The development of rechargeable magnesium(Mg) batteries is of practical significance to upgrade the electric energy storage devices due to exceptional capacity and abundant resources of Mg-metal anode.However,the reve...The development of rechargeable magnesium(Mg) batteries is of practical significance to upgrade the electric energy storage devices due to exceptional capacity and abundant resources of Mg-metal anode.However,the reversible Mg electrochemistry suffers from unsatisfied rate capability and lifespan,mainly caused by non-uniform distribution of electrodeposits.In this work,a fresh design concept of threedimensional carbon cloths scaffolds is proposed to overcome the uncontrollable Mg growth via homogenizing electric field and improving magnesiophilicity.A microscopic smooth and nitrogen-containing defective carbonaceous layer is constructed through a facile pyrolysis of ZIF8 on carbon cloths.As revealed by finite element simulation and DFT calculation results,the smooth surface endows with uniform electric field distribution and simultaneously the nitrogen-doping species enable good magnesiophilicity of scaffolds.The fine and uniform Mg nucleus as well as the inner electrodeposit behavior are also disclosed.As a result,an exceptional cycle life of 500 cycles at 4.0 mA cm^(-2) and 4.0 mA h cm^(-2) is firstly realized to our best knowledge.Besides,the functional scaffolds can be cycled for over 2200 h at 2.0 mA cm^(-2) under a normalized capacity of 5.0 mA h cm^(-2),far exceeding previous results.This work offers an effective approach to enable the full potential of carbon cloths-based scaffolds towards metal storage for next generation battery applications.展开更多
Magnesium metal batteries are considered as viable alternatives of lithium-ion batteries for their low cost and high capacity of magnesium.Nevertheless,the practical application of magnesium metal batteries is extreme...Magnesium metal batteries are considered as viable alternatives of lithium-ion batteries for their low cost and high capacity of magnesium.Nevertheless,the practical application of magnesium metal batteries is extremely challenging due to a lack of suitable electrolyte that can stabilize magnesium metal anode and high-voltage cathode simultaneously.Herein,we found that in-situ formed lithium/magnesium hybrid electrolyte interphases in conventional LiPF6-containing carbonate-based electrolyte can not only prevent the production of passivation layer on the magnesium metal anode,but also inhibit the oxidation of the electrolyte under high voltage.The symmetric magnesium‖magnesium battery can achieve reversible stripping/plating for 1600 and 600 h at 0.02 and 0.1 mA cm^(-2),respectively.In addition,when coupled with a carbon fiber cathode,the magnesium metal battery exhibited a capacity retention rate of 96.3% for 1000 cycles at a current density of 500 mA g^(-1)and presented a working voltage of ~3.1 V.This research paves a new and promising path to the commercialization process of rechargeable magnesium metal batteries.展开更多
Microstructures and mechanical properties of transient liquid phase (TLP) bonded magnesium metal matrix composite ( MMC) joints using copper interlayer have been investigated. With an increase of bonding times fro...Microstructures and mechanical properties of transient liquid phase (TLP) bonded magnesium metal matrix composite ( MMC) joints using copper interlayer have been investigated. With an increase of bonding times from 5 min to 50 min at bonding temperature of 510 ℃ , the average concentration of copper in the bonded zone decreased, the microstructure in the zone changed from Cu, α-Mg and CuMg2 to α-Mg, CuMg2 and TiC, and mechanical properties of the joint increased. The shear strength of the joint bonded at 510 ℃ for 50 min reached 64 MPa due to the metallurgical bonding of the joint and improving its homogeneity of composition and microstructure. It is favorable to increase the bonding time for improving mechanical properties of TLP bonded magnesium MMC joint.展开更多
A magnesium metal organic framework, [N-H2(CH3)2][-N(CH3)4][Mgs(bpdc)3(O2CH)6]· 3H2O (1, bpdcH2 = 4,4'-biphenyldicarboxylic acid), has been solvothermally synthesized and structurally characterized. 1 ...A magnesium metal organic framework, [N-H2(CH3)2][-N(CH3)4][Mgs(bpdc)3(O2CH)6]· 3H2O (1, bpdcH2 = 4,4'-biphenyldicarboxylic acid), has been solvothermally synthesized and structurally characterized. 1 crystallizes in the trigonal system, space group R-3, with a = 11.3427(3), c = 41.5662(18) A, V = 4631.3(3) A^3, Z = 3 and the final R = 0.0457. Its structure features a pillared-layered three-dimensional network with 8.21 A cavities, in which cationic [NH2(CH3)2]^+ or [N(CH3)4]^+ and lattice water molecules are located. Thermal stability of the title compound has also been investigated.展开更多
Rechargeable magnesium metal batteries need an electrolyte that forms a stable and ionically conductive solid electrolyte interphase(SEI)on the anodes.Here,we used molecular dynamic simulation,density functional theor...Rechargeable magnesium metal batteries need an electrolyte that forms a stable and ionically conductive solid electrolyte interphase(SEI)on the anodes.Here,we used molecular dynamic simulation,density functional theory calculation,and X-ray photoelectron spectroscopy analysis to investigate the solvation structures and SEI compositions in electrolytes consisting of dual-salts,magnesium bis(trifluoromethanesulfonyl)imide(MgTFSI_(2)),and MgCl_(2),with different additives in 1,2-dimethoxyethane(DME)solvent.We found that the formed[Mg_(3)(μ-Cl)_(4)(DME)mTFSI_(2)](m=3,5)inner-shell solvation clusters in MgTFSI_(2)-MgCl_(2)/DME electrolyte could easily decompose and form a MgO-and MgF_(2)-rich SEI.Such electron-rich inorganic species in the SEI,especially MgF_(2),turned out to be detrimental for Mg plating/stripping.To reduce the MgF_(2)and MgO contents in SEI,we introduce an electron-deficient tri(2,2,2-trifluoroethyl)borate(TFEB)additive in the electrolyte.Mg//Mg cells using the MgTFSI_(2)-MgCl_(2)/DME-TFEB electrolyte could cycle stably for over 400 h with a small polarization voltage of~150 mV.Even with the presence of 800 ppm H_(2)O,the electrolyte with TFEB additive could still preserve its good electrochemical performance.The optimized electrolyte also enabled stable cycling and high-rate capability for Mg//Mo6S8 and Mg//CuS full cells,showing great potential for future applications.展开更多
To meet the low-cost concept advocated by the sodium metal anode,this paper reports the use of a pulsed electrodeposition technology with ionic liquids as electrolytes to achieve uniform nanoplating of metallic magnes...To meet the low-cost concept advocated by the sodium metal anode,this paper reports the use of a pulsed electrodeposition technology with ionic liquids as electrolytes to achieve uniform nanoplating of metallic magnesium films at around 20 nm on spaced titanium dioxide(TiO_(2))nanotubes(STNA-Mg).First,the sodiophilic magnesium metal coating can effectively reduce the nucleation overpotential of sodium metal.Moreover,three-dimensional STNA can limit the volume expansion during sodium metal plating and stripping to achieve the ultrastable deposition and stripping of sodium metals with a high Coulombic efficiency of up to 99.5%and a small voltage polarization of 5 mV in symmetric Na||Na batteries.In addition,the comparative study of sodium metal deposition behavior of STNA-Mg and STNA-Cu prepared by the same route further confirmed the advantage of magnesium metal to guide sodium metal growth.Finally,the prepared STNA-Mg-Na metal anode and commercial sodium vanadium phosphate cathode were assembled into a full cell,delivering a discharge capacity of 110.2 mAh·g^(-1)with a retention rate of 95.6%after 110 cycles at 1C rate.展开更多
In recent years,various particulate materials have played important roles in medical applications.However,nano-and micron-sized particles of the same material could exhibit distinct properties due to different particl...In recent years,various particulate materials have played important roles in medical applications.However,nano-and micron-sized particles of the same material could exhibit distinct properties due to different particle sizes.This finding provided a simple and effective way to improve the biological applications of particulate materials.Therefore,as a highly promising member,the effect of the particle size change of the magnesium metal organic framework-74(Mg-MOF74)was well worth evaluating.Here we firsth assessed the in vitro and in vivo toxicity of micron/nanoscale Mg-MOF74(m-Mg-MOF74/n-Mg-MOF74)in detail.Our in vitro study revealed that compared to micron-sized subjects,n-Mg-MOF74 provided a wider range of safe concentrations.Furthermore,both micron/nanoscale Mg-MOF74 showed good biocompatibility and allowed all the rats under the treatment to survive through the expected experimental periods,with n-Mg-MOF74 still showing lower cardiotoxicity.These advantages of nanoscale Mg-MOF74might benefit from its sustainable and balanced release of Ma^2+both inside and outside the cells.Based on the biosafety evaluation,advanced bio-functional assessments of m/n-Mg-MOF74 including early osteogenesis and angiogenesis were alsoperformed.Similarly,the suitable dose groups of n-Mg-MOF74 achieved optimal early osteogenic promotion and angiogenic stimulation effects.Overall,our combined data delineated the toxicity and biological behaviors of Ma-MOF74 of different scales,and sugqested nanoscale Mg-MOF74 as a better choice for future applications.This result revealed that particle size reductior might be a viable strategy to improve and expand medical applications of MOFs or other particulate materials.展开更多
We investigate experimentally and analytically the combustion behavior of a high-metal magnesium-based hydro- reactive fuel under high temperature gaseous atmosphere. The fuel studied in this paper contains 73% magnes...We investigate experimentally and analytically the combustion behavior of a high-metal magnesium-based hydro- reactive fuel under high temperature gaseous atmosphere. The fuel studied in this paper contains 73% magnesium powders. An experimental system is designed and experiments are carried out in both argon and water vapor atmo- spheres. It is found that the burning surface temperature of the fuel is higher in water vapor than that in argon and both of them are higher than the melting point of magnesium, which indicates the molten state of magnesium particles in the burning surface of the fuel. Based on physical considerations and experimental results, a mathematical one-dimensional model is formulated to describe the combustion behavior of the high-metal magnesium-based hydro-reactive fuel. The model enables the evaluation of the burning surface temperature, the burning rate and the flame standoff distance each as a function of chamber pressure and water vapor concentration. The results predicted by the model show that the burning rate and the surface temperature increase when the chamber pressure and the water vapor concentration increase, which are in agreement with the observed experimental trends.展开更多
The spheroidiser is a necessary additive to manufacture ductile iron.Sometimes with the same hot metal,spheroidisers and treated technology,reactions differ greatly from each other.The reaction may be quite normal in ...The spheroidiser is a necessary additive to manufacture ductile iron.Sometimes with the same hot metal,spheroidisers and treated technology,reactions differ greatly from each other.The reaction may be quite normal in one case,but very intensive for another one.The effects of kinetic factors such as size,surface area and morphology o f spheroidiser on the reaction of spheoidization are studied.展开更多
Magnesium-bearing minerals discovered on the earth so far occur mainly as solid or liquid.The former include magnesite(Mg CO3),dolomite(Mg CO3·Ca CO3),carnallite(Mg Cl2·KCl·6H2O),bischofite(Mg Cl2·...Magnesium-bearing minerals discovered on the earth so far occur mainly as solid or liquid.The former include magnesite(Mg CO3),dolomite(Mg CO3·Ca CO3),carnallite(Mg Cl2·KCl·6H2O),bischofite(Mg Cl2·6H2O)and展开更多
基金supported by the National Natural Science Foundation of China(51972187,22279068,52374306)the Natural Science Foundation of Shandong Province(ZR2021QE166)Qingdao New Energy Shandong Laboratory Open Project(QNESL OP202312)。
文摘The development of rechargeable magnesium(Mg) batteries is of practical significance to upgrade the electric energy storage devices due to exceptional capacity and abundant resources of Mg-metal anode.However,the reversible Mg electrochemistry suffers from unsatisfied rate capability and lifespan,mainly caused by non-uniform distribution of electrodeposits.In this work,a fresh design concept of threedimensional carbon cloths scaffolds is proposed to overcome the uncontrollable Mg growth via homogenizing electric field and improving magnesiophilicity.A microscopic smooth and nitrogen-containing defective carbonaceous layer is constructed through a facile pyrolysis of ZIF8 on carbon cloths.As revealed by finite element simulation and DFT calculation results,the smooth surface endows with uniform electric field distribution and simultaneously the nitrogen-doping species enable good magnesiophilicity of scaffolds.The fine and uniform Mg nucleus as well as the inner electrodeposit behavior are also disclosed.As a result,an exceptional cycle life of 500 cycles at 4.0 mA cm^(-2) and 4.0 mA h cm^(-2) is firstly realized to our best knowledge.Besides,the functional scaffolds can be cycled for over 2200 h at 2.0 mA cm^(-2) under a normalized capacity of 5.0 mA h cm^(-2),far exceeding previous results.This work offers an effective approach to enable the full potential of carbon cloths-based scaffolds towards metal storage for next generation battery applications.
基金supported by the National Natural Science Foundation of China,China(51972351,51802361)the Guangdong Basic and Applied Basic Research Foundation,China(2019B151502045)the Fundamental Research Funds for the Central Universities of China,China(22lgqb01)。
文摘Magnesium metal batteries are considered as viable alternatives of lithium-ion batteries for their low cost and high capacity of magnesium.Nevertheless,the practical application of magnesium metal batteries is extremely challenging due to a lack of suitable electrolyte that can stabilize magnesium metal anode and high-voltage cathode simultaneously.Herein,we found that in-situ formed lithium/magnesium hybrid electrolyte interphases in conventional LiPF6-containing carbonate-based electrolyte can not only prevent the production of passivation layer on the magnesium metal anode,but also inhibit the oxidation of the electrolyte under high voltage.The symmetric magnesium‖magnesium battery can achieve reversible stripping/plating for 1600 and 600 h at 0.02 and 0.1 mA cm^(-2),respectively.In addition,when coupled with a carbon fiber cathode,the magnesium metal battery exhibited a capacity retention rate of 96.3% for 1000 cycles at a current density of 500 mA g^(-1)and presented a working voltage of ~3.1 V.This research paves a new and promising path to the commercialization process of rechargeable magnesium metal batteries.
文摘Microstructures and mechanical properties of transient liquid phase (TLP) bonded magnesium metal matrix composite ( MMC) joints using copper interlayer have been investigated. With an increase of bonding times from 5 min to 50 min at bonding temperature of 510 ℃ , the average concentration of copper in the bonded zone decreased, the microstructure in the zone changed from Cu, α-Mg and CuMg2 to α-Mg, CuMg2 and TiC, and mechanical properties of the joint increased. The shear strength of the joint bonded at 510 ℃ for 50 min reached 64 MPa due to the metallurgical bonding of the joint and improving its homogeneity of composition and microstructure. It is favorable to increase the bonding time for improving mechanical properties of TLP bonded magnesium MMC joint.
基金supported by the NNSFC (No. 20873149)the Knowledge Innovation Program of the Chinese Academy of Sciences (KJCX2-XW-H21)
文摘A magnesium metal organic framework, [N-H2(CH3)2][-N(CH3)4][Mgs(bpdc)3(O2CH)6]· 3H2O (1, bpdcH2 = 4,4'-biphenyldicarboxylic acid), has been solvothermally synthesized and structurally characterized. 1 crystallizes in the trigonal system, space group R-3, with a = 11.3427(3), c = 41.5662(18) A, V = 4631.3(3) A^3, Z = 3 and the final R = 0.0457. Its structure features a pillared-layered three-dimensional network with 8.21 A cavities, in which cationic [NH2(CH3)2]^+ or [N(CH3)4]^+ and lattice water molecules are located. Thermal stability of the title compound has also been investigated.
基金supported by the National Natural Science Foundation of China(22150710516,U1832218).
文摘Rechargeable magnesium metal batteries need an electrolyte that forms a stable and ionically conductive solid electrolyte interphase(SEI)on the anodes.Here,we used molecular dynamic simulation,density functional theory calculation,and X-ray photoelectron spectroscopy analysis to investigate the solvation structures and SEI compositions in electrolytes consisting of dual-salts,magnesium bis(trifluoromethanesulfonyl)imide(MgTFSI_(2)),and MgCl_(2),with different additives in 1,2-dimethoxyethane(DME)solvent.We found that the formed[Mg_(3)(μ-Cl)_(4)(DME)mTFSI_(2)](m=3,5)inner-shell solvation clusters in MgTFSI_(2)-MgCl_(2)/DME electrolyte could easily decompose and form a MgO-and MgF_(2)-rich SEI.Such electron-rich inorganic species in the SEI,especially MgF_(2),turned out to be detrimental for Mg plating/stripping.To reduce the MgF_(2)and MgO contents in SEI,we introduce an electron-deficient tri(2,2,2-trifluoroethyl)borate(TFEB)additive in the electrolyte.Mg//Mg cells using the MgTFSI_(2)-MgCl_(2)/DME-TFEB electrolyte could cycle stably for over 400 h with a small polarization voltage of~150 mV.Even with the presence of 800 ppm H_(2)O,the electrolyte with TFEB additive could still preserve its good electrochemical performance.The optimized electrolyte also enabled stable cycling and high-rate capability for Mg//Mo6S8 and Mg//CuS full cells,showing great potential for future applications.
基金financially supported by the National Natural Science Foundation of China (No.51874099)the National Science Foundation of Fujian Province’s Key Project,China (No.2021J02031)the support from the open fund from the Academy of Carbon Neutrality of Fujian Normal University,China (No.CZH2022-06)。
文摘To meet the low-cost concept advocated by the sodium metal anode,this paper reports the use of a pulsed electrodeposition technology with ionic liquids as electrolytes to achieve uniform nanoplating of metallic magnesium films at around 20 nm on spaced titanium dioxide(TiO_(2))nanotubes(STNA-Mg).First,the sodiophilic magnesium metal coating can effectively reduce the nucleation overpotential of sodium metal.Moreover,three-dimensional STNA can limit the volume expansion during sodium metal plating and stripping to achieve the ultrastable deposition and stripping of sodium metals with a high Coulombic efficiency of up to 99.5%and a small voltage polarization of 5 mV in symmetric Na||Na batteries.In addition,the comparative study of sodium metal deposition behavior of STNA-Mg and STNA-Cu prepared by the same route further confirmed the advantage of magnesium metal to guide sodium metal growth.Finally,the prepared STNA-Mg-Na metal anode and commercial sodium vanadium phosphate cathode were assembled into a full cell,delivering a discharge capacity of 110.2 mAh·g^(-1)with a retention rate of 95.6%after 110 cycles at 1C rate.
基金This study was supported by the National Natural Science Foundation of China(Nos.81601613,81771122,81970985,and 81970984)Key research program of Sichuan Science and technology Department(No.2018SZ0037).
文摘In recent years,various particulate materials have played important roles in medical applications.However,nano-and micron-sized particles of the same material could exhibit distinct properties due to different particle sizes.This finding provided a simple and effective way to improve the biological applications of particulate materials.Therefore,as a highly promising member,the effect of the particle size change of the magnesium metal organic framework-74(Mg-MOF74)was well worth evaluating.Here we firsth assessed the in vitro and in vivo toxicity of micron/nanoscale Mg-MOF74(m-Mg-MOF74/n-Mg-MOF74)in detail.Our in vitro study revealed that compared to micron-sized subjects,n-Mg-MOF74 provided a wider range of safe concentrations.Furthermore,both micron/nanoscale Mg-MOF74 showed good biocompatibility and allowed all the rats under the treatment to survive through the expected experimental periods,with n-Mg-MOF74 still showing lower cardiotoxicity.These advantages of nanoscale Mg-MOF74might benefit from its sustainable and balanced release of Ma^2+both inside and outside the cells.Based on the biosafety evaluation,advanced bio-functional assessments of m/n-Mg-MOF74 including early osteogenesis and angiogenesis were alsoperformed.Similarly,the suitable dose groups of n-Mg-MOF74 achieved optimal early osteogenic promotion and angiogenic stimulation effects.Overall,our combined data delineated the toxicity and biological behaviors of Ma-MOF74 of different scales,and sugqested nanoscale Mg-MOF74 as a better choice for future applications.This result revealed that particle size reductior might be a viable strategy to improve and expand medical applications of MOFs or other particulate materials.
基金Project supported by the Young Scientist Fund of the National Natural Science Foundation of China(Grant No.51006118)
文摘We investigate experimentally and analytically the combustion behavior of a high-metal magnesium-based hydro- reactive fuel under high temperature gaseous atmosphere. The fuel studied in this paper contains 73% magnesium powders. An experimental system is designed and experiments are carried out in both argon and water vapor atmo- spheres. It is found that the burning surface temperature of the fuel is higher in water vapor than that in argon and both of them are higher than the melting point of magnesium, which indicates the molten state of magnesium particles in the burning surface of the fuel. Based on physical considerations and experimental results, a mathematical one-dimensional model is formulated to describe the combustion behavior of the high-metal magnesium-based hydro-reactive fuel. The model enables the evaluation of the burning surface temperature, the burning rate and the flame standoff distance each as a function of chamber pressure and water vapor concentration. The results predicted by the model show that the burning rate and the surface temperature increase when the chamber pressure and the water vapor concentration increase, which are in agreement with the observed experimental trends.
文摘The spheroidiser is a necessary additive to manufacture ductile iron.Sometimes with the same hot metal,spheroidisers and treated technology,reactions differ greatly from each other.The reaction may be quite normal in one case,but very intensive for another one.The effects of kinetic factors such as size,surface area and morphology o f spheroidiser on the reaction of spheoidization are studied.
基金co-funded by Chinese Academy of Engineering major consultation projects "Comprehensive Utilization and Sustainable Development of Qinghai Salt Lake" and the "Strategic Research on the Sustainable Mineral Resources Development in China (Chemical and Salt Lake Projects)"
文摘Magnesium-bearing minerals discovered on the earth so far occur mainly as solid or liquid.The former include magnesite(Mg CO3),dolomite(Mg CO3·Ca CO3),carnallite(Mg Cl2·KCl·6H2O),bischofite(Mg Cl2·6H2O)and