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Design of low-alloying and high-performance solid solution-strengthened copper alloys with element substitution for sustainable development

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International Journal of Minerals,Metallurgy and Materials 2024年第5期31卷 826-832页

作者： Jiaqiang Li Hongtao Zhang Jingtai Sun Huadong Fu Jianxin Xie Beijing Advanced Innovation Center for Materials Genome Engineering University of Science and Technology BeijingBeijing 100083China Key Laboratory for Advanced Materials Processing(MOE) University of Science and Technology BeijingBeijing 100083China Beijing Laboratory of Metallic Materials and Processing for Modern Transportation University of Science and Technology BeijingBeijing 100083China Liaoning Academy of Materials Shenyang 110004China

Solid solution-strengthened copper alloys have the advantages of a simple composition and manufacturing process,high mechanical and electrical comprehensive performances,and low cost;thus,they are widely used in high-speed rail contact wires,electronic component connectors,and other devices.Overcoming the contradiction between low alloying and high performance is an important challenge in the development of solid solution-strengthened copper alloys.Taking the typical solid solution-strengthened alloy Cu-4Zn-1Sn as the research object,we proposed using the element In to replace Zn and Sn to achieve low alloying in this work.Two new alloys,Cu-1.5Zn-1Sn-0.4In and Cu-1.5Zn-0.9Sn-0.6In,were designed and prepared.The total weight percentage content of alloying elements decreased by 43%and 41%,respectively,while the product of ultimate tensile strength(UTS)and electrical conductivity(EC)of the annealed state increased by 14%and 15%.After cold rolling with a 90%reduction,the UTS of the two new alloys reached 576 and 627MPa,respectively,the EC was 44.9%IACS and 42.0%IACS,and the product of UTS and EC(UTS×EC)was 97%and 99%higher than that of the annealed state alloy.The dislocations proliferated greatly in cold-rolled alloys,and the strengthening effects of dislocations reached 332 and 356 MPa,respectively,which is the main reason for the considerable improvement in mechanical properties.

关键词： element substitution copper alloy solid solution strengthening microstructure and performance

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Effect of different metal element substitution on microstructural and comprehensive hydrogen storage performance of Ti0.9Zr0.1Mn0.95Cr0.7V0.2M0.15（M=Fe,Co,Ni,Cu,Mo） alloy

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Progress in Natural Science:Materials International 2024年第2期34卷 304-313页

作者： Baojia Ni Jianhui Zhu Guo Yang Linhua Xu Haiyan Leng Wei Liu Taijun Pan Xingbo Han Lijun Lv School of Materials Science and Engineering Changzhou University Shanghai Institute of Applied Physics Chinese Academy of Sciences School of Materials Science and Engineering Shanghai University

Hydrogen is now being used as a renewable clean energy carrier.One of the main issues with the application of hydrogen energy is a shortage of security and efficient hydrogen storage technology.TiMn-based alloys are considered promising hydrogen storage materials,but their comprehensive hydrogen storage properties and cyclic stable performance limit their further practical application.The hydrogen storage properties of alloys can be enhanced by substituting transition metal elements.Therefore,the comprehensive hydrogen storage performance of the Ti0.9Zr0.1Mn0.95Cr0.7V0.2M0.15（M=Fe,Co,Ni,Cu,Mo） alloys was systematically investigated according to the Mn element on the B side is partially replaced by variety of transition metal elements.The M=Ni alloy,which showed the highest hydrogen storage capacity among the group of alloys,was used to explore cycle stability.The plateau pressures of the series alloys decreased in order,Fe>Co>Ni>Cu>Mo.Aspects of hydrogen absorption kinetics,all of the alloys can reach full hydrogen absorption saturation within 400 s at 303 K.The Ti0.9Zr0.1Mn0.95Cr0.7V0.2Mo0.15alloy possessed the fastest hydrogen absorption kinetic rate(t0.9=65 s) and the smallest hysteresis factor.This suggests that the substitution of Mo elements is effective in improving the hysteresis of the Laves phase alloys.Among the series of alloys,the M=Ni alloy exhibited the best overall hydrogen storage performance,which hydrogen storage capacity can reach 1.81 wt% and 97% of its capacity is kept after 100 cycles.

关键词： Cyclic stable performance element substitution Hydrogen storage properties Laves phase TiMn-Based hydrogen storage alloy

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V-substituted pyrochlore-type polyantimonic acid for highly enhanced lithium-ion storage

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Chinese Chemical Letters 2023年第5期34卷 539-547页

作者： Haoyu Fang Kai Yong Boya Wang Kaipeng Wu Yun Zhang Hao Wu College of Materials Science and Engineering Sichuan UniversityChengdu 610064China

Pyrochlore-structured polyantimonic acid(PAA)is a potential high-capacity electrode material,but its innately poor electroconductivity(~10^(-10)S/cm)seriously impairs its electrochemical reversibility for lithium-ion storage.Herein,we report design and synthesis of a novel V-substituted PAA(PAA-V),where V^(5+)are introduced to partially replace Sb^(5+).Owing to identical valence and close ionic radius relative to Sb^(5+),the V^(5+)cation can constitute the covalent VO_6octahedra framework without changing the pyrochlore crystal structure of PAA.As a result,the V^(5+)-substitution is capable to modulate the electronic structure of PAA with significantly improved electrical conductivity(~10^(-6)S/cm for PAA-V)and meanwhile decreases the size of crystals with reduced diffusion length for Li^(+)-ions.With varying the ratio of V^(5+)-substitution,the PAA-V with optimized substitution molar ratio(18%)exhibits the best lithium-ion storage performance,delivering a long cycling life with high reversible capacity(731 m Ah/g after 1200cycles at 1 A/g)and outstanding rate capability(279 mAh/g at 15 A/g).More importantly,by pairing the PAA-V as anode and commercial LiFePO_(4)as cathode,the full cell with a limited negative/positive capacity ratio of 1.2 exhibits decent cycling stability at 1 C after 150 cycles with 85.5%capacity retention.

关键词： Lithium-ion batteries Anode materials Polyantimonic acid element substitution Electrochemical reaction mechanism

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Study on structure and electrochemical properties of the (LaGdMg)Ni_(3.35-x)Co_xAl_(0.15)(x=0-2.0) hydrogen storage alloys

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Journal of Rare Earths 2010年第S1期28卷 425-430页

作者：高志杰罗永春林振李嵘峰汪建义康龙 College of Materials Science and Engineering Lanzhou University of Technology State Key Laboratory of Gansu Advanced Non-Ferrous Metal Materials Lanzhou University of Technology

Hydrogen storage alloys(LaGdMg)Ni3.35-xCoxAl0.15(x=0,0.1,0.3,0.5,1.0,1.5,2.0) were prepared by induction melting followed by annealing treatment in argon atmosphere.The effects of partly replacing Ni by Co element in(LaGdMg)Ni3.35Al0.15 on the phase structure and electrochemical properties of(LaGdMg)Ni3.35-xCoxAl0.15 alloys were investigated.Structure analysis showed that the alloys consisted of Ce2Ni7-type(Gd2Co7-type),CaCu5-type,Pr5Co19-type,PuNi3-type phase structure.The addition of Co element obviously reduced the contents of CaCu5-type phase and increased the contents of Ce2Ni7-type phase.However,Pr5Co19-type and CaCu5-type phase obviously increased with the high content of Co.Rietveld analysis showed that the c-axis lattice parameters and cell volumes of the component phases increased with increasing Co content.The electrochemical measurements showed that as the Co content increased,the maximum discharge capacity and the cyclic stability of the annealed alloys both first increased then decreased.The(LaGdMg)Ni3.05Co0.3Al0.15 alloy electrode exhibited the maximum discharge capacity(392.92 mAh/g),and the(LaGdMg)Ni1.85Co1.0Al0.15 alloy electrode showed the best cyclic stability(S100=96.1%).

关键词： hydrogen storage alloy element substitution Ce2Ni7-type phase structure electrochemical properties rare earths

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Electrochemical hydrogen storage characteristics of La_(0.75-x) M_xMg_(0.25)Ni_(3.2)Co_(0.2)Al_(0.1)(M=Zr,Pr;x=0,0.1) alloys prepared by melt spinning

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Rare Metals 2012年第5期31卷 -页

作者： ZHANG Yanghuan YANG Tai CAI Ying HOU Zhonghui REN Huiping ZHAO Dongliang Key Laboratory of Integrated Exploitation of Baiyun Obo Mutti-Metal Resources Inner Mongolia University of Science and Technology Baotou 014010 China Department of Functional Material Research Central Iron and Steel Research Institute Beijing 100081 China

In order to ameliorate the electrochemical hydrogen storage performances of La-Mg–Ni system A_2B_7-type electrode alloys, the partial substitution of M (M = Zr, Pr) for La was performed. The melt spinning technology was used to fabricate the La_(0.75-x)M_xMg_0.25Ni_3.2Co_0.2Al_0.1 (M = Zr, Pr; x = 0, 0.1) electrode alloys. The influences of the melt spinning and substituting La with M (M = Zr, Pr) on the structures and the electrochemical hydrogen storage characteristics of the alloys were investigated. The analysis of XRD, SEM, and TEM reveals that the as-cast and spun alloys have a multiphase structure composed of two main phases (La, Mg)_2Ni_7 and LaNi_5 as well as a residual phase LaNi_2 . The as-spun (M = Pr) alloy displays an entire nanocrystalline structure, while an amorphous-like structure is detected in the as-spun (M = Zr) alloy, implying that the substitution of Zr for La facilitates the amorphous formation. The electrochemical measurements exhibit that the substitution of Pr for La clearly increases the discharge capacity of the alloys; however, the Zr substitution brings on an adverse impact. Meanwhile, the M (M = Zr, Pr) substitution significantly enhances its cycle stability. The melt spinning exerts an evident effect on the electrochemical performances of the alloys, whose discharge capacity and high rate discharge ability (HRD) first mount up and then fall with the growing spinning rate, whereas their cycle stabilities monotonously augment as the spinning rate increases.

关键词： A_2B_7-type electrode alloy element substitution melt spinning electrochemical performance

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The electrochemical hydrogen storage characteristics of as-spun nanocrystalline and amorphous Mg_(20)Ni_(10-x)M_x(M=Cu, Co, Mn;x=0–4) alloys

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Rare Metals 2014年第6期33卷 663-673页

作者： Yang-Huan Zhang Tai Yang Hong-Wei Shang Chen Zhao Chao Xu Dong-Liang Zhao Key Laboratory of Integrated Exploitation of Baiyun Obo Multi-Metal Resources Inner Mongolia University of Science and Technology Department of Functional Material Research Central Iron and Steel Research Institute

In this paper, we comprehensively investigate the influences of M（M=Cu, Co, Mn） substitution for Ni on the structures and electrochemical hydrogen storage characteristics of the nanocrystalline and amorphous Mg20Ni10-xMx（M=Cu, Co, Mn; x = 0–4） alloys prepared by melt spinning. The as-spun（M=None, Cu） alloys display an entire nanocrystalline structure, whereas the as-spun（M=Co, Mn） alloys hold a mixed structure of both nanocrystalline and amorphous when x = 4（M content）. These results indicate that the substitution of M（M=Co, Mn） for Ni facilitates the glass formation in Mg2Ni-type alloy. All the as-spun alloys have the Mg2 Ni major phase, but M（M=Co, Mn） substitution brings on some secondary phases,such as Mg Co2, Mg phases for M=Co, and Mn Ni, Mg phases for M=Mn. The substitution of M（M=Cu, Co, Mn）for Ni also makes a positive contribution to the cycle stability of the alloys in the following orders：（M=Cu） [（M=Co） [（M=Mn） for x = 1 and（M=Co） [（M=Mn）[（M=Cu） for x = 2–4. Meanwhile, it notably enhances the discharge capacity of the alloys in the sequence of（M=Co） [（M=Mn） [（M=Cu）. As for the high rate discharge ability, it visibly upgrades with the growing of M content for（M=Cu, Co）, while it grows at first and then declines for（M=Mn）.

关键词： Mg2Ni-type alloy element substitution Melt spinning Nanocrystalline and amorphous Electrochemical characteristics

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Barium-doped Pr_(2)Ni_(0.6)Cu_(0.4)O_(4+δ) with triple conducting characteristics as cathode for intermediate temperature proton conducting solid oxide fuel cell

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Chinese Journal of Chemical Engineering 2021年第11期34卷 269-276页

作者： Chengyi Ai Tingting Li Rongzheng Ren Zhenhua Wang Wang Sun Jinsheng Feng Kening Sun Jinshuo Qiao Beijing Key Laboratory for Chemical Power Source and Green Catalysis School of Chemistry and Chemical EngineeringBeijing Institute of TechnologyBeijing 100081China

Proton conducting solid oxide fuel cell(H-SOFC)is an emerging energy conversion device,with lower activation energy and higher energy utilization efficiency.However,the deficiency of highly active cathode materials still remains a major challenge for the development of H-SOFC.Therefore,in this work,K_(2)NiF_(4)-type cathode materials Pr_(2-x)Ba_(x)Ni_(0.6)Cu_(0.4)O_(4+δ)(x=0,0.1,0.2,0.3),single-phase tripleconducting(e-/O^(2-)/H^(+))oxides,are prepared for intermediate temperature H-SOFCs and exhibit good oxygen reduction reaction activity.The investigation demonstrates that doping Ba into Pr_(2-x)BaxNi_(0.6)Cu_(0.4)O_(4+δ) can increase its electrochemical performance through enhancing electrical conductivity,oxygen vacancy concentration and proton conductivity.EIS tests are carried at 750℃ and the minimum polarization impedances are obtained when x=0.2,which are 0.068 Ω·cm^(2) in air and 1.336 Ω·cm^(2) in wet argon,respectively.The peak power density of the cell with Pr_(1.8)Ba_(0.2)Ni_(0.6)Cu_(0.4)O_(4+δ) cathode is 298 mW·cm^(-2) at 750℃ in air with humidified hydrogen as fuel.Based on the above results,Ba-doped Pr_(2-x)Ba_(x)Ni_(0.6)Cu_(0.4)O_(4+δ) can be a good candidate material for SOFC cathode applications.

关键词： Protonic conducting solid oxide fuel cells Cathode materials element substitution

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Microstructure and Thermoelectric Properties of Bi- and Cu-Substituted Ca_3Co_4O_9 Oxides

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Journal of Materials Science & Technology 2009年第1期25卷 105-108页

作者： Haoshan Hao Limin Zhao Xing Hu Department of Mathematical and Physical Sciences Henan Institute of Engineering Zhengzhou 451191 China School of Physical Engineering and Material Physics Laboratory Zhengzhou University Zhengzhou 450052 China

Bi- and Cu-substituted Ca3Co4O9 samples were prepared by conventional solid-state reaction method and the effect of element substitution on the microstructures and thermoelectric properties was investigated. Partial substitution of Cu for Co leads to an increase in electrical conductivity and a decrease in Seebeck coefficient due to the rise of hole concentration. The microstructure of Cu-substituted sample is almost unchanged compared with undoped Ca3Co4O9. On the other hand, partial substitution of Bi for Ca gives rise to a significant increase in the grain size, and c-axis-oriented structure can be formed in Ca2.7Bi0.3Co4O9, resulting in an obvious increase in electrical conductivity. Cu and Bi co-substitution further increases the grain growth and the electrical conductivity of Ca2.7Bi0.3Co3.7Cu0.3O9. Thus, Cu and Bi co-substitution samples possess the optimal thermoelectric performance at high temperature and the highest value of power factor can reach 3.1×10^-4 Wm^-1.K^-2 at 1000 K.

关键词： Ca3Co4O9 element substitution Microstructure Thermoelectric properties

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Recent progress on the hydrogen storage properties of ZrCo-based alloys applied in International Thermonuclear Experimental Reactor(ITER)

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Progress in Natural Science:Materials International 2017年第3期27卷 58-65页

作者： Feng Wang Rongfeng Li Cuiping Ding Wukui Tang Yibo Wang Shimeng Xu Ronghai Yu Ying Wu School of Materials Science and Engineering Beihang University China Iron & Steel Research Institute Group Advanced Technology & Materials Co. Ltd

Under the development of International Thermonuclear Experimental Reactor（ITER） system aimed at realizing the controllable fusion reaction to solve the energy crisis fundamentally, there is an urgent need to find an appropriate material for tritium handling. ZrCo alloy is considered to be a promising candidate for the storage and delivery of hydrogen isotopes due to the favorable characteristics such as low plateau pressure for absorption, high dissociation pressure at moderate temperature and better ability of trapping;He. However, the hydrogen induced disproportionation and the slower recovery/deliverty rate of ZrCo-based alloys have limited their further application in ITER system. This review summarizes the efforts towards enhancing the hydrogen storage properties of ZrCo-based alloys including element substitution, surface modification, disproportionation mechanism investigation and the isotope effect study. element substitution and surface modification play positive role to improve the anti-disproportionation ability and kinetic property of the alloys. However, the ZrCo-based alloys require to be further modified by more attempts such as new composition, novelty modification method or catalyst addition in order to better satisfy the application demands for tritium handling. Moreover, new insight for further understanding the inner disproportionation mechanisms of this material is needed by combining the advance characterization and theoretical analysis, which is in favor of addressing the disproportionation problem of the ZrCo-based alloys essentially.

关键词： ZrCo-based alloy Hydrogen storage properties Disproportionation reaction element substitution Surface modification

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Cycle Stabilities of La_(0.7)Mg_(0.3)Ni_(2.55-x)Co_(0.45)M_x (M=Fe, Cu, Al;x=0, 0.1) Electrode Alloys Prepared by Casting and Rapid Quenching

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Journal of Rare Earths 2007年第S1期25卷 419-425页

作者：张羊换赵栋梁董小平郭世海祁焱王新林 Department of Functional Material Research Central Iron and Steel Research Institute School of Materials University of Science and Technology Beijing

La-Mg-Ni system (PuNi3-type) hydrogen storage alloys La0.7Mg0.3Ni2.55-xCo0.45Mx (M=Fe, Cu, Al; x=0, 0.1) were prepared by casting and rapid quenching. Aiming to improve the cycle stabilities of the alloys, Ni in the alloy was partly substituted by Fe, Cu and Al. The effects of the substitution of Fe, Cu and Al for Ni and the rapid quenching on the microstructures and electrochemical properties of the alloys were investigated in detail. The results obtained by XRD, SEM and TEM indicate that the element substitution has no influence on the phase compositions of the alloys, but it changes the phase abundances of the alloys. Particularly, the substitution of Al and Cu obviously increases the amount of the LaNi2 phase. The substitution of Al and Fe leads to a great refinement of the as-quenched alloy′s grains. The substitution of Al strongly restrains the formation of the amorphous in the as-quenched alloy, but the substitution of Fe and Cu is quite helpful for the formation of an amorphous phase. The effects of the substitution of Fe, Cu and Al on the cycle stabilities of the as-cast and quenched alloys are different. The positive impact of the substitution elements on the cycle stabilities of the as-cast alloys is ranked in proper order Al>Fe>Cu, and for as-quenched alloys, the order is Fe>Al>Cu. Rapid quenching engenders an unconscious influence on the phase composition, but it markedly enhances the cycle stabilities of the alloys.

关键词： La-Mg-Ni system electrode alloy element substitution rapid quenching microstructures cycle stability rare earths

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