrated circuits with ASCs demonstrated typical series and parallel connection characteristics. In addition, CS-ZCMO exhibited good electrochemical performance for energy-efficient hydrolysis, achieving a voltage of 1.324 V at 10 mA/cm 2 in KOH + urea solutions. The self-powered electrocatalytic system was constructed using charged ASCs powered by a commercial solar panel and a hydrolysis electrolytic bath.
关键词：
Energy transfer;Metal-organic framework;Photocatalytic oxidation;Singlet oxygen
摘要：
Integrating energy donor and acceptor chromophores as ligands within one MOF for advanced artificial photosynthesis is of great interest but appears to be a major challenge. Herein, via a simple one-pot synthetic strategy, an energy acceptor porphyrin ligand 5,15-di( p -benzoato)porphyrin (H 2 DPBP) was successfully integrated into an energy donor 1,4-naphthalenedicarboxylic acid (H 2 NDC)-based MOF (UiO-66-NDC) to construct a mixed-ligand MOF, donated as UiO-66-NDC-H 2 DPBP. Benefiting from the ample overlap between the emission spectrum of H 2 NDC and the absorption spectrum of H 2 DPBP, an efficient energy transfer ( EnT ) process from the donor H 2 NDC to the acceptor H 2 DPBP within UiO-66-NDC-H 2 DPBP can occur and be captured by time-resolved spectroscopy. Furthermore, the singlet oxygen ( 1 O 2 ) generation efficiency of UiO-66-NDC-H 2 DPBP mediated by this EnT process as well as the EnT process from the triplet state (T 1 ) of the photosensitizer H 2 DPBP ligand to the ground state of molecular oxygen ( 3 O 2 ) upon light irradiation can be maximized via simply regulating the loading amount of H 2 DPBP, leading to boosted photocatalytic activities toward important aerobic oxidation reactions of amines and sulfides, even under sunlight and ambient air. This work explores an avenue to construct high-efficiency energy donor and acceptor-based light-harvesting systems by utilizing mixed-ligand MOFs as platforms to advanced artificial photosynthesis.
Integrating energy donor and acceptor chromophores as ligands within one MOF for advanced artificial photosynthesis is of great interest but appears to be a major challenge. Herein, via a simple one-pot synthetic strategy, an energy acceptor porphyrin ligand 5,15-di( p -benzoato)porphyrin (H 2 DPBP) was successfully integrated into an energy donor 1,4-naphthalenedicarboxylic acid (H 2 NDC)-based MOF (UiO-66-NDC) to construct a mixed-ligand MOF, donated as UiO-66-NDC-H 2 DPBP. Benefiting from the ample overlap between the emission spectrum of H 2 NDC and the absorption spectrum of H 2 DPBP, an efficient energy transfer ( EnT ) process from the donor H 2 NDC to the acceptor H 2 DPBP within UiO-66-NDC-H 2 DPBP can occur and be captured by time-resolved spectroscopy. Furthermore, the singlet oxygen ( 1 O 2 ) generation efficiency of UiO-66-NDC-H 2 DPBP mediated by this EnT process as well as the EnT process from the triplet state (T 1 ) of the photosensitizer H 2 DPBP ligand to the ground state of molecular oxygen ( 3 O 2 ) upon light irradiation can be maximized via simply regulating the loading amount of H 2 DPBP, leading to boosted photocatalytic activities toward important aerobic oxidation reactions of amines and sulfides, even under sunlight and ambient air. This work explores an avenue to construct high-efficiency energy donor and acceptor-based light-harvesting systems by utilizing mixed-ligand MOFs as platforms to advanced artificial photosynthesis.
摘要：
Introducing foreign elements is regarded as a promising strategy for realizing bulk doping/grain boundary (GB) coating to enhance structural/interfacial stabilities of Ni-rich cathodes. However, directionally achieving control over simultaneous bulk doping and GB coating dual-modification is difficult due to the unclear interdiffusion constant between foreign element and primary components (Ni, Co, and Mn). Herein, a novel mechanism for tungsten (W) diffusion into the interior of Ni-rich cathode has been elucidated, in which the interdiffusion coefficients between W 6+ and transition metal cations have been firstly measured. Due to the fastest interdiffusivity of W 6+ /Mn n+ ( n = 3 and 4) couple proved by incorporating thermodynamic and dynamic results, the modification discrepancy foreign W element in the multi-component Ni-rich cathode has been successfully achieved by altering Mn content. It is found that single bulk W-doping has been obtained in LiNi 0.8 Mn 0.2 O 2 cathode. Encouragingly, when Mn proportion is decreased to 10 %, Li 6 WO 6 GB coating and bulk W-doping have been achieved in LiNi 0.9 Mn 0.1 O 2 and LiNi 0.8 Co 0.1 Mn 0.1 O 2 cathodes. Inspired by dual-modification, cyclic stabilities of W-modified LiNi 0.9 Mn 0.1 O 2 have been prominently improved. The work provides the in-depth understanding of W diffusion into Ni-rich cathodes, exploiting new approaches for engineering bulk/GB modification.
Introducing foreign elements is regarded as a promising strategy for realizing bulk doping/grain boundary (GB) coating to enhance structural/interfacial stabilities of Ni-rich cathodes. However, directionally achieving control over simultaneous bulk doping and GB coating dual-modification is difficult due to the unclear interdiffusion constant between foreign element and primary components (Ni, Co, and Mn). Herein, a novel mechanism for tungsten (W) diffusion into the interior of Ni-rich cathode has been elucidated, in which the interdiffusion coefficients between W 6+ and transition metal cations have been firstly measured. Due to the fastest interdiffusivity of W 6+ /Mn n+ ( n = 3 and 4) couple proved by incorporating thermodynamic and dynamic results, the modification discrepancy foreign W element in the multi-component Ni-rich cathode has been successfully achieved by altering Mn content. It is found that single bulk W-doping has been obtained in LiNi 0.8 Mn 0.2 O 2 cathode. Encouragingly, when Mn proportion is decreased to 10 %, Li 6 WO 6 GB coating and bulk W-doping have been achieved in LiNi 0.9 Mn 0.1 O 2 and LiNi 0.8 Co 0.1 Mn 0.1 O 2 cathodes. Inspired by dual-modification, cyclic stabilities of W-modified LiNi 0.9 Mn 0.1 O 2 have been prominently improved. The work provides the in-depth understanding of W diffusion into Ni-rich cathodes, exploiting new approaches for engineering bulk/GB modification.
期刊：
Journal of Materials Chemistry A,2025年 ISSN：2050-7488
通讯作者：
Zhu, XB;Wang, LZ;Hawker, W
作者机构：
[Huang, Yu; Zhu, Xiaobo; Chu, Gui] Changsha Univ Sci & Technol, Coll Mat Sci & Engn, Changsha 410114, Peoples R China.;[Wang, Lianzhou] Univ Queensland, Sch Chem Engn, Nanomat Ctr, Australian Inst Bioengn & Nanotechnol, Brisbane, Qld 4072, Australia.;[Wang, Lianzhou] Hong Kong Polytech Univ, Dept Appl Biol & Chem Technol, Hung Hom, Hong Kong, Peoples R China.;[Hawker, William] Pure Battery Technol, Brisbane, Qld 4000, Australia.
通讯机构：
[Hawker, W ] P;[Wang, LZ ] U;[Zhu, XB ] C;Changsha Univ Sci & Technol, Coll Mat Sci & Engn, Changsha 410114, Peoples R China.;Univ Queensland, Sch Chem Engn, Nanomat Ctr, Australian Inst Bioengn & Nanotechnol, Brisbane, Qld 4072, Australia.
摘要：
Sustainable end-of-life management is crucial for widely used lithium-ion batteries (LIBs), particularly those employing high-energy and expensive nickel-rich layered oxides (NRLOs). Unlike other cathode active materials, NRLOs face higher production costs and exhibit more complex, severe degradation-including phase evolution, stoichiometric imbalance, surface contamination, and morphological damage-necessitating the development of efficient and high-value recycling technologies. Direct recycling including direct regeneration and direct upcycling offers promising closed-loop solutions specifically tailored to address these intricate structural and chemical changes. Regeneration restores original performance, while upcycling enhances properties through methods like compositional tuning, morphological control, doping, and surface engineering. This review uniquely contextualizes recent advances in the direct recycling of NRLOs by linking degradation analysis with recovery strategies. Despite significant progress, practical challenges in impurity management, process complexity, scalability, and economics remain. The discussion highlights future perspectives for developing efficient and sustainable NRLO direct recycling technologies.
摘要：
The combination of "DPE-alternating chemistry" and "Pentadiene-alternating strategy" offers a novel LAP routine to afford well-defined and sequence-controlled copolymers with diversified alternating series modules. By adjusting the feed ratio of comonomers (1,1-diphenylethylene = D, 1,3-pentadiene = P, and styrene derivatives = S), the polymer composition can be controlled to prepare a series of sequence-controlled terpolymers with constant composition, ternary random sequence, and gradient alternating block structure. "One-pot" terpolymerization kinetic analysis indicated that the polymer yields and polymerization rates were strongly dependent on the feed composition and the type of the "alternating sequence." Additionally, the instantaneous monomer composition containing a predominant alternating structure rather than a homopolymerization sequence was tracked by H-1 NMR analysis. The real-time H-1 NMR spectrum monitoring the characteristic peak change of [D]/[P]/[S] (i.e., [aromatic ring]/[C = C]/[alkyl-CH3]) monomer units indicated the distinctive copolymerization behavior of the selected "alternating-modules" including [D/P], [D/S], and [S/P] repeating units. In addition, the thermal property of the resulting terpolymer was investigated by DSC analysis. The glass transition temperature (T-g) was very sensitive to the polymer composition, and most terpolymers had only one T-g. In contrast with poly([D/P]-ran-[S/P]) with high randomness distribution and strictly alternating modules, which had the lowest T-g, there were relatively higher T(g)s in the DPE-rich and S-rich terpolymers. Moreover, poly([D/P]-co-[D/S]) copolymerization can be viewed as the random copolymerization of the standard [D/P] module and the default [D/S] module; therefore, the abundant residual D monomer was observed due to the unavoidable S homopolymerization. Meanwhile, poly([S/P]-gradient-[D/S]) with a special gradient block-alternating sequence can be obtained in an S-rich case due to the huge reactivity ratios of the two modules (r([S/P]) > > r([D/S])). Finally, the "bond-forming initiation" theory was proposed to interpret the unique terpolymerization behavior.
摘要：
The shuttling of lithium polysulfides (LiPSs), sluggish reaction kinetics, and uncontrolled lithium deposition/stripping remain the main challenges in lithium-sulfur batteries (LSBs), which are aggravated under practical working conditions, i.e., high sulfur loading and lean electrolyte in large-capacity pouch cells. This study introduces a Ti(3)C(2)T(x) MXene@CuCo(2)O(4) (MCC) composite on a polyethylene (PE) separator to construct an ultrathin MXene@CuCo(2)O(4)/PE (MCCP) film. The MCCP functional separator can deliver superior LiPSs adsorption/catalysis capabilities via the MCC composite and regulate the Li(+) deposition through a conductive Ti(3)C(2)T(x) MXene framework, enhancing redox kinetics and cycling lifetime. When paired with sulfur/carbon (S/C) cathode and lithium metal anode, the resultant 10 Ah-level pouch cell with the ultrathin MCCP separator achieves an energy density of 417Wh kg(-1) based on the whole cell and a stable running of 100 cycles under practical operation conditions (cathode loading = 10.0 mg cm(-2), negative/positive areal capacity ratio (N/P ratio) = 2, and electrolyte/sulfur weight ratio (E/S ratio) = 2.6 µL mg(-1)). Furthermore, through a systematic evaluation of the as-prepared Li-S pouch cell, the study unveils the operational and failure mechanisms of LSBs under practical conditions. The achievement of ultrahigh energy density in such a large-capacity lithium-sulfur pouch cell will accelerate the commercialization of LSBs.
通讯机构：
[Wu, XQ; Chou, SL ; Tan, X] W;[Yu, Y ] U;Wenzhou Univ, Inst Carbon Neutralizat Technol, Coll Chem & Mat Engn, Wenzhou 325035, Zhejiang, Peoples R China.;Wenzhou Univ Technol, Innovat Inst Carbon Neutralizat, Wenzhou Key Lab Sodium Ion Batteries, Wenzhou 325035, Zhejiang, Peoples R China.;Univ Sci & Technol China, Hefei Natl Res Ctr Phys Sci Microscale, Dept Mat Sci & Engn, CAS Key Lab Mat Energy Convers, Hefei 230026, Anhui, Peoples R China.
摘要：
The electrochemical performance of hard carbon anode for sodium-ion batteries is primarily determined by the microstructure of the materials, and the challenge lies in establishing a structure-performance relationship at the molecular level. Thus far, an understanding of the intricate relationship between the structure and performance of hard carbon remains piecemeal, with research efforts scattered across various aspects. Hence, numerous controversies have arisen in this field. Herein, we provide new insights into the structure-performance relationship in hard carbon by coupling key structural parameters based on integrating theoretical computations and experimental data. Density functional theory calculations showed that the interlayer spacing determined the diffusion behavior of sodium ions in hard carbon, while appropriate defects and curvatures secured a high-quality intercalation capacity. Inspired by these theoretical results, we successfully developed a high-performance hard carbon with optimal microstructures through in situ molecular reconfiguration of biomass via a thermodynamically driven approach, which was demonstrated as an effective strategy to rationally regulate the microstructure of hard carbon by comprehensive physical characterizations from macroscopic to atomic level. More importantly, cylindrical batteries (18 650 and 33 140 types) fabricated from industrial-scale hard carbon exhibited fabulous sodium storage behaviors with excellent wide-range temperature performance (-40 to 100 degrees C), demonstrating great potential for achieving practical sodium-ion batteries with high energy density and durability in the future.
期刊：
CHEMICAL SOCIETY REVIEWS,2025年54(8):3775-3818 ISSN：0306-0012
通讯作者：
Zhang, Suojiang;Zhang, HT
作者机构：
[Wei, Zewei; Zhang, Haitao; Zhang, Suojiang; Zhang, Yalin; Zhang, SJ; Yuan, Xuedi] Chinese Acad Sci, Inst Proc Engn, Beijing Key Lab Solid State Battery & Energy Stora, Beijing 100190, Peoples R China.;[Yuan, Du] Changsha Univ Sci & Technol, Coll Mat Sci & Engn, Changsha 410004, Peoples R China.;[Ma, Jianmin] Tiangong Univ, Sch Chem, Tianjin 300387, Peoples R China.
通讯机构：
[Zhang, HT ; Zhang, SJ] C;Chinese Acad Sci, Inst Proc Engn, Beijing Key Lab Solid State Battery & Energy Stora, Beijing 100190, Peoples R China.
摘要：
The energy density of lithium-ion batteries (LIBs) is primarily determined by the working potential of devices and the specific capacity of cathode compounds. Carbonate-based electrolytes have received considerable attention due to their significance for advancing current cell-assembly process. However, the commercially available liquid LiPF(6) based electrolytes cannot withstand the harsh high-voltage environment and the effects of cathode, due to issues such as the undesired oxidative decomposition of ethylene carbonate (EC), the catalytic influence of dissolved transition metal ions (TMs), and the poor performance of interphases with unstable morphologies and components. Furthermore, the complex working mechanisms of high-voltage electrolytes (HVEs) are not fully understood. This review presents a comprehensive summary of the HVEs, including their physical properties, solvation structures, and interface chemistry. Specifically, chemical environment of high-voltage cathode compounds and failure mechanisms of commercial electrolytes are investigated, followed by a discussion of expected functions of HVEs. Then, screening criteria for single-component electrolytes, considering their oxidation resistance and decomposition mechanism, and screening mechanism of interphase species are explored based on their energy level positions. Next, a cross-scale evolution framework is proposed, from the solvation structure to interphase characteristics, aimed at uncovering the formulation principles and synergistic effects of HVEs. Operational mechanisms are systematically scrutinized, starting from the conventional tuning of solvation structure to the incorporation of multiple components and further to the role of entropy-driven effects, all of which will favor the understanding of formulation principles and synergistic effects. Finally, integration of advanced computational methods and mature experimental techniques is expected to foster the development of novel perspectives and promising electrolyte candidates.
作者：
Liu, D. H.;Chen, X. Z.;Sun, R.;Wu, X.;Bai, H. W.;...
期刊：
Journal of Materials Research and Technology,2025年35:7204-7214 ISSN：2238-7854
通讯作者：
Liu, X;Gao, Y
作者机构：
[Chen, X. Z.; Sun, R.; Wu, X.; Bai, H. W.; Liu, D. H.; Liu, X. C.] Changsha Univ Sci & Technol, Inst Met, Coll Mat Sci & Engn, Changsha 410004, Peoples R China.;[Gao, Y. H.] North Univ China, Sch Aerosp Engn, Taiyuan 030051, Peoples R China.;[Zhao, Y. F.] North Univ China, Sch Mech Engn, Taiyuan 030051, Peoples R China.
通讯机构：
[Gao, Y ] N;[Liu, X ] C;Changsha Univ Sci & Technol, Inst Met, Coll Mat Sci & Engn, Changsha 410004, Peoples R China.;North Univ China, Sch Aerosp Engn, Taiyuan 030051, Peoples R China.
关键词：
Al alloys;Microalloying;Interfacial segregation;Dispersoid;Precipitation
摘要：
Manganese (Mn) is widely recognized for its effect on modifying the size and morphology of coarse Fe-rich constituents in Al-based alloys by forming fine Mn-rich dispersoids. However, this study suggests that in a Cd-micraolloyed Al–Cu–Mn-based alloy, Mn-rich dispersoids significantly promote Cu-rich precipitation at the interface during artificial aging (AA), leading to undesirable solute consumption of Cu and potential suppression of nanoprecipitation. With the help of atomic-resolution high-angle annular dark-field (HAADF) scanning transmission electron microscopy (STEM) and energy dispersive spectroscopy (EDS), an interesting finding is that interfacial Cu segregation at the dispersoid/matrix interface can be assembled during natural aging (NA, approximately for ∼30 days) after quenching, consequently feeding the early-stage interfacial Cu-rich precipitation during AA. Intriguingly, the microalloying effect of Cd, as the fast diffuser, is highly possible to promotes this process, which is also simultaneously and increasingly collected by the dispersoids during AA. These findings are expected to provide new insights on microstructural architecture in multicomponent Al–Cu-based alloys, highlighting the synergistic effect between Cd microalloying and Mn-rich dispersoids.
Manganese (Mn) is widely recognized for its effect on modifying the size and morphology of coarse Fe-rich constituents in Al-based alloys by forming fine Mn-rich dispersoids. However, this study suggests that in a Cd-micraolloyed Al–Cu–Mn-based alloy, Mn-rich dispersoids significantly promote Cu-rich precipitation at the interface during artificial aging (AA), leading to undesirable solute consumption of Cu and potential suppression of nanoprecipitation. With the help of atomic-resolution high-angle annular dark-field (HAADF) scanning transmission electron microscopy (STEM) and energy dispersive spectroscopy (EDS), an interesting finding is that interfacial Cu segregation at the dispersoid/matrix interface can be assembled during natural aging (NA, approximately for ∼30 days) after quenching, consequently feeding the early-stage interfacial Cu-rich precipitation during AA. Intriguingly, the microalloying effect of Cd, as the fast diffuser, is highly possible to promotes this process, which is also simultaneously and increasingly collected by the dispersoids during AA. These findings are expected to provide new insights on microstructural architecture in multicomponent Al–Cu-based alloys, highlighting the synergistic effect between Cd microalloying and Mn-rich dispersoids.
作者机构：
[Wenjie Peng; Huajun Guo; Junchao Zheng; Guochun Yan; Hui Duan; Xing Ou; Yucen Yan; Zhixing Wang; Zilan Zhao; Jiexi Wang; Junjie Wang; Wang, Jiexi] Cent South Univ, Sch Met & Environm, Natl Energy Met Resources & New Mat Key Lab, Engn Res Ctr,Minist Educ Adv Battery Mat,Hunan Pro, Changsha 410083, Peoples R China.;[Jiayi Li] Univ Washington, Dept Chem, Seattle, WA 98195 USA.;[Duo Deng; Wenjie Peng; Zhixing Wang; Gui Luo] BASF Shanshan Battery Mat Co LTD, Res Inst, Changsha 410205, Peoples R China.;[Wenjie Peng; Huajun Guo; Guochun Yan; Hui Duan; Mingxia Dong; Wang, Jiexi] Natl Engn Res Ctr Anvanced Energy Storage Mat, Changsha 410205, Peoples R China.;[Lingjun Li] Changsha Univ Sci & Technol, Sch Mat Sci & Engn, Changsha 410114, Peoples R China.
通讯机构：
[Wang, JX ] C;Cent South Univ, Sch Met & Environm, Natl Energy Met Resources & New Mat Key Lab, Engn Res Ctr,Minist Educ Adv Battery Mat,Hunan Pro, Changsha 410083, Peoples R China.
关键词：
Lithium ion battery;LiNiO 2;Tungsten doping;Grain boundary phase;H2↔H3 phase transition
摘要：
LiNiO 2 (LNO) is one of the most promising cathode materials for lithium-ion batteries. Tungsten element in enhancing the stability of LNO has been researched extensively. However, the understanding of the specific doping process and existing form of W are still not perfect. This study proposes a lithium-induced grain boundary phase W doping mechanism. The results demonstrate that the introduced W atoms first react with the lithium source to generate a Li–W–O phase at the grain boundary of primary particles. With the increase of lithium ratio, W atoms gradually diffuse from the grain boundary phase to the interior layered structure to achieve W doping. The feasibility of grain boundary phase doping is verified by first principles calculation. Furthermore, it is found that the Li 2 WO 4 grain boundary phase is an excellent lithium ion conductor, which can protect the cathode surface and improve the rate performance. The doped W can alleviate the harmful H2↔H3 phase transition, thereby inhibiting the generation of microcracks, and improving the electrochemical performance. Consequently, the 0.3 wt% W-doped sample provides a significant improved capacity retention of 88.5 % compared with the pristine LNO (80.7 %) after 100 cycles at 2.8–4.3 V under 1C.
LiNiO 2 (LNO) is one of the most promising cathode materials for lithium-ion batteries. Tungsten element in enhancing the stability of LNO has been researched extensively. However, the understanding of the specific doping process and existing form of W are still not perfect. This study proposes a lithium-induced grain boundary phase W doping mechanism. The results demonstrate that the introduced W atoms first react with the lithium source to generate a Li–W–O phase at the grain boundary of primary particles. With the increase of lithium ratio, W atoms gradually diffuse from the grain boundary phase to the interior layered structure to achieve W doping. The feasibility of grain boundary phase doping is verified by first principles calculation. Furthermore, it is found that the Li 2 WO 4 grain boundary phase is an excellent lithium ion conductor, which can protect the cathode surface and improve the rate performance. The doped W can alleviate the harmful H2↔H3 phase transition, thereby inhibiting the generation of microcracks, and improving the electrochemical performance. Consequently, the 0.3 wt% W-doped sample provides a significant improved capacity retention of 88.5 % compared with the pristine LNO (80.7 %) after 100 cycles at 2.8–4.3 V under 1C.
