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Reinforcing oxygen electrocatalytic activity via selective dualphase heterointerface engineering for rechargeable Zn-air batteries

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Rare Metals 2024年第4期43卷 1524-1536页

作者： Chao Cheng Chuang Zhi Zhong-Ti Sun Yong-Qiang Ming Ting-Ting Xiang Qing-Chao Zhu Zi-Rui Wu Bing Li Yi Li Cheng Jin Yong Cao Juan Yang School of materials science and engineering Jiangsu University faculty of Material science and engineering Kunming University of Science and Technology

Dual-phase heterointerface electrocatalysts（DPHE） constructed by oxygen reduction reaction（ORR）-and oxygen evolution reaction（OER）-active elements exhibit excellent bifunctional activity and long-term durability due to the abundant interface exposure and synergistic catalytic effect.Herein,low-dimensional N-doped graphene nanoribbons（N-GNRs） coupling with ultrathin CoO nanocomposites（N-GNRs/CoO） were controllably fabricated through a facile two-step approach using synthesized Co（OH）2nanosheet as CoO precursor.Density functional theory（DFT） calculations and experimental characterizations prove that the formation of interface between N-GNRs and CoO can induce local charge redistribution,contributing to the improvement of catalytic activity and stability.The optimal N-GNRs/CoO DPHE possesses hierarchically porous architectures and presents outstanding bifunctional activities with a small potential gap of 0.729 V between the potential at 10 mA·cm-2for OER and the halfwave potential for ORR,which outperforms Pt/C+IrO2and the majority of noble-metal-free bifunctional catalysts.Liquid-and solid-state rechargeable Zn-air batteries assembled with N-GNRs/CoO as the cathode also display high peak power density and fantastic cycle stability,superior to that of benchmark Pt/C +IrO2catalyst.It is anticipated to offer significant benefits toward high activity,stability and mechanical flexibility bifunctional oxygen electrocatalysts for rechargeable Zn-air batteries.

关键词： Interface engineering Graphene nanoribbons CoO Bifunctional electrocatalyst Zn–air batteries

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Construction of electron rich Fe active sites by FeCu alloy anchoring on carbon nitride for photocatalytic nitrogen reduction

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Rare Metals 2024年第4期43卷 1570-1579页

作者： Gang Dong Cong Huang Fei-Yang Chen Xue-Qin Liu Zhen Li Xiao-Li Su Tao Zeng Yun-Xia Chen Yi-Huang Chen Yang Wang School of materials science and engineering Jingdezhen Ceramic University faculty of materials science and Chemistry China University of Geosciences College of Chemistry and materials engineering Wenzhou University

Given the clean and inexhaustible solar energy from solar light,photocatalytic ammonia synthesis is extremely appealing.However,high electron-hole recombination rates and insufficient active sites severely limited N2 photoreaction reduction.Herein,we designed and fabricated FeCu alloy nanoparticles anchored on carbon nitride nanosheets with excellent photocatalyt ic ammonia synthesis performance.As a coupler between Fe and carbon nitride,Cu promotes the separation of photogenerated charge carriers in carbon nitride under solar light irradiation,and renters the semiconductor a forceful electron donor for the Fe active sites.The accumulated electrons at Fe sites furtherly facilitated the adsorption and activation of the molecular nitrogen.Besides,the uniform dispersed FeCu alloy nanoparticles were on carbon nitride nanosheets enhanced the stability of photocataly tic nitrogen reduction reaction,making the artificial photocataly tic ammonia synthesis more sustainable for application.This work highlights that a direct electron transfer channel can be used to regulate the photochemical nitrogen fixation network.

关键词： Photocatalytic N 2 fixation Carbon nitride FeCu alloy Active sites Hydrogenation pathway

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Highly efficient recovery of waste LiNi_(x)Co_(y)Mn_(z)O_(2) cathode materials using a process involving pyrometallurgy and hydrometallurgy

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Frontiers of Environmental science & engineering 2024年第2期18卷 149-160页

作者： Tianwei Zhang Juanye Dao Jinsong Wang Yuzhong Guo Rundong Wan Chengping Li Xian Zhou Zhengfu Zhang faculty of materials science and engineering Kunming University of Science and TechnologyKunming 650093China

Substantial environmental and economic benefits can be achieved by recycling used lithium-ion batteries. Hydrometallurgy is often employed to recover waste LiNi_(x)Co_(y)Mn_(z)O_(2) cathode materials. As Ni, Co and Mn are transition metals, they exhibit similar properties;therefore, separating them is difficult. Thus, most researchers have focused on leaching processes, while minimal attention has been devoted to the separation of valuable metals from waste LiNi_(x)Co_(y)Mn_(z)O_(2) cathode materials. Herein, we propose an environment-friendly, gentle process involving the usage of pyrometallurgy and hydrometallurgy to gradually leach valuable metals and effectively separate them. Interestingly, Li is recovered through a reduction roasting and water leaching process using natural graphite powder, Ni and Co are recovered through ammonia leaching and extraction processes and Mn is recovered through acid leaching and evaporation–crystallization processes. Results show that ~87% Li, 97.01% Co, 97.08% Ni and 99% Mn can be leached using water, ammonia and acid leaching processes. The result obtained using the response surface methodology shows that the concentration of (NH4)2SO3 is a notable factor affecting the leaching of transition metals. Under optimal conditions, ~97.01% Co, 97.08% Ni and 0.64% Mn can be leached out. The decomposition of LiNi_(x)Co_(y)Mn_(z)O_(2) is a two-step process. This study provides valuable insights to develop an environment-friendly, gentle leaching process for efficiently recycling valuable metals, which is vital for the lithium-ion battery recycling industry.

关键词： Waste LiNixCoyMnzO2 cathode materials Leaching Effective separation Series process

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Capturing and visualizing the phase transition mediated thermal stress of thermal barrier coating materials via a cross-scale integrated computational approach

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Journal of Advanced Ceramics 2024年第4期13卷 413-428页

作者： Mengdi Gan Tianlong Lu Wei Yu Jing Feng Xiaoyu Chong faculty of materials science and engineering Kunming University of Science and TechnologyKunming 650093China

The generation and evaluation of severely high thermal stress(σ)is known to be responsible for failure of thermal barrier coatings(TBCs)during thermal cycling.It is crucial and challenging to capture fluctuations inσcaused by the phase transition,which has motivated us to develop a high-throughput multiscale evaluation method forσin TBCs that considers the phase transition of the top ceramic materials by coupling first-principles calculations with finite element simulations.The method quantitatively evaluates and visualizesσof the real TBC structure under thermal cycling by multifield coupling.Additionally,the thermophysical properties calculated by the first-principles calculations consider the effects of temperature and phase transition,which not only reduces the cost of obtaining data but also has a more physical connotation.In this work,rare earth tantalites(RETaO4)are introduced as ceramic layers,and the results demonstrate thatσundergoes a rapid escalation near the phase transition temperature(Tt),particularly in the TBCs_GdTaO4 system,where it rises from 224 to 435 MPa.This discontinuity inσmay originate from the significant alterations in Young’s modulus(increase by 27%–78%)and thermal conductivity(increase by 53%–146%)near Tt.The TBCs_NdTaO4 and TBCs_SmTaO4 systems exhibit noteworthy temperature drop gradients and minimalσfluctuations,which are beneficial for extending service lifetime of TBCs.This approach facilitates the prediction of failure mechanisms and provides theoretical guidance for the reverse design of TBC materials to obtain low thermal stress systems.

关键词： thermal conductivity first-principles calculations thermodynamics thermal stress thermophysical properties

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Highly enhanced thermoelectric and mechanical performance of copper sulfides via natural mineral in-situ phase separation

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Journal of Advanced Ceramics 2024年第5期13卷 641-651页

作者： Xi Yan Hongjiang Pan Yixin Zhang Tianyu Yang Yangwei Wang Kun Huang Chongyu Wang Jing Feng Zhenhua Ge faculty of materials science and engineering Kunming University of Science and TechnologyKunming 650093China

In situ phase separation precipitates play an important role in enhancing the thermoelectric properties of copper sulfides by suppressing phonon transmission.In this study,Cu1.8S composites were fabricated by melting reactions and spark plasma sintering.The complex structures,namely,micron-PbS,Sb_(2)S_(3),nano-FeS,and multiscale pores,originate from the introduction of FePb_(4)Sb_(6)S_(14)into the Cu1.8S matrix.Using effective element(Fe)doping and multiscale precipitates,the Cu_(1.8)S+0.5 wt%FePb_(4)Sb_(6)S_(14)bulk composite reached a high dimensionless figure of merit(ZT)value of 1.1 at 773 K.Furthermore,the modulus obtained for this sample was approximately 40.27 GPa,which was higher than that of the pristine sample.This study provides a novel strategy for realizing heterovalent doping while forming various precipitates via in situ phase separation by natural minerals,which has been proven to be effective in improving the thermoelectric and mechanical performance of copper sulfides and is worth promoting in other thermoelectric systems.

关键词： in situ precipitates jamesonite natural mineral thermoelectric copper sulfides

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Effect of Sc on Al_(3)Fe phase and mechanical properties of as-cast AA5052 aluminum alloy

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China Foundry 2024年第3期21卷 257-264页

作者： Yang Li Qing Yu Feng-feng Chen Jia-wen He Hong-mei Yang Meng-nie Li faculty of materials science and engineering Kunming University of Science and TechnologyKunming 650093China

The AA5052 aluminum alloy is widely used in automobile and aerospace manufacturing,and with the development of light-weight alloys,it is required that these materials exhibit better mechanical properties.Previous studies have demonstrated that the addition of Sc to aluminum alloys can improve both the microstructure and properties of the alloys.In this study,the effect of Sc on the Fe-rich phase and properties of the AA5052 aluminum alloy was studied by adding 0%,0.05%,0.2%,and 0.3%Sc.The results show that with the increase of Sc,the coarse needle-like Fe-rich phase gradually transforms into Chinese-script and then nearly spherical particles,reduce the size of Fe-rich phase,and refine the grain with increase of high angle grain boundaries(HAGBs).These microstructure changes enhance the strength of the AA5052 alloy through Sc addition.The ductility of the alloy is obviously improved because the addition of a lower amount of Sc changes the morphology of Fe-rich phase from needle-like into a Chinese-script,and it is subsequently reduced as a result of significant increase in HAGBs with increasing Sc content.

关键词： AA5052 aluminum alloy Al3Fe phase mechanical properties grain boundary

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On-surface synthesis and characterization of polyynic carbon chains

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National science Review 2024年第3期11卷 192-199页

作者： Wenze Gao Wei Zheng Luye Sun Faming Kang Zheng Zhou Wei Xu Interdisciplinary materials Research Center School of Materials Science and Engineering Tongji University

Carbyne, an elusive sp-hybridized linear carbon allotrope, has fascinated chemists and physicists for decades. Due to its high chemical reactivity and extreme instability, carbyne was much less explored in contrast to the sp2-hybridized carbon allotropes such as graphene. Herein, we report the on-surface synthesis of polyynic carbon chains by demetallization of organometallic polyynes on the Au（111） surface;the longest one observed consists of ～60 alkyne units（120 carbon atoms）. The polyynic structure of carbon chains with alternating triple and single bonds was unambiguously revealed by bond-resolved atomic force microscopy. Moreover, an atomically precise polyyne, C14, was successfully produced via tip-induced dehalogenation and ring-opening of the decachloroanthracene molecule(C14Cl10) on a bilayer NaCl/Au（111） surface at 4.7 K, and a band gap of 5.8 eV was measured by scanning tunnelling spectroscopy,in a good agreement with the theoretical HOMO–LUMO gap（5.48 eV）.

关键词： polyyne scanning probe microscopy carbon allotrope on-surface synthesis organometallic polyyne

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Synergistic Effects of Carbon Nanotube(CNT)and Reduced Graphene Oxide(RGO)on Mechanical and Thermal Properties of ZK61 Alloy

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Acta Metallurgica Sinica(English Letters) 2024年第3期37卷 577-585页

作者： Fanjing Meng Wenbo Du Ning Ding Jian Sun Xian Du Ke Liu Shubo Li College of materials science and engineering Faculty of Materials and ManufacturingBeijing University of TechnologyBeijing 100124China

The hybrid of carbon nanotube(CNT)and reduced graphene oxide(RGO)reinforced ZK61 composite was fabricated by a hot extrusion process.Compared with the raw ZK61 alloy and single-reinforced composites,the hybrid-reinforced by RGO+CNT complex exhibited significant enhancements both in mechanical and thermal performance.By adjusting the proportion of RGO and CNT in ZK61 alloy,the obtained optimum ZK61/(0.06 wt%RGO+0.54 wt%CNT)composite exhibited increase of 25.4%in yield strength,26.5%in ultimate tensile strength,104%in failure strain and 30.4%in thermal conductivity,respectively,in comparison with ZK61 alloy.The superior properties of the nano-hybrid composite are attributed to the synergetic effects of RGO and CNT,leading to a uniform dispersion and integrated structure as well as the enhanced interfacial bonding with matrix.The strengthening ability of RGO and CNT was calculated to quantify their individual contribution to the improvement in mechanical and thermal properties of the ZK61 matrix composite.The RGO+CNT hybrids provide a promising way to develop Mg matrix composites with impressive performances.

关键词： Mg matrix composite Carbon nanotube Reduced graphene oxide Mechanical performance Thermal conductivity

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Attaining synergetic equilibrium of electrical conductivity and tensile strength in GQDs@GN/Cu composites through multi-scale intragranular and intergranular reinforcements

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Rare Metals 2024年第1期43卷 366-379页

作者： Shuang-Yin Zhang Liang Liu Rui Bao Jian-Hong Yi Sheng-Da Guo faculty of materials science and engineering Kunming University of Science and TechnologyKunming 650093China Key Laboratory of Advanced materials of Yunnan Province Kunming University of Science and TechnologyKunming 650093China faculty of materials Metallurgy and Chemistry Jiangxi University of Science and TechnologyGanzhou 341000China

The configuration and quality of reinforcements, as well as the robustness of interfacial bonding,holding a critical significance in determining the concurrence between electrical conductivity and mechanical strength in metal matrix composites. In this study, citric acid was employed as the precursor for synthesizing multiscale carbon nanomaterials(graphene quantum dots and graphene, abbreviated as GQDs and GN). The GQDs@GN/Cu composites were fabricated through a segmented ball milling process in conjunction with subsequent spark plasma sintering(SPS). The intragranular GQDs and intergranular GQDs@GN had synergistically reinforced Cu composites through Orowan strengthening, load transfer strengthening and refinement strengthening. Furthermore,the robust interface bonding between GQDs@GN and Cu effectively mitigated interfacial impedance stemming from electron-boundary scattering. The yield strength and ultimate tensile strength of the GQDs@GN/Cu composites were recorded as 270 and 314 MPa, respectively, representing an improvement of 92 and 28% over pure Cu, while maintaining electrical conductivity at a level comparable to that of pure Cu. This study advances the understanding of the possibility of realizing a synergistic compatibility between electrical conductivity and mechanical strength in Cu composites.

关键词： Cu matrix composites Interface bonding Mechanical property Graphene quantum dots(GQDs) Electrical conductivity

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Negative enthalpy alloys and local chemical ordering:a concept and route leading to synergy of strength and ductility

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National science Review 2024年第4期11卷 172-184页

作者： Zibing An Tao Yang Caijuan Shi Shengcheng Mao Lihua Wang Ang Li Wei Li Xianmeng Xue Ming Sun Yifan Bai Yapeng He Fuzeng Ren Zhouguang Lu Ming Yan Yang Ren Chain-Tsuan Liu Ze Zhang Xiaodong Han Beijing Key Lab of Microstructure and Property of Advanced materials College of Materials Science &Engineering Beijing University of Technology Department of materials science and engineering City University of Hong Kong Key Laboratory of Partial Acceleration Physics& Technology Institute of High Energy PhysicsChinese Academy of Sciences Department of materials science &engineering Southern University of Science and Technology Department of Physics City University of Hong Kong State Key Laboratory of Silicon materials Department of Materials Science and Engineering Zhejiang University

Solid solutions are ubiquitous in metals and alloys. Local chemical ordering(LCO) is a fundamental sub-nano/nanoscale process that occurs in many solid solutions and can be used as a microstructure to optimize strength and ductility. However, the formation of LCO has not been fully elucidated, let alone how to provide efficient routes for designing LCO to achieve synergistic effects on both superb strength and ductility. Herein, we propose the formation and control of LCO in negative enthalpy alloys. With engineering negative enthalpy in solid solutions, genetic LCO components are formed in negative enthalpy refractory high-entropy alloys(RHEAs). In contrast to conventional ‘trial-and-error' approaches, the control of LCO by using engineering negative enthalpy in RHEAs is instructive and results in superior strength(1160 MPa) and uniform ductility(24.5%) under tension at ambient temperature, which are among the best reported so far. LCO can promote dislocation cross-slip, enhancing the interaction between dislocations and their accumulation at large tensile strains; sustainable strain hardening can thereby be attained to ensure high ductility of the alloy. This work paves the way for new research fields on negative enthalpy solid solutions and alloys for the synergy of strength and ductility as well as new functions.

关键词： negative enthalpy alloys local chemical ordering strength ductility dislocation

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