Given the considerable global interest in the preparation of Ti and TiC,a novel reduction method for TiO_(2) in a CH_(4)-H_(2) atmosphere was proposed,and the reduction thermodynamic behavior,phase equilibrium,and ene...Given the considerable global interest in the preparation of Ti and TiC,a novel reduction method for TiO_(2) in a CH_(4)-H_(2) atmosphere was proposed,and the reduction thermodynamic behavior,phase equilibrium,and energy consumption of TiO_(2) during its reaction with a CH_(4)-H_(2) gas mixture were investigated.The results indicate that the reaction proceeds via a stepwise reduction pathway from TiO_(2) to Ti(C,O),with the Magnéli phase(TinO_(2n-1))and Ti_(3)O_(5) serving as intermediate phases.Notably,the reduction of TiO_(2) by H_(2) is more challenging than that by CH_(4),which may be attributed to the inhibitory effect of H_(2) on the surface carbon precipitation.For the complete carbonization of 1 mol TiO_(2),the total energy required at 1000,1100,and 1200℃is 1159,925,and 977 kJ/mol,respectively,which may be related to the shift of gas-phase equilibrium and the increase in side reactions at high temperatures.展开更多
Herein,we report a novel,visible-light-induced approach for the selective construction of both gem-difluoroalkenes and trifluoromethyl alkanes from α-trifluoromethyl olefins using alcohol-derived N-alkoxyphthalimides...Herein,we report a novel,visible-light-induced approach for the selective construction of both gem-difluoroalkenes and trifluoromethyl alkanes from α-trifluoromethyl olefins using alcohol-derived N-alkoxyphthalimides as alkyl radical precursors.This strategy leverages Eosin Y as a photocatalyst in a defluorinative alkylation reaction and a catalyst-free electron donor-acceptor(EDA)complex-mediated hydroalkylation process.By modulating the reaction conditions,the desired products were selectively obtained with excellent chemo-selectivity and in high yields.The protocol accommodates a wide variety of substrates,including primary,secondary,and tertiary alcohols,as well as diverse α-trifluoromethyl styrenes,and is applicable to late-stage functionalization of natural products and bioactive molecules.展开更多
The effect of trace addition of 0.1wt%Y on the grain refinement and mechanical properties of Al-2.2Li-1.5Cu-0.5Mg-1Zn-0.2Zr-0.2Sc alloys at as-cast and heat-treated states was investigated.Results show that the additi...The effect of trace addition of 0.1wt%Y on the grain refinement and mechanical properties of Al-2.2Li-1.5Cu-0.5Mg-1Zn-0.2Zr-0.2Sc alloys at as-cast and heat-treated states was investigated.Results show that the addition of 0.1wt%Y into the Al-2.2Li-1.5Cu-0.5Mg-1Zn-0.2Zr-0.2Sc alloys can elevate the nucleation temperature of the Al_(3)(Sc,Zr)phase,leading to the preferential precipitation of the Al_(3)(Sc,Zr)phase and increasing the amount of Al_(3)(Sc,Zr)phase in the matrix.Al_(3)(Sc,Zr)phase can also act as a heterogeneous nucleation site in theα-Al matrix to promote nucleation and refine grains.The addition of element Y changes the precipitation phase characteristics at the grain boundaries in the as-cast alloy,which changes the distribution characteristics of secondary phases from initially continuous and coarse strip-like distribution at grain boundaries into the discontinuous dot-like and rod-like distribution.Besides,the size of secondary phases becomes smaller and their amount increases.Under the combined effects of grain refinement strengthening and precipitation strengthening,the Al-2.2Li-1.5Cu-0.5Mg-1Zn-0.2Zr-0.2Sc-0.1Y alloy after 175℃/10 h aging treatment achieves an ultimate tensile strength of 412 MPa and an elongation of 6.3%.Compared with those of the alloy without Y addition,the ultimate tensile strength and elongation of the added alloy increase by 16.1%and 53.7%,respectively.展开更多
Achieving room-temperature superconductivity has been an enduring scientific quest,while hydrogen-rich compounds have emerged as highly promising candidates.Here,we systematically investigated the thermodynamic stabil...Achieving room-temperature superconductivity has been an enduring scientific quest,while hydrogen-rich compounds have emerged as highly promising candidates.Here,we systematically investigated the thermodynamic stability,crystal structure,electronic properties,and superconductivity within the ternary Y-Hf-H system under high pressure.Several distinct hydrides have been revealed,in which the hydrogen atoms are present in various hydrogenic motifs.A15-type hydride P_(m)3-YHfH_(6)with isolated H−is predicted to be dynamically stabilized down to 10GPa.The H atoms form pentagonal graphene-like layered-H10 anions in the Hf plane of P6-YHfH_(19),with aT_(c)of 95K at 100GPa.There are H cages in C_(mmm)-Y_(3)HfH_(24),and attributed to the robust electron–phonon coupling and high electronic density of states of hydrogen at the Fermi level,it demonstrates near-room temperature superconductivity with a T_(c)of 275K at 250GPa.Our work makes contributions to the understanding of the fundamental properties of ternary hydrides under high pressure and provides essential references for further research in this field.展开更多
The influence of homogenization parameters on element segregation,dendritic structure,and the precipitate evolution in the GH3535-0.08wt%Y alloy was investigated.Additionally,some specific homogenization parameters we...The influence of homogenization parameters on element segregation,dendritic structure,and the precipitate evolution in the GH3535-0.08wt%Y alloy was investigated.Additionally,some specific homogenization parameters were maintained constant throughout the experiments.Results indicate that the heat treatment at 1150℃for 10 h is the optimal homogenization condition.Following this optimal treatment,dendrite structures and element segregation are eliminated.Furthermore,both SiC and Y_(5)Si_(3)precipitates in the as-cast alloy decrease significantly.Conversely,the homogenization at 1188℃induces overheating defects within the alloy.Although SiC and Y_(5)Si_(3)phases also decrease,some large M6C phases can still be observed,adversely affecting subsequent forging processes.展开更多
To address the performance limitations of conventional LiPF6-carbonate electrolytes under extreme temperatures and high-rate charging,lithium difluoro(oxalato)borate(LiDFOB)is introduced into the LiPF6-carbonate elect...To address the performance limitations of conventional LiPF6-carbonate electrolytes under extreme temperatures and high-rate charging,lithium difluoro(oxalato)borate(LiDFOB)is introduced into the LiPF6-carbonate electrolyte to form a dual-salt system.The optimization mechanism enhancing the fast-charging capability of LiNi_(0.52)Co_(0.2)Mn_(0.28)O_(2)(NCM523)cathode is systematically explored.Molecular dynamics simulations and electrochemical characterization demonstrate the reconstruction of Li+solvation structures,expanding the voltage window and reducting Li^(+)desolvation barriers.In addition,the incorporation of LiDFOB induces the generation of a LiF/Li_(x)BO_(y)F_(z)-enriched cathode-electrolyte interphase,which effectively suppresses the dissolution of transition metals.In situ impedance measurements reveal the accelerated interfacial charge transfer kinetics.As expected,the NCM523 cathode achieves an 82%state-of-charge(SOC)in 12 min at 5 C(25°C)with 87%capacity retention after 100 cycles,and exhibits a 65%higher discharge capacity at 1 C than the baseline at−20°C.The 1 Ah pouch cells based on LiNi_(0.52)Co_(0.2)Mn_(0.28)O_(2)cathodes,graphite anodes,and 0.5 wt%LiDFOB-modified electrolyte demonstrate fast-charging capabilities:charging 97%of the pouch cell capacity within 30 min(2 C)and 80%within 15 min(4 C)at 25°C.This study offers a practical electrolyte design strategy that enhances the fast-charging performance of lithium-ion batteries(LIBs)over a wide temperature range(from−20 to 25°C).展开更多
It is of great importance to explore sustainable and eco-friendly recycling strategies for spent Li-ion batteries(LIBs).As such,the closed-loop resynthesis of LiNi_(x)CoyMn_(z)O_(2)(NCM)becomes recently popular as exe...It is of great importance to explore sustainable and eco-friendly recycling strategies for spent Li-ion batteries(LIBs).As such,the closed-loop resynthesis of LiNi_(x)CoyMn_(z)O_(2)(NCM)becomes recently popular as exemplified by the commercialization of low-and mid-Ni content NCM(33%-60%).However,there has been suspicion as to the successful deployment of Ni-rich NCM resynthesis process.Therefore,we systematically increase the Ni content of NCM from 60%to 90%from the industrial leachate of spent LIBs containing various metallic and nonmetallic impurities.The utilization rate of the leachate decreases from 71.8 mol%for NCM622 to 18.0 mol%for NCM955 as the Ni content in the NCM composition increases with the Co recycling rate being 100%in all resynthesized NCM(RNCM).The physicochemical and electrochemical properties of RNCM are systematically compared with its pristine NCM counterparts.As a result,various physicochemical properties of RNCM including impurity content,crystallographic information,morphology,particle size,porosity,specific surface area,elemental distribution,residual lithium compounds,and thermal stability are correlated with its electrochemical properties.It is found out that Al is the most critical impurity that determines the physicochemical and electrochemical properties of RNCM.It is noteworthy that RNCM955 prepared from spent LIBs without any purification step surpasses NCM955 in terms of rate and cycle performance.Further,this resynthesis approach toward Nirich NCM could meet the forthcoming 2031 EU's legislative target on the mandatory minimum recycling usage of valuable metals from spent LIBs.The anode active material was resynthesized using industrial leachate as the maximum.The amount of leachate used and the amount of impurities were proportional.展开更多
文摘Given the considerable global interest in the preparation of Ti and TiC,a novel reduction method for TiO_(2) in a CH_(4)-H_(2) atmosphere was proposed,and the reduction thermodynamic behavior,phase equilibrium,and energy consumption of TiO_(2) during its reaction with a CH_(4)-H_(2) gas mixture were investigated.The results indicate that the reaction proceeds via a stepwise reduction pathway from TiO_(2) to Ti(C,O),with the Magnéli phase(TinO_(2n-1))and Ti_(3)O_(5) serving as intermediate phases.Notably,the reduction of TiO_(2) by H_(2) is more challenging than that by CH_(4),which may be attributed to the inhibitory effect of H_(2) on the surface carbon precipitation.For the complete carbonization of 1 mol TiO_(2),the total energy required at 1000,1100,and 1200℃is 1159,925,and 977 kJ/mol,respectively,which may be related to the shift of gas-phase equilibrium and the increase in side reactions at high temperatures.
基金supported by the National Natural Science Foundation of China(22401151)the Basic Research Program of Jiangsu Province(BK20220408)+1 种基金the Innovation and Entrepreneurship Team of Jiangsu Province(JSSCTD202345)the Specially Appointed Professor Plan of Jiangsu Province。
文摘Herein,we report a novel,visible-light-induced approach for the selective construction of both gem-difluoroalkenes and trifluoromethyl alkanes from α-trifluoromethyl olefins using alcohol-derived N-alkoxyphthalimides as alkyl radical precursors.This strategy leverages Eosin Y as a photocatalyst in a defluorinative alkylation reaction and a catalyst-free electron donor-acceptor(EDA)complex-mediated hydroalkylation process.By modulating the reaction conditions,the desired products were selectively obtained with excellent chemo-selectivity and in high yields.The protocol accommodates a wide variety of substrates,including primary,secondary,and tertiary alcohols,as well as diverse α-trifluoromethyl styrenes,and is applicable to late-stage functionalization of natural products and bioactive molecules.
基金National Natural Science Foundation of China(52071065)Fundamental Research Funds for the Central Universities(N2007007)+2 种基金Joint Fund of Henan Province Science and Technology R&D Program(N225200810040)High-Level Talent Research Start-Up Project Funding of Henan Academy of Sciences(N242017003)Liaoning Provincial Department of Education Basic Research Projects for Colleges and Universities(LJ212410142093)。
文摘The effect of trace addition of 0.1wt%Y on the grain refinement and mechanical properties of Al-2.2Li-1.5Cu-0.5Mg-1Zn-0.2Zr-0.2Sc alloys at as-cast and heat-treated states was investigated.Results show that the addition of 0.1wt%Y into the Al-2.2Li-1.5Cu-0.5Mg-1Zn-0.2Zr-0.2Sc alloys can elevate the nucleation temperature of the Al_(3)(Sc,Zr)phase,leading to the preferential precipitation of the Al_(3)(Sc,Zr)phase and increasing the amount of Al_(3)(Sc,Zr)phase in the matrix.Al_(3)(Sc,Zr)phase can also act as a heterogeneous nucleation site in theα-Al matrix to promote nucleation and refine grains.The addition of element Y changes the precipitation phase characteristics at the grain boundaries in the as-cast alloy,which changes the distribution characteristics of secondary phases from initially continuous and coarse strip-like distribution at grain boundaries into the discontinuous dot-like and rod-like distribution.Besides,the size of secondary phases becomes smaller and their amount increases.Under the combined effects of grain refinement strengthening and precipitation strengthening,the Al-2.2Li-1.5Cu-0.5Mg-1Zn-0.2Zr-0.2Sc-0.1Y alloy after 175℃/10 h aging treatment achieves an ultimate tensile strength of 412 MPa and an elongation of 6.3%.Compared with those of the alloy without Y addition,the ultimate tensile strength and elongation of the added alloy increase by 16.1%and 53.7%,respectively.
基金supported by the National Natural Science Foundation of China(Grant Nos.52072188,12122405,and 12274169)Program for Science and Technology Innovation Team in Zhejiang Province,China(Grant No.2021R01004)+2 种基金Natural Science Foundation of Zhejiang Province,China(Grant No.LQ24A040001)the Natural Science Foundation of Ningbo City,China(Grant No.2024J200)the Fundamental Research Funds for the Provincial Universities of Zhejiang(Grant No.SJLY2023003)。
文摘Achieving room-temperature superconductivity has been an enduring scientific quest,while hydrogen-rich compounds have emerged as highly promising candidates.Here,we systematically investigated the thermodynamic stability,crystal structure,electronic properties,and superconductivity within the ternary Y-Hf-H system under high pressure.Several distinct hydrides have been revealed,in which the hydrogen atoms are present in various hydrogenic motifs.A15-type hydride P_(m)3-YHfH_(6)with isolated H−is predicted to be dynamically stabilized down to 10GPa.The H atoms form pentagonal graphene-like layered-H10 anions in the Hf plane of P6-YHfH_(19),with aT_(c)of 95K at 100GPa.There are H cages in C_(mmm)-Y_(3)HfH_(24),and attributed to the robust electron–phonon coupling and high electronic density of states of hydrogen at the Fermi level,it demonstrates near-room temperature superconductivity with a T_(c)of 275K at 250GPa.Our work makes contributions to the understanding of the fundamental properties of ternary hydrides under high pressure and provides essential references for further research in this field.
基金National Natural Science Foundation of China(51801227,52071331)。
文摘The influence of homogenization parameters on element segregation,dendritic structure,and the precipitate evolution in the GH3535-0.08wt%Y alloy was investigated.Additionally,some specific homogenization parameters were maintained constant throughout the experiments.Results indicate that the heat treatment at 1150℃for 10 h is the optimal homogenization condition.Following this optimal treatment,dendrite structures and element segregation are eliminated.Furthermore,both SiC and Y_(5)Si_(3)precipitates in the as-cast alloy decrease significantly.Conversely,the homogenization at 1188℃induces overheating defects within the alloy.Although SiC and Y_(5)Si_(3)phases also decrease,some large M6C phases can still be observed,adversely affecting subsequent forging processes.
基金financially supported by the National Natural Science Foundation of China (Grant No. 52372191)the National Natural Science Foundation of China (Grant No. 22271106)+2 种基金the National Science Foundation of China (Grant Nos. 52073286 (C.-Z.L.), 22275185 (C.-Z.L.))the Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China(2021ZZ115 (C.-Z.L.)the XMIREM Autonomously Deployment Project (2023GG01 (C.-Z.L.))
文摘To address the performance limitations of conventional LiPF6-carbonate electrolytes under extreme temperatures and high-rate charging,lithium difluoro(oxalato)borate(LiDFOB)is introduced into the LiPF6-carbonate electrolyte to form a dual-salt system.The optimization mechanism enhancing the fast-charging capability of LiNi_(0.52)Co_(0.2)Mn_(0.28)O_(2)(NCM523)cathode is systematically explored.Molecular dynamics simulations and electrochemical characterization demonstrate the reconstruction of Li+solvation structures,expanding the voltage window and reducting Li^(+)desolvation barriers.In addition,the incorporation of LiDFOB induces the generation of a LiF/Li_(x)BO_(y)F_(z)-enriched cathode-electrolyte interphase,which effectively suppresses the dissolution of transition metals.In situ impedance measurements reveal the accelerated interfacial charge transfer kinetics.As expected,the NCM523 cathode achieves an 82%state-of-charge(SOC)in 12 min at 5 C(25°C)with 87%capacity retention after 100 cycles,and exhibits a 65%higher discharge capacity at 1 C than the baseline at−20°C.The 1 Ah pouch cells based on LiNi_(0.52)Co_(0.2)Mn_(0.28)O_(2)cathodes,graphite anodes,and 0.5 wt%LiDFOB-modified electrolyte demonstrate fast-charging capabilities:charging 97%of the pouch cell capacity within 30 min(2 C)and 80%within 15 min(4 C)at 25°C.This study offers a practical electrolyte design strategy that enhances the fast-charging performance of lithium-ion batteries(LIBs)over a wide temperature range(from−20 to 25°C).
基金supported by the Basic Science Research Program through the National Research Foundation of Korea(NRF)funded by the Ministry of Science and ICT(RS-2023-00254424)by the ITRC(Information Technology Research Center)support program(IITP-2024-RS-2024-00437494)supervised by the IITP(Institute for Information&Communications Technology Planning&Evaluation)funded by the MSIT(Ministry of Science and ICT),Korea。
文摘It is of great importance to explore sustainable and eco-friendly recycling strategies for spent Li-ion batteries(LIBs).As such,the closed-loop resynthesis of LiNi_(x)CoyMn_(z)O_(2)(NCM)becomes recently popular as exemplified by the commercialization of low-and mid-Ni content NCM(33%-60%).However,there has been suspicion as to the successful deployment of Ni-rich NCM resynthesis process.Therefore,we systematically increase the Ni content of NCM from 60%to 90%from the industrial leachate of spent LIBs containing various metallic and nonmetallic impurities.The utilization rate of the leachate decreases from 71.8 mol%for NCM622 to 18.0 mol%for NCM955 as the Ni content in the NCM composition increases with the Co recycling rate being 100%in all resynthesized NCM(RNCM).The physicochemical and electrochemical properties of RNCM are systematically compared with its pristine NCM counterparts.As a result,various physicochemical properties of RNCM including impurity content,crystallographic information,morphology,particle size,porosity,specific surface area,elemental distribution,residual lithium compounds,and thermal stability are correlated with its electrochemical properties.It is found out that Al is the most critical impurity that determines the physicochemical and electrochemical properties of RNCM.It is noteworthy that RNCM955 prepared from spent LIBs without any purification step surpasses NCM955 in terms of rate and cycle performance.Further,this resynthesis approach toward Nirich NCM could meet the forthcoming 2031 EU's legislative target on the mandatory minimum recycling usage of valuable metals from spent LIBs.The anode active material was resynthesized using industrial leachate as the maximum.The amount of leachate used and the amount of impurities were proportional.
