Currently,the major challenge in terms of research on K-ion batteries is to ensure that they possess satisfactory cycle stability and specific capacity,especially in terms of the intrinsically sluggish kinetics induce...Currently,the major challenge in terms of research on K-ion batteries is to ensure that they possess satisfactory cycle stability and specific capacity,especially in terms of the intrinsically sluggish kinetics induced by the large radius of K+ions.Here,we explore high-performance K-ion half/full batteries with high rate capability,high specific capacity,and extremely durable cycle stability based on carbon nanosheets with tailored N dopants,which can alleviate the change of volume,increase electronic conductivity,and enhance the K+ion adsorption.The as-assembled K-ion half-batteries show an excellent rate capability of 468 mA h g^(−1) at 100 mA g^(−1),which is superior to those of most carbon materials reported to date.Moreover,the as-assembled half-cells have an outstanding life span,running 40,000 cycles over 8 months with a specific capacity retention of 100%at a high current density of 2000 mA g^(−1),and the target full cells deliver a high reversible specific capacity of 146 mA h g^(−1) after 2000 cycles over 2 months,with a specific capacity retention of 113%at a high current density of 500 mA g^(−1),both of which are state of the art in the field of K-ion batteries.This study might provide some insights into and potential avenues for exploration of advanced K-ion batteries with durable stability for practical applications.展开更多
Two-dimensional(2D)oxides have been the focus of substantial research interest recently,owing to their fascinating physico-chemical properties.However,fabrication of large-area 2D oxide materials in a controlled manne...Two-dimensional(2D)oxides have been the focus of substantial research interest recently,owing to their fascinating physico-chemical properties.However,fabrication of large-area 2D oxide materials in a controlled manner under mild conditions still remains a formidable challenge.Herein,we develop a facile and universal strategy based on the sonochemistry approach for controllable and large-area growth of quasi-aligned single-crystalline ZnO nanosheets on a Zn substrate(Zn@SC-ZnO)under ambient conditions.The obtained ZnO nanosheets possess the desired exclusively exposed(001)facets,which have been confirmed to play a critical role in significantly reducing the activation energy and facilitating the stripping/plating processes of Zn.Accordingly,the constructed Zn@SC-ZnO||Zn@SC-ZnO symmetric cell has very low polarization overpotential down to~20 mV,with limited dendrite growth and side reactions for Zn anodes.The developed Zn@SC-ZnO//MnO_(2)aqueous Zn-ion batteries(ZIBs)show a voltage efficiency of 88.2%under 500 mA g^(-1)at the stage of 50%depth of discharge,which is state of the art for ZIBs reported to date.Furthermore,the as-assembled large-size cell(5 cm×5 cm)delivers an open circuit potential of 1.648 V,and can be robustly operated under a high current of 20 mA,showing excellent potential for future scalable applications.展开更多
The exploration of cheap,efficient,and durable bifunctional electrocatalysts for oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)is highly desired to push forward the commercialization of rechargeable ...The exploration of cheap,efficient,and durable bifunctional electrocatalysts for oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)is highly desired to push forward the commercialization of rechargeable metal–air batteries.Here,bifunctional ORR/OER electrocatalysts based on CoxP(0<x<2,i.e.,Co_(2)P,Co_(2)P/CoP mixture,and CoP)nanoparticles(NPs)anchored on N,P-doped carbon framework(Co_(x)P@NPC)are developed via one-step carbonization of the mixture of as-synthesized ZIF-67 and melamine–phytic acid supermolecular aggregate(MPSA).The stoichiometric ratio of resultant Co_(x)P NPs can be rationally designed by adjusting the introduced ratio of ZIF-67 to MPSA,enabling their fabrication in a controlled manner.It is found that the as-synthesized Co_(2)P@NPC exhibits the best bifunctional ORR/OER activity among the Co_(x)P@NPC analogues,with a reversible oxygen electrode index(ΔE=E_(j10)−E_(1/2))down to~0.75 V.The constructed Zn–air battery based on Co_(2)P@NPC delivers a peak power density of 157 mW cm^(−2) and an excellent charge-discharge stability with negligible voltage decay for 140 h at 10 mA cm^(−2),superior to those based on Pt/C+RuO_(2) and most Co_(x)P-based electrodes ever reported.展开更多
The design of efficient cathode with great cycle performance,high flexibility,and low cost is essential for the commercialization of zinc–air battery(ZAB).Herein,we report the exploration of freestanding bifunctional...The design of efficient cathode with great cycle performance,high flexibility,and low cost is essential for the commercialization of zinc–air battery(ZAB).Herein,we report the exploration of freestanding bifunctional cathode with rationally designed structures,namely,tiny Co nanoparticles embedded in Ndoped carbon nanofiber aerogels,which have desired features including uniform Co dispersity,balanced distribution of N-C species,hierarchically porous structure with increased fraction of meso-to micropores,and moderate amounts of defects.Accordingly,the as-fabricated cathodes exhibit positive half-wave potential of 0.82 V for oxygen reduction and small overpotential of 350 mV at 10 mA cm^(−2) for oxygen evolution,respectively,which deliver smaller reversible oxygen electrode index(0.76 V)than the commercial Pt/C+RuO_(2)(0.80 V)and most Co-based electrocatalysts ever reported.Impressively,the as-constructed liquid rechargeable ZAB behaves high peak power density(160 mW cm^(−2)),large specific capacity(759.7 mAh g^(−1) at 10 mA cm^(−2),tested after 120 h of OCV tests),and robust stability over 277 h.Moreover,the as-assembled quasi-solid-state ZAB using such freestanding cathode represents excellent mechanical flexibility and outstanding cycle performance,regardless of being serviced under extremely bending conditions from 0°to 180°,underscoring their promising applications as durable bifunctional cathode for portable metalair batteries.展开更多
Sn doping is usually adopted to prepare Ti_(3)AlC_(2)in mass production because it can reduce the synthesis temperature while increasing the phase purity.However,excessive Sn doping usually deteriorates the oxidation ...Sn doping is usually adopted to prepare Ti_(3)AlC_(2)in mass production because it can reduce the synthesis temperature while increasing the phase purity.However,excessive Sn doping usually deteriorates the oxidation resistance of Ti_(3)AlC_(2).Therefore,an appropriate Sn doping concentration is a vital issue.In this work,the effect of Sn doping concentration on the oxidation behavior of Ti_(3)AlC_(2)was systematically investigated by combining theoretical calculations and experimental methods.Density function theory calculations suggest that the oxygen adsorption mechanisms for the(001)surface of Ti_(3)AlC_(2)with and without Sn doping are similar,and Ti-O bonds are always preferentially formed.The molecular dynamics simulation further indicates that Al atoms have a faster diffusion rate during the oxidation process.Therefore,a continuous Al_(2)O_(3)layer can form rapidly at high temperature.Nevertheless,when the Sn doping concentration exceeds 10 mol%,the continuity of the Al_(2)O_(3)layer is destroyed,thereby impairing the oxidation resistance of Ti_(3)AlC_(2).Furthermore,oxidation experiments verify the above results.The oxidation mechanisms of Ti3AlC2 with different Sn doping concentrations are also proposed.展开更多
As the dominated composition of Si_(3)N_(4)ceramics,α-silicon nitride(α-Si_(3)N_(4))can satisfy the strength and fracture toughness demand in the applications.However,α-Si_(3)N_(4)is oxygen-sensitive at high temper...As the dominated composition of Si_(3)N_(4)ceramics,α-silicon nitride(α-Si_(3)N_(4))can satisfy the strength and fracture toughness demand in the applications.However,α-Si_(3)N_(4)is oxygen-sensitive at high temperatures,which limits its high-temperature performance.To improve the oxidation resistance ofα-Si_(3)N_(4)ceramics,it is necessary to shed light on the oxidation mechanism.Herein,the initial oxidation ofα-Si_(3)N_(4)was systematically studied at the atomic and molecular levels.The density functional theory(DFT)calculation denotes that the(001)surface ofα-Si_(3)N_(4)has the best stability at both room temperature and high temperature.Besides,the oxidation process of theα-Si_(3)N_(4)(001)surface consists of O adsorption and N desorption,and the consequent formation of nitrogen-vacancy(VN)is the key step for further oxidation.Moreover,the molecular dynamics(MD)simulation indicates that the oxidation rate ofα-Si_(3)N_(4)(100)surface is slower than that ofα-Si_(3)N_(4)(001)surface due to the lower N concentration at the outermost layer.Therefore,the oxidation resistance ofα-Si_(3)N_(4)can be improved by regulating the(100)surface as the dominant exposure surface.In addition,reducing the concentration of N on the final exposed surface ofα-Si_(3)N_(4)by mean of constructing the homojunction of the Si-terminal(100)surface and other N-containing surfaces(such as(001)surface)should be also a feasible approach.展开更多
In the present work,we report the growth of all-inorganic perovskite nanorings with dual compositional phases of CsPbBr_(3)and CsPb_(2)Br5 via a facile hot injection process.The self-coiling of CsPbBr_(3)-CsPb_(2)Br5 ...In the present work,we report the growth of all-inorganic perovskite nanorings with dual compositional phases of CsPbBr_(3)and CsPb_(2)Br5 via a facile hot injection process.The self-coiling of CsPbBr_(3)-CsPb_(2)Br5 nanorings is driven by the axial stress generated on the outside surface of the as-synthesized nanobelts,which results from the lattice mismatch during the transformation of CsPbBr_(3)to CsPb_(2)Br5.The tailored growth of nanorings could be achieved by adjusting the key experimental parameters such as reaction temperature,reaction time and stirring speed during the cooling process.The photoluminescence intensity and quantum yield of nanorings are higher than those of CsPbBr_(3)nanobelts,accompanied by a narrower full width at half maximum(FWHM),suggesting their high potential for constructing self-assembled optoelectronic nanodevices.展开更多
基金National Natural Science Foundation of China,Grant/Award Numbers:51972178,52202061Hunan Provincial Nature Science Foundation,Grant/Award Number:2022JJ40068。
文摘Currently,the major challenge in terms of research on K-ion batteries is to ensure that they possess satisfactory cycle stability and specific capacity,especially in terms of the intrinsically sluggish kinetics induced by the large radius of K+ions.Here,we explore high-performance K-ion half/full batteries with high rate capability,high specific capacity,and extremely durable cycle stability based on carbon nanosheets with tailored N dopants,which can alleviate the change of volume,increase electronic conductivity,and enhance the K+ion adsorption.The as-assembled K-ion half-batteries show an excellent rate capability of 468 mA h g^(−1) at 100 mA g^(−1),which is superior to those of most carbon materials reported to date.Moreover,the as-assembled half-cells have an outstanding life span,running 40,000 cycles over 8 months with a specific capacity retention of 100%at a high current density of 2000 mA g^(−1),and the target full cells deliver a high reversible specific capacity of 146 mA h g^(−1) after 2000 cycles over 2 months,with a specific capacity retention of 113%at a high current density of 500 mA g^(−1),both of which are state of the art in the field of K-ion batteries.This study might provide some insights into and potential avenues for exploration of advanced K-ion batteries with durable stability for practical applications.
基金the National Natural Science Foundation of China(NSFC,Grant No.51972178)the Natural Science Foundation of Ningbo(2022J139)the Ningbo Yongjiang Talent Introduction Programme(2022A-227-G).
文摘Two-dimensional(2D)oxides have been the focus of substantial research interest recently,owing to their fascinating physico-chemical properties.However,fabrication of large-area 2D oxide materials in a controlled manner under mild conditions still remains a formidable challenge.Herein,we develop a facile and universal strategy based on the sonochemistry approach for controllable and large-area growth of quasi-aligned single-crystalline ZnO nanosheets on a Zn substrate(Zn@SC-ZnO)under ambient conditions.The obtained ZnO nanosheets possess the desired exclusively exposed(001)facets,which have been confirmed to play a critical role in significantly reducing the activation energy and facilitating the stripping/plating processes of Zn.Accordingly,the constructed Zn@SC-ZnO||Zn@SC-ZnO symmetric cell has very low polarization overpotential down to~20 mV,with limited dendrite growth and side reactions for Zn anodes.The developed Zn@SC-ZnO//MnO_(2)aqueous Zn-ion batteries(ZIBs)show a voltage efficiency of 88.2%under 500 mA g^(-1)at the stage of 50%depth of discharge,which is state of the art for ZIBs reported to date.Furthermore,the as-assembled large-size cell(5 cm×5 cm)delivers an open circuit potential of 1.648 V,and can be robustly operated under a high current of 20 mA,showing excellent potential for future scalable applications.
基金supported by National Natural Science Foundation of China(NSFC,Grant Nos.51702176,51572133,and 51972178)Zhejiang Provincial Nature Science Foundation(Grant No.LY20E020009)。
文摘The exploration of cheap,efficient,and durable bifunctional electrocatalysts for oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)is highly desired to push forward the commercialization of rechargeable metal–air batteries.Here,bifunctional ORR/OER electrocatalysts based on CoxP(0<x<2,i.e.,Co_(2)P,Co_(2)P/CoP mixture,and CoP)nanoparticles(NPs)anchored on N,P-doped carbon framework(Co_(x)P@NPC)are developed via one-step carbonization of the mixture of as-synthesized ZIF-67 and melamine–phytic acid supermolecular aggregate(MPSA).The stoichiometric ratio of resultant Co_(x)P NPs can be rationally designed by adjusting the introduced ratio of ZIF-67 to MPSA,enabling their fabrication in a controlled manner.It is found that the as-synthesized Co_(2)P@NPC exhibits the best bifunctional ORR/OER activity among the Co_(x)P@NPC analogues,with a reversible oxygen electrode index(ΔE=E_(j10)−E_(1/2))down to~0.75 V.The constructed Zn–air battery based on Co_(2)P@NPC delivers a peak power density of 157 mW cm^(−2) and an excellent charge-discharge stability with negligible voltage decay for 140 h at 10 mA cm^(−2),superior to those based on Pt/C+RuO_(2) and most Co_(x)P-based electrodes ever reported.
基金supported by National Natural Science Foundation of China(Grant No.51972178)Zhejiang Provincial Nature Science Foundation(Grant No.LY20E020009).
文摘The design of efficient cathode with great cycle performance,high flexibility,and low cost is essential for the commercialization of zinc–air battery(ZAB).Herein,we report the exploration of freestanding bifunctional cathode with rationally designed structures,namely,tiny Co nanoparticles embedded in Ndoped carbon nanofiber aerogels,which have desired features including uniform Co dispersity,balanced distribution of N-C species,hierarchically porous structure with increased fraction of meso-to micropores,and moderate amounts of defects.Accordingly,the as-fabricated cathodes exhibit positive half-wave potential of 0.82 V for oxygen reduction and small overpotential of 350 mV at 10 mA cm^(−2) for oxygen evolution,respectively,which deliver smaller reversible oxygen electrode index(0.76 V)than the commercial Pt/C+RuO_(2)(0.80 V)and most Co-based electrocatalysts ever reported.Impressively,the as-constructed liquid rechargeable ZAB behaves high peak power density(160 mW cm^(−2)),large specific capacity(759.7 mAh g^(−1) at 10 mA cm^(−2),tested after 120 h of OCV tests),and robust stability over 277 h.Moreover,the as-assembled quasi-solid-state ZAB using such freestanding cathode represents excellent mechanical flexibility and outstanding cycle performance,regardless of being serviced under extremely bending conditions from 0°to 180°,underscoring their promising applications as durable bifunctional cathode for portable metalair batteries.
基金the National Science Fund for Distinguished Young Scholars(Grant No.52025041)the National Natural Science Foundation of China(Grants No.51904021,51902020,and 51974021)the Fundamental Research Funds for the Central Universities(Grants No.FRF-TP-19-008A1 and FRF-TP-19-004B2Z).
文摘Sn doping is usually adopted to prepare Ti_(3)AlC_(2)in mass production because it can reduce the synthesis temperature while increasing the phase purity.However,excessive Sn doping usually deteriorates the oxidation resistance of Ti_(3)AlC_(2).Therefore,an appropriate Sn doping concentration is a vital issue.In this work,the effect of Sn doping concentration on the oxidation behavior of Ti_(3)AlC_(2)was systematically investigated by combining theoretical calculations and experimental methods.Density function theory calculations suggest that the oxygen adsorption mechanisms for the(001)surface of Ti_(3)AlC_(2)with and without Sn doping are similar,and Ti-O bonds are always preferentially formed.The molecular dynamics simulation further indicates that Al atoms have a faster diffusion rate during the oxidation process.Therefore,a continuous Al_(2)O_(3)layer can form rapidly at high temperature.Nevertheless,when the Sn doping concentration exceeds 10 mol%,the continuity of the Al_(2)O_(3)layer is destroyed,thereby impairing the oxidation resistance of Ti_(3)AlC_(2).Furthermore,oxidation experiments verify the above results.The oxidation mechanisms of Ti3AlC2 with different Sn doping concentrations are also proposed.
基金financially supported by the National Science Fund for Distinguished Young Scholars(No.52025041)the National Natural Science Foundation of China(Nos.51904021,51974021,51902020)+1 种基金the Fundamental Research Funds for the Central Universities(No.FRF-TP-19-008A1)the State Key Laboratory of Refractories and Metallurgy,Wuhan University of Science and Technology(No.G202003)。
文摘As the dominated composition of Si_(3)N_(4)ceramics,α-silicon nitride(α-Si_(3)N_(4))can satisfy the strength and fracture toughness demand in the applications.However,α-Si_(3)N_(4)is oxygen-sensitive at high temperatures,which limits its high-temperature performance.To improve the oxidation resistance ofα-Si_(3)N_(4)ceramics,it is necessary to shed light on the oxidation mechanism.Herein,the initial oxidation ofα-Si_(3)N_(4)was systematically studied at the atomic and molecular levels.The density functional theory(DFT)calculation denotes that the(001)surface ofα-Si_(3)N_(4)has the best stability at both room temperature and high temperature.Besides,the oxidation process of theα-Si_(3)N_(4)(001)surface consists of O adsorption and N desorption,and the consequent formation of nitrogen-vacancy(VN)is the key step for further oxidation.Moreover,the molecular dynamics(MD)simulation indicates that the oxidation rate ofα-Si_(3)N_(4)(100)surface is slower than that ofα-Si_(3)N_(4)(001)surface due to the lower N concentration at the outermost layer.Therefore,the oxidation resistance ofα-Si_(3)N_(4)can be improved by regulating the(100)surface as the dominant exposure surface.In addition,reducing the concentration of N on the final exposed surface ofα-Si_(3)N_(4)by mean of constructing the homojunction of the Si-terminal(100)surface and other N-containing surfaces(such as(001)surface)should be also a feasible approach.
基金supported by the National Natural Science Foundation for Excellent Young Scholars of China(No.51522402)the National Natural Science Foundation of China(No.51972178),the Zhejiang Provincial Nature Science Foundation(No.LQ17E020002)The authors thank Engineer Dongsheng He for the help on double Cs-corrected transmission electron microscopy.
文摘In the present work,we report the growth of all-inorganic perovskite nanorings with dual compositional phases of CsPbBr_(3)and CsPb_(2)Br5 via a facile hot injection process.The self-coiling of CsPbBr_(3)-CsPb_(2)Br5 nanorings is driven by the axial stress generated on the outside surface of the as-synthesized nanobelts,which results from the lattice mismatch during the transformation of CsPbBr_(3)to CsPb_(2)Br5.The tailored growth of nanorings could be achieved by adjusting the key experimental parameters such as reaction temperature,reaction time and stirring speed during the cooling process.The photoluminescence intensity and quantum yield of nanorings are higher than those of CsPbBr_(3)nanobelts,accompanied by a narrower full width at half maximum(FWHM),suggesting their high potential for constructing self-assembled optoelectronic nanodevices.
