Micro silicon(mSi)is a promising anode candidate for all-solid-state batteries due to its high specific capacity,low side reactions,and high tap density.However,silicon suffers from its poor electronic and ionic condu...Micro silicon(mSi)is a promising anode candidate for all-solid-state batteries due to its high specific capacity,low side reactions,and high tap density.However,silicon suffers from its poor electronic and ionic conductivity,which is particularly severe on a micro scale and in solid-state systems,leading to increased polarization and inferior electrochemical performance.Doping can broaden the transmission pathways and reduce the diffusion energy barrier for electrons and lithium ions.However,achieving effective,uniform doping in mSi is challenging due to its longer diffusion paths and higher energy barriers.Therefore,current doping research is primarily limited to nanosilicon.In this study,we successfully used a Joule-heating activated staged thermal treatment to achieve full-depth doping of germanium(Ge)in the mSi substrate.The Joule-heating process activated the mSi substrate,resulting in abundant vacancy defects that reduced the diffusion barrier of Ge into the silicon lattice and facilitated full-depth Ge doping.Surprisingly,the resulting Si-Ge anode exhibited significantly enhanced electrical conductivity(70 times).Meanwhile,the improved Li-ion conductivity in mSi and the reduced Young’s modulus enhance the electrode reaction kinetics and integrity after cycling.Ge-doped silicon anodes demonstrate excellent electrochemical performance when applied in sulfide solid-state half-cells and full-cells.This work provides substantial insights into the rational structural design of mSi alloyed anode materials,paving the way for the development of high-performance solid-state Li-ion batteries.展开更多
Mn^(2+)-doped CsPbCl_(3)(Mn^(2+):CsPbCl_(3)) nanocrystals(NCs) have attracted considerable attention due to their unique strong and broad orange-red emission band,presenting promising applications in the field of phot...Mn^(2+)-doped CsPbCl_(3)(Mn^(2+):CsPbCl_(3)) nanocrystals(NCs) have attracted considerable attention due to their unique strong and broad orange-red emission band,presenting promising applications in the field of photoelectric devices.However,pristine Mn^(2+):CsPbCl_(3)NCs commonly suffer from low photoluminescence quantum yield(PL QY) and stability issues.Herein,we introduced europium ions(Eu^(3+))into Mn^(2+):CsPbCl_(3)NCs via the thermal injection synthesis method to obtain high performance Eu^(3+)and Mn^(2+)codoped CsPbCl_(3)(Eu^(3+)/Mn^(2+):CsPbCl_(3)) NCs.The maximum PL QY of the resulting Eu^(3+)/Mn^(2+):CsPbCl_(3)NCs reaches up to 90.92%.It is found that the doping of Eu^(3+)ions significantly reduces the non-radiative recombination caused by high defect states,and improves the energy transfer efficiency from exciton to Mn^(2+),thereby boosting the PL performance.Moreover,doping Eu^(3+)ions notably improves the UV-light and water stability of Mn^(2+):CsPbCl_(3)NCs.We further demonstrate the application versatility of Eu^(3+)/Mn^(2+):CsPbCl_(3)NCs in white light emitting diodes(WLEDs) and optical anticounterfeiting applications.This work provides a valuable perspective for the attainment of high performance Mn^(2+):CsPbCl_(3)NCs and lays a foundation for the codoping of other lanthanide ions to adjust the luminescence properties of Mn^(2+):CsPbCl_(3)NCs.展开更多
The design of cost-effective and efficient metal-free carbon-based catalysts for the hydrogen evolution reaction(HER)is of great significance for increasing the production of clean hydrogen by the electrolysis of alka...The design of cost-effective and efficient metal-free carbon-based catalysts for the hydrogen evolution reaction(HER)is of great significance for increasing the production of clean hydrogen by the electrolysis of alkaline water.Precise control of the electronic structure by heteroatom doping has proven to be efficient for increasing catalytic activity.Nevertheless,both the structural characteristics and the underlying mechanism are not well understood,especially for doping with two different atoms,thus limiting the use of these catalysts.We report the production of phosphorus and nitrogen co-doped hollow carbon nanospheres(HCNs)by the copolymerization of pyrrole and aniline at a Triton X-100 micelle-interface,followed by doping with phytic acid and carbonization.The unique pore structure and defect-rich framework of the HCNs expose numerous active sites.Crucially,the combined effect of graphitic nitrogen and phosphorus-carbon bonds modulate the local electronic structure of adjacent C atoms and facilitates electron transfer.As a res-ult,the HCN carbonized at 1100°C exhibited superior HER activity and an outstanding stability(70 h at a current density of 10 mA cm^(−2))in alkaline water,because of the large number of graphitic nitrogen and phosphorus-carbon bonds.展开更多
As a 3D printing method,laser powder bed fusion(LPBF)technology has been extensively proven to offer significant advantages in fabricating complex structured specimens,achieving ultra-fine microstructures,and enhancin...As a 3D printing method,laser powder bed fusion(LPBF)technology has been extensively proven to offer significant advantages in fabricating complex structured specimens,achieving ultra-fine microstructures,and enhancing performances.In the domain of manufacturing melt-grown oxide ceramics,it encounters substantial challenges in suppressing crack defects during the rapid solidification process.The strategic integration of high entropy alloys(HEA),leveraging the significant ductility and toughness into ceramic powders represents a major innovation in overcoming the obstacles.The ingenious doping of HEA parti-cles preserves the eutectic microstructures of the Al_(2)O_(3)/GdAlO_(3)(GAP)/ZrO_(2)ceramic composite.The high damage tolerance of the HEA alloy under high strain rates enables the absorption of crack energy and alleviation of internal stresses during LPBF,effectively reducing crack initiation and growth.Due to in-creased curvature forces and intense Marangoni convection at the top of the molt pool,particle collision intensifies,leading to the tendency of HEA particles to agglomerate at the upper part of the molt pool.However,this phenomenon can be effectively alleviated in the remelting process of subsequent layer de-position.Furthermore,a portion of the HEA particles partially dissolves and sinks into the molten pool,acting as heterogeneous nucleation particles,inducing the formation of equiaxed eutectic and leading pri-mary phase nucleation.Some HEA particles diffuse into the lamellar ternary eutectic structures,further promoting the refinement of eutectic microstructures due to increased undercooling.The innovative dop-ing of HEA particles has effectively facilitated the fabrication of turbine-structured,conical,and cylindrical ternary eutectic ceramic composite specimens with diameters of about 70 mm,demonstrating significant developmental potential in the field of ceramic composite manufacturing.展开更多
Herein,an external crosslinker facilitated the hypercrosslinking of ferrocene and a nitrogen heterocyclic compound(either melamine or imidazole)through a direct Friedel-Crafts reaction,which led to the formation of ni...Herein,an external crosslinker facilitated the hypercrosslinking of ferrocene and a nitrogen heterocyclic compound(either melamine or imidazole)through a direct Friedel-Crafts reaction,which led to the formation of nitrogen-containing hypercrosslinked fer-rocene polymer precursors(HCP-FCs).Subsequent carbonization of these precursors results in the production of iron-nitrogen-doped por-ous carbon absorbers(Fe-NPCs).The Fe-NPCs demonstrate a porous structure comprising aggregated nanotubes and nanospheres.The porosity of this structure can be modulated by adjusting the iron and nitrogen contents to optimize impedance matching.The uniform dis-tribution of Fe-N_(x)C,N dipoles,andα-Fe within the carbon matrix can be ensured by using hypercrosslinked ferrocenes in constructing porous carbon,providing the absorber with numerous polarization sites and a conductive network.The electromagnetic wave absorption performance of the specially designed Fe-NPC-M_(2)absorbers is satisfactory,revealing a minimum reflection loss of-55.3 dB at 2.5 mm and an effective absorption bandwidth of 6.00 GHz at 2.0 mm.By utilizing hypercrosslinked polymers(HCPs)as precursors,a novel method for developing highly efficient carbon-based absorbing agents is introduced in this research.展开更多
In contrast to research on active sites in nanomaterials,lithium tantalate single crystals,known for their exceptional optical properties and long-range ordered lattice structure,present a promising avenue for in-dept...In contrast to research on active sites in nanomaterials,lithium tantalate single crystals,known for their exceptional optical properties and long-range ordered lattice structure,present a promising avenue for in-depth exploration of photocatalytic reaction systems with fewer constraints imposed by surface chemistry.Typically,the isotropy of a specific facet provides a perfect support for studying heteroatom doping.Herein,this work delves into the intrinsic catalytic sites for photocatalytic nitrogen fixation in iron-doped lithium tantalate single crystals.The presence of iron not only modifies the electronic structure of lithium tantalate,improving its light absorption capacity,but also functions as an active site for the nitrogen adsorption and activation.The photocatalytic ammonia production rate of the iron-doped lithium tantalate in pure water is maximum 26.95μg cm^(−2)h^(−1),which is three times higher than that of undoped lithium tantalate.The combination of first-principles simulations with in situ characterizations confirms that iron doping promotes the rate-determining step and changes the pathway of hydrogenation to associative alternating.This study provides a new perspective on in-depth investigation of intrinsic catalytic active sites in photocatalysis and other catalytic processes.展开更多
Magnetostrictive Fe-Ga alloys have captivated substantial focus in biomedical applications because of their exceptional transition efficiency and favorable cytocompatibility.Nevertheless,Fe-Ga alloys always exhibit fr...Magnetostrictive Fe-Ga alloys have captivated substantial focus in biomedical applications because of their exceptional transition efficiency and favorable cytocompatibility.Nevertheless,Fe-Ga alloys always exhibit frustrating magnetostriction coefficients when presented in bulk dimensions.It is well-established that the magnetostrictive performance of Fe-Ga alloys is intimately linked to their phase and crystal structures.In this study,various concentrations of boron(B)were doped into Fe_(81)Ga_(19) alloys via the laser-beam powder bed fusion(LPBF)technique to tailor the crystal and phase structures,thereby improving the magnetostrictive performance.The results revealed the capacity for quick solidification of the LPBF process in expediting the solid solution of B element,which increased both lattice distortion and dislocations within the Fe-Ga matrix.These factors contributed to an elevation in the density of the modified-D0_(3) phase structure.Moreover,the prepared Fe-Ga-B alloys also exhibited a(001)preferred grain orientation caused by the high thermal gradients during the LPBF process.As a result,a maximum magnetostriction coefficient of 105 ppm was achieved in the(Fe_(81)Ga_(19))_(98.5)B_(1.5) alloy.In alternating magnetic fields,all the LPBF-prepared alloys showed good dynamic magnetostriction response without visible hysteresis,while the(Fe_(81)Ga_(19))_(98.5)B_(1.5) alloy presented a notable enhancement of~30%in magnetostriction coefficient when compared with the Fe_(81)Ga_(19) alloy.Moreover.the(Fe_(81)Ga_(19))_(98.5)B_(1.5) alloy exhibited favorable biocompatibility and osteogenesis,as confirmed by increased alkaline phosphatase(ALP)activity and the formation of mineralized nodules.These findings suggest that the B-doped Fe-Ga alloys combined with the LPBF technique hold promise for the development of bulk magnetostrictive alloys that are applicable for bone repair applications.展开更多
基金financially supported by the National Key Research and Development Program(2022YFE0127400)the National Natural Science Foundation of China(52172040,52202041,and U23B2077)+1 种基金Taishan Scholar Project of Shandong Province(tsqn202211086,ts202208832,tsqnz20221118)the Fundamental Research Funds for the Central Universities(23CX06055A).
文摘Micro silicon(mSi)is a promising anode candidate for all-solid-state batteries due to its high specific capacity,low side reactions,and high tap density.However,silicon suffers from its poor electronic and ionic conductivity,which is particularly severe on a micro scale and in solid-state systems,leading to increased polarization and inferior electrochemical performance.Doping can broaden the transmission pathways and reduce the diffusion energy barrier for electrons and lithium ions.However,achieving effective,uniform doping in mSi is challenging due to its longer diffusion paths and higher energy barriers.Therefore,current doping research is primarily limited to nanosilicon.In this study,we successfully used a Joule-heating activated staged thermal treatment to achieve full-depth doping of germanium(Ge)in the mSi substrate.The Joule-heating process activated the mSi substrate,resulting in abundant vacancy defects that reduced the diffusion barrier of Ge into the silicon lattice and facilitated full-depth Ge doping.Surprisingly,the resulting Si-Ge anode exhibited significantly enhanced electrical conductivity(70 times).Meanwhile,the improved Li-ion conductivity in mSi and the reduced Young’s modulus enhance the electrode reaction kinetics and integrity after cycling.Ge-doped silicon anodes demonstrate excellent electrochemical performance when applied in sulfide solid-state half-cells and full-cells.This work provides substantial insights into the rational structural design of mSi alloyed anode materials,paving the way for the development of high-performance solid-state Li-ion batteries.
基金Project supported by the National Natural Science Foundation of China (12174075)the Scientific and Technological Bases and Talents of Guangxi (Guike AD21220016)+1 种基金Guangxi Science and Technology Major Project(AA23073018)the special fund for Guangxi Bagui Scholars。
文摘Mn^(2+)-doped CsPbCl_(3)(Mn^(2+):CsPbCl_(3)) nanocrystals(NCs) have attracted considerable attention due to their unique strong and broad orange-red emission band,presenting promising applications in the field of photoelectric devices.However,pristine Mn^(2+):CsPbCl_(3)NCs commonly suffer from low photoluminescence quantum yield(PL QY) and stability issues.Herein,we introduced europium ions(Eu^(3+))into Mn^(2+):CsPbCl_(3)NCs via the thermal injection synthesis method to obtain high performance Eu^(3+)and Mn^(2+)codoped CsPbCl_(3)(Eu^(3+)/Mn^(2+):CsPbCl_(3)) NCs.The maximum PL QY of the resulting Eu^(3+)/Mn^(2+):CsPbCl_(3)NCs reaches up to 90.92%.It is found that the doping of Eu^(3+)ions significantly reduces the non-radiative recombination caused by high defect states,and improves the energy transfer efficiency from exciton to Mn^(2+),thereby boosting the PL performance.Moreover,doping Eu^(3+)ions notably improves the UV-light and water stability of Mn^(2+):CsPbCl_(3)NCs.We further demonstrate the application versatility of Eu^(3+)/Mn^(2+):CsPbCl_(3)NCs in white light emitting diodes(WLEDs) and optical anticounterfeiting applications.This work provides a valuable perspective for the attainment of high performance Mn^(2+):CsPbCl_(3)NCs and lays a foundation for the codoping of other lanthanide ions to adjust the luminescence properties of Mn^(2+):CsPbCl_(3)NCs.
基金financially supported by the project of the National Natural Science Foundation of China(52322203)the Key Research and Development Program of Shaanxi Province(2024GHZDXM-21)。
文摘The design of cost-effective and efficient metal-free carbon-based catalysts for the hydrogen evolution reaction(HER)is of great significance for increasing the production of clean hydrogen by the electrolysis of alkaline water.Precise control of the electronic structure by heteroatom doping has proven to be efficient for increasing catalytic activity.Nevertheless,both the structural characteristics and the underlying mechanism are not well understood,especially for doping with two different atoms,thus limiting the use of these catalysts.We report the production of phosphorus and nitrogen co-doped hollow carbon nanospheres(HCNs)by the copolymerization of pyrrole and aniline at a Triton X-100 micelle-interface,followed by doping with phytic acid and carbonization.The unique pore structure and defect-rich framework of the HCNs expose numerous active sites.Crucially,the combined effect of graphitic nitrogen and phosphorus-carbon bonds modulate the local electronic structure of adjacent C atoms and facilitates electron transfer.As a res-ult,the HCN carbonized at 1100°C exhibited superior HER activity and an outstanding stability(70 h at a current density of 10 mA cm^(−2))in alkaline water,because of the large number of graphitic nitrogen and phosphorus-carbon bonds.
基金supported by the National Natural Science Foundation of China(Nos.52130204,52174376,52202070,51822405)Guangdong Basic and Applied Basic Research Foundation(No.2021B1515120028)+6 种基金TQ Innovation Foundation(No.23-TQ09-02-ZT-01-005)Aeronautical Science Foundation of China(No.20220042053001)Science and Technology Innovation Team Plan of Shaanxi Province(No.2021TD-17)Key R&D Project of Shaanxi Province(No.2024GX-YBXM-220)Thousands Person Plan of Jiangxi Province(JXSQ2020102131)Fundamental Research Funds for the Central Universities(Nos.D5000230348,D5000220057)China Scholarship Council(Nos.202206290133,202306290190).
文摘As a 3D printing method,laser powder bed fusion(LPBF)technology has been extensively proven to offer significant advantages in fabricating complex structured specimens,achieving ultra-fine microstructures,and enhancing performances.In the domain of manufacturing melt-grown oxide ceramics,it encounters substantial challenges in suppressing crack defects during the rapid solidification process.The strategic integration of high entropy alloys(HEA),leveraging the significant ductility and toughness into ceramic powders represents a major innovation in overcoming the obstacles.The ingenious doping of HEA parti-cles preserves the eutectic microstructures of the Al_(2)O_(3)/GdAlO_(3)(GAP)/ZrO_(2)ceramic composite.The high damage tolerance of the HEA alloy under high strain rates enables the absorption of crack energy and alleviation of internal stresses during LPBF,effectively reducing crack initiation and growth.Due to in-creased curvature forces and intense Marangoni convection at the top of the molt pool,particle collision intensifies,leading to the tendency of HEA particles to agglomerate at the upper part of the molt pool.However,this phenomenon can be effectively alleviated in the remelting process of subsequent layer de-position.Furthermore,a portion of the HEA particles partially dissolves and sinks into the molten pool,acting as heterogeneous nucleation particles,inducing the formation of equiaxed eutectic and leading pri-mary phase nucleation.Some HEA particles diffuse into the lamellar ternary eutectic structures,further promoting the refinement of eutectic microstructures due to increased undercooling.The innovative dop-ing of HEA particles has effectively facilitated the fabrication of turbine-structured,conical,and cylindrical ternary eutectic ceramic composite specimens with diameters of about 70 mm,demonstrating significant developmental potential in the field of ceramic composite manufacturing.
基金supported by the National Natural Science Foundation of China(No.51803041)the University and Local Integration Development Project of Yantai,China(No.2022 XDRHXMXK08).
文摘Herein,an external crosslinker facilitated the hypercrosslinking of ferrocene and a nitrogen heterocyclic compound(either melamine or imidazole)through a direct Friedel-Crafts reaction,which led to the formation of nitrogen-containing hypercrosslinked fer-rocene polymer precursors(HCP-FCs).Subsequent carbonization of these precursors results in the production of iron-nitrogen-doped por-ous carbon absorbers(Fe-NPCs).The Fe-NPCs demonstrate a porous structure comprising aggregated nanotubes and nanospheres.The porosity of this structure can be modulated by adjusting the iron and nitrogen contents to optimize impedance matching.The uniform dis-tribution of Fe-N_(x)C,N dipoles,andα-Fe within the carbon matrix can be ensured by using hypercrosslinked ferrocenes in constructing porous carbon,providing the absorber with numerous polarization sites and a conductive network.The electromagnetic wave absorption performance of the specially designed Fe-NPC-M_(2)absorbers is satisfactory,revealing a minimum reflection loss of-55.3 dB at 2.5 mm and an effective absorption bandwidth of 6.00 GHz at 2.0 mm.By utilizing hypercrosslinked polymers(HCPs)as precursors,a novel method for developing highly efficient carbon-based absorbing agents is introduced in this research.
基金supported by Natural Science Foundation of Shandong Province(Nos.ZR2022YQ42,ZR2021JQ15,ZR2021QE011,ZR2021ZD20,2022GJJLJRC-01)Innovative Team Project of Jinan(No.2021GXRC019)the National Natural Science Foundation of China(Nos.52022037,52202366).
文摘In contrast to research on active sites in nanomaterials,lithium tantalate single crystals,known for their exceptional optical properties and long-range ordered lattice structure,present a promising avenue for in-depth exploration of photocatalytic reaction systems with fewer constraints imposed by surface chemistry.Typically,the isotropy of a specific facet provides a perfect support for studying heteroatom doping.Herein,this work delves into the intrinsic catalytic sites for photocatalytic nitrogen fixation in iron-doped lithium tantalate single crystals.The presence of iron not only modifies the electronic structure of lithium tantalate,improving its light absorption capacity,but also functions as an active site for the nitrogen adsorption and activation.The photocatalytic ammonia production rate of the iron-doped lithium tantalate in pure water is maximum 26.95μg cm^(−2)h^(−1),which is three times higher than that of undoped lithium tantalate.The combination of first-principles simulations with in situ characterizations confirms that iron doping promotes the rate-determining step and changes the pathway of hydrogenation to associative alternating.This study provides a new perspective on in-depth investigation of intrinsic catalytic active sites in photocatalysis and other catalytic processes.
基金supported by the National Natural Science Foundation of China(Nos.52275395,51935014,and 82072084)the Science and Technology Innovation Program of Hunan Province(No.2023RC3046)+4 种基金the Young Elite Scientists Sponsorship Program byCAST(No.2020QNRC002)the NationalKeyResearchand Development Program of China(No.2023YFB4605800)the Central South University Innovation-Driven Research Programme(No.2023CXQD023)the Jiangxi Provincial Natural Science Foundation of China(No.20224ACB204013)the Project of State Key Laboratory of Precision Manufacturing for Extreme Service Performance,Central South University.
文摘Magnetostrictive Fe-Ga alloys have captivated substantial focus in biomedical applications because of their exceptional transition efficiency and favorable cytocompatibility.Nevertheless,Fe-Ga alloys always exhibit frustrating magnetostriction coefficients when presented in bulk dimensions.It is well-established that the magnetostrictive performance of Fe-Ga alloys is intimately linked to their phase and crystal structures.In this study,various concentrations of boron(B)were doped into Fe_(81)Ga_(19) alloys via the laser-beam powder bed fusion(LPBF)technique to tailor the crystal and phase structures,thereby improving the magnetostrictive performance.The results revealed the capacity for quick solidification of the LPBF process in expediting the solid solution of B element,which increased both lattice distortion and dislocations within the Fe-Ga matrix.These factors contributed to an elevation in the density of the modified-D0_(3) phase structure.Moreover,the prepared Fe-Ga-B alloys also exhibited a(001)preferred grain orientation caused by the high thermal gradients during the LPBF process.As a result,a maximum magnetostriction coefficient of 105 ppm was achieved in the(Fe_(81)Ga_(19))_(98.5)B_(1.5) alloy.In alternating magnetic fields,all the LPBF-prepared alloys showed good dynamic magnetostriction response without visible hysteresis,while the(Fe_(81)Ga_(19))_(98.5)B_(1.5) alloy presented a notable enhancement of~30%in magnetostriction coefficient when compared with the Fe_(81)Ga_(19) alloy.Moreover.the(Fe_(81)Ga_(19))_(98.5)B_(1.5) alloy exhibited favorable biocompatibility and osteogenesis,as confirmed by increased alkaline phosphatase(ALP)activity and the formation of mineralized nodules.These findings suggest that the B-doped Fe-Ga alloys combined with the LPBF technique hold promise for the development of bulk magnetostrictive alloys that are applicable for bone repair applications.
