Considering the growing pre-lithiation demand for high-performance Si-based anodes and consequent additional costs caused by the strict pre-lithiation environment,developing effective and environmentally stable pre-li...Considering the growing pre-lithiation demand for high-performance Si-based anodes and consequent additional costs caused by the strict pre-lithiation environment,developing effective and environmentally stable pre-lithiation additives is a challenging research hotspot.Herein,interfacial engineered multifunctional Li_(13)Si_(4)@perfluoropolyether(PFPE)/LiF micro/nanoparticles are proposed as anode pre-lithiation additives,successfully constructed with the hybrid interface on the surface of Li_(13)Si_(4)through PFPE-induced nucleophilic substitution.The synthesized multifunctional Li_(13)Si_(4)@PFPE/LiF realizes the integration of active Li compensation,long-term chemical structural stability in air,and solid electrolyte interface(SEI)optimization.In particular,the Li_(13)Si_(4)@PFPE/LiF with a high pre-lithiation capacity(1102.4 mAh g^(-1))is employed in the pre-lithiation Si-based anode,which exhibits a superior initial Coulombic efficiency of 102.6%.Additionally,in situ X-ray diffraction/Raman,density functional theory calculation,and finite element analysis jointly illustrate that PFPE-predominant hybrid interface with modulated abundant highly electronegative F atoms distribution reduces the water adsorption energy and oxidation kinetics of Li_(13)Si_(4)@PFPE/LiF,which delivers a high pre-lithiation capacity retention of 84.39%after exposure to extremely moist air(60%relative humidity).Intriguingly,a LiF-rich mechanically stable bilayer SEI is constructed on anodes through a pre-lithiation-driven regulation for the behavior of electrolyte decomposition.Benefitting from pre-lithiation via multifunctional Li_(13)Si_(4)@PFPE/LiF,the full cell and pouch cell assembled with pre-lithiated anodes operate with long-time stability of 86.5%capacity retention over 200 cycles and superior energy density of 549.9 Wh kg^(-1),respectively.The universal multifunctional pre-lithiation additives provide enlightenment on promoting large-scale applications of pre-lithiation on commercial high-energy-density and long-cycle-life lithium-ion batteries.展开更多
New materials have become one of the most important and fastest-growing industries all over the world.Important progress in materials science and technology has produced profound influences on the national economy,dai...New materials have become one of the most important and fastest-growing industries all over the world.Important progress in materials science and technology has produced profound influences on the national economy,daily life and national defense of our country.In this paper,we review the state of the art of materials science and technology in China,with emphasis on recent research focuses and advanced technology.展开更多
A simple and effective method for constructing highly efficient oxygen reduction catalysts with trace amount of isolated cobalt was firstly developed by the pyrolysis of Co-centered polyoxometalate@metalorganic framew...A simple and effective method for constructing highly efficient oxygen reduction catalysts with trace amount of isolated cobalt was firstly developed by the pyrolysis of Co-centered polyoxometalate@metalorganic framework (Co-POM@MOF).The Co-centered polyoxometalate ([Co W_(12)O_(40)]^(6-)) was confined in the well-defined void space of ZIF-8 to achieve homogeneous dispersion of polyoxoanions,where the isolated Co centers were well surrounded by the W-O shell and ZIF-8 framework.The Co-POM@MOF-derived N-doping porous carbon (Co-W-NC) with trace cobalt content was facilely prepared by the pyrolysis of the Co-POM@MOF under Ar atmosphere.The single dispersion of polyoxoanions in the metal-organic framework with complete separation of Co center surrounding by W-O shell and ZIF-8 framework ensures the uniform dispersion of Co atoms,confirmed by the Fourier transform extended X-ray absorption fine structure measurement.The Co-W-NC composite catalysts exhibit high performance for oxygen reduction reactions with a half-wave potential of 0.835 V in 0.1 mol/L KOH solution with excellent durability,which is much superior to that of the control samples derived from the[PW_(12)O_(40)]@ZIF-8,and the commercial Pt/C.This work highlights a new insight for constructing highly efficient catalysts via the introduction of metal-centered polyoxometalate into metal-organic framework following the high temperature treatment process.展开更多
Li metal batteries using high-voltage layered oxides cathodes are of particular interest due to their high energy density.However,they suffer from short lifespan and extreme safety concerns,which are attributed to the...Li metal batteries using high-voltage layered oxides cathodes are of particular interest due to their high energy density.However,they suffer from short lifespan and extreme safety concerns,which are attributed to the degradation of layered oxides and the decomposition of electrolyte at high voltage,as well as the high reactivity of metallic Li.The key is the development of stable electrolytes against both highvoltage cathodes and Li with the formation of robust interphase films on the surfaces.Herein,we report a highly fluorinated ether,1,1,1-trifluoro-2-[(2,2,2-trifluoroethoxy)methoxy]ethane(TTME),as a cosolvent,which not only functions as a diluent forming a localized high concentration electrolyte(LHCE),but also participates in the construction of the inner solvation structure.The TTME-based electrolyte is stable itself at high voltage and induces the formation of a unique double-layer solid electrolyte interphase(SEI)film,which is embodied as one layer rich in crystalline structural components for enhanced mechanical strength and another amorphous layer with a higher concentration of organic components for enhanced flexibility.The Li||Cu cells display a noticeably high Coulombic efficiency of 99.28%after 300 cycles and Li symmetric cells maintain stable cycling more than 3200 h at 0.5 mA/cm^(2) and 1.0m Ah/cm^(2).In addition,lithium metal cells using LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2) and Li CoO_(2) cathodes(both loadings~3.0 m Ah/cm^(2))realize capacity retentions of>85%over 240 cycles with a charge cut-off voltage of 4.4 V and 90%for 170 cycles with a charge cut-off voltage of 4.5 V,respectively.This study offers a bifunctional ether-based electrolyte solvent beneficial for high-voltage Li metal batteries.展开更多
Rational design and controllable synthesis of practical electrodes with high sta bility and activity at high current density for a hydrogen evolution reaction(HER)are critical for renewable and sustainable energy conv...Rational design and controllable synthesis of practical electrodes with high sta bility and activity at high current density for a hydrogen evolution reaction(HER)are critical for renewable and sustainable energy conversion.However,high-performance TiO_(2)-based electrocatalysts for HER are quite limited,and the cat alytic active centers still remain elusive.Herein,a simple strategy is demonstrated for the synthesis of TiO_(2)-carbon composite(TiO_(2)/C)with high HER performance and stability.The remarkable HER performance of TiO_(2)/C can be ascribed to the doping of carbon atoms,which leads to stronger hybridization of Ti 3d and O 2p orbitals,thus substantially improving the electrocatalytic efficiency.This study elucidates that the hydrogen evolution activity of oxide electrocatalysts can be largely improved by regulating their electronic structures by doping carbon atoms and also provides an effective strategy for designing heterostructured electro catalysts with high catalytic activity and stability at high current density for HER.展开更多
Electronic tuning by para substitutions was explored to achieve a highly active manganese N-heterocyclic carbene pincer complex for the selective electrocatalytic reduction of CO_(2)to CO.[MnCNC^(OMe)]BF_(4)(L2-Mn)bea...Electronic tuning by para substitutions was explored to achieve a highly active manganese N-heterocyclic carbene pincer complex for the selective electrocatalytic reduction of CO_(2)to CO.[MnCNC^(OMe)]BF_(4)(L2-Mn)bearing an electron-donating group(-OMe)showed high activity with 63×catalytic current enhancement,average Faradaic efficiency of 104%,and a TOF_(max) value of 26,127 s^(-1),which is 127 times higher than that of unsubstituted[MnCNCH]Br(L1-Mn)reported previously.In contrast,the electron-withdrawing group(-COOMe)in[MnCNC^(CO^(OMe))]PF_(6)(L3-Mn)inhibited the electrocatalytic activity.Ambient Brønstic acid,however,suppressed the activity of L2-Mn probably due to the protonation of the-OMe group.These findings indicate a potential electronic tuning strategy to improved manganese N-heterocyclic carbene catalysts for CO_(2)reduction.展开更多
A photoredox/nickel-catalyzed selective 1,4-arylsulfonation of 1,3-enynes to access structurally diverse sulfone-containing allenes has been established.This radical cascade transformation featured easy manipulation,m...A photoredox/nickel-catalyzed selective 1,4-arylsulfonation of 1,3-enynes to access structurally diverse sulfone-containing allenes has been established.This radical cascade transformation featured easy manipulation,mild conditions,low catalyst loading,broad substrate scope,and large-scale synthesis.The preliminary mechanistic studies indicated a possible radical-relay process enabled by the radical capture of nickel(0)species.展开更多
Alkali and alkaline ion substitutions enhance the electrochemical properties of P2 sodium layered oxide,while the effect on electrochemical property enhancement of alkali and alkaline ions co-substitution is still unc...Alkali and alkaline ion substitutions enhance the electrochemical properties of P2 sodium layered oxide,while the effect on electrochemical property enhancement of alkali and alkaline ions co-substitution is still unclear.In this work,the structural and electrochemical properties of the Li alkali and Mg alkaline ions co-substituted P2 layered oxide Na_(0.67)(Li_(0.5)Mg_(0.5))_(0.1)(Ni_(0.33)Mn_(0.67))_(0.9)O_(2)are investigated in detail.Compared to the pristine and single-ion substituted materials,the co-substituted material shows an enhanced cycling performance with a reversible ca-pacity of 127 mAh/g and a capacity retention of 75%over 100 cycles at 0.5C.Galvanostatic intermittent titration technique(GITT)and cyclic voltammetry(CV)results show that the Li and Mg synergistically improve the ion diffusion.Moreover,the structure stability is also improved by the Li and Mg co-substitution that is clarified by operando X-ray diffraction(XRD)measurements.These results explain the origin of the enhanced electrochemical properties of the Li/Mg co-substituted P2 layered oxides for sodium ion batteries.展开更多
基金Huaiyu Shao acknowledges the Shenzhen-Hong Kong-Macao Science and Technology Plan Project(Category C)(Grant No.SGDX20220530111004028)the Macao Science and Technology Development Fund(FDCT)for funding(FDCT No.0013/2024/RIB1,FDCT-MOST joint project No.0026/2022/AMJ and No.006/2022/ALC of the Macao Centre for Research and Development in Advanced Materials[2022–2024])+2 种基金the Multi-Year Research Grant(MYRG)from University of Macao(project No.MYRG-GRG2023-00140-IAPME-UMDF and No.MYRG-GRG2024-00206-IAPME)Natural Science Foundation of Guangdong Province(Grant No.2023A1515010765)Science and Technology Program of Guangdong Province of China(Grant No.2023A0505030001)。
文摘Considering the growing pre-lithiation demand for high-performance Si-based anodes and consequent additional costs caused by the strict pre-lithiation environment,developing effective and environmentally stable pre-lithiation additives is a challenging research hotspot.Herein,interfacial engineered multifunctional Li_(13)Si_(4)@perfluoropolyether(PFPE)/LiF micro/nanoparticles are proposed as anode pre-lithiation additives,successfully constructed with the hybrid interface on the surface of Li_(13)Si_(4)through PFPE-induced nucleophilic substitution.The synthesized multifunctional Li_(13)Si_(4)@PFPE/LiF realizes the integration of active Li compensation,long-term chemical structural stability in air,and solid electrolyte interface(SEI)optimization.In particular,the Li_(13)Si_(4)@PFPE/LiF with a high pre-lithiation capacity(1102.4 mAh g^(-1))is employed in the pre-lithiation Si-based anode,which exhibits a superior initial Coulombic efficiency of 102.6%.Additionally,in situ X-ray diffraction/Raman,density functional theory calculation,and finite element analysis jointly illustrate that PFPE-predominant hybrid interface with modulated abundant highly electronegative F atoms distribution reduces the water adsorption energy and oxidation kinetics of Li_(13)Si_(4)@PFPE/LiF,which delivers a high pre-lithiation capacity retention of 84.39%after exposure to extremely moist air(60%relative humidity).Intriguingly,a LiF-rich mechanically stable bilayer SEI is constructed on anodes through a pre-lithiation-driven regulation for the behavior of electrolyte decomposition.Benefitting from pre-lithiation via multifunctional Li_(13)Si_(4)@PFPE/LiF,the full cell and pouch cell assembled with pre-lithiated anodes operate with long-time stability of 86.5%capacity retention over 200 cycles and superior energy density of 549.9 Wh kg^(-1),respectively.The universal multifunctional pre-lithiation additives provide enlightenment on promoting large-scale applications of pre-lithiation on commercial high-energy-density and long-cycle-life lithium-ion batteries.
基金supported by the National Natural Science Foundation of China (51272009)
文摘New materials have become one of the most important and fastest-growing industries all over the world.Important progress in materials science and technology has produced profound influences on the national economy,daily life and national defense of our country.In this paper,we review the state of the art of materials science and technology in China,with emphasis on recent research focuses and advanced technology.
基金supported by the Natural Science Foundation of Tianjin City of China (No.18JCJQJC47700)。
文摘A simple and effective method for constructing highly efficient oxygen reduction catalysts with trace amount of isolated cobalt was firstly developed by the pyrolysis of Co-centered polyoxometalate@metalorganic framework (Co-POM@MOF).The Co-centered polyoxometalate ([Co W_(12)O_(40)]^(6-)) was confined in the well-defined void space of ZIF-8 to achieve homogeneous dispersion of polyoxoanions,where the isolated Co centers were well surrounded by the W-O shell and ZIF-8 framework.The Co-POM@MOF-derived N-doping porous carbon (Co-W-NC) with trace cobalt content was facilely prepared by the pyrolysis of the Co-POM@MOF under Ar atmosphere.The single dispersion of polyoxoanions in the metal-organic framework with complete separation of Co center surrounding by W-O shell and ZIF-8 framework ensures the uniform dispersion of Co atoms,confirmed by the Fourier transform extended X-ray absorption fine structure measurement.The Co-W-NC composite catalysts exhibit high performance for oxygen reduction reactions with a half-wave potential of 0.835 V in 0.1 mol/L KOH solution with excellent durability,which is much superior to that of the control samples derived from the[PW_(12)O_(40)]@ZIF-8,and the commercial Pt/C.This work highlights a new insight for constructing highly efficient catalysts via the introduction of metal-centered polyoxometalate into metal-organic framework following the high temperature treatment process.
基金the financial supports from the KeyArea Research and Development Program of Guangdong Province (2020B090919001)the National Natural Science Foundation of China (22078144)the Guangdong Natural Science Foundation for Basic and Applied Basic Research (2021A1515010138 and 2023A1515010686)。
文摘Li metal batteries using high-voltage layered oxides cathodes are of particular interest due to their high energy density.However,they suffer from short lifespan and extreme safety concerns,which are attributed to the degradation of layered oxides and the decomposition of electrolyte at high voltage,as well as the high reactivity of metallic Li.The key is the development of stable electrolytes against both highvoltage cathodes and Li with the formation of robust interphase films on the surfaces.Herein,we report a highly fluorinated ether,1,1,1-trifluoro-2-[(2,2,2-trifluoroethoxy)methoxy]ethane(TTME),as a cosolvent,which not only functions as a diluent forming a localized high concentration electrolyte(LHCE),but also participates in the construction of the inner solvation structure.The TTME-based electrolyte is stable itself at high voltage and induces the formation of a unique double-layer solid electrolyte interphase(SEI)film,which is embodied as one layer rich in crystalline structural components for enhanced mechanical strength and another amorphous layer with a higher concentration of organic components for enhanced flexibility.The Li||Cu cells display a noticeably high Coulombic efficiency of 99.28%after 300 cycles and Li symmetric cells maintain stable cycling more than 3200 h at 0.5 mA/cm^(2) and 1.0m Ah/cm^(2).In addition,lithium metal cells using LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2) and Li CoO_(2) cathodes(both loadings~3.0 m Ah/cm^(2))realize capacity retentions of>85%over 240 cycles with a charge cut-off voltage of 4.4 V and 90%for 170 cycles with a charge cut-off voltage of 4.5 V,respectively.This study offers a bifunctional ether-based electrolyte solvent beneficial for high-voltage Li metal batteries.
基金supported bythe Natural Scientific Foundation of China(Grants 21878001,22078002,21776001,21875001,21978002,21808002,22008001,and U1710114).
文摘Rational design and controllable synthesis of practical electrodes with high sta bility and activity at high current density for a hydrogen evolution reaction(HER)are critical for renewable and sustainable energy conversion.However,high-performance TiO_(2)-based electrocatalysts for HER are quite limited,and the cat alytic active centers still remain elusive.Herein,a simple strategy is demonstrated for the synthesis of TiO_(2)-carbon composite(TiO_(2)/C)with high HER performance and stability.The remarkable HER performance of TiO_(2)/C can be ascribed to the doping of carbon atoms,which leads to stronger hybridization of Ti 3d and O 2p orbitals,thus substantially improving the electrocatalytic efficiency.This study elucidates that the hydrogen evolution activity of oxide electrocatalysts can be largely improved by regulating their electronic structures by doping carbon atoms and also provides an effective strategy for designing heterostructured electro catalysts with high catalytic activity and stability at high current density for HER.
基金supported by the National Natural Science Foundation of China(No.21973113)the Guangdong Natural Science Funds for Distinguished Young Scholar(No.2015A030306027)the Fundamental Research Funds for the Central Universities。
文摘Electronic tuning by para substitutions was explored to achieve a highly active manganese N-heterocyclic carbene pincer complex for the selective electrocatalytic reduction of CO_(2)to CO.[MnCNC^(OMe)]BF_(4)(L2-Mn)bearing an electron-donating group(-OMe)showed high activity with 63×catalytic current enhancement,average Faradaic efficiency of 104%,and a TOF_(max) value of 26,127 s^(-1),which is 127 times higher than that of unsubstituted[MnCNCH]Br(L1-Mn)reported previously.In contrast,the electron-withdrawing group(-COOMe)in[MnCNC^(CO^(OMe))]PF_(6)(L3-Mn)inhibited the electrocatalytic activity.Ambient Brønstic acid,however,suppressed the activity of L2-Mn probably due to the protonation of the-OMe group.These findings indicate a potential electronic tuning strategy to improved manganese N-heterocyclic carbene catalysts for CO_(2)reduction.
文摘A photoredox/nickel-catalyzed selective 1,4-arylsulfonation of 1,3-enynes to access structurally diverse sulfone-containing allenes has been established.This radical cascade transformation featured easy manipulation,mild conditions,low catalyst loading,broad substrate scope,and large-scale synthesis.The preliminary mechanistic studies indicated a possible radical-relay process enabled by the radical capture of nickel(0)species.
基金supported by Guangdong Basic and Applied Basic Research Foundation(2019A1515110897 and 2019B1515120028)supported by Ministry of Higher Education of Malaysia for the Fundamental Research Grant(FRGS/1/2018/STG02/UM/02/10)awarded to Woo Haw JiunnUniversity of Malaya research grant(GPF 038B-2018)
文摘Alkali and alkaline ion substitutions enhance the electrochemical properties of P2 sodium layered oxide,while the effect on electrochemical property enhancement of alkali and alkaline ions co-substitution is still unclear.In this work,the structural and electrochemical properties of the Li alkali and Mg alkaline ions co-substituted P2 layered oxide Na_(0.67)(Li_(0.5)Mg_(0.5))_(0.1)(Ni_(0.33)Mn_(0.67))_(0.9)O_(2)are investigated in detail.Compared to the pristine and single-ion substituted materials,the co-substituted material shows an enhanced cycling performance with a reversible ca-pacity of 127 mAh/g and a capacity retention of 75%over 100 cycles at 0.5C.Galvanostatic intermittent titration technique(GITT)and cyclic voltammetry(CV)results show that the Li and Mg synergistically improve the ion diffusion.Moreover,the structure stability is also improved by the Li and Mg co-substitution that is clarified by operando X-ray diffraction(XRD)measurements.These results explain the origin of the enhanced electrochemical properties of the Li/Mg co-substituted P2 layered oxides for sodium ion batteries.
