Magnesium-based energy materials, which combine promising energy-related functional properties with low cost, environmental compatibility and high availability, have been regarded as fascinating candidates for sustain...Magnesium-based energy materials, which combine promising energy-related functional properties with low cost, environmental compatibility and high availability, have been regarded as fascinating candidates for sustainable energy conversion and storage. In this review,we provide a timely summary on the recent progress in three types of important Mg-based energy materials, based on the fundamental strategies of composition and structure engineering. With regard to Mg-based materials for batteries, we systematically review and analyze different material systems, structure regulation strategies as well as the relevant performance in Mg-ion batteries(MIBs) and Mg-air batteries(MABs), covering cathodes, electrolytes, anodes for MIBs, and anodes for MABs;as to Mg-based hydrogen storage materials, we discuss how catalyst adding, composite, alloying and nanostructuring improve the kinetic and thermodynamic properties of de/hydrogenation reactions, and in particular, the impacts of composition and structure modification on hydrogen absorption/dissociation processes and free energy modification mechanism are focused;regarding Mg-based thermoelectric materials, the relations between composition/structure and electrical/thermal transport properties of Mg_(3)X_(2)(X = Sb, Bi), Mg_(2)X(X = Si, Ge, Sn) and Mg Ag Sb-based materials, together with the representative research progress of each material system, are summarized and discussed. Finally, by pointing out remaining challenges and providing possible solutions, this review aims to shed light on the directions and perspectives for practical applications of magnesium-based energy materials in the future.展开更多
While TiFe alloy has recently attracted attention as the efficient catalyst to enhance de/hydrogenation rates of Mg/MgH_(2),the difficulty of its activation characteristics has hindered further improvement of reaction...While TiFe alloy has recently attracted attention as the efficient catalyst to enhance de/hydrogenation rates of Mg/MgH_(2),the difficulty of its activation characteristics has hindered further improvement of reaction kinetics.Herein,we report that the TiFe_(0.92)Mn_(0.04)Co_(0.04) catalyst can overcome the abovementioned challenges.The synthesized MgH_(2)-30 wt% TiFe_(0.92)Mn_(0.04)Co_(0.04) can release 4.5 wt%of hydrogen in 16 min at 250℃,three times as fast as MgH_(2).The activation energy of dehydrogenation was as low as 84.6 kJ mol^(-1),which is 46.8%reduced from pure MgH_(2).No clear degradation of reaction rates and hydrogen storage capacity was observed for at least 30 cycles.Structural studies reveal that TiFe_(0.92)Mn_(0.04)Co_(0.04) partially decomposes to in-situ generatedα-Fe particles dispersed on TiFe_(0.92)Mn_(0.04)Co_(0.04).The presence ofα-Fe reduces the formation of an oxide layer on TiFe_(0.92)Mn_(0.04)Co_(0.04),enabling the activation processes.At the same time,the hydrogen incorporation capabilities of TiFe_(0.92)Mn_(0.04)Co_(0.04) can provide more hydrogen diffusion paths,which promote hydrogen dissociation and diffusion.These discoveries demonstrate the advanced nature and importance of combining the in-situ generatedα-Fe with TiFe_(0.92)Mn_(0.04)Co_(0.04).It provides a new strategy for designing highly efficient and stable catalysts for Mg-based hydrogen storage materials.展开更多
Rechargeable magnesium batteries(RMBs),as a low-cost,high-safety and high-energy storage technology,have attracted tremendous attention in large-scale energy storage applications.However,the key anode/electrolyte inte...Rechargeable magnesium batteries(RMBs),as a low-cost,high-safety and high-energy storage technology,have attracted tremendous attention in large-scale energy storage applications.However,the key anode/electrolyte interfacial issues,including surface passivation,uneven Mg plating/stripping,and pulverization after cycling still result in a large overpotential,short cycling life,poor power density,and possible safety hazards of cells,severely impeding the commercial development of RMBs.In this review,a concise overview of recently advanced strategies to address these anode/electroyte interfacial issues is systematically classified and summarized.The design of magnesiophilic substrates,construction of artificial SEI layers,and modification of electrolyte are important and effective strategies to improve the uniformity/kinetics of Mg plating/stripping and achieve the stable anode/electrolyte interface.The key opportunities and challenges in this field are advisedly put forward,and the insights into future directions for stabilizing Mg metal anodes and the anode/electrolyte interface are highlighted.This review provides important references fordeveloping the high-performance and high-safety RMBs.展开更多
Rechargeable Mg batteries(RMBs)have become one of the best subsitutes for lithium-ion batteries due to the high volumetric capacity,abundant resources,and uniform plating behavior of Mg metal anode.However,the safety ...Rechargeable Mg batteries(RMBs)have become one of the best subsitutes for lithium-ion batteries due to the high volumetric capacity,abundant resources,and uniform plating behavior of Mg metal anode.However,the safety hazard induced by the formation of high-modulue Mg dendrites under a high current density(10 mA cm^(-1))was still revealed in recent years.It has forced researchers to re-examine the safety of RMBs.In this review,the intrinsic safety factors of key components in RMBs,such as uneven plating,pitting and flammability of Mg anode,heat release and crystalline water decomposition of cathode,strong corrosion,low oxidition stability and flammability of electrolytes,and soforth,are systematacially summarized.Their origins,formation mechanisms,and possible safety hazards are deeply discussed.To develop high-performance Mg anode,current strategies including designing artificial SEI,three-dimensional substrates,and Mg alloys are summarized.For practical electrolytes,the configurations of boron-centered anions and simple Mg salts and the functionalized solvent with high boiling point and low flammability are suggested to comprehensively design.In addition,the future study should more focus on the investigation on the thermal runaway and decomposition of cathode materials and separa-tors.This review aims to provide fundamental insights into the relationship between electrochemistry and safety,further promoting the sustainable development of RMBs.展开更多
The design of an excellent active catalyst to improve the sluggish kinetic and thermodynamic properties of magnesium hydride(MgH_(2))remains a great challenge to achieve its practical application.In this study,a novel...The design of an excellent active catalyst to improve the sluggish kinetic and thermodynamic properties of magnesium hydride(MgH_(2))remains a great challenge to achieve its practical application.In this study,a novel Ni-Nb/rGO nanocomposite catalyst was successfully prepared by one-spot hydrothermal and sub-sequent calcination methods.The novel Ni-Nb/rGO nanocomposite exhibits an exceptional catalytic effect on improving MgH_(2) sorption properties.Specifically,the onset desorption temperature of MgH_(2)+10 wt%Ni-Nb/rGO composite is reduced to 198℃,much lower than that of undoped MgH_(2)(330℃).In-terestingly,the composite can release 5.0,5.9,and 6.0 wt%H_(2) within 10 min at 245,260,and 275℃,respectively.Furthermore,the dehydrogenated MgH_(2)+10 wt%Ni-Nb/rGO composite starts to absorb hydrogen even at room temperature with approximate 2.75 wt%H_(2) uptake at 75℃under 3 MPa H_(2) pressure within 30 min and exhibits excellent stability by maintaining 6.0 wt%hydrogen content after 20 cycles at 300℃.Chou’s model suggests that the de/hydrogenation kinetics of Ni-Nb/rGO-modified MgH_(2) switches from surface penetration model to diffusion model at lower temperatures.Additionally,the ac-tivation energies(E a)for the de/hydrogenation of MgH_(2)+10 wt%Ni-Nb/rGO are reduced to 57.8 kJ/mol and 33.9 kJ/mol,which are significantly lower than those of undoped MgH_(2).The work demonstrates that the addition of a novel ternary Ni-Nb/rGO catalyst is an effective strategy to not only boost the sorption kinetics of MgH_(2) but also maintain its cycling property.展开更多
基金financial support from the National Key Research and Development Program of China (No.2021YFB3502200)the National Natural Science Foundation of China (Grants Nos.52271202,51971040,52171101)+2 种基金the Shanghai Rising-Star Program (No.21QA1403200)supported by a start-up fund from Chongqing University (02110011044171)Liuchuang Program of Chongqing Municipality (cx2022038)。
文摘Magnesium-based energy materials, which combine promising energy-related functional properties with low cost, environmental compatibility and high availability, have been regarded as fascinating candidates for sustainable energy conversion and storage. In this review,we provide a timely summary on the recent progress in three types of important Mg-based energy materials, based on the fundamental strategies of composition and structure engineering. With regard to Mg-based materials for batteries, we systematically review and analyze different material systems, structure regulation strategies as well as the relevant performance in Mg-ion batteries(MIBs) and Mg-air batteries(MABs), covering cathodes, electrolytes, anodes for MIBs, and anodes for MABs;as to Mg-based hydrogen storage materials, we discuss how catalyst adding, composite, alloying and nanostructuring improve the kinetic and thermodynamic properties of de/hydrogenation reactions, and in particular, the impacts of composition and structure modification on hydrogen absorption/dissociation processes and free energy modification mechanism are focused;regarding Mg-based thermoelectric materials, the relations between composition/structure and electrical/thermal transport properties of Mg_(3)X_(2)(X = Sb, Bi), Mg_(2)X(X = Si, Ge, Sn) and Mg Ag Sb-based materials, together with the representative research progress of each material system, are summarized and discussed. Finally, by pointing out remaining challenges and providing possible solutions, this review aims to shed light on the directions and perspectives for practical applications of magnesium-based energy materials in the future.
基金supported by The National Key Research and Development Program of China(2023YFB3809100)the National Natural Science Foundation of China(U23A200722)the Fundamental Research Funds for the Central Universities(2023CDJXY-016).
文摘While TiFe alloy has recently attracted attention as the efficient catalyst to enhance de/hydrogenation rates of Mg/MgH_(2),the difficulty of its activation characteristics has hindered further improvement of reaction kinetics.Herein,we report that the TiFe_(0.92)Mn_(0.04)Co_(0.04) catalyst can overcome the abovementioned challenges.The synthesized MgH_(2)-30 wt% TiFe_(0.92)Mn_(0.04)Co_(0.04) can release 4.5 wt%of hydrogen in 16 min at 250℃,three times as fast as MgH_(2).The activation energy of dehydrogenation was as low as 84.6 kJ mol^(-1),which is 46.8%reduced from pure MgH_(2).No clear degradation of reaction rates and hydrogen storage capacity was observed for at least 30 cycles.Structural studies reveal that TiFe_(0.92)Mn_(0.04)Co_(0.04) partially decomposes to in-situ generatedα-Fe particles dispersed on TiFe_(0.92)Mn_(0.04)Co_(0.04).The presence ofα-Fe reduces the formation of an oxide layer on TiFe_(0.92)Mn_(0.04)Co_(0.04),enabling the activation processes.At the same time,the hydrogen incorporation capabilities of TiFe_(0.92)Mn_(0.04)Co_(0.04) can provide more hydrogen diffusion paths,which promote hydrogen dissociation and diffusion.These discoveries demonstrate the advanced nature and importance of combining the in-situ generatedα-Fe with TiFe_(0.92)Mn_(0.04)Co_(0.04).It provides a new strategy for designing highly efficient and stable catalysts for Mg-based hydrogen storage materials.
基金supported by the National Key R&D Program of China(No.2023YFB3809500)the National Natural Science Foundation of China(No.U23A20555,52202211)+3 种基金the Ninth Young Elite Scientists Sponsorship Program by CAST(2023QNRC001)the Chongqing Technology Innovation and Application Development Project(No.CSTB2022TIAD-KPX0028)the Fundamental Research Funds for the Central Universities(2023CDJXY-018)the Venture&Innovation Support Program for Chongqing Overseas Returnees(cx2022119,cx2023087).
文摘Rechargeable magnesium batteries(RMBs),as a low-cost,high-safety and high-energy storage technology,have attracted tremendous attention in large-scale energy storage applications.However,the key anode/electrolyte interfacial issues,including surface passivation,uneven Mg plating/stripping,and pulverization after cycling still result in a large overpotential,short cycling life,poor power density,and possible safety hazards of cells,severely impeding the commercial development of RMBs.In this review,a concise overview of recently advanced strategies to address these anode/electroyte interfacial issues is systematically classified and summarized.The design of magnesiophilic substrates,construction of artificial SEI layers,and modification of electrolyte are important and effective strategies to improve the uniformity/kinetics of Mg plating/stripping and achieve the stable anode/electrolyte interface.The key opportunities and challenges in this field are advisedly put forward,and the insights into future directions for stabilizing Mg metal anodes and the anode/electrolyte interface are highlighted.This review provides important references fordeveloping the high-performance and high-safety RMBs.
基金supported by the National Key R&D Program of China(No.2023YFB3809500)the National Natural Science Foundation of China(No.U23A20555,52202211)+1 种基金the Ninth Young Elite Scientists Sponsorship Program by CAST(2023QNRC001)the Chongqing Technology Innovation and Application Development Project(No.CSTB2022TIAD-KPX0028).
文摘Rechargeable Mg batteries(RMBs)have become one of the best subsitutes for lithium-ion batteries due to the high volumetric capacity,abundant resources,and uniform plating behavior of Mg metal anode.However,the safety hazard induced by the formation of high-modulue Mg dendrites under a high current density(10 mA cm^(-1))was still revealed in recent years.It has forced researchers to re-examine the safety of RMBs.In this review,the intrinsic safety factors of key components in RMBs,such as uneven plating,pitting and flammability of Mg anode,heat release and crystalline water decomposition of cathode,strong corrosion,low oxidition stability and flammability of electrolytes,and soforth,are systematacially summarized.Their origins,formation mechanisms,and possible safety hazards are deeply discussed.To develop high-performance Mg anode,current strategies including designing artificial SEI,three-dimensional substrates,and Mg alloys are summarized.For practical electrolytes,the configurations of boron-centered anions and simple Mg salts and the functionalized solvent with high boiling point and low flammability are suggested to comprehensively design.In addition,the future study should more focus on the investigation on the thermal runaway and decomposition of cathode materials and separa-tors.This review aims to provide fundamental insights into the relationship between electrochemistry and safety,further promoting the sustainable development of RMBs.
基金the financial support from the National Natural Science Foundation of China(Grant No.51801078).
文摘The design of an excellent active catalyst to improve the sluggish kinetic and thermodynamic properties of magnesium hydride(MgH_(2))remains a great challenge to achieve its practical application.In this study,a novel Ni-Nb/rGO nanocomposite catalyst was successfully prepared by one-spot hydrothermal and sub-sequent calcination methods.The novel Ni-Nb/rGO nanocomposite exhibits an exceptional catalytic effect on improving MgH_(2) sorption properties.Specifically,the onset desorption temperature of MgH_(2)+10 wt%Ni-Nb/rGO composite is reduced to 198℃,much lower than that of undoped MgH_(2)(330℃).In-terestingly,the composite can release 5.0,5.9,and 6.0 wt%H_(2) within 10 min at 245,260,and 275℃,respectively.Furthermore,the dehydrogenated MgH_(2)+10 wt%Ni-Nb/rGO composite starts to absorb hydrogen even at room temperature with approximate 2.75 wt%H_(2) uptake at 75℃under 3 MPa H_(2) pressure within 30 min and exhibits excellent stability by maintaining 6.0 wt%hydrogen content after 20 cycles at 300℃.Chou’s model suggests that the de/hydrogenation kinetics of Ni-Nb/rGO-modified MgH_(2) switches from surface penetration model to diffusion model at lower temperatures.Additionally,the ac-tivation energies(E a)for the de/hydrogenation of MgH_(2)+10 wt%Ni-Nb/rGO are reduced to 57.8 kJ/mol and 33.9 kJ/mol,which are significantly lower than those of undoped MgH_(2).The work demonstrates that the addition of a novel ternary Ni-Nb/rGO catalyst is an effective strategy to not only boost the sorption kinetics of MgH_(2) but also maintain its cycling property.
