期刊：
Materials Science and Engineering B-Advanced Functional Solid-State Materials,2026年323:118759 ISSN：0921-5107
通讯作者：
Jincheng Fan
作者机构：
[Yifan Fang; Jincheng Fan; Risheng Hu; Haiou Liu; Bo Wu; Zhenqiang Tang; Wenbin Luo; Zisheng Chao] College of Materials Science and Engineering, Changsha University of Science and Technology, Changsha, Hunan 410114, China
通讯机构：
[Jincheng Fan] C;College of Materials Science and Engineering, Changsha University of Science and Technology, Changsha, Hunan 410114, China
摘要：
Supercapacitors are gaining prominence as energy storage devices due to their advantages such as fast charging and discharging, so there is an urgent need to develop higher performance devices. The electrode materials play a decisive role in the performance of supercapacitors. In this study, spinel CuNi 2 S 4 were synthesized by CuNi layered double hydroxides from Cu Metal-Organic Frameworks, which has a high specific capacitance of 7.1 F cm −2 (2784.3 F g −1 ). The capacitance retention rate of 79 % was retained after 5000 long cycles. A hybrid supercapacitor with CuNi 2 S 4 as cathode and activated carbon as anode was assembled with a specific capacitance of 423.6 mF cm −2 . The manufactured quasi-solid-state supercapacitor devices exhibit unique capacitance superposition properties in parallel configurations and voltage additive behavior in serial configurations. The fabricated solid-state supercapacitor-like devices show unique voltage stacking behavior in series configuration and capacitance stacking characteristics in parallel configuration.
Supercapacitors are gaining prominence as energy storage devices due to their advantages such as fast charging and discharging, so there is an urgent need to develop higher performance devices. The electrode materials play a decisive role in the performance of supercapacitors. In this study, spinel CuNi 2 S 4 were synthesized by CuNi layered double hydroxides from Cu Metal-Organic Frameworks, which has a high specific capacitance of 7.1 F cm −2 (2784.3 F g −1 ). The capacitance retention rate of 79 % was retained after 5000 long cycles. A hybrid supercapacitor with CuNi 2 S 4 as cathode and activated carbon as anode was assembled with a specific capacitance of 423.6 mF cm −2 . The manufactured quasi-solid-state supercapacitor devices exhibit unique capacitance superposition properties in parallel configurations and voltage additive behavior in serial configurations. The fabricated solid-state supercapacitor-like devices show unique voltage stacking behavior in series configuration and capacitance stacking characteristics in parallel configuration.
期刊：
Journal of Physics and Chemistry of Solids,2026年208:113148 ISSN：0022-3697
通讯作者：
Junfei Duan
作者机构：
[Jinyan Tang; Jingtian Tong; Hao He; Tianjian Xu; Jinzheng Yang; Dan Huang; Zhaoyong Chen; Junfei Duan] School of Materials Science and Engineering, Changsha University of Science and Technology, Changsha, 410114, China
通讯机构：
[Junfei Duan] S;School of Materials Science and Engineering, Changsha University of Science and Technology, Changsha, 410114, China
摘要：
Aqueous zinc-nickel batteries suffer from severe anode challenges including dendrite growth, self-corrosion, and hydrogen precipitation, which drastically limit their cycle life and performance. Herein, a novel chemical foaming strategy was proposed to scalably fabricate ZnO@Bi 2 O 3 heterostructures. ZnO nanocrystals (∼30–80 nm) intimately integrate with Bi 2 O 3 via chemically bonded heterointerfaces were prepared combined with thermal decomposition of zinc nitrate hexahydrate and the physical confinement of polyvinylpyrrolidone. Depth-profiling XPS analysis confirms that Bi 2 O 3 not only forms a permeable barrier against alkaline electrolyte penetration but also induces interfacial charge redistribution via Bi–O–Zn covalent bonding, which regulates Zn(OH) 4 2− migration pathways and suppresses dendrite formation and electrode corrosion. The optimized ZnO@Bi 2 O 3 -M electrode delivers a coulombic efficiency of over 80 % after 600 cycles at 25 mA cm −2 , accompanied by a specific capacity of 481.8 mAh g −1 , and maintains 167.7 mAh g −1 even at 60 mA cm −2 . This study proposes a novel design strategy for high-performance aqueous zinc-nickel battery anode materials via interfacial engineering, coupled with a scalable synthesis route paving the way for industrial implementation.
Aqueous zinc-nickel batteries suffer from severe anode challenges including dendrite growth, self-corrosion, and hydrogen precipitation, which drastically limit their cycle life and performance. Herein, a novel chemical foaming strategy was proposed to scalably fabricate ZnO@Bi 2 O 3 heterostructures. ZnO nanocrystals (∼30–80 nm) intimately integrate with Bi 2 O 3 via chemically bonded heterointerfaces were prepared combined with thermal decomposition of zinc nitrate hexahydrate and the physical confinement of polyvinylpyrrolidone. Depth-profiling XPS analysis confirms that Bi 2 O 3 not only forms a permeable barrier against alkaline electrolyte penetration but also induces interfacial charge redistribution via Bi–O–Zn covalent bonding, which regulates Zn(OH) 4 2− migration pathways and suppresses dendrite formation and electrode corrosion. The optimized ZnO@Bi 2 O 3 -M electrode delivers a coulombic efficiency of over 80 % after 600 cycles at 25 mA cm −2 , accompanied by a specific capacity of 481.8 mAh g −1 , and maintains 167.7 mAh g −1 even at 60 mA cm −2 . This study proposes a novel design strategy for high-performance aqueous zinc-nickel battery anode materials via interfacial engineering, coupled with a scalable synthesis route paving the way for industrial implementation.
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.
关键词：
Powder bed fusion;Beta titanium;Three-point bending;Transformation-induced plasticity (TRIP);Twinning-induced plasticity (TWIP)
摘要：
Compared to other loading conditions, studies on deformation mechanisms of additive manufacturing (AM)-produced β-type Ti alloys under bending remain limited. This study investigates a metastable β-type Ti–25Nb–3Zr–3Mo–2Sn (TLM, wt.%) alloy fabricated via laser powder bed fusion (L-PBF) during in-situ three-point bending. In-situ observations using scanning electron microscopy (SEM) combined with electron backscatter diffraction (EBSD) and ex-situ transmission electron microscopy (TEM) imaging during bending provided evaluation of microstructural changes and deformation mechanisms. These mechanisms are characterized by dislocation slip, {332}<113> β deformation twin, α" phase, and ω phase formation during plastic bending stage. The {112}<111> slip system dominates in the compression zone, while the {123}<111> slip system governs in the tension zone during bending. The synergistic effect of twinning-induced plasticity (TWIP) and transformation-induced plasticity (TRIP) significantly enhances the ductility of L-PBF-produced TLM alloy. The deformation involves stress-induced α" and ω phases, with the latter can form within grains/twinning band and at twinning boundaries. Importantly, the presence of the interfacial twin boundary (ITB)-ω thin layers at twinning band boundaries exerts a pinning effect, restraining the outward extension of stress-induced α" phase. This mechanism suggests optimized utilization of space within twinning bands, facilitating α" nucleation and uniform growth, thereby providing insights into further enhancing ductility.
Compared to other loading conditions, studies on deformation mechanisms of additive manufacturing (AM)-produced β-type Ti alloys under bending remain limited. This study investigates a metastable β-type Ti–25Nb–3Zr–3Mo–2Sn (TLM, wt.%) alloy fabricated via laser powder bed fusion (L-PBF) during in-situ three-point bending. In-situ observations using scanning electron microscopy (SEM) combined with electron backscatter diffraction (EBSD) and ex-situ transmission electron microscopy (TEM) imaging during bending provided evaluation of microstructural changes and deformation mechanisms. These mechanisms are characterized by dislocation slip, {332}<113> β deformation twin, α" phase, and ω phase formation during plastic bending stage. The {112}<111> slip system dominates in the compression zone, while the {123}<111> slip system governs in the tension zone during bending. The synergistic effect of twinning-induced plasticity (TWIP) and transformation-induced plasticity (TRIP) significantly enhances the ductility of L-PBF-produced TLM alloy. The deformation involves stress-induced α" and ω phases, with the latter can form within grains/twinning band and at twinning boundaries. Importantly, the presence of the interfacial twin boundary (ITB)-ω thin layers at twinning band boundaries exerts a pinning effect, restraining the outward extension of stress-induced α" phase. This mechanism suggests optimized utilization of space within twinning bands, facilitating α" nucleation and uniform growth, thereby providing insights into further enhancing ductility.
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.
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 Science,2025年:1-10 ISSN：0022-2461
通讯作者：
Cheng, Juanjuan;Ou, Y;Cheng, JJ
作者机构：
[Yin, Ting; Han, Changxin; Ou, Yun; Liu, Longfei; Xiao, Yuxuan; Zheng, Yuhong; Cheng, Juanjuan; Chou, Juan] Hunan Univ Sci & Technol, Sch Mat Sci & Engn, Xiangtan 411201, Peoples R China.;[Cheng, Juanjuan] Hunan Univ Sci & Technol, Hunan Prov Key Lab Adv Mat New Energy Storage & Co, Xiangtan 411201, Peoples R China.;[Yang, Li] Xiangtan Univ, Hunan Key Lab Environmentally Friendly Chem & Appl, Minist Educ, Xiangtan 411105, Peoples R China.;[Dai, Cuiying] Changsha Univ Sci & Technol, Sch Mat Sci & Engn, Changsha 410114, Peoples R China.
通讯机构：
[Cheng, JJ; Ou, Y ; Cheng, JJ ] H;Hunan Univ Sci & Technol, Sch Mat Sci & Engn, Xiangtan 411201, Peoples R China.;Hunan Univ Sci & Technol, Hunan Prov Key Lab Adv Mat New Energy Storage & Co, Xiangtan 411201, Peoples R China.
摘要：
Manganese dioxide (MnO2) is a promising cathode material for aqueous zinc-ion batteries (AZIBs) due to its high operating voltage, rich resources and environmental friendliness. However, its slow electrochemical kinetics and poor cycling stability constrain its practical application. In the study, Sn-BiOCl prepared by hydrothermal method was used as a bimetallic cation dopant to investigate the effect of tin and bismuth on the structure and properties of K+ pre-intercalated delta-MnO2 (K0.27MnO2<middle dot>0.54H2O). The electrode shows a discharge specific capacity of up to 464 mAh g-1 at a current density of 0.1 A g-1, and the capacity retention rate was 110% after 200 cycles. The long-cycle life and excellent capacity retention rate have been induced due to the doping of Sn2+ improving the electrical conductivity and the doping of Bi3+ effectively maintaining the laminar structure of the cathode. Bimetallic cation doping resulted in larger nanoflower size of the material and increased specific surface area of manganese dioxide, which improved the ion diffusion rate. The work provides a rational way to design high-performance Mn-based AZIBs cathode materials.
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.
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：
SiCnw with special morphology, such as bamboo-like and beaded shapes, has better reinforcing effect on metal and ceramic-based composite coatings. In this study, SiCnw was prepared in situ on the surface of C/C composites by chemical vapor reaction (CVR) method using Si, SiO 2 and graphite as raw materials. The effects of heat treatment temperature, holding time and raw material ratio on the growth of SiCnw were investigated. The synthesized SiCnw is 3C-SiC with diameters between 100 nm and 300 nm and lengths up to tens of micrometers. Due to the influence of Si, SiO and CO saturation vapor pressures, with the heat treatment temperature and holding time increase, SiCnw’s yield increases and diameter becomes more homogeneous. The optimal preparation process for SiCnw was heat treatment at 1600 ℃ for 3 h. And SiCnw grows in different forms depending on the ration of raw material, such as hexagonal prisms (SiO 2 : 70 %, Si:25 %, C:5 %), linear (SiO 2 : 70 %, Si:20 %, C:10 %), pagod-like and needle-pricked shapes (SiO 2 : 60 %, Si:25 %, C:15 %). The growth of SiCnw followed the vapor-solidification (VS) and spiral dislocation growth mechanism, grow in the direction of [111], and forms a tapered tip and leaves a cylindrical nanofilament at the tip.
SiCnw with special morphology, such as bamboo-like and beaded shapes, has better reinforcing effect on metal and ceramic-based composite coatings. In this study, SiCnw was prepared in situ on the surface of C/C composites by chemical vapor reaction (CVR) method using Si, SiO 2 and graphite as raw materials. The effects of heat treatment temperature, holding time and raw material ratio on the growth of SiCnw were investigated. The synthesized SiCnw is 3C-SiC with diameters between 100 nm and 300 nm and lengths up to tens of micrometers. Due to the influence of Si, SiO and CO saturation vapor pressures, with the heat treatment temperature and holding time increase, SiCnw’s yield increases and diameter becomes more homogeneous. The optimal preparation process for SiCnw was heat treatment at 1600 ℃ for 3 h. And SiCnw grows in different forms depending on the ration of raw material, such as hexagonal prisms (SiO 2 : 70 %, Si:25 %, C:5 %), linear (SiO 2 : 70 %, Si:20 %, C:10 %), pagod-like and needle-pricked shapes (SiO 2 : 60 %, Si:25 %, C:15 %). The growth of SiCnw followed the vapor-solidification (VS) and spiral dislocation growth mechanism, grow in the direction of [111], and forms a tapered tip and leaves a cylindrical nanofilament at the tip.
期刊：
Advanced Energy Materials,2025年15(19):2404933 ISSN：1614-6832
通讯作者：
Richard, Marie-Ingrid;Schulli, T;Richard, MI
作者机构：
[Richard, Marie-Ingrid; Schulli, T; Zatterin, Edoardo; Richard, MI; Schulli, Tobias; Leake, Steven; Colalongo, Mattia; Martens, Isaac; Vostrov, Nikita] ESRF The European Synchrotron, 71 Ave Martyrs, Grenoble, France.;[Ronovsky, Michal] Univ Grenoble Alpes, CNRS, Grenoble INP, LEPMI, F-38402 St Martin Dheres, France.;[Boulineau, Adrien] Univ Grenoble Alpes, CEA Liten, F-38000 Grenoble, France.;[Zhu, Xiaobo] Changsha Univ Sci & Technol, Coll Mat Sci & Engn, Changsha 410114, Peoples R China.;[Wang, Lianzhou] Univ Queensland, Nanomat Ctr, Sch Chem Engn, St Lucia, Qld 4072, Australia.
通讯机构：
[Schulli, T ; Richard, MI] E;[Richard, MI ] U;ESRF The European Synchrotron, 71 Ave Martyrs, Grenoble, France.;Univ Grenoble Alpes, CEA Grenoble, IRIG, MEM,NRX, 17 Rue Martyrs, F-38000 Grenoble, France.
关键词：
high voltage cathode;Li-ion batteries;LMNO;spinel;SXDM
作者机构：
[Wang, Jiaoli; Huang, Zimo; Liu, Yexiang; Bai, Maohui; Hong, Bo] Cent South Univ, Sch Met & Environm, Changsha 410083, Peoples R China.;[Wang, Xuhui; Bai, Maohui] Changsha Univ Sci & Technol, Coll Mat Sci & Engn, Changsha 410004, Peoples R China.;[Liu, Yexiang; Hong, Bo] Cent South Univ, Hunan Prov Key Lab Nonferrous Value Added Met, Changsha 410083, Peoples R China.
通讯机构：
[Bai, MH ] C;Cent South Univ, Sch Met & Environm, Changsha 410083, Peoples R China.;Changsha Univ Sci & Technol, Coll Mat Sci & Engn, Changsha 410004, Peoples R China.
关键词：
Pentaerythritol acrylate;N,N-dimethylacrylamide;Cross-linking gel electrolyte;Oxidation stability;Lithium-ion batteries
摘要：
Nitrogen-containing gel electrolyte has the advantages of high safety and strong compatibility, which can improve the electrochemical performance of lithium-ion batteries (LIBs). However, its inherent issues of oxidation stability and insufficient conductivity limit its large-scale application. Here, Pentaerythritol acrylate (PETEA) is used as a cross-linking agent to build a cross-linking framework with nitrogen-containing N,N-dimethylacrylamide (PNDA) gel monomer to improve the electrochemical performance of gel electrolyte (PNDET). The three-dimensional cross-linked PNDET electrolyte has a continuous Li-ion fast conduction network (7.02 mS cm-1), and its self-supporting structure improves its mechanical strength (220.0 MPa). Meanwhile, through calculation, PNDET has a lower HOMO energy level, which increases its oxidation voltage from 4.3 to 4.5 V. In addition, the cross-linked PNDET enhances the overall thermal stability of the electrolyte, and the flame retardant properties of the nitrogen-containing skeleton are significantly improved. When the PNDET matched with Ah-class NCM811/Gr pouch cells, the capacity retention rate still remains 93.5% after 600 cycles at the temperature of 60 degrees C. However, due to its extremely poor oxidation stability and thermal stability, the capacity of pouch cells with PNDA electrolyte rapidly decreases at high voltage of 4.35 V and high temperature of 60 degrees C. The cross linking strategy provides a direction for the practical application of gel electrolyte and promotes the development of gel semi-solid battery.
期刊：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2025年147(37):34019-34026 ISSN：0002-7863
通讯作者：
Liu, M;Jing, Lihong;Han, BX;Zhang, J
作者机构：
[Chen, Kejun; Mei, Ziwen; Liu, Min; Cao, Maoqi; Li, Hongmei; Liu, Kang; Fu, Junwei] Cent South Univ, Hunan Joint Int Res Ctr Carbon Dioxide Resource U, Sch Phys, State Key Lab Powder Met, Changsha 410083, Peoples R China.;[Jing, Lihong; Han, Buxing] Chinese Acad Sci, Beijing Natl Lab Mol Sci, Ctr Carbon Neutral Chem, Inst Chem,CAS Lab Colloid & Interface & Thermodyn, Beijing 100190, Peoples R China.;[Ou, Pengfei] Natl Univ Singapore, Dept Chem, Singapore 117543, Singapore.;[Cao, Maoqi] Bozhou Univ, Dept Elect & Informat Engn, Bozhou 236800, Peoples R China.;[Li, Wenzhang; Wu, Linlin] Cent South Univ, Sch Chem & Chem Engn, Changsha 410083, Peoples R China.
通讯机构：
[Han, BX ; Jing, LH; Liu, M ] C;[Zhang, J ] U;Cent South Univ, Hunan Joint Int Res Ctr Carbon Dioxide Resource U, Sch Phys, State Key Lab Powder Met, Changsha 410083, Peoples R China.;Chinese Acad Sci, Beijing Natl Lab Mol Sci, Ctr Carbon Neutral Chem, Inst Chem,CAS Lab Colloid & Interface & Thermodyn, Beijing 100190, Peoples R China.;Cent South Univ, Sch Met & Environm, Changsha 410083, Peoples R China.
摘要：
CO(2) electroreduction to produce fuels and chemicals is of great significance. Molecular catalysts offer valuable advantages in light of their well-defined active sites and tunable structural and electronic properties. However, their stability is often compromised by rigid conjugated structures. Herein, we proposed a hydrogen-bond regulation strategy that enables reversible structural deformation of metal phthalocyanines (MPcs) by incorporating methoxy groups into the phthalocyanine framework, thereby improving the flexibility and stability of MPcs. Calculations suggested that intermediate absorption induced structural deformation in MPcs. Moreover, hydrogen-bond interactions and conformational changes enriched with substituted methoxy groups in MPcs enhance structural flexibility. Operando Raman studies revealed that these hydrogen bonds correlated with the reversible structural deformation of NiPc. The optimized catalysts, facilitated by hydrogen bonds, achieved stable operation for over 500 h at 100 mA cm(-2) with >98% Faradaic efficiency in CO(2)-to-CO electrocatalytic reduction, significantly outperforming molecular catalysts lacking appropriate hydrogen-bond interactions.
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.
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.
作者机构：
["Tong, Zhuoya] College of Materials Science and Engineering, Changsha University of Science and Technology, Changsha 410114, China;[Zhu, Xiaobo"] Author to whom correspondence should be addressed.
通讯机构：
[Xiaobo Zhu] A;Author to whom correspondence should be addressed.
摘要：
The massive production and utilization of lithium-ion batteries (LIBs) has intensified concerns about raw material shortage and end-of-life battery management. The development of effective recycling/reusing strategies, especially for the valuable active positive electrode materials, has attracted much interest from both academia and industry. This study presents a comprehensive patent analysis on the recycling technologies of spent LIBs. We screened and examined 672 patent filings associated with 367 application families, covering the period from 1994 to 2024. The analysis reveals an explosive growth in patenting activity since 2020, with China and the United States leading in geographical coverage. Hydrometallurgy continues as the most patented recycling technology, followed by direct regeneration, separation, and pyrometallurgy. Key innovations focus on improving leaching efficiency, developing novel purification methods, and exploring various relithiation strategies. The study also highlights the significant involvement of both companies and academic institutions in driving innovation. Our findings provide insights into the technological landscape, identify emerging trends, and lead to the discussion of potential future developments in LIB positive electrode recycling. This analysis serves as a valuable resource for researchers, industry stakeholders, and policymakers working towards sustainable energy storage solutions and circular economy strategies in the battery sector.
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：
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.
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.
作者机构：
[Peng, Wenjie (7202994938); Guo, Huajun (7404404226); Zheng, Junchao (12772675700); Yan, Guochun (55607429800); Duan, Hui (57195422677); Ou, Xing (57189729504); Yan, Yucen (57218509552); Wang, Zhixing (7410045624); Zhao, Zilan (59416271400); Wang, Jiexi (56191368700); Wang, Junjie (57322107100); 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.;[Li, Jiayi (57210323427)] Univ Washington, Dept Chem, Seattle, WA 98195 USA.;[Deng, Duo (59273476200); Peng, Wenjie (7202994938); Wang, Zhixing (7410045624); Luo, Gui (57455297100)] BASF Shanshan Battery Mat Co LTD, Res Inst, Changsha 410205, Peoples R China.;[Peng, Wenjie (7202994938); Guo, Huajun (7404404226); Yan, Guochun (55607429800); Duan, Hui (57195422677); Dong, Mingxia (57194504905); Wang, Jiexi] Natl Engn Res Ctr Anvanced Energy Storage Mat, Changsha 410205, Peoples R China.;[Li, Lingjun (55730888000)] 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.
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.
